AN INVESTIGATION OF FLOTATION REAGENTS

Publication No. 02-158-227

AN INVESTIGATION OF FLOTATION REAGENTS FINAL REPORT

Prepared by FLORIDA INSTITUTE OF PHOSPHATE RESEARCH

June 2008

The Florida Institute of Phosphate Research was created in 1978 by the Florida Legislature (Chapter 378.101, Florida Statutes) and empowered to conduct research supportive to the responsible development of the state’s phosphate resources. The Institute has targeted areas of research responsibility. These are: reclamation alternatives in mining and processing, including wetlands reclamation, phosphogypsum storage areas and phosphatic clay containment areas; methods for more efficient, economical and environmentally balanced phosphate recovery and processing; disposal and utilization of phosphatic clay; and environmental effects involving the health and welfare of the people, including those effects related to radiation and water consumption. FIPR is located in Polk County, in the heart of the Central Florida phosphate district. The Institute seeks to serve as an information center on phosphate-related topics and welcomes information requests made in person, or by mail, email, or telephone.

Executive Director Paul R. Clifford G. Michael Lloyd, Jr. Director of Research Programs Research Directors G. Michael Lloyd, Jr. J. Patrick Zhang Steven G. Richardson Brian K. Birky

-Chemical Processing -Mining & Beneficiation -Reclamation -Public & Environmental Health Publications Editor Karen J. Stewart

Florida Institute of Phosphate Research 1855 West Main Street Bartow, Florida 33830 (863) 534-7160 Fax: (863) 534-7165 http://www.fipr.state.fl.us

AN INVESTIGATION OF FLOTATION REAGENTS

FINAL REPORT

Patrick Zhang Principal Investigator with Robert E. Snow and Michael D. Bogan

FLORIDA INSTITUTE OF PHOSPHATE RESEARCH 1855 West Main Street Bartow, Florida 33830 USA

Contract Manager: Patrick Zhang FIPR Project Numbers: 97-02-125 and 02-02-158

June 2008

DISCLAIMER

The contents of this report are reproduced herein as received from the contractor. The report may have been edited as to format in conformance with the FIPR Style Manual. The opinions, findings and conclusions expressed herein are not necessarily those of the Florida Institute of Phosphate Research, nor does mention of company names or products constitute endorsement by the Florida Institute of Phosphate Research.

© 2008, Florida Institute of Phosphate Research.

PERSPECTIVE SELECTION OF FATTY ACIDS FOR PHOSPHATE FLOTATION The commercial fatty acids used in floating phosphate in Florida may be classified in two major categories, tall oil and its soaps. Although there are not many producers that supply fatty acids for the mines in Florida, one rarely finds the same product being used in two plants. Currently, each company has its own specifications for fatty acids. These specifications may include acid number, rosin content, moisture and unsaponifiables. Unlike flotation of sulfide minerals, flotation of phosphate has not been investigated extensively in terms of reagent schemes, particularly selective collectors and depressants for phosphate-silica, dolomite-phosphate, and dolomite-silica separations. Selection of fatty acid is generally mine-specific. Currently, each mine selects a product by conducting extensive flotation tests. No attempt has been made to correlate flotation performance with physico-chemical properties of fatty acids (such as organic compound compositions, surface tension, surface charge density, carbon chain length and viscosity), characteristics of flotation feed (such as particle size distribution and clay content) and water (such as hardness). The following questions have not yet been answered satisfactorily: (1) chemically, what makes one fatty acid a good collector and another one poor? (2) what chemical tests can be run to improve reagent quality? (3) what roles do feed characteristics play? (4) what roles does water quality play? and (5) what are the major physical parameters of fatty acid collectors that influence flotation performance? THE ROLE OF FUEL OIL AND DEFOAMING Non-polar hydrocarbon oils have an essential role in flotation. The Florida phosphate industry consumes about 150 million tons a year of fuel oil in the forms of No.5 oil or kerosene. One of the effects of oil or kerosene is to increase the resulting contact angle of a mineral against air bubbles substantially over the value in its absence, thereby accelerating kinetics and making possible the flotation of larger particles, both as a result of stronger adhesion of individual particles to bubbles and, equally, of the flotation of air/mineral/oil aggregates as well as individual particles. Fuel oil and kerosene also act as solvents for tall oil fatty acids and tallow amines, making them easier to handle. Furthermore, they also boost (extend) the floatability of the collectors. However, the industry has been using an excessive amount of fuel oil, mainly for controlling foaming. Long-chain fatty acids used for commercial flotation applications go through an ionization process between pH 4 and 10. At pH of around 8.0 there is an ion molecular complex (RCOOH-RCOO-) present in 1:1 proportion. In this pH range these surfactants have distinct dual functionality as collector and frother. This phenomenon causes excessive foaming in phosphate flotation. Current practice is to add a large quantity of fuel oil. Although a tremendous amount of fuel oil is being used for controlling foaming, excessive foaming still occurs in many plants, causing an appreciable loss of fatty acids. Fuel oil may not be the most effective defoamer for phosphate flotation. A small amount of an additive or a commercial defoamer could reduce fuel oil usage dramatically. Excessive

iii

use of fuel oil is not only costly, but also causes environmental concern because fuel oil does not biodegrade as fast as other flotation reagents such as fatty acids and amines. AMINE COLLECTORS FOR SILICA (SANDS) The chemical processing plants are becoming more and more tolerant to Insol content in the acidulation feeds. As a result, the Insol levels in flotation concentrates have been relaxed from 3-5% to 5-8%. This trend warrants a fresh look at the available amine collectors as well as additives for amine flotation. In particular, this trend should make selectivity more important. DEVELOPMENT OF ALTERNATIVE TO THE CRAGO PROCESS Although the Crago "double float" process is a very mature technique for phosphate beneficiation, the potential benefits of a single-collector flotation process have encouraged some investigators to search for a substitute for the Crago process. The advantages of a single-collector system over the double float process include reduced capital and energy costs, a simplified flowsheet, and minimized discharge of chemicals into the environment. Several research programs have generated promising results, including the Anionic Rougher-Cleaner Process developed by Zellars-Williams, the Double Depression Process proposed by the USBM, and the Reagent Starvation Process invented by the University of Florida. Unfortunately, these processes achieved singlecollector flotation by sacrificing either recovery or concentrate grade. Replacement of the Crago process with a single-collector process can only be realized by using either a very selective collector or a highly efficient depressant. Although anionic flotation of phosphate with silica depression seems to be the logical approach for developing a singlecollector process, inverse flotation of silica with phosphate depression also has potential. Most of the previous studies on phosphate depressants were focused on separating carbonate from phosphate. The ideal depression conditions for carbonates separation may not be those suitable for silica removal. PROJECT EVALUATION The project reported here followed another FIPR in-house project, “A Screening Study on Phosphate Depressants for Beneficiating Florida Phosphate Ores.” The current two projects eventually evolved into seven phases. Phase I investigated potential substitutes for fuel oil, and found that the addition of rosin oil not only reduced fuel oil dosages, but also improved selectivity. Phase II was designed to compare results obtained using various C12-C22 fatty acids. Inferior flotation results were obtained using the unsaturated C16 palmitoleic acid and the unsaturated C22 erucic acid. In terms of pulling power for coarse phosphate particles, erucic acid did the best on the +28 mesh fraction, and linoleic proved to be the weakest, with the rest being similar. For the 28 x 35 mesh fraction, oleic acid was the most effective, with the rest being more or less the same.

iv

In Phase III, a composite sample of low-grade feed was subjected to preliminary laboratory rougher flotation testwork using five different anionic collectors. The best flotation results were obtained using a mixture of tall oil and oleic acid. Relatively pure isostearic/iso-oleic acid type fatty acid collectors were evaluated in Phase IV. The most selective collector evaluated appeared to be Century 1108, a high isostearic acid type reagent. However, this excellent-performing reagent was concluded to be too expensive, at $1.25/lb., for commercial use. The overall most promising reagent was Century MO-5. This collector was essentially an iso-oleic acid/stearic acid mixture (not isostearic acid) priced at $0.35/lb. This phase laid a sound foundation for developing single-collector, all-anionic flotation processes. The relatively high-grade, more expensive collectors, such as MO-5 and F12, proved to be not only more selective, but also more powerful for coarse particles. Phase V produced four all-anionic phosphate flotation processes, which do not require the acid scrubbing and amine flotation steps. These flowsheets were evolved from the FIPR/SAPR process. SAPR stands for Single-collector, All-anionic Phosphate Recovery. The FIPR/SAPR process offers a universal flowsheet for any anionic reagent system and flotation feed of varying sizes. For an unsized or fine flotation feed, the basic FIPR/SAPR process consists of the following steps: (1) high-solids conditioning with an anionic collector; (2) anionic rougher flotation, with the rougher concentrate sized at 48 (or 65) mesh and the +48 mesh recovered as a final product; and (3) cleaning flotation of the -48 mesh fraction from Step 2. In another all-anionic flowsheet (#2), rougher flotation is conducted under “reagent starvation” conditions so that low-Insol rougher concentrate can be achieved, which would not require further cleaning. The rougher tail is then sized at 48 mesh. The coarser (+48 mesh) fraction of the tail is subject to scavenging flotation, while the -48 fraction is discarded. This rougher-scavenger flowsheet achieved excellent results on lab scale, but required fine tuning of fatty acid dosage in rougher flotation. In flowsheet #3, the flotation feed is first sized at 48 mesh (or somewhere between 35 and 48 mesh). The coarse feed is subject to one-step flotation, while the finer feed is processed using a straight rougher-cleaner flowsheet. Flowsheet #4 was developed based on the fact that in rougher flotation, phosphate floats first with the least amount of sands in the initial stage. Therefore, the rougher concentrate from the first two cells (in a bank of four cell configuration) may be collected as a final product, while the rougher concentrate from the last two cells goes through a cleaner flotation step. The amine study, Phase VI, investigated the performance of six types of amines (primary, secondary, tertiary, quaternary, ether, and condensate) on the cleaning step of the rougher concentrates for the Crago process, and the effect of particle size on the performance of each type of amine. The research also studied the effect of slimes (tolerance) of these six types of amines and Percol 90L polymer addition on the amine flotation step of the Reverse Crago process. The Reverse Crago process was developed under a different FIPR in-house project. In this process, the sands are floated first with an amine plus an anionic polymer to “blind” the slime, followed by fatty acid flotation. Patrick Zhang Research Director, Mining and Beneficiation

v

ACKNOWLEDGMENTS This study would not have been possible without the financial support of the Florida Institute of Phosphate Research under research grants FIPR #97-02-125 and #0202-158. The support and technical input of the FIPR Beneficiation Technical Advisory Committee is highly appreciated. The following companies have been very cooperative in sample collection: Cargill Fertilizer, CF Industries, IMC Phosphates, PCS Phosphate, and Mosaic Phosphates. Glenn Gruber of Jacobs Engineering Group was instrumental in conducting pilot scale testing of the new flotation processes developed under this project. The staff of the FIPR Met Lab and Analytical Lab worked hard on sample collection, preparation and analysis. Francisco Sotillo of PerUsa conducted all the laboratory tests or the Amine Study drafted the report on this phase.

vi

ABSTRACT This multi-year research program investigated many aspects of phosphate flotation reagents, both in terms of improving current practice and developing new flotation processes. A dozen of petroleum additives were first screened as froth modifier/fatty acid extender. The partial substitution of rosin oil for fuel oil was found to be beneficial. Preliminary optimization tests indicated that fuel oil use could be reduced by about 25% using rosin oil, with higher cost for rosin oil being compensated by improved P2O5 recovery. Eleven pure fatty acid compounds (C12-C22 fatty acids, 6 unsaturated and 5 saturated) were compared as Florida phosphate collectors. The saturated fatty acids were found to be very poor collectors when using the standard conditioning procedure, whereas the unsaturated C16-C22 fatty acids showed fair to good phosphate collecting ability. The C18 fatty acids oleic, impure oleic, linoleic and the C20 eicosenoic acid were shown to be the best phosphate collectors. Five commonly used fatty acid based collectors were tested on a composite, lowgrade feed. These collectors included an oleic acid, a tall oil, a Petronate CR sulfonate, a cottonseed soapstock, and a mixture of tall oil/pitch soap. The relatively inexpensive cottonseed soapstock and tall oil pitch soap did not perform well, while the oleic acid, tall oil fatty acid, and the mixture of petroleum sulfonate and tall oil fatty acid met the industry requirement in terms of recovery and selectivity. Four isostearic/iso-oleic acid type fatty acid collectors, supplied by divisions of International Paper, were compared with a commercial grade oleic acid and a tall oil as phosphate collectors using standard laboratory conditioning and flotation procedures. The most selective collector evaluated appeared to be Century 1108, a high isostearic acid type reagent. However, this excellent performing reagent was concluded to be too expensive. The overall most promising reagent was Century MO-5. This collector was essentially an iso-oleic acid/stearic acid mixture. Four all-anionic flotation flowsheets were developed. These flowsheets simplify the current practice by eliminating the acid scrubbing and amine flotation steps. These flowsheets achieved higher recovery with an overall lower cost, but produced higher Insol (9-11%) products. This research investigated the performance of six types of amines (primary, secondary, tertiary, quaternary, ether, and condensate) on the cleaning step of the rougher concentrates for the Crago process, and the effect of particle size on the performance of each type of amine. The research also studied the effect of slimes (tolerance) of these six types of amines and Perco 90L polymer addition on the amine flotation step of the Reverse Crago process. To improve the all anionic flotation processes, several selectivity enhancement methods were evaluated, with addition of lignosulfonates showing promising results. vii

TABLE OF CONTENTS PERSPECTIVE.................................................................................................................. iii ACKNOWLEDGMENTS ................................................................................................. iv ABSTRACT...................................................................................................................... vii EXECUTIVE SUMMARY .................................................................................................1 Part I. Investigation of Fuel Oil Substitutes ............................................................1 Part II. Study of Pure Fatty Acid Compounds ........................................................2 Part 3. Comparison of Various Anionic Collectors ................................................3 Part 4. Study of Iso-Acids .......................................................................................4 Part 5. Development of Single-Collector Processes ...............................................4 Part 6. Amine Study ................................................................................................6 Selectivity ....................................................................................................7 Effect of Particle Size ..................................................................................7 Effect of Slime on the Reverse Crago Process ............................................8 Part 7. Selectivity Enhancement for All-Anionic Flotation ..................................10 PART I. INVESTIGATION OF FUEL OIL SUBSTITUTES Introduction .......................................................................................................... 1-1 Experimental ........................................................................................................ 1-3 Flotation Feed Samples ............................................................................ 1-3 Flotation Reagents Evaluated .................................................................. 1-3 Results and Discussion ........................................................................................ 1-5 Comparison of Various Hydrocarbon-Type Froth Modifiers .................. 1-5 Effect of Rosin Oil ................................................................................... 1-6 Generalized Flotation Observations and Comments................................ 1-8 Froth Modifiers as Partial Substitute for Fuel Oil ............................................... 1-9 Partial Substitution of Various Surfactant Froth Modifiers for No. 5 Fuel Oil ..................................................................................... 1-9 Effect of Rosin Oil Addition Levels ...................................................... 1-10 Effect of Sodium Silicate Addition ........................................................ 1-11 Extra Desliming to Reduce Fuel Oil Use........................................................... 1-12 ix

TABLE OF CONTENTS (CONT.) Summary ................................................................................................ 1-12 Cargill Feed Flotation Using Partial Substitution of Various Surfactant Froth Modifiers for No. 5 Fuel Oil .................................. 1-13 Cargill Feed Flotation Using Various Degrees of Conditioner Discharge Desliming ......................................................................... 1-15 Benefits Analysis of Rosin Oil Substitution and Extra Desliming .................... 1-16 Summary ................................................................................................ 1-16 Flotation of Cargill Scrubbed/Deslimed Feed Using Various Levels of Liqro GA Tall Oil at 1.0:0.6 Constant Ratio to No. 5 Fuel Oil ................................................................................... 1-17 Flotation of Natural vs. Scrubbed, Deslimed Cargill Feed Using Liqro GA Tall Oil at 1.0:0.4 Ratio to No. 5 Fuel Oil with and without Rosin Oil Addition ........................................................ 1-18 Flotation of Natural vs. Scrubbed, Deslimed PCS Feed Using PCS Tall Oil at 1.0:0.4 Ratio to PCS Fuel Oil with and without Rosin Oil or Extra Fuel Oil Addition .................................. 1-19 Preliminary Cost Comparison Calculations for Rosin Oil Partial Substitution for Fuel Oil and for Feed Scrubbing and Desliming .......................................................................................... 1-19 Conclusions ........................................................................................................ 1-21 References .......................................................................................................... 1-23 For Additional Reading...................................................................................... 1-25 Appendix 1. Tables for Part 1 .......................................................................... 1A-1 PART 2. STUDY OF PURE FATTY ACID COMPOUNDS Summary .............................................................................................................. 2-1 Experimental ........................................................................................................ 2-3 Description of Phosphate Collectors Evaluated ....................................... 2-3 Results and Discussion ........................................................................................ 2-5 Flotation Using Various “Pure” Fatty Acids............................................ 2-5 Flotation Using Cottonseed Soapstock Fatty Acid Extract .................... 2-10 Flotation Using Liqro GA Tall Oil/Cottonseed Fatty Acid Extract Mixtures ............................................................................... 2-10 Size/Assay Analyses of Selected Flotation Tails ................................... 2-10 Relevant Phosphate Rougher Flotation References ............................... 2-11 Conclusions ........................................................................................................ 2-13 x

TABLE OF CONTENTS (CONT.) References .......................................................................................................... 2-15 For Additional Reading...................................................................................... 2-17 Appendix 2. Tables for Part 2 .......................................................................... 2A-1 PART 3. COMPARISON OF VARIOUS ANIONIC COLLECTORS Introduction .......................................................................................................... 3-1 Summary .............................................................................................................. 3-3 Experimental ........................................................................................................ 3-5 Description of Flotation Feed Sample ..................................................... 3-5 Phosphate Flotation Collectors ................................................................ 3-5 Results and Discussion ........................................................................................ 3-7 Flotation of Four Corners Feed ................................................................ 3-7 Oleic Acid .................................................................................... 3-7 Liqro GA Tall Oil ...................................................................... 3-11 Petronate CR Sulfonate .............................................................. 3-14 Cottonseed Soapstock ................................................................ 3-16 Custofloat 27AR Tall Oil/Pitch Soap ........................................ 3-20 Petronate CR (20%) and Liqro GA Tall Oil (80%) Mixture ..... 3-23 Comparison of All Collectors ................................................................ 3-26 Size/Assay Analyses of Selected Flotation Tails ................................... 3-27 Appendix 3. Tables for Part 3 .......................................................................... 3A-1 PART 4. STUDY OF ISO-ACIDS Preliminary Screening .......................................................................................... 4-1 Introduction .............................................................................................. 4-1 Summary .................................................................................................. 4-1 Experimental ............................................................................................ 4-1 Results and Discussion ............................................................................ 4-2 Flotation of IMC Feed Using Various Fatty Acid Collectors ...... 4-4 Flotation of IMC Feed Using Century MO-5 with N-Silicate ... 4-10 Size/Assay Analyses of Selected IMC Flotation Tails............... 4-11 Flotation of PCS Feed Using Various Fatty Acid Collectors .... 4-13 Flotation of PCS Feed Using Century MO-5 with N-Silicate ... 4-18

xi

TABLE OF CONTENTS (CONT.) Detailed Tests Using the Best Iso-Collectors .................................................... 4-24 Introduction ............................................................................................ 4-24 Experimental .......................................................................................... 4-24 Description of Flotation Feed Samples ...................................... 4-25 Results and Discussion .......................................................................... 4-27 Flotation of Cargill Fine Feed Using Various Fatty Acid Collectors .............................................................................. 4-27 Flotation of Cargill Feed Using Century 1108 and Century MO-5 with N-Silicate ........................................................... 4-31 Flotation of IMC Coarse Feed Using Various Fatty Acid Collectors .............................................................................. 4-31 Flotation of IMC Coarse Feed Using Century MO-5 with N-Silicate .............................................................................. 4-36 Flotation of CF Feed Using Various Fatty Acid Collectors ....... 4-36 Flotation of CF Feed Using Century MO-5 with N-Silicate ...... 4-39 Appendix 4. Tables for Iso-Acid Evaluation ................................................... 4A-1 PART 5. DEVELOPMENT OF SINGLE-COLLECTOR (FIPR/SAPR) FLOTATION PROCESSES Summary .............................................................................................................. 5-1 Introduction .......................................................................................................... 5-3 The Reserve Shortage and Recovery Issue .............................................. 5-3 Analysis of the Current Practice (Crago Double Float) ........................... 5-3 The Benefits of Single-Collector Flotation .............................................. 5-4 Literature Review..................................................................................... 5-4 The FIPR/SAPR Process.......................................................................... 5-5 Single-Collector Flowsheet #2 ................................................................. 5-6 Single-Collector Flowsheet #3 ................................................................. 5-7 Single-Collector Flowsheet #4 ................................................................. 5-8 Experimental ...................................................................................................... 5-11 Flotation Feed Samples .......................................................................... 5-11 Rougher Flotation .................................................................................. 5-11 Sizing and Cleaner Flotation.................................................................. 5-11 Results and Discussion ...................................................................................... 5-13 xii

TABLE OF CONTENTS (CONT.) Initial Comparison of Various Fatty-Acid-Based Collectors ................. 5-13 Comparison of Commercial Collectors with Iso-Stearic/ Iso-Oleic Acids ................................................................................. 5-13 Effect of Sodium Silicate ....................................................................... 5-17 Performance of the FIPR/SAPR Process ............................................... 5-18 Rougher Flotation Time/Rate Measurements ........................................ 5-19 Test Results Using Flowsheet #2 ........................................................... 5-24 Investigation of High-Purity Fatty Acid Collectors ............................... 5-26 Summary .................................................................................... 5-26 Experimental .............................................................................. 5-27 Phosphate Flotation Collectors Tested........................... 5-27 Lab Flotation Test Procedure ......................................... 5-28 Test Results and Discussion ...................................................... 5-28 Using Century MO-5 Collector (Acid No. =>166) ........ 5-28 Using Sylfat FA-12 and FA-11 (Acid No. = >186, >188) ......................................................................... 5-28 Using Liqro GA Tall Oil (Acid No. = 148) ................... 5-29 Using Century MO-5/Sylfat FA-11 Mixture (1:1) (Acid No. =>176) ...................................................... 5-29 Using Century MO-5/Liqro GA Mixture (1:1) (Acid No. =>157) ...................................................... 5-29 Using Arizona 2122 Heads/Sylfat FA-11 Mixture (1:1) (Acid No. =>160) ............................................. 5-29 General Comments......................................................... 5-30 Pilot Test Indications ............................................................................. 5-30 Results Using the FIPR/SAPR Flowsheet ................................. 5-30 Results Using All-Anionic Flowsheet #2 .................................. 5-33 Results Using All-Anionic Flowsheet #3 .................................. 5-33 Conclusions ........................................................................................................ 5-37 References .......................................................................................................... 5-39 For Additional Reading...................................................................................... 5-41 Appendix 5. Test Data for FIPR/SAPR Flowsheet Development ................... 5A-1 PART 6. AMINE STUDY Summary, Conclusions and Recommendations ................................................... 6-1 Introduction .......................................................................................................... 6-7 xiii

TABLE OF CONTENTS (CONT.) Literature Review................................................................................................. 6-9 Information Gaps ............................................................................................... 6-11 Objectives .......................................................................................................... 6-13 Materials and Methods....................................................................................... 6-15 Flotation Feeds ....................................................................................... 6-15 Reagents ................................................................................................. 6-16 Experimental Results and Discussion ................................................................ 6-17 Evaluation of Different Types of Amines .............................................. 6-17 Effect of Particle Size ............................................................................ 6-28 Effect of Slimes on the Amine Flotation Step of the Reverse Crago Process.................................................................................... 6-36 Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Process ................................................................ 6-40 References .......................................................................................................... 6-40 Appendix 6A. Screen Analysis of Test Feeds.................................................. 6A-1 Appendix 6B. Data for Unsized Amine Feed ...................................................6B-1 Appendix 6C. Tree Analysis .............................................................................6C-1 Appendix 6D. Detailed Results from Locked Cycle Tests .............................. 6D-1 Appendix 6E. Tests on Particle Size Effect ...................................................... 6E-1 Appendix 6F. Screen Analysis of Flotation Tails ............................................. 6F-1 Appendix 6G. Effect of Slime on Reverse Crago ............................................ 6G-1 Appendix 6H. Effect of Percol on Reverse Crago ........................................... 6H-1 PART 7. SELECTIVITY ENHANCEMENT IN ALL-ANIONIC FLOTATION OF FLORIDA PHOSPHATES Abstract ................................................................................................................ 7-1 Introduction .......................................................................................................... 7-3 Experimental ........................................................................................................ 7-5 Materials and Reagents ............................................................................ 7-5 Flotation Collectors...................................................................... 7-5 Flotation Feed Samples ................................................................ 7-5 Flotation Modifiers ...................................................................... 7-6 Collector Adsorbing Powers ........................................................ 7-6 Test Procedures ........................................................................................ 7-7 Rougher Flotation ........................................................................ 7-7 xiv

TABLE OF CONTENTS (CONT.) Sizing and Cleaner Flotation........................................................ 7-7 Addition of Sodium Silicate ........................................................ 7-7 Addition of Modifiers .................................................................. 7-7 Flotation Procedure with Solid Powder Additives....................... 7-7 Results and Discussion ........................................................................................ 7-9 Effect of Lignosulfonates ......................................................................... 7-9 Effect of Frothers ................................................................................... 7-12 Effect of Various Solid Powders............................................................ 7-13 The “Rinse Process” .............................................................................. 7-14 Rougher Flotation Using Oxalic Acid Modifier .................................... 7-14 Sizing as a Means to Improve Selectivity and Grade ............................ 7-22 Conclusions ........................................................................................................ 7-25 References .......................................................................................................... 7-27

xv

LIST OF FIGURES Figure

Page

1-1. 1-2. 1-3. 1-4.

Flotation Recoveries from Feed A Using Different Froth Modifiers ........... 1-5 Effect of Rosin Oil on the Performance of Different Oils for Feed A ......... 1-7 Effect of Rosin Oil on Flotation Recovery for Feed B ................................ 1-7 Effect of Froth Modifier Type and Addition Point on Recovery for Feed B .................................................................................................... 1-10 Effect of Rosin Oil Dosage with 1 Lb. Tall Oil and 0.6 Lb. No. 5 Fuel Oil per Ton of Feed B ............................................................................ 1-11 Effect of Froth Modifiers on Flotation Recovery from Feed B Using 1 Lb./Ton Collector .................................................................... 1-14 Effect of Froth Modifiers on Concentrate Grade for Feed B Using 1 Lb./Ton Collector Flotation of Deslimed and Scrubbed/Deslimed Cargill Feed Levels................................................................................. 1-14 Collector Dosage vs. Concentrate Grade and Recovery of a Deslimed Feed ....................................................................................................... 1-18

1-5. 1-6. 1-7. 1-8. 2-1. 2-2. 2-3. 2-4.

3-1. 3-2. 3-3. 3-4. 3-5. 3-6. 3-7. 3-8. 3-9. 3-10.

Concentrate Grades Using Various Unsaturated C16-C22 Fatty Acids at Collector Dosage of 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil ............ 2-6 Flotation Recovery Using Various Unsaturated C16-C22 Fatty Acids at Collector Dosage of 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil. ........... 2-7 Effect of Silicate on Concentrate Grade Using Unsaturated C16-C22 Fatty Acids at 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil and 0.5 Lb. Silicate ......................................................................................... 2-8 Effect of Silicate on Flotation Recovery Using Unsaturated C16-C22 Fatty Acids at 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil and 0.5 Lb. Silicate ......................................................................................... 2-9 Concentrate P2O5 vs. Oleic Acid Dosage ....................................................... 3-8 Concentrate Insol vs. Oleic Acid Dosage ....................................................... 3-9 Flotation Recovery vs. Oleic Acid Dosage .................................................. 3-10 Concentrate P2O5 vs. Liqro GA Dosage at Different Fuel Oil Ratios ........... 3-11 Concentrate Insol vs. Liqro GA Dosage at Different Fuel Oil Ratios ........... 3-12 Flotation Recovery vs. Liqro GA Dosage at Different Fuel Oil Ratios ...... 3-13 Concentrate % P2O5 vs.. Petroleum Sulfonate Dosage with 37.5% Fuel Oil................................................................................................... 3-14 Concentrate % Insol vs. Petroleum Sulfonate Dosage with 37.5% Fuel Oil................................................................................................... 3-15 Flotation Recovery vs. Petroleum Sulfonate Dosage with 37.5% Fuel Oil .................................................................................................. 3-16 Concentrate % P2O5 vs. Cottonseed Soap Dosage at Collector-toFuel-Oil Ratio of 1:0.5 ............................................................................ 3-17

xvii

LIST OF FIGURES (CONT.) Figure 3-11. 3-12. 3-13. 3-14. 3-15. 3-16. 3-17. 3-18. 3-19. 4-1. 4-2. 4-3. 4-4. 4-5. 4-6. 4-7. 4-8. 4-9. 4-10. 4-11. 4-12. 4-13.

Page Concentrate % Insol vs. Cottonseed Soap Dosage at Collector-toFuel-Oil Ratio of 1:0.5 ............................................................................ 3-18 Flotation Recovery vs. Cottonseed Soap Dosage at Collector-toFuel-Oil Ratio of 1:0.5 ............................................................................ 3-19 Concentrate % P2O5 vs. Tall Oil Pitch Soap Dosage.................................... 3-20 Concentrate % Insol vs. Tall Oil Pitch Soap Dosage ................................... 3-21 Flotation Recovery vs. Tall Oil Pitch Soap Dosage ..................................... 3-22 Concentrate % P2O5 vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6.............. 3-23 Concentrate Insol vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6.............. 3-24 Flotation Recovery vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6.............. 3-25 Grade-Recovery Curves for All Tests of Different Collectors...................... 3-26 Concentrate % P2O5 vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 ......................................................................... 4-6 Concentrate % Insol vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using Four Corners Feed ................................ 4-7 Flotation % P2O5 Recovery vs. Dosage of Various Collectors at Collector-to-Fuel-Oil ratio of 1:0.6 Using Four Corners Feed .................. 4-8 Concentrate Grade vs. Recovery for Various Collectors ................................ 4-9 Concentrate % P2O5 vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using the PCS Feed ....................................... 4-14 Concentrate % Insol vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using the PCS Feed ....................................... 4-15 Flotation Recovery vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using the PCS Feed ....................................... 4-16 Concentrate Grade vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using the PCS Feed ....................................... 4-17 Concentrate % P2O5 vs. Collector Dosage and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed .......................................................... 4-27 Concentrate % Insol vs. Collector Dosage and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed .......................................................... 4-28 Flotation Recovery vs. Collector Dosage and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed .......................................................... 4-29 Concentrate Grade vs. Recovery at pH9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed .......................................................... 4-30 Concentrate Grade vs. Recovery at pH 9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed with N-Silicate ................................... 4-32

xviii

LIST OF FIGURES (CONT.) Figure 4-14. 4-15. 4-16. 4-17. 4-18.

Page Concentrate % P2O5 vs. Collector Dosage at pH 9 and Collectorto-Fuel-Oil Ratio of 1:0.8 for Kingsford Coarse Feed ............................. 4-33 Concentrate % Insol vs. Collector Dosage at pH 9 and Collectorto-Fuel-Oil Ratio of 1:0.8 for Kingsford Coarse Feed........................... 4-34 Concentrate % P2O5 vs. Recovery at pH 9 and Collector-to-FuelOil Ratio of 1:0.8 for Kingsford Coarse Feed .......................................... 4-35 Concentrate % P2O5 and Insol vs. Collector Dosage at pH 9 and Collector-to-Fuel-Oil Ratio of 1:0.8 for CF Unsized Feed.................... 4-37 Concentrate % P2O5 vs. Recovery at pH 9 and Collector-to-FuelOil Ratio of 1:0.8 for CF Unsized Feed ................................................. 4-38

5-1. 5-2. 5-3. 5-4. 5-5. 5-6. 5-7. 5-8. 5-9. 5-10. 5-11.

Basic Flowsheet of the FIPR/SAPR Process ................................................ 5-6 Single-Collector Flotation with Scavenging Flotation ................................. 5-7 Single-Collector Flotation Flowsheet #3. ..................................................... 5-8 Modified FIPR/SAPR Flowsheet without Sizing ........................................ 5-9 Rougher Flotation Results Using the Cargill Feed ..................................... 5-14 Rougher Flotation Results Using the IMC-K Feed..................................... 5-15 Rougher Flotation Results Using the CF Feed ........................................... 5-16 Concentrate Grade (% P2O5) vs. Flotation Time ........................................ 5-20 Concentrate Grade (% Insol) vs. Flotation Time ........................................ 5-21 Accumulative P2O5 Distribution in Timed Concentrates ........................... 5-22 Accumulative Weight Distribution in Timed Concentrates ....................... 5-23

6-1. 6-2.

Particle Size Distribution for all Feeds ...................................................... 6-15 P2O5 Recovery and Insol Grade in the Concentrate as a Function of Armeen HT Primary Amine Addition for Plant I, Unsized Amine Feed ............................................................................................ 6-18 P2O5 Recovery as a Function of Insol Grade in the Concentrate for Plant I, Unsized Amine Feed Using Armeen HT Primary Amine, with Tree Analysis Results Shown for Comparison. ............................. 6-19 P2O5 Recovery and Insol Grade in the Concentrate as a Function of Armeen 2HT Secondary Amine Addition for Plant I, Unsized Amine Feed ............................................................................................ 6-20 P2O5 Recovery and Insol in the Concentrate as a Function of Armeen DMHTD Tertiary Amine Addition for Plant I, Unsized Amine Feed ............................................................................................ 6-21 P2O5 Recovery as a Function of Insol in the Concentrate for Plant I, Unsized Amine Feed Using Armeen DMHTD Tertiary Amine, with Tree Analysis Results Shown for Comparison .............................. 6-22

6-3. 6-4. 6-5. 6-6.

xix

LIST OF FIGURES (CONT.) Figure

Page

6-7.

P2O5 Recovery and Insol Grade in the Concentrate as a Function of Arquad 2HT-75 Quaternary Amine Addition for Plant I, Unsized Amine Feed.............................................................................. 6-23 P2O5 Recovery as a Function of Insol Grade in the Concentrate for Plant I, Unsized Amine Feed Using Arquad 2HT-75 Quaternary Amine, with Tree Analysis Results Shown for Comparison ................. 6-23 P2O5 Recovery and Insol Grade in the Concentrate as a Function of Adogen 185 Ether Amine Acetate Addition for Plant I, Unsized Amine Feed.............................................................................. 6-25 P2O5 Recovery as a Function of Insol Grade in the Concentrate for Plant I, Unsized Amine Feed Using Adogen 185 Ether Amine Acetate, with Tree Analysis Results Shown for Comparison ................ 6-25 P2O5 Recovery and Insol Grade as a Function of ARR-MAZ Condensate Amine Addition for Plant I, Unsized Amine Feed ............. 6-26 P2O5 Recovery as a Function of Insol Grade in the Concentrate for Plant I, Unsized Amine Feed Using ARR-MAZ Condensate Amine, with Tree Analysis Results Shown for Comparison ................. 6-27 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen HT Primary Amine............................... 6-30 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen 2HT Secondary Amine......................... 6-31 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen DMHTD Tertiary Amine. .................... 6-31 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Arquad 2HT-75 Quaternary Amine. .................. 6-32 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Adogen 185 Ether Amine Acetate. .................... 6-32 Weight Frequency Distributions for Insol and P2O5 of Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using ARR-MAZ Condensate Amine.. ....................... 6-33 Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen HT Primary Amine ........................................................ 6-33 Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen 2HT Secondary Amine .................................................. 6-34

6-8. 6-9. 6-10. 6-11. 6-12. 6-13. 6-14. 6-15. 6-16. 6-17. 6-18. 6-19. 6-20.

xx

LIST OF FIGURES (CONT.) Figure 6-21. 6-22. 6-23. 6-24. 6-25. 6-26. 6-27. 6-28. 6-29. 6-30.

7-1. 7-2. 7-3. 7-4. 7-5. 7-6. 7-7. 7-8. 7-9. 7-10.

Page Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen DMHTD Tertiary Amine ............................................... 6-34 Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Arquad 2HT-75 Quaternary Amine ............................................ 6-35 Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Adogen 185 Ether Amine Acetate .............................................. 6-35 Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using ARR-MAZ Condensate Amine ................................................... 6-36 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition in the Presence of 0.1 Lb./Ton Armeen HT Primary Amine .................................................................. 6-43 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition at 1.6 Lb./Ton Armeen HT Secondary Amine ................................................................................... 6-43 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition Using 0.3 Lb./Ton Armeen DMHTD Tertiary Amine ....................................................................... 6-44 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition in Using 0.2 Lb./Ton Arquad 2HT-75 Quaternary Amine .................................................................... 6-46 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition Using 0.2 Lb./Ton Adogen 185 Ether Amine Acetate.............................................................................. 6-47 Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function of Percol 90L Polymer Addition Using 0.4 lb./ton ARR-MAZ Condensate Amine ................................................................................. 6-47 Effect of Lignosulfonates on Flotation Recovery ....................................... 7-10 Effect of Lignosulfonates on Concentrate Grade........................................ 7-11 Selectivity Comparison of Silicate with Lignosulfonates........................... 7-12 Concentrate % Recovery P2O5 for CF Feed #1 with Oxalic Acid .............. 7-16 Concentrate % P2O5 for CF Feed #1 with Oxalic Acid .............................. 7-17 Concentrate % Insol for CF Feed #1 with Oxalic Acid .............................. 7-18 Concentrate % Recovery P2O5 for CF Feed #2 with Oxalic Acid .............. 7-19 Concentrate % P2O5 for CF Feed #2 with Oxalic Acid .............................. 7-20 Concentrate % Insol for CF Feed #2 with Oxalic Acid .............................. 7-21 Concentrate % P2O5 for Cargill Fine Feed (JPP) with Oxalic Acid ........... 7-22

xxi

LIST OF TABLES Table ES-1. 1-1. 1-2. 1-3. 1-4. 1A-1. 1A-2. 1A-3. 1A-4. 1A-5. 1A-6. 1A-7. 1A-8. 1A-9. 1A-10. 1A-11. 1A-12. 1A-13. 1A-14. 1A-15. 1A-16. 1A-17. 1A-18. 1A-19. 1A-20. 1A-21.

Page Pilot Testing Results Using Various Single-Collector, All-Anionic Flowsheets ...................................................................................................6 Analyses of the Three Test Samples ............................................................. 1-3 Test Petroleum Additives ............................................................................. 1-3 Froth Modifiers Tested ................................................................................. 1-4 Standard Deviations Calculated from Test Data......................................... 1-15 Screen Analyses for Various Feed Samples Tested ................................... 1A-1 Flotation Test Results Using Various Froth Modifiers with PCS Feed ............................................................................................ 1A-2 to 1A-3 Flotation of PCS Feed Using PCS Tall Oil (1.0 Lb./TF) with Various Fuel Oil and Rosin Oil Additions ......................................................... 1A-4 Flotation of Cargill Feed Using Liqro GA Tall Oil (1.0 Lb./TF with Various No. 5 Fuel Oil and Rosin Oil Additions.................................. 1A-5 Flotation of IMC Feed Using Liqro GA Tall Oil (1.0 Lb./TF with Various No. 5 Fuel Oil and Rosin Oil Additions.................................. 1A-6 Results on Feed B with 1 Lb./Ton Tall Oil at Various Froth Modifier Levels .................................................................................................... 1A-7 Flotation Results Using Various Froth Modifiers with PCS (A) Feed...............................................................................................1A-8 to 1A-9 Flotation of Cargill Feed Using Liqro GA Tall Oil (1.0 Lb./TF) with Various Froth Modifier Combinations ........................................... 1A-10 Flotation Material Balances Using Deslimed and Scrubbed/Deslimed Feed.......................................................................................................... 1A-11 Flotation Material Balances Using Various Degrees of Conditioner Discharge Desliming ........................................................................... 1A-12 Flotation of Cargill Scrubbed, Deslimed Feed Using Various Levels of Liqro GA Tall Oil at 1.0:0.6 Constant Ratio to No. 5 Fuel Oil.............. 1A-13 Flotation of Natural Vs. Scrubbed, Deslimed Cargill Feed Using Liqro GA Tall Oil at 1.0:0.4 Ratio to No. 5 Fuel Oil with and without Rosin Oil Addition .................................................................................. 1A-14 Flotation of Natural vs. Scrubbed, Deslimed PCS Feed Using PCS Tall Oil at 1.0:0.4 Ratio to PCS Fuel Oil with and without Rosin Oil or Extra Fuel Oil Addition ........................................................................... 1A-15 Summary of Preliminary Economic Calculations ....................................... 1A-16 Estimated Overall Flotation Balances--Cargill Feed ................................... 1A-17 Estimated Overall Flotation Balances--PCS Feed ....................................... 1A-18 Estimated Overall Flotation Balances--Cargill Feed ................................... 1A-19 Estimated Overall Flotation Balances--PCS Feed ....................................... 1A-20 Economic Calculations (Rosin Oil Substitution) ........................................ 1A-21 Economic Calculations (Scrubbed vs. Unscrubbed Feed) .......................... 1A-22 Economic Calculations (Scrubbed vs. Unscrubbed Feed) .......................... 1A-23 xxiii

LIST OF TABLES (CONT.) Table 2A-1. 2A-2. 2A-3. 2A-4. 2A-5. 2A-6. 2A-7. 2A-8. 2A-9. 3-1. 3-2. 3-3. 3-4. 3A-1. 3A-2. 3A-3. 3A-4. 3A-5. 3A-6. 4-1. 4-2. 4-3. 4-4. 4-5. 4-6. 4-7. 4-8.

Page Physical Values for Various Fatty Acids ................................................... 2A-1 Specific Gravity (S.G.) and Sources for Various Fatty Acids ................... 2A-2 Phosphate Flotation Material Balances for Tests Using Various Unsaturated C16-C22 Fatty Acid Type Collectors ................................... 2A-3 Phosphate Flotation Material Balances for Tests Using Various Unsaturated C16-C22 Fatty Acid Type Collectors and N-Silicate .......... 2A-4 Flotation Material Balances Using Various Oleic/Palmitic Acid Mixes ...... 2A-5 Phosphate Flotation Material Balances Using Cottonseed Soapstock Fatty Acid Extract as the Phosphate Collector ..................................... 2A-6 Phosphate Flotation Material Balances Using Various Ratios of Liqro GA Tall Oil to Cottonseed Soapstock Acids as the Collector Blend ....... 2A-6 Detailed % P2O5 Analyses and % P2O5 Distributions from Feed for Various Flotation Tailing Size Fractions .............................................. 2A-7 P2O5 Losses in Various Flotation Tailing Size Fractions .............................. 2A-8 Size/Assay Analyses of Test Flotation Feed ................................................. 3-5 Commercial Fatty Acid-Based Collectors Tested......................................... 3-6 Sizing Analysis of Flotation Tails Using Liqro GA Collector for Tests with 65+% Recovery ............................................................................. 3-27 Sizing Analysis of Flotation Tails Using Oleic Acid Collector for Tests with 65+% Recovery ............................................................................. 3-27 Flotation Concentrates Analyses Using Oleic Acid Collector at pH 9 ...... 3A-1 Flotation Concentrates Analyses Using Liqro GA Collector at pH 9 ........ 3A-1 Flotation Concentrates Analyses Using Petro Sulfonate Collector ........... 3A-1 Flotation Concentrates Analyses Using Cottonseed Soap Collector ......... 3A-2 Flotation Concentrates Analyses Using Tall Oil Pitch Soap Collector ..... 3A-2 Flotation Concentrates Analyses Using a Mixture of 20% Sulfonate and 20% Liqro GA Collector at pH 9 ................................................... 3A-3 Size/Assay Analysis of the PCS Feed for Iso-Acids Evaluation ...................... 4-2 List of Collectors for Evaluation of Selective Collectors ................................ 4-3 Comparison of Century Reagent Characteristics and Compositions ............ 4-4 Flotation Test Results Using Century MO-5 Collector Plus IMC Feed with and without N-Silicate Addition .................................................... 4-10 Detailed % P2O5 Analyses and % P2O5 Distributions from Feed for Various Flotation Tailings Size Fractions ............................................. 4-12 P2O5 Losses in Various Flotation Tailing Size Fractions ........................... 4-13 Size/Assay Analysis of a Concentrate from PCS Feed Using MO-5 Collector ..................................................................................................... 4-18 Flotation Test Results Using Century MO-5 Collector Plus PCS Feed with and without N-Silicate Addition .................................................... 4-19 xxiv

LIST OF TABLES (CONT.) Table 4-9. 4-10. 4-11. 4-12. 4-13. 4-14. 4-15. 4A-1. 4A-2. 4A-3. 4A-4. A4-5. 4A-6. 5-1. 5-2. 5-3. 5-4. 5-5. 5-6. 5-7. 5-8. 5-9.

Page Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Feed (5% P2O5) ........................................ 4-20 to 4-21 Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with PCS Feed (10% P2O5) ...................................... 4-22 to 4-23 Size/Assay Analysis of the Flotation Feed from Cargill............................. 4-25 Size/Assay Analysis of the IMC Kingsford Coarse Flotation Feed............ 4-26 Size/Assay Analysis of the CF Unsized Flotation Feed ............................. 4-26 Size/Assay Analysis of a Rougher Concentrate from Cargill Feed Using MO-5 Collector ........................................................................... 4-31 Size/Assay Analysis of Rougher Concentrate from CF Feed Using MO-5...................................................................................................... 4-36 Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with Cargill Feed .................................................... 4A-1 to 4A-2 Flotation Test Results Using Century MO-5 and Century 1108 Collector Plus Cargill Feed with N-Silicate Addition .......................... 4A-3 Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Kingsford Coarse Feed (11% P2O5) ...... 4A-4 to 4A-5 Flotation Test Results Using Century MO-5 Collector Plus IMC Kingsford Coarse Feed with N-Silicate Addition ................................. 4A-6 Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with CF Feed (9% P2O5) ........................................ 4A-7 to 4A-8 Flotation Test Results Using Century MO-5 Collector Plus CF Feed with N-Silicate Addition ....................................................................... 4A-9 Basic Properties of Test Flotation Feeds .................................................... 5-11 Rougher Flotation of IMC-F Feed Using Different Anionic Collectors ............................................................................................... 5-13 Size/Assay Analyses of Rougher Concentrate from Cargill Feed .............. 5-14 Size/Assay Analyses of Rougher Concentrate from CF Feed .................... 5-17 Anionic Rougher-Cleaner Flotation Results of All Feeds .......................... 5-18 Test Results Using the Rougher-Sizing-Scavenging Flowsheet on Four Corners Coarse Feed ..................................................................... 5-24 Test Results Using the Rougher-Sizing-Scavenging Flowsheet on Four Corners Fine Feed ......................................................................... 5-25 Test Results Using the Rougher-Sizing-Scavenging Flowsheet on CF Unsized Feed.................................................................................... 5-26 Pilot Test Run #1 Using the FIPR/SAPR Process on Feed #1 at 2.40 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.6 Lb. Fuel Oil, and 0.25 Lb. Silicate per Ton of Feed ........................ 5-30

xxv

LIST OF TABLES (CONT.) Table 5-10. 5-11. 5-12. 5-13. 5-14. 5-15. 5-16. 5-17. 5-18. 5-19. 5-20. 5-21. 5-22. 5A-1. 5A-2.

Page Pilot Test Run #2 Using the FIPR/SAPR Process on Feed #1 at 2.24 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.6 Lb. Fuel Oil, and 0.24 Lb. Silicate per Ton of Feed ........................ 5-31 Pilot Test Run #3 Using the FIPR/SAPR Process on Feed #1 at 1.34 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.81 Lb. Fuel Oil, and 0.24 Lb. Silicate per Ton of Feed ...................... 5-31 Pilot Test Run #4 Using the FIPR/SAPR Process on Feed #1 at 1.36 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.81 Lb. Fuel Oil, and 0.32 Lb. Silicate per Ton of Feed ...................... 5-31 Pilot Test Run #5 Using the FIPR/SAPR Process on Feed #1 at 1.46 Lb. of Collector (FA12), 0.88 Lb. Fuel Oil, and 0.61 Lb. Silicate per Ton of Feed ......................................................................... 5-32 Pilot Test Run #1 Using the FIPR/SAPR Process on Feed #2 at 1.02 Lb. of Collector (FA12), 0.26 Lb. Fuel Oil and 0.39 Lb. Silicate per Ton of Feed ......................................................................... 5-32 Pilot Test Run #2 Using the FIPR/SAPR Process on Feed #2 at 1.28 Lb. of Collector (FA12), 0.14 Lb. Fuel Oil, and 0.44 Lb. Silicate per Ton of Feed ......................................................................... 5-32 Pilot Test Run #1 Using All-Anionic Flowsheet #2 on Feed #2 at 0.61 Lb. of Collector (1:1 Mixture of FA12 and CC41601), 0.50 Lb. Fuel Oil, and 0.64 Lb. Silicate per Ton of Feed ...................... 5-33 Pilot Test Run #2 Using All-Anionic Flowsheet #2 on Feed #2 at 1.43 Lb. of Collector (1:1 mixture of FA12 and CC41601), 0.89 Lb. Fuel Oil, and 0.93 Lb. Silicate per Ton of Feed ...................... 5-33 Feed Sizing for the All-Anionic Flowsheet #3 on Feed #1 ........................ 5-34 Pilot Test Run #1 Using the All-Anionic Flowsheet #3 on the Fine Fraction of Feed #1 at 1.65 Lb. of Collector (FA12) and 0.99 Lb. Fuel Oil per Ton of Feed ......................................................... 5-34 Pilot Test Run #1 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.81 Lb. of Collector (FA12) and 1.09 Lb. Fuel Oil per Ton of Feed ......................................................... 5-34 Pilot Test Run #2 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.34 Lb. of Collector (FA12) and 0.80 Lb. Fuel Oil per Ton of Feed ......................................................... 5-34 Pilot Test Run #3 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.15 Lb. of Collector and 0.69 Lb. or Fuel Oil per Ton of Feed ................................................................... 5-35 Flotation Test Material Balances Using Century MO-5 Collector Plus PCS Swift Creek Feed with N-Silicate Addition .................................. 5A-1 Flotation Test Material Balances Using Century MO-5 Collector Plus Cargill S. Ft. Meade Fine Feed with N-Silicate Addition .................... 5A-2 xxvi

LIST OF TABLES (CONT.) Table 5A-3.

Page

5A-18.

Flotation Test Material Balances Using Century MO-5 Collector Plus CF Industries Hardee Feed with N-Silicate Addition ........................... 5A-3 Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Fine Feed with N-Silicate Addition .......... 5A-4 to 5A-7 Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Coarse Feed with N-Silicate Addition ................... 5A-8 Summary of Anionic Flotation/Sizing Process Results ............................. 5A-9 Summary of Flotation Concentrate and Middling Yields, Grades and P2O5 Recoveries .................................................................................. 5A-10 Detailed Flotation Material Balances for IMC Four Corners Coarse Feed—Timed Floats ........................................................................... 5A-11 Detailed Flotation Material Balances for IMC Four Corners Fine Feed—Timed Floats ........................................................................... 5A-12 Detailed Flotation Material Balances for CF Chemicals Hardee Feed—Timed Floats ........................................................................... 5A-13 Detailed Flotation Material Balances for PCS Swift Creek Feed— Timed Floats ....................................................................................... 5A-14 Flotation Test Material Balances Using Century MO-5 Collector Plus PCS Swift Creek Feed with N-Silicate Addition ......... 5A-15 to 5A-16 Flotation Test Material Balances Using Sylfat FA-12 and 11 Plus PCS Swift Creek Feed with N-Silicate Addition ................................ 5A-17 Flotation Test Material Balances Using Liqro GA T.O. Collector Plus PCS Swift Creek Feed with N-Silicate Addition ........................ 5A-18 Flotation Test Material Balances Using Century MO-5/Sylfat FA-11 Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition .............................................................................................. 5A-19 Flotation Test Material Balances Using Century MO-5/Liqro GA Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition .............................................................................................. 5A-20 Flotation Test Material Balances Using Ariz. 2122/Sylfat FA-11 Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition .............................................................................................. 5A-21 Summary of Laboratory Rougher Flotation Test Results ......... 5A-22 to 5A-23

6-1. 6-2. 6-3. 6-4. 6-5. 6-6. 6-7.

Basic Properties of Test Samples ............................................................... 6-15 Amines Tested ............................................................................................ 6-16 Armeen HT Primary Amine Series ............................................................. 6-18 Armeen 2HT Secondary Amine Series ....................................................... 6-19 Armeen DMHTD Tertiary Amine Series ................................................... 6-21 Arquad 2H-75 Quaternary Amine Series .................................................... 6-22 Adogen 185 Ether Amine Acetate Series ................................................... 6-24

5A-4. 5A-5. 5A-6. 5A-7. 5A-8. 5A-9. 5A-10. 5A-11. 5A-12. 5A-13. 5A-14. 5A-15. 5A-16. 5A-17.

xxvii

LIST OF TABLES (CONT.) Table 6-8. 6-9. 6-10. 6-11. 6-12. 6-13. 6-14. 6-15. 6-16. 6-17. 6-18. 6-19. 6-20. 6-21. 6-22. 6-23. 6-24. 6A-1A. 6A-1B. 6A-2A. 6A-2B.

Page ARR-MAZ Condensate Amine Series........................................................ 6-26 Summary of Batch Flotation Tests ............................................................. 6-27 Summary of Locked Cycle Tests ................................................................ 6-28 Summary of Screen Assays for Tailings Using the Relative Effect on Distributions; R, D ................................................................................. 6-29 Summary of Semi-Quantitative Evaluation of the Effect of Particle Size ........................................................................................................ 6-30 Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen HT Primary Amine ............................... 6-37 Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen 2HT Secondary Amine ......................... 6-38 Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen DMHTD Tertiary Amine ...................... 6-38 Summary of the Effect of Slimes on the Amine Flotation Step of the the Reverse Crago Using Arquad 2HT-75 Quaternary Amine .............. 6-39 Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Adogen 185 Ether Amine Acetate ...................... 6-40 Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using ARR-MAZ Condensate Amine .......................... 6-40 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Armeen HT Primary Amine ............. 6-42 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Armeen 2HT Secondary Amine .................................................................................................... 6-42 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Armeen DMHTD Tertiary Amine .................................................................................................... 6-44 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Arquad 2HT-75 Quaternary Amine .................................................................................................... 6-45 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Adogen 185 Ether Amine Acetate ................................................................................................... 6-45 Summary of the Effect of Percol 90L Polymer on the Amine Flotation Flotation Step of the Reverse Crago Using ARR-MAZ Condensate Amine .................................................................................................... 6-46 Screen Analysis for Fort Green Amine Feed Unsized ............................... 6A-1 Screen Analysis for Fort Green Amine Feed Unsized ............................... 6A-1 Screen Analysis for Four Corners Coarse Amine Feed ............................. 6A-2 Screen Analysis for Four Corners Coarse Amine Feed ............................. 6A-2 xxviii

LIST OF TABLES (CONT.) Table 6A-3A. 6A-3B. 6A-4A. 6A-4B. 6B-1. 6B-2. 6B-3. 6B-4. 6B-5. 6B-6. 6C-1. 6C-2. 6C-3. 6C-4. 6C-5. 6D-1. 6D-2. 6D-3. 6D-4. 6D-5. 6D-6. 6D-7. 6E-1. 6E-2. 6E-3. 6E-4. 6E-5. 6E-6. 6F-1A. 6F-1B. 6F-2A. 6F-2B. 6F-3A. 6F-3B.

Page Screen Analysis for Four Corners Fine Amine Feed ................................. 6A-3 Screen Analysis for Four Corners Fine Amine Feed ................................. 6A-3 Screen Analysis for CF Industries, Inc. Flotation Feed ............................. 6A-4 Screen Analysis for CF Industries, Inc. Flotation Feed ............................. 6A-4 Armeen HT Primary Amine Series ................................................6B-1 to 6B-2 Armeen 2HT Secondary Amine Series ........................................... 6B3 to 6B-4 Armeen DMHTD Tertiary Amine Series ......................................6B-5 to 6B-6 Arquad 2HT-75 Quaternary Amine Series ....................................6B-7 to 6B-8 Adogen 185 Ether Amine Acetate Series ....................................6B-9 to 6B-10 ARR-MAZ Condensate Amine Series.......................................6B-11 to 6B-12 Tree Analysis Using Armeen HT Primary Amine ........................ 6C-1 to 6C-2 Tree Analysis Using Armeen DMHTD Tertiary Amine............... 6C-3 to 6C-4 Tree Analysis Using Arquad 2HT-75 Quaternary Amine ............ 6C-5 to 6C-6 Tree Analysis Using Adogen 185 Ether Amine Acetate .............. 6C-7 to 6C-8 Tree Analysis Using ARR-MAZ Condensate Amine ................. 6C-9 to 6C-10 Armeen HT Primary Amine Series ............................................... 6D-1 to 6D-2 Armeen 2HT Secondary Amine Series ......................................... 6D-3 to 6D-4 Armeen DMHTD Tertiary Amine Series ..................................... 6D-5 to 6D-6 Arquad 2HT-75 Quaternary Amine Series ................................... 6D-7 to 6D-8 Adogen 185 Ether Amine Acetate Series ................................... 6D-9 to 6D-10 ARR-MAZ Condensate Amine Series...................................... 6D-11 to 6D-12 ARR-MAZ Condensate Amine Series—Reverse Crago Process ................................................................................. 6D-13 to 6D-15 Armeen HT Primary Amine Series ................................................ 6E-1 to 6E-2 Armeen 2HT Secondary Amine Series ....................................................... 6E-3 Armeen DMHTD Tertiary Amine Series ...................................... 6E-4 to 6E-5 Arquad 2HT-75 Quaternary Amine Series .................................... 6E-6 to 6E-7 Adogen 185 Ether Amine Acetate Series ...................................... 6E-8 to 6E-9 ARR-MAZ Condensate Amine Series....................................... 6E-10 to 6E-11 Screen Analysis for Flotation Tailings—Armeen HT Primary Amine, Plant I, Unsized Amine Feed .................................................... 6F-1 Screen Analysis for Flotation Concentrate—Armeen HT Primary Amine, Plant I, Unsized Amine Feed .................................................... 6F-2 Screen Analysis for Flotation Tailings—Armeen 2HT Secondary Amine, Plant I, Unsized Amine Feed .................................................... 6F-3 Screen Analysis for Flotation Concentrate—Armeen 2HT Secondary Amine, Plant I, Unsized Amine Feed .................................................... 6F-4 Screen Analysis for Flotation Tailings—Armeen DMHTD Tertiary Amine, Plant I, Unsized Amine Feed .................................................... 6F-5 Screen Analysis for Flotation Concentrate—Armeen DMHTD Tertiary Amine, Plant I, Unsized Amine Feed ...................................... 6F-6 xxix

LIST OF TABLES (CONT.) Table

Page

6F-4A. Screen Analysis for Flotation Tailings—Arquad 2HT-75 Quaternary Amine, Plant I, Unsized Amine Feed ................................. 6F-7 6F-4B. Screen Analysis for Flotation Concentrate—Arquad 2HT-75 Quaternary Amine, Plant I, Unsized Amine Feed ................................. 6F-8 6F-5A. Screen Analysis for Flotation Tailings—Adogen 185 Ether Amine Acetate, Plant I, Unsized Amine Feed ................................................... 6F-9 6F-5B. Screen Analysis for Flotation Concentrate—Adogen 185 Ether Amine Acetate, Plant I, Unsized Amine Feed ..................................... 6F-10 6F-6A. Screen Analysis for Flotation Tailings—ARR-MAZ Condensate Amine, Plant I, Unsized Amine Feed .................................................. 6F-11 6F-6B. Screen Analysis for Flotation Concentrate—ARR-MAZ Condensate Amine, Plant I, Unsized Amine Feed .................................................. 6F-12 6G-1. Armeen HT Primary Amine Series—Clay Effect—Reverse Crago. ......... 6G-1 6G-2. Armeen 2HT Secondary Amine Series—Clay Effect—Reverse Crago..................................................................................................... 6G-2 6G-3. Armeen DMHTD Tertiary Amine Series—Clay Effect—Reverse Crago..................................................................................................... 6G-3 6G-4. Arquad 2HT-75 Quaternary Amine Series—Clay Effect—Reverse Crago..................................................................................................... 6G-4 6G-5. Adogen 185 Ether Amine Acetate Series—Clay Effect—Reverse Crago..................................................................................................... 6G-5 6G-6. ARR-MAZ Modified 1054 Condensate Amine Series—Clay Effect—Reverse Crago ......................................................................... 6G-6 6H-1. Armeen HT Primary Amine Series—Percol 90L Effect— Reverse Crago .......................................................................... 6H-1 to 6H-2 6H-2. Armeen 2HT Secondary Amine Series—Percol 90L Effect— Reverse Crago .......................................................................... 6H-3 to 6H-4 6H-3. Armeen DMHTD Tertiary Amine Series—Percol 90L Effect— Reverse Crago .......................................................................... 6H-5 to 6H-6 6H-4. Arquad 2HT-75 Quaternary Amine Series—Percol 90L Effect— Reverse Crago .......................................................................... 6H-7 to 6H-8 6H-5. Adogen 185 Ether Amine Acetate Series—Percol 90L Effect— Reverse Crago ........................................................................ 6H-9 to 6H-10 6H-6. ARR-MAZ Condensate Amine Series—Percol 90L Effect— Reverse Crago ...................................................................... 6H-11 to 6H-12 7-1. 7-2. 7-3. 7-4. 7-5.

Some Laboratory Testing Results Using Various Flowsheets ...................... 7-4 Size Distribution and Analysis of the CF Feed #1........................................ 7-5 Size Distribution and Analysis of the CF Feed #2........................................ 7-5 Size Distribution and Analysis of the IMC Feed. ......................................... 7-6 Flotation Modifiers Tested ........................................................................... 7-6 xxx

LIST OF TABLES (CONT.) Table 7-6. 7-7. 7-8.

Page Effectiveness of Phosphate Powers as Flotation Modifiers in Rougher Flotation of Phosphate at 1.1 Lb./Ton Collector ................................... 7-13 “Rinse” Process Performance ..................................................................... 7-14 Effect of Cleaner Cut Size on Concentrate Grade and Recovery ............... 7-23

xxxi

EXECUTIVE SUMMARY Unlike flotation of sulfide minerals, flotation of phosphate has not been investigated extensively in terms of reagent schemes. Currently, each mine selects a fatty acid collector by conducting extensive flotation tests, both in the lab and plant. No attempt has been made to correlate flotation performance with physico-chemical properties of fatty acids (such as organic compound compositions, surface tension, surface charge density, carbon chain length and viscosity) with the characteristics of flotation feed (such as particle size distribution and clay content). The following questions remain to be answered: (1) Chemically, what makes one fatty acid a good collector and another one poor? (2) What chemical tests can be run to improve reagent quality? (3) What roles do feed characteristics play? (4) What roles does water quality play? and (5) What are the major physical parameters of fatty acid collectors that influence flotation performance? The same holds true for amines. In addition, the chemical processing plants are becoming more and more tolerant to Insol content in the acidulation feeds. As a result, the Insol levels in flotation concentrates have been relaxed from 3-5% to as high as 10%. Because of the industry’s efforts in reducing deep well pumping and increasing storage capacity of clay settling ponds, the quality of amine flotation water is deteriorating. These trends warrant a fresh look at the available amine collectors as well as additives for amine flotation. This project is quite possibly the most comprehensive investigation of flotation reagents used in phosphate beneficiation ever carried out. Therefore, this research was divided into six programs. Major findings from each of the programs are discussed below. PART 1. INVESTIGATION OF FUEL OIL SUBSTITUTES The fuel oils currently used to control froth character and increase tall oil collector "pull power" include No. 5 oil, reclaimed oil and possibly Bunker C/diesel mixtures. These petroleum derivatives are currently priced at about $0.04-$0.07 per pound (in bulk quantities). Locating cheap reagents suitable as partial substitutes for these petroleum products is a challenging task. An effective substitute reagent must not only help prevent excessive frothing, but must not result in a decrease in "pull power" without using extra collector during rougher flotation. The first step of this research program was to document the relative performance of various petroleum derivatives as froth modifiers/auxiliary collectors during anionic rougher flotation of Florida phosphate, followed by determination of the potential value of rosin oil as a partial substitute for some of the petroleum derivatives, thereby reducing the flotation water contamination by these reagents. A dozen petroleum additives were first screened as froth modifiers/fatty acid extenders. The results indicated that PCS fuel oil, IPC reclaimed oil, Coastal No. 5 fuel oil, 1

and diesel were the most effective froth modifiers from a cost/performance standpoint. White mineral oil and Westvaco rosin oil were also very effective from a recovery/performance standpoint; however, their higher current unit cost would limit their complete substitution for fuel oil in operating flotation plants. Rosin oil is produced by thermal decarboxylation of natural rosin and/or tall oil rosin acids. Basically, it contains a mixture of cyclic hydrocarbons plus variable amounts of impurities. When produced from tall oil high-rosin acid fractions, the rosin oil contains some fatty acids and unreacted rosin acids. The rosin oil used for the current testwork was produced by Westvaco many years ago and had an acid number of 50. When no froth modifier was used for lab flotation, very poor results were obtained. The successful performance of the two froth modifiers containing cyclic hydrocarbons (Philflo oil and Westvaco rosin oil) is noteworthy. The partial substitution of rosin oil for fuel oil was considered to be worthy of additional flotation testwork. The four most effective petroleum-based froth modifiers were selected for flotation tests using partial substitution of rosin oil. The results showed that when rosin oil was substituted for 1/3 of each petroleum-based oil modifier, a 1.3-5.5% increase in flotation recovery of P2O5 was obtained along with an increase in concentrate Insol ranging from 0.95-7.89%. The use of some rosin oil assured a persistent froth that lasted for at least two minutes during flotation. This feature of the rosin oil is believed to be at least partially responsible for the % P2O5 recovery increases that occurred. The presence of some fatty acids and rosin acids in the commercial rosin oil (Acid No. = 50) could also be partially responsible for the higher % P2O5 recoveries obtained. Rosin oil appeared to be the most suitable partial substitute for fuel oil in terms of both flotation recovery and total economics. Preliminary optimization tests indicated that fuel oil use could be reduced by about 25% using rosin oil, with the higher cost of rosin oil being compensated for by improved P2O5 recovery. PART 2. STUDY OF PURE FATTY ACID COMPOUNDS This program was designed to compare results obtained using various C12-C22 fatty acids (6 unsaturated and 5 saturated) as Florida phosphate collectors. The unsaturated C20 fatty acid, eicosenoic acid, was of particular interest since its use as a flotation reagent has not been found in the literature. Also, preliminary laboratory flotation evaluation of an "extract" of fatty acids obtained by acidulation and washing of the comparatively cheap cottonseed soapstock sample was considered to be a worthwhile endeavor. A literature review of C8-C22 fatty acids’ properties and sources was performed in order to prepare reference tables for the selection of collectors for preliminary flotation comparison testwork. Laboratory rougher flotation tests were performed on Four Corners 2

feed using selected C12-C22 fatty acids with No. 5 fuel oil as the phosphate collector. The saturated fatty acids were found to be very poor collectors when using the standard conditioning procedure, whereas the unsaturated C16-C22 fatty acids showed fair to good phosphate collecting ability. The C18 fatty acids (oleic, impure oleic, linoleic) and the C20 eicosenoic acid were shown to be the best phosphate collectors both with and without Nsilicate addition. Flotation concentrates analyzing approximately 15-25% P2O5 at 78-87% P2O5 recovery were produced using these four fatty acid collectors. Inferior flotation results were obtained using the unsaturated C16 palmitoleic acid and the unsaturated C22 erucic acid. Two mixtures containing 15% and 25% commercial grade palmitic acid added to commercial grade oleic acid were observed to perform somewhat similarly to the oleic acid as phosphate collectors. Palmitic acid was selected as the saturated fatty acid for addition to oleic acid because of its presence in most natural fatty acid mixtures produced from vegetable oils. In terms of pulling power for coarse phosphate particles, erucic acid did the best on the +28 mesh fraction, and linoleic proved to be the weakest, with the rest being similar. For the 28 by 35 mesh fraction, oleic acid was the most effective, with the rest more or less the same. PART 3. COMPARISON OF VARIOUS ANIONIC COLLECTORS A composite sample of low-grade (approx. 5.2% P2O5 ) IMC Four Corners feed was subjected to preliminary laboratory rougher flotation testwork using five different anionic collectors. Oleic acid, Liqro GA tall oil, Petronate CR sulfonate, cottonseed soapstock and Custofloat 27AR T.O./pitch soap were the five collectors evaluated. A mixture of Petronate CR (20%) and Liqro GA (80%) was also tested. Some of the flotation variables used at different levels included collector quantity, conditioning pH, fuel-oil-to-collector ratio, and the use of N-Brand sodium silicate for selectivity improvement. The best flotation results were obtained using Liqro GA tall oil and oleic acid. Liqro GA produced rougher concentrates analyzing 17.1-21.5% P2O5 at 91.3-87.6% P2O5 recovery, and oleic acid produced rougher concentrates analyzing 16.7-21.8% P2O5 at 87.391.2% P2O5 recovery under the best test conditions. Size/assay analyses performed on tailings obtained from selected flotation tests using Liqro GA tall oil and oleic acid as the collectors showed that P2O5 recoveries as high as 94-95% were attainable from the -35 mesh feed sizes, and recoveries as high as 86-87% were obtained from the 28/35 mesh feed sizes for some of the best tests. The highest P2O5 recovery obtained from the +28 mesh fraction was about 54% for only one test.

3

PART 4. STUDY OF ISO-ACIDS Four isostearic/iso-oleic acid type fatty acid collectors, supplied by divisions of International Paper, were compared with a commercial grade oleic acid and with Liqro GA tall oil as phosphate collectors using standard laboratory conditioning and flotation procedures. The most selective collector evaluated appeared to be Century 1108. This high isostearic acid type reagent produced phosphate rougher concentrates analyzing 28% P2O5/17% Insol and 31% P2O5/7+% Insol at about 80% and 92% P2O5 recovery from the IMC feed and the PCS feed, respectively. However, this excellent-performing reagent was concluded to be too expensive at $1.25/lb. for commercial use. The overall most promising reagent was probably Century MO-5. This collector was essentially an iso-oleic acid/stearic acid mixture (not isostearic acid) priced at $0.35/lb. Century MO-5 produced rougher phosphate concentrates analyzing 25% P2O5/25+% Insol and 29+% P2O5/13+% Insol at about 80% and 95% P2O5 recovery from the IMC and PCS feed samples, respectively. Using N-Brand sodium silicate to improve selectivity, Century MO-5 yielded phosphate rougher concentrates analyzing 29+% P2O5/13+% Insol at about 84% P2O5 recovery from the IMC feed, and 30+% P2O5/9+% Insol at about 94% P2O5 recovery from the PCS feed. A 29+% P2O5/13+% Insol phosphate rougher concentrate produced from the PCS feed at 95+% P2O5 recovery was subjected to a brief size/assay analysis. The +100 mesh fraction of the concentrate analyzed 30+% P2O5/10+% Insol and represented about 95% P2O5 recovery from the total concentrate. Size/assay analyses also were performed on selected rougher tailings obtained from four flotation tests that used two levels of Century MO-5 collector, with and without N-silicate, and IMC-Agrico feed. The results showed that concentrate P2O5 recoveries ranged from about 85-96% for the -35 mesh feed size, 55-92+% for the 28/35 mesh feed size, and less than 58% for the +28 mesh feed size. Further upgrading of the selected rougher concentrate -65 mesh or -100 mesh size fractions was concluded to be necessary to produce overall rougher concentrates containing less than 10% Insol. These finely sized fractions comprised 26% by weight or less of the total flotation concentrates. Future tests will emphasize rougher concentrate sizing and cleaner flotation of only the fines without additional reagent usage. This program laid a sound foundation for developing single collector, all anionic flotation processes. The relatively high-grade, more expensive collectors, such as MO-5 and F12, proved to be not only more selective, but also more powerful for coarse particles. It was also proven that a cleaner flotation step is necessary to achieve consistent concentrates of low Insol. PART 5. DEVELOPMENT OF SINGLE-COLLECTOR PROCESSES The FIPR/SAPR process is FIPR’s third approach to develop a viable alternative to the Crago “Double Float” process for phosphate flotation. SAPR stands for Singlecollector, All-anionic Phosphate Recovery. The FIPR/SAPR process offers a universal flowsheet for any anionic reagent system and flotation feed of varying sizes. For an 4

unsized or fine flotation feed, the FIPR/SAPR process consists of the following steps: (1) high-solids conditioning with an anionic collector; (2) anionic rougher flotation, with the rougher concentrate sized at 48 (or 65) mesh and the +48 mesh recovered as a final product; and (3) cleaning flotation of the -48 mesh fraction from Step 2. In a variation of Step 2, the rougher concentrate from the first two cells may be collected as a final product, and the rougher concentrate from the last two cells sized at 48 or 65 mesh. The new process was tested with a blend of anionic collectors, achieving single-digit Insol at 85+% recoveries. Pilot testing obtained concentrates of about 63% BPL and 10-11% Insol at around 88% recovery. Sizing of the rougher concentrate (reagentized material) proved to be challenging on pilot scale. In another all-anionic flowsheet (#2), rougher flotation is conducted under “reagent starvation” conditions so that a low-Insol rougher concentrate that would not require further cleaning can be achieved. The rougher tail is then sized at 48 mesh. The coarser (+48 mesh) fraction of the tail is subject to scavenging flotation, while the -48 fraction is discarded. This rougher-scavenger flowsheet achieved excellent results on lab scale, but required fine-tuning of fatty acid dosage in rougher flotation. Recognizing some of the limitations of the above-discussed flowsheets, another conceptual flowsheet (#3) was proposed. In this process, the flotation feed is first sized at 48 mesh (or somewhere between 35 and 48 mesh). The coarse feed is subject to one-step flotation, while the finer feed is processed using a straight rougher-cleaner flowsheet. To achieve low-Insol product, the coarser fraction may also be floated using the roughercleaner approach. This process was not tested extensively in the lab. However, a brief pilot test showed great potential for this process. One pilot test run achieved concentrate analyzing 64.4% BPL and 10.6% Insol at a flotation recovery of 89.7%. It must be pointed out that this single-shop test was far from optimized. Table ES-1 below summarizes some results from pilot testing of the three flowsheets. These data indicate that low-Insol concentrate is difficult to achieve using the basic FIPR/SAPR flowsheet. The inefficient sizing of rougher concentrate is the primary reason for high-Insol product. The sizer oversize fractions contain 25-70% -48 mesh material, indicating obvious inefficient sizing. Flowsheet #2 could generally achieve lower Insol than the basic flowsheet, but at lower total flotation recovery. Delicate control is required in both the rougher and scavenger flotation steps to achieve the optimal balance between recovery and grade. However, mechanical cell flotation on the coarse scavenger feed is a major factor for the low recovery. It is widely accepted that mechanical cells may achieve recoveries of 50-60% for coarse feed on commercial scale. The application of column cells is called for if this process is ever considered for commercial application. It is expected that a recovery improvement of 5% could be achieved using columns. It must be pointed out that Flowsheet #3 was not investigated in any detail in the lab, and was only tested in single-shot pilot testing. However, the results look quite promising, particularly for the coarser fraction of the float feed, achieving less than 9% Insol concentrate at recovery of about 90%. 5

Table ES-1. Pilot Testing Results Using Various Single-Collector, All-Anionic Flowsheets. Flowsheet Basic FIPR/SAPR Basic FIPR/SAPR Basic FIPR/SAPR Basic FIPR/SAPR Basic FIPR/SAPR Basic FIPR/SAPR Flowsheet #2 Flowsheet #2 Flowsheet #3 Flowsheet #3

Feed/Reagent #1/F12 #2/F12 #2/F12 #1/MO-5 and Liqro GA #1/MO-5 and Liqro GA #1/MO-5 and Liqro GA #2/F12-CC41601 #2/F12-CC41601 #3 coarse/F12 #3 coarse/F12

Concentrate Grade % BPL % Insol 64.12 9.97 64.32 11.49 62.52 11.16 62.47 11.35 63.44 9.94 63.38 11.05 64.00 8.20 63.40 10.10 66.33 8.33 66.11 8.26

% P2O5 Recovery 89.42 88.10 91.60 84.92 88.78 88.48 73.10 87.30 88.98 90.98

PART 6. AMINE STUDY This research investigated the performance of six types of amines (primary, secondary, tertiary, quaternary, ether, and condensate) on the cleaning step of the rougher concentrates for the Crago process, and the effect of particle size on the performance of each type of amine. The research also studied the effect of slimes (tolerance) of these six types of amines and Perco 90L polymer addition on the amine flotation step of the Reverse Crago process. The Reverse Crago process was developed under a different FIPR in-house project. In this process, the sands are floated first with an amine plus an anionic polymer to “blind” the slime, followed by fatty acid flotation. The flotation results shown in this report are influenced by the type, origin, and characteristics of the amine flotation feed and/or flotation feed sample used for the tests. Moreover, two different samples from the same plant that were taken on different occasions show different flotation results. Thus absolute values of grades and recoveries changed, but the trends were still valid. In addition, it should be noted that the data shown in the report do not correspond to optimum flotation conditions with respect to any variable. The parameters and techniques used in the evaluation of the different types of amines include Selectivity Index (SI); the ratio of Insol rejection to the tailings weight percentage (R*); the shape of the recovery-grade curve (selectivity curve) represented by the tangent (Tang) at the keen of the curve; the tree analysis results; and locked cycle tests. Even though the tree analysis technique was not able to describe the whole locus of the recovery-grade curve due to an improper distribution of the amine addition during the different steps of the test, this technique was able to obtain results close to those obtained by several batch flotation tests. The tree analysis eliminates the effect of feed grade variation on each batch flotation test, and requires less time, effort, and amount of material to obtain the selectivity curve. More work is recommended to develop this technique for phosphate ores. 6

Selectivity The comparison of the flotation results of the batch tests of the cleaning step of the Crago process for Plant I, Unsized Amine Feed, generates the following rank from the most selective to the least selective amine: Quaternary > Primary = Tertiary = Condensate > Ether > Secondary (?). Similar flotation results follow for the strength of the amine addition for this feed, from strongest to weakest: Ether > Quaternary > Primary = Tertiary = Condensate > Secondary (?). A similar comparison was carried out for the corresponding locked cycle tests for each type of amine used. The ranking of the selectivity of these amines from the most selective to the least selective follows: Quaternary > Primary = Tertiary > Ether > Condensate > Secondary (?). The question mark by secondary amine indicates our lack of confidence in the tests using this amine because it is insoluble and was not well dispersed in the tests. These locked cycle tests could be also an indication of the tolerance of each amine tested to the presence (effect) of slimes. By evaluating the increase in amine consumption to achieve quasi-steady state conditions, the tolerance can be inferred. The rank from the most tolerant to the least tolerant follows: Primary > Tertiary = Condensate > Ether > Quaternary. Effect of Particle Size The effect of particle size on the performance of all six types of amines in the cleaning step of the Crago process was evaluated by screen assays of the concentrates and tailings of the best batch flotation tests performed. The results indicate that the primary amine is more efficient in the 65 x 150-mesh particle size range, secondary amine in the 100 x 150-mesh range, tertiary in the 35 x 200-mesh range, quaternary and ether amine acetate in the 65 x 200-mesh range, and condensate amine in the 100 x 200-mesh particle size fraction. The distribution of P2O5 and Insol in the concentrate and tailings of each particle size fraction studied for the best tests using all six types of amines were evaluated based on the PInsol50. This parameter corresponds to the particle size at which an Insol particle has a 50% probability to report to the concentrate or tailings. The flotation rank from coarser to finer Insol based on the batch flotation tests conducted on Plant I, Unsized Amine Feed and Plant II, Coarse and Fine Amine Feeds, follows: Primary > Ether = Condensate > Tertiary > Quaternary. 7

Effect of Slime on the Reverse Crago Process The effect of slimes on the amine flotation step of the Reverse Crago process was studied using Plant III, Unsized Flotation Feed, but using the dosage determined by the best test for each type of the six amines for Plant I, Unsized Amine Feed. In general, it was observed that the effect of slimes was complex since slimes affect the water quality, surface of silica and phosphate particles, and amine consumption by increasing the specific surface area available for amine adsorption. In addition, the use of scrubbing in the experimental procedure to generate slimes contributes to the complexity of the effect of slimes by altering their composition; i.e., clay, fine silica and phosphate. Again, the results were analyzed on a relative basis using the relative Insol rejection, relative P2O5 losses (rejection) and the selectivity ratio, [R]. When using Armeen HT primary amine, a maximum in relative Insol rejection, P2O5 losses and selectivity ratio was observed at 0.32% of slimes content. Using Armeen 2HT secondary amine and Armeen DMHTD tertiary amine showed a maximum at 0.42% of slimes content. For Arquad 2HT-75 quaternary amine and Adogen 185 ether amine acetate, a maximum in the relative Insol rejection was shown at 0.46% and 0.48% of slimes content, respectively. Arr-Maz condensate amine showed no maximum in the relative Insol rejection, relative P2O5 losses, or selectivity ratio. In general, the presence of the maximum in the relative Insol rejection and relative P2O5 losses is related to the slimes composition. The relative increase in clay over fine silica and phosphate particles at low slimes content may be responsible for the decrease in relative Insol rejection and relative P2O5 losses. At slimes content above the maximum, the large amount of clay, fine silica and phosphate increases the overall specific surface area for amine adsorption (decrease in amine adsorption density), thus depressing the systems. The behavior of the selectivity ratio is related to the rate at which the relative Insol rejection changes with respect to that of the relative P2O5 losses as the slimes content increases; thus, the selectivity of the amine for silica for Plant III, Unsized Flotation Feed. This selectivity ratio presented a maximum at the same slimes content at which a maximum for the relative Insol rejection and relative P2O5 losses appeared, with the exception of Armeen DMHTD tertiary amine, Arquad 2HT-75 quaternary amine, and Arr-Maz condensate amine. In the case of Armeen DMHTD tertiary amine, the selectivity ratio decreased continuously as the slimes content increased, showing high sensitivity to slimes and poor selectivity. The selectivity ratio in the presence of Arquad 2HT-75 quaternary amine did not decrease significantly as the slimes content increased. This indicated the high selectivity of this amine. Arr-Maz condensate amine showed an apparent sharp increase in selectivity at high slimes content that was related to the depression of the system and the poor selectivity of this amine. Condensate amine showed poor selectivity over lowand medium-slime content.

8

The rank from most selective to least selective amine for Plant II, Unsized Flotation Feed appears to be: Quaternary > Ether > Primary > Tertiary > Secondary > Condensate. The effect of Percol 90L polymer addition on the amine flotation step of the reverse Crago process for Plant III, Unsized Flotation Feed was also evaluated on a relative basis for this type of feed since no optimization of the amine dosage was carried out on any of the six types of amines tested. Insol rejection, P2O5 losses (rejection) and selectivity ratio were used to evaluate the effect of Percol 90L polymer. In general, the Insol rejection increases to a maximum as the Percol 90L polymer addition increases. At this Percol 90L polymer addition, the P2O5 losses also increase, decreasing the selectivity ratio. A further increase in Percol 90L polymer addition depresses the system, the Insol rejection, P2O5 losses, and selectivity ratio decreases. This optimum in Percol 90L polymer addition corresponded to 0.024 lb./ton in the presence of Armeen HT primary amine; 0.016 lb./ton in the presence of Armeen DMHTD tertiary amine, Arquad 2HT-75 quaternary amine, Adogen 185 ether amine acetate, and Arr-Maz condensate amine; and 0.031 lb./ton in the presence of Armeen 2HT secondary amine. Locked cycle tests carried out in the presence of Arr-Maz condensate amine confirmed this behavior. The amine and the Percol 90L polymer additions had to be doubled, in this case, in order to obtain the maximum in Insol rejection due to the increase in slimes in the water as the number of cycles increased. As in the case of batch flotation tests, an increase in Percol 90L polymer over 0.032 lb./ton depressed the system. The data obtained for all six types of amines can be interpreted according to the following proposed mechanism. In the absence of Percol 90L polymer, the presence of slimes (large specific surface area) may consume the amine in bulk, reducing the flotation of silica particles. As Percol 90L polymer addition increases, this high-molecular-weight (MW) anionic polymer flocculates the slimes, mainly clay. Flocs are formed, which reduce the overall specific surface area available for amine adsorption, thus increasing the amine adsorption density. Therefore, the Insol rejection increases. As the polymer addition further increases, these flocs grow larger and entrap fine silica and phosphate particles. Under these conditions, the specific surface area available for the amine to adsorb increases again (highly negatively charged flocs), reducing the overall amine adsorption density. Thus, the system is depressed. Therefore, it is expected that an optimum balance of polymer and amine should be obtained to achieve the best Insol rejection and selectivity. Consequently, choosing the appropriate polymer and preparing a condensate amine more selective for a given feed is of the utmost importance for the amine flotation of the Reverse Crago process. Apparently, a low MW polymer that produces smaller flocs, avoiding entrapment and/or adsorption of fine silica and phosphate particles, would benefit the process. Also, a condensate amine with an increased quaternary amine content could be beneficial for the amine flotation step of the Reverse Crago process. 9

PART 7. SELECTIVITY ENHANCEMENT FOR ALL-ANIONIC FLOTATION One major problem with most of the previously developed anionic flotation processes for phosphate is the conflict between recovery and concentrate grade. Although this conflict exists in all flotation processes, it is more remarkable in anionic flotation of phosphate. For example, to reduce the Insol in the concentrate from 10% to 6% would generally entail a sacrifice of recovery of up to 10%. Coarse phosphate particles are the main reason for the big gap between recovery and grade. Over-reagentizing in rougher flotation could ensure better recovery of coarse phosphate particles, but would make it impossible to achieve low-Insol product in cleaner flotation. On the other hand, if reagent starvation were practiced in rougher flotation, coarse phosphate particles would not float readily in cleaner flotation. Another problem with some of the previous processes is the high cost for purer and more expensive collectors. The four all-anionic flotation processes discussed in Part 5 of this report achieved extremely encouraging results in the in the lab and on pilot scale. However, Insol level of around 10% is not the current industry norm, even though it is regularly accepted by some fertilizer plants. To further reduce Insol while maintaining a recovery of 90% or higher, one has to improve selectivity. The following selectivity enhancement methods were tested in this study: 1. Addition of collector-absorbing powders, such as ground phosphate rock and CaHPO4 to take up the extra fatty acids 2. Removal of detrimental Ca++ ions using the complexing agent oxalic acid 3. Discharge (“rinse”) of conditioning liquid to remove secondary slime and residual fatty acid 4. Comparison of flotation modifiers focusing on the silica depressants sodium silicate and lignosulfonates 5. Proper sizing of flotation feed, rougher concentrate, and tailings. Lignosulfonates offer the most potential for improving selectivity in anionic flotation of phosphate by acting as both “slime blinder” and silica depressant. They could also reduce fatty acid consumption to some extent. Ground phosphate rock is somewhat helpful in enhancing selectivity by taking up extra fatty acid. Oxalic acid is an effective complexing agent for calcium in flotation water, but its cost and potential toxicity may prohibit its use. Discharging conditioning water is very effective, but its practicality and economic feasibility require further investigation.

10

PART 1. INVESTIGATION OF FUEL OIL SUBSTITUTES

INTRODUCTION Long-chain fatty acids used for commercial flotation applications go through an ionization process between pH 4 and 10. At pH of around 8.0 there is an ion molecular complex (RCOOH-RCOO-) present in 1:1 proportion (Rosano and others 1966; DuRietz 1964). In this pH range these surfactants have distinct dual functionality as collector and frother. This phenomenon often causes excessive foaming in phosphate flotation. Current practice is to add a large quantity of fuel oil to reduce foaming. Non-polar hydrocarbon oils have an essential role in flotation. The Florida phosphate industry uses about 150 million pounds a year of fuel oil in the forms of No.5 oil or kerosene. One of the effects of oil or kerosene is to increase the resulting contact angle of a mineral against air bubbles substantially over the value in its absence, thereby accelerating kinetics and making possible the flotation of larger particles, both as a result of stronger adhesion of individual particles to bubbles and, equally, of the flotation of air/mineral/oil aggregates as well as individual particles (Cooper and others 1985). Fuel oil and kerosene also act as solvents for tall oil fatty acids and tallow amines, making them easier to handle. Furthermore, they also boost (extend) the floatability of the collectors. Fuel oil also plays a significant role in controlling foaming. According to one study, however, fuel oil does not have a significant effect on the kinetics of oleate adsorption on phosphate (Gruber and others 1995). This study also found that fuel oil promotes fatty acid adsorption on quartz when plant water was used. The industry has been using an excessive amount of fuel oil, mainly for controlling foaming. There are two principal techniques for destroying foams. Defoaming may be accomplished by either neutralization of the surfactant responsible for foam formation or its displacement. Thus, an addition of suitable metallic ions to produce insoluble salts with anionic surfactants may be effective in foam suppression whenever surfactants such as alcohols and nonionic polyoxyethylenes are absent in the system. Equally effective may be an addition of an oppositely charged surfactant, which gives a reaction product with the foam-forming surfactant in the form of an insoluble precipitate or mixed micelles with extremely low residual concentrations of both surfactants. Insoluble fatty acids esters, alkyl phosphates, and alkyl amides probably act in this manner. The second means of eliminating the surface elasticity relies on displacing the adsorbed surfactant from the interface with a nearly insoluble film of oil. Silicone and perfluorohydrocarbon oils are very effective foam inhibitors if dispersed in aqueous solutions as an emulsion, with or without a diluent (Leja 1982). Although a tremendous amount of fuel oil is being used to control foaming, excessive foaming still occurs in many plants, causing an appreciable waste of fatty acids. Fuel oil may not be the most effective defoamer for phosphate flotation. A small amount of an additive or a commercial defoamer could reduce fuel oil usage dramatically. Excessive use of fuel oil is not only costly, but also of environmental concern, because fuel oil does not biodegrade as fast as other flotation reagents such as fatty acids. 1-1

The first step of this research program was to document the relative performance of various petroleum derivatives as froth modifiers/auxiliary collectors during anionic rougher flotation of Florida phosphate, followed by determination of the potential value of rosin oil as a partial substitute for some of the petroleum derivatives, thereby reducing the flotation water contamination by these reagents. The fuel oils currently used to control froth character and increase tall oil collector "pull power" include No. 5 oil, reclaimed oil and possibly Bunker C/diesel mixtures. These petroleum derivatives are currently priced at about $0.04-$0.07 per pound in bulk quantities. Locating cheap reagents suitable as partial substitutes for these petroleum products is a challenging task. An effective substitute reagent must not only help prevent excessive frothing, but must not result in a decrease in "pull power" without using extra collector during rougher flotation. If a more costly substitute reagent (or reagent combination) is found that increases collector strength without adversely affecting the flotation selectivity, any resultant phosphate recovery increase should improve the overall processing cost. For example, using sodium silicate plus some rosin oil substitution for fuel oil might increase both rougher and amine (cleaner) circuit recoveries resulting from beneficial changes in froth character and higher rougher concentrate (amine feed) grade. Rosin oil is produced by thermal decarboxylation of natural rosin and/or tall oil rosin acids. Basically, it contains a mixture of cyclic hydrocarbons plus variable amounts of impurities. When produced from tall oil high-rosin acid fractions, the rosin oil contains some fatty acids and unreacted rosin acids. The rosin oil used for the current testwork was produced by Westvaco many years ago and had an acid number of 50.

1-2

EXPERIMENTAL FLOTATION FEED SAMPLES Three samples of flotation feed were used for the current laboratory testwork. These samples are designated as A, B and C. Table 1-1 shows analyses of the feed samples. The A and B samples contained mostly tan-colored phosphate, whereas the C sample contained mostly black phosphate. The B feed contained over four times as many -200 mesh "slime" particles when compared to the A and C samples. Detailed sizing analysis of these feeds are shown in Table 1A-1 (see Appendix 1). Table 1-1. Analyses of the Three Test Samples. Feed ID A B C

% Solids 92.0 82.8 83.8

% P2O5 10.12 7.82 4.26

% Insol 69.19 75.67 86.62

FLOTATION REAGENTS EVALUATED Rougher flotation of Feed A was performed using NH3 for conditioning pH regulation and Plant A tall oil with 11 different hydrocarbon-type froth modifiers. Rougher flotation of Feeds B and C was performed using soda ash for pH regulation and Liqro GA (Custom Chem.) tall oil with two selected froth modifiers previously used to process Feed A. N-Brand sodium silicate was also used to enhance selectivity and improve froth character during some of the flotation tests performed using Feeds B and C. A list of the froth modifiers initially tested using Feed A is presented in Table 1-2 along with measured specific gravities and price ranges. Table 1-3 shows the froth modifiers evaluated as a partial substitute for fuel oil. Table 1-2. Test Petroleum Additives. Product Mineral Spirits Kerosene Diesel Fuel White Mineral Oil No. 5 Fuel Oil PCS Fuel Oil IPC Fuel Oil Bunker C Fuel Oil Philflo Oil Rosin Oil Petrolatum

Specific Gravity 0.75 0.81 0.86 0.88 0.89 0.91 0.92 0.96 0.98 0.98 0.84 1-3

Cost, $/Lb. 0.248 0.074 0.063 0.381 0.049 -0.060 0.033 0.140 0.300 0.425

Table 1-3. Froth Modifiers Tested. Product No. 5 Fuel Oil Rosin Oil Tributyl Phosphate Polyglycol P-4000 Mazu DF 160-178 CC6983-16A CC6983-16B Oreprep 507 (Polyglycol) Emigol (Oil Emulsifier) Liqro GA (Tall Oil)

Specific Gravity 0.88 0.98 0.97 1.01 1.02 1.01 0.98 1.01 0.98 0.96

1-4

Cost, $/Lb. 0.049 0.300 1.80 1.06 3.35 --0.79 -0.14

RESULTS AND DISCUSSION EVALUATION OF ROSIN OIL AND PETROLEUM DERIVATIVES Comparison of Various Hydrocarbon-Type Froth Modifiers The current lab flotation tests used 0.70-0.86 lb. of NH3 per ton of feed (TF) to obtain 9.0-9.2 pH during 2-minute conditioning at 74-75% solids. Flotation Plant A uses NH3 for pH regulation. The flotation tests were performed using 1.0 lb. of Tall Oil A plus either 0.4 lb. or 0.6 lb. of froth modifier per ton of feed, using the 11 different hydrocarbon "oil" type reagents (0.4:1.0 froth modifier/tall oil mixture was used). Additional froth modifier was added separately to obtain a ratio of 0.6:1.0. Tap water was used for all tests. The P2O5 recovery results are presented for each reagent as bar graphs for easier visualization in Figure 1-1. Table 1A-2 in Appendix 1 shows detailed test results.

100 0.6 lb/TF

95

0.4 lb/TF

90

% P2O5 Recovery

85 80 75 70 65 60 55

O il Ro si n

O il Ph ilf lo

Ke ro se ne Di es el Fu el #5 Fu el O il PC S Fu el O il IP C Fu el O il Bu nk er C O W il hi te M in .O il Pe tro la tu m

M in er al Sp iri ts

50

Figure 1-1. Flotation Recoveries from Feed A Using Different Froth Modifiers. 1-5

The results illustrated in Figure 1-1 indicate that PCS fuel oil, IPC reclaimed oil, Coastal No. 5 fuel oil, and diesel were the most effective froth modifiers from a cost/performance standpoint. White mineral oil and Westvaco rosin oil were also very effective from a recovery/performance standpoint, their higher current unit cost would limit their complete substitution for fuel oil in operating flotation plants. When no froth modifier was used for lab flotation, very poor results were obtained. The successful performance of the two froth modifiers containing cyclic hydrocarbons (Philflo oil and Westvaco rosin oil) is noteworthy. The partial substitution of rosin oil for fuel oil was considered to be worthy of additional flotation testwork. Effect of Rosin Oil Four petroleum-based froth modifiers were selected for flotation tests using partial substitution of rosin oil: diesel, PCS fuel oil, Coastal No. 5 fuel oil and IPC reclaimed oil. Westvaco rosin oil (0.2 lb./TF) was used with each selected modifier (0.4 lb./TF) in place of the selected modifier (0.6 lb./TF). Flotation test results are presented for comparison in Figure 1-2, with details shown in Table 1A-3. The results for Samples B and C are shown in Tables 1A-4 and 1A-5. These results show that when rosin oil was substituted for 1/3 of each petroleum-based oil modifier, a 1.3-5.5% increase in flotation recovery of P2O5 was obtained along with an increase in concentrate Insol ranging from 0.95-7.89%. The use of some rosin oil assured a persistent froth that lasted for at least 2 minutes during flotation. This feature of the rosin oil is believed to be at least partially responsible for the % P2O5 recovery increases that occurred. The presence of some fatty acids and rosin acids in the commercial rosin oil (acid no.=50) could also be partially responsible for the higher % P2O5 recoveries obtained. In order to further evaluate the potential use of rosin oil as a partial substitute for fuel oil, three exploratory flotation tests were performed using Plant B feed. Soda ash (0.84-1.44 lb./TF) was used to obtain a conditioning pH of 9.0-9.2. Liqro GA tall oil collector was used at the 1.0 lb./ton feed level for all but the final test. Again, rosin oil improved flotation recovery, as shown in Figure 1-3.

1-6

96

0.6 lb oil/TF 0.4 lb oil + 0.2 lb rosin/TF

95 94

% P2O5 recovery

93 92 91 90 89 88 87 86 Diesel

PCS Fuel Oil

#5 Fuel Oil

IPC Oil

Figure 1-2. Effect of Rosin Oil on the Performance of Different Oils for Feed A. 96

% P2O5 Recovery

95

94

93

92

91 0

0 .1

0 .2

0 .3

R o s i n O il D o s a g e , lb /to n f e e d

Figure 1-3. Effect of Rosin Oil on Flotation Recovery for Feed B.

1-7

0 .4

0 .5

It should be pointed out that when only rosin oil (plus N-silicate) was used as the froth modifier, excellent selectivity but poor P2O5 recovery and slow flotation rate resulted. When only tall oil (1.8 lb./TF) was substituted for the total froth modifier(s), foamy froth plus poor concentrate recovery resulted. To further evaluate the potential use of rosin oil as a froth modifier during flotation of Southern Extension black phosphate, eight flotation tests were performed using Plant C feed. Soda ash (0.80-1.32 lb./TF) was used to obtain a conditioning pH of 9.0-9.2. Liqro GA tall oil collector was used at the 1.0 lb./ton feed level for all but the final test. N-silicate was used at the 0.4 lb./ton feed level for some tests, as shown in Table 1A-6. The conditioning and flotation parameters used with the PCS and Cargill feeds were used again. Very poor selectivity occurred using No. 5 fuel oil (0.6 lb./TF) without using Nsilicate. The selectivity was greatly improved when N-silicate was used. The combination of fuel oil (0.6 lb.), rosin oil (0.2 lb.) and N-silicate (0.4 lb.) gave the best results from an overall concentrate grade/recovery standpoint. This flotation concentrate analyzed 29.67% P2O5/13.19% Insol at 90.6% P2O5 recovery from this low-grade feed. Generalized Flotation Observations and Comments Rosin acid soap (Dresinate) was tested many years ago as a Florida phosphate collector. It performed poorly and usually produced voluminous "foamy" froths. For the current tests wherein rosin oil was substituted for 1/4-1/3 of the fuel oil requirement, flotation froth was concluded to be very good and persistent throughout each two-minute test period. It is possible that interactions occur between rosin oil, fuel oil, tall oil composition and sodium silicate that affect flotation rate and froth character, but are not completely understood at the present time. Sodium silicate use in local phosphate flotation plants has been shown to improve froth character and probably flotation rate as well as improving selectivity. The development of a customized phosphate collector by direct decarboxylation of a high-rosin tall oil vapor at the producer's tall oil fractionation plant is an interesting concept. This collector ideally would contain fatty acids and rosin oil with minor rosin acids and would require less fuel oil when used in phosphate flotation. The economics of producing this type of reagent are beyond our ability to determine. At present, we do not even know if the decarboxylation stage would work in the presence of a relatively large fatty acid content in the processing feedstock. If not, blending of the fatty acids with rosin oil produced at the fractionation plant might be desirable. The practicality of this approach should probably be discussed with an appropriate tall oil fractionation chemist, if we can locate one who is willing to help.

1-8

FROTH MODIFIERS AS PARTIAL SUBSTITUTE FOR FUEL OIL Flotation tests discussed in Part 1 of this study confirmed that No. 5 fuel oil is the most feasible frother/extender for fatty acid flotation of phosphate when both flotation performance and cost are considered. It was also demonstrated that partial replacement for No. 5 fuel oil was possible, achieving equivalent or better phosphate recovery. This part of the research was focused on optimizing the partial replacement of No. 5 fuel oil, particularly by rosin oil. In addition to No. 5 fuel oil and rosin oil, five froth modifiers were used to replace about 25% of the No. 5 fuel oil during laboratory flotation tests. The froth modifiers were added to the conditioner along with the pH regulator (soda ash) and the phosphate collector (Liqro GA tall oil and No. 5 fuel oil). Follow-up flotation tests were also performed adding the froth modifier surfactant to the flotation cell water for comparison purposes. The various froth modifiers tested and their current approximate cost per pound are listed in Table 1-3. All of the froth modifiers listed above were found to be readily soluble in kerosene (1 part reagent : 4 parts kerosene), whereas solubility in water was very low or nearly non-existent, with the exception of CC6983-16B. This surfactant formed a somewhat stable milky emulsion in water. The two Custom Chemicals surfactants are condensation products resulting from the reaction of tall oil fatty acids with 5 or 8 mols of ethylene oxide. Partial Substitution of Various Surfactant Froth Modifiers for No. 5 Fuel Oil Flotation recoveries for the tests performed using the various froth modifiers as partial fuel oil substitutes are presented in Figure 1-4 and Table 1A-6 for Sample B. Results on Sample A are shown in Table 1A-7. Results are presented for both modifier addition to the conditioner and addition to the cell water before adding the conditioned feed slurry to the cell. All tests were performed using 500g of feed (dry basis). Conditioning for 2 minutes at about 75% solids was employed as in all previously reported tests. Flotation time was normally 2 minutes except for tests with tributyl phosphate, wherein 3 minutes was required as a result of the slow flotation rate observed. Tall oil collector and No. 5 fuel oil base levels were 1.0 and 0.6 lb./TF for all tests, respectively. Soda ash use was 0.84-0.92 lb./TF to produce a conditioning pH of about 9.0-9.2+. The use of 0.2 lb. of froth modifier per ton of feed equates to about 20ppm of the modifier in the flotation cell water. The data presented in Figure 1-4 show that the % P2O5 recovery ranged from 92.6% to 97.0%, and flotation concentrate grade ranged from 16.98% P2O5 to 27.75% P2O5 for the 14 tests performed. All of the froth modifiers used produced satisfactory flotation recoveries of phosphate; however, flotation froth character varied from very good to "too foamy." The use of tributyl phosphate caused an excessive flotation time to be necessary to complete flotation. The two tall oil/ethylene oxide condensation products resulted in excessively foamy froths when added to the conditioning stage. The best froth 1-9

character was obtained using Mazu DF 160 silicone, Dow P-4000 polyglycol, Westvaco rosin oil and No.5 fuel oil. Different froth characteristics were noticed for some of the surfactants depending upon whether or not they were added to the conditioner or to the flotation cell water.

98 97 To cell To conditioner

96

% P2O5 recovery

95 94 93 92 91 90 89

P40 00 Do w

oi l Ro sin

69 83 -1 6A CC

69 83 -1 6B CC

Tr ib ut yl ph os ph at e M az u DF 16 017 8

No

m od ifi er

88

Figure 1-4. Effect of Froth Modifier Type and Addition Point on Recovery for Feed B. Effect of Rosin Oil Addition Levels Four flotation tests were performed wherein rosin oil was added during conditioning in quantities of 0.0, 0.1, 0.2 and 0.4 lb./TF along with constant standard tall oil plus fuel oil 1-10

amounts of 1.0 and 0.6 lb./TF, respectively. Mean values for concentrate % P2O5 and % P2O5 recovery along with calculated standard deviations showed that the mean values for these two tests were probably not different statistically. At least 0.2 lb. of rosin oil per ton of feed were required to obtain 95+% P2O5 recovery. Figure 1-5 presents a graph of the test results. 100 90 80 70

%

60 50

Concentrate % P2O5

40

% P2O5 recovery

30 20 10 0 0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

Rosin Oil Dosage, lb/ton

Figure 1-5. Effect of Rosin Oil Dosage with 1 Lb. Tall Oil and 0.6 Lb. No. 5 Fuel Oil per Ton of Feed B. Effect of Sodium Silicate Addition Three froth modifiers were selected for a brief flotation test series to illustrate the effect of using 0.4 lb. of N-brand sodium silicate to improve rougher flotation selectivity and possibly froth characteristics. As with previous tests, 1.0 lb. of tall oil plus 0.6 lb. of fuel oil were used as the standard phosphate collector. The sodium silicate was added during the final 20 seconds of conditioning. All other independent flotation variables were the same as those used in previous flotation tests. 1-11

The results, Tables 1A-4 and 1A-5, showed that the use of sodium silicate resulted in about 5-6% P2O5 higher concentrate grade. Concentrate phosphate recovery was about 2-3% lower for tests using Westvaco rosin oil and Dow P-4000; and about 1% higher using Custom Chemicals CC6983-16B froth modifier when sodium silicate was used. Froth character was moderately to notably improved when sodium silicate was used. EXTRA DESLIMING TO REDUCE FUEL OIL USE Summary Clay minerals (slime) in the flotation feed is one of the reasons excessive foaming occurs in phosphate flotation where insufficient fuel oil is used. It would therefore be possible to reduce fuel oil usage by getting more of the slime out from flotation feed. This short program was designed to determine the beneficial effects of feed desliming and scrubbing/desliming on the phosphate flotation performance and the fuel oil consumption required to obtain at least 93% P2O5 recovery in rougher flotation. Another purpose is to observe the effects upon phosphate flotation and froth character resulting from partially dewatering the feed conditioner discharge (to reject excess dispersed reagents and slimes) before flotation. The same general flotation procedures discussed above were used for the tests reported herein unless otherwise described. The same Cargill S. Ft. Meade flotation feed (Sample B, 7.8% P2O5) used for previous tests was used for all current tests. Additional tests were also performed to compare three more froth modifier surfactants as potential partial substitutes for No. 5 fuel oil. Only one of the froth modifiers, the polyglycol Oreprep 507, showed favorable froth characteristics when substituted for 25% of the fuel oil normally required for 92-93% P2O5 recovery during rougher flotation. Once again, the flotation performance for these tests varied depending upon the point of addition of the froth modifier. The two other reagents tested, Emigol (oil emulsifier) and Liqro GA tall oil, failed to yield acceptable flotation P2O5 recovery and/or froth character. The tall oil was tested only because of its relatively low price of $0.14 per lb. The potential benefits derived from desliming and scrubbing plus desliming of the feed before flotation were investigated. Desliming of the Cargill feed at 200 mesh rejected about 0.6% wt. of slime; however, subsequent standard flotation of the deslimed feed required 0.8 lb. of fuel oil per ton of feed to obtain 94.6% overall P2O5 recovery from the original feed. When a mild two-minute scrub was used before desliming and flotation, about 0.9% wt. of slime was rejected, and subsequent standard flotation required only 0.6 lb. of fuel oil per ton of feed to obtain 95.2% overall P2O5 recovery from the original feed. The scrubbing plus desliming procedure was very effective in producing a compact froth, fast float and excellent flotation P2O5 recovery. 1-12

Another series of flotation tests was performed in which the reagentized conditioner discharge slurry was partially de-watered before phosphate flotation using two different procedures. Three fuel oil levels were used for comparison of froth character and P2O5 recoveries obtained during flotation. In the first test procedure, the partially dewatered feed was subjected directly to flotation testing. Using the second test procedure, extra fresh water was added to the conditioner discharge slurry with mild stirring, followed by partial dewatering of the washed feed slurry before flotation. Part of the slimy water removed was added to the flotation cell water before phosphate flotation. The partial removal of very fine feed particles and excess unadsorbed reagents was intended to reduce excessive frothing during phosphate flotation. Good froth characteristics were obtained only when the fuel oil level was 0.8 or 1.0 lb./TF. Compared to standard flotation, the conditioner discharge desliming procedure yielded somewhat higher-grade phosphate concentrates at a P2O5 recovery loss of 1.3%-3.7% using equivalent fuel oil levels. The target value of at least 93% P2O5 recovery was not obtained using 0.8 lb. of fuel oil per ton of feed or less. All of these potential froth modifiers were found to be readily soluble in kerosene (1 part reagent:4 parts kerosene). Emigol formed a milky emulsion in water. Oreprep 507 formed a yellowish-brown fairly stable emulsion (or partial solution) in water. Cargill Feed Flotation Using Partial Substitution of Various Surfactant Froth Modifiers for No. 5 Fuel Oil Flotation material balances for these flotation tests performed using three potential froth modifiers as partial fuel oil substitutes are compared with using only fuel oil in Table 1A-8. Results are shown for both modifier addition to the conditioner and addition to the cell water before adding the conditioned flotation feed slurry to the cell. The concentrate grade/recovery relationships for these tests are also shown as bar graphs in Figures 1-6 and 1-7 for easier comparison. All tests were performed using 500 g feed samples and the same conditioning procedure previously discussed. Flotation time was usually 2 minutes except for Test 45 (4 minutes), Test 46 (2-1/2 minutes) and Test 35 (3 minutes). Tall oil collector and No. 5 fuel oil base levels again were 1.0 and 0.6 lb./TF for all tests. The flotation results presented in Table 1A-9 and Figures 1-6 and 1-7 show that the % P2O5 recovery ranged from 87.1% to 94.3% except for Test C-45, wherein adding Liqro GA (0.2 lb./TF) to the conditioner produced very poor results (64.6% P2O5 recovery). The Liqro GA tall oil did not behave like a froth modifier surfactant. Flotation concentrate grades ranged from 22.48% P2O5 to 27.03% P2O5. Only the use of Oreprep 507 (polyglycol) compared favorably with results obtained using only No. 5 fuel oil. Table 1A-11 describes froth character and flotation times required to complete flotation for these tests and for all additional tests described later.

1-13

100 90 % P2O5 Recovery

80 70 60 50 40 30 20 10 0 Fuel Oil in cell

Fuel Oil in Oreprep 507 Oreprep 507 Conditioner in Cell in Conditioner

Emigol in Cell

Emigol in Liqro GA in Liqro GA in Conditioner Cell Conditioner

Figure 1-6. Effect of Froth Modifiers on Flotation Recovery from Feed B Using 1 Lb./Ton Collector. 30

25

% P2O5

20

15

10

5

0 Fuel Oil in cell

Fuel Oil in Oreprep 507 Oreprep 507 Conditioner in Cell in Conditioner

Emigol in Cell

Emigol in Conditioner

Liqro GA in Cell

Liqro GA in Conditioner

Figure 1-7. Effect of Froth Modifiers on Concentrate Grade for Feed B Using 1 Lb./Ton Collector Flotation of Deslimed and Scrubbed/Deslimed Cargill Feed. 1-14

Laboratory flotation tests were performed on samples of Cargill feed after (1) desliming at 200 mesh, and (2) mild scrubbing at approximately 74% solids for 2 minutes, using the laboratory conditioner at 480 rpm, followed by desliming at 200 mesh. Desliming was performed by pulping the feed several times with tap water and decanting over a 200 mesh screen. Liqro GA tall oil use was 1.0 lb./TF, and No. 5 fuel oil levels of 0.6 and 0.8 lb./TF were employed. The flotation material balances and slime removal data for these tests are shown in Table 1A-9. Parallel tests using no special feed preparation are shown in Table 1A-10 for comparison (Test C-1 Avg. and C-27 Avg.). The Table 1A-10 tests labeled "Avg." represent the arithmetic average of four tests performed at each fuel oil level. Standard deviations of important variables were calculated from the test data. Results are shown in Table 1-4. Table 1-4. Standard Deviations Calculated from Test Data. Flotation Concentrate % Wt. % P2O5 % Insol % Recov. P2O5 % Recov. Insol

Test C-1 Using 0.6 Lb. F.O./TF Arith. Mean Std. Dev. 27.90 1.10 25.66 1.06 22.18 3.23 91.50 0.90 7.70 1.10

Test C-27 Using 0.8 Lb. F.O./TF Arith. Mean Std. Dev. 28.50 0.50 26.08 0.40 21.58 0.73 93.70 2.00 8.40 0.70

Comparing the Table 1A-9 and Table 1A-10 (C-1 Avg. and C-27 Avg.) test data sets shows that desliming alone was not very beneficial in reducing the fuel oil required for flotation to obtain over 93% P2O5 recovery. However, scrubbing plus desliming yielded over 96% P2O5 recovery by flotation using only 0.6 lb. of fuel oil per ton of clean feed. These results would exceed 94% P2O5 recovery overall, including the -200 mesh slime loss of 1.4% P2O5 recovery value. The high P2O5 recoveries, compact froth, and fast float character of these tests (C-50 and C-51) make them the best overall since the start of this project, considering that no special froth modifier surfactant was required in addition to the 0.6 lb./ton of fuel oil. Cargill Feed Flotation Using Various Degrees of Conditioner Discharge Desliming Two series of flotation tests, using three different fuel oil levels, were performed with the Cargill feed. In these tests the reagentized conditioner discharge was partially dewatered in order to remove excess reagents and slimes present in the liquid phase before flotation. Removal of a portion of these substances could reduce foaming and excess frothing during subsequent phosphate flotation. The two procedures tested were (1) partial dewatering of the conditioner discharge by pouring it onto a 200 mesh screen to allow about 40% (67-72g.) of the slimy liquid phase to pass through the screen openings, and (2) adding 300g. (with stirring) of "wash" tap water to the conditioner discharge, partial dewatering of the resulting slurry by pouring it onto a 200 mesh screen to remove about 59% (312-322g.) of the slimy liquid phase, and adding one-half of the slimy liquid phase to the flotation cell 1-15

water before phosphate flotation. The results of these flotation tests are compared with regular tests, using no conditioner discharge treatment, in Table 1A-10. The Table 1A-10 flotation material balances show that both of the conditioner discharge dewatering processes yielded flotation concentrates containing lower % Insol; however, about 2.5-3.5% lower P2O5 recoveries for equivalent fuel oil consumption also occurred compared to the regular test procedure results. No obvious direct fuel oil savings resulted using either of the dewatering processes. The froth character was visually good only for tests that used 0.8 or 1.0 lb. of fuel oil per ton of flotation feed. BENEFITS ANALYSIS OF ROSIN OIL SUBSTITUTION AND EXTRA DESLIMING Summary This test program was designed to evaluate the technical and economic benefits of partial substitution of fuel oil with rosin oil as well as extra desliming under nearoptimized conditions. The specific objectives are as follows: 1. To further evaluate the beneficial effects of Cargill feed scrubbing/desliming upon the collector and froth modifier consumptions required for optimum rougher flotation. 2. To compare the flotation results obtained for natural vs. scrubbed/deslimed Cargill feed at minimal fuel oil usage with and without rosin oil addition. 3. To compare the flotation results obtained for natural vs. scrubbed/deslimed PCS feed at minimal fuel oil usage without rosin oil addition. 4. To calculate preliminary processing costs per ton of feed for selected tests using either partial rosin oil substitution for fuel oil or mild feed scrubbing/desliming utilizing approximate power consumption and costs obtained for IMC’s Noralyn plant processing equipment (basis: 600 TPH of fine feed to one rougher flotation circuit). All flotation tests were performed using the previously described feed samples and previously reported laboratory test procedures. The minimum ratio of total froth modifier to tall oil that yielded at least 93% P2O5 rougher flotation recovery was concluded to be about 0.8:1.0 for the natural Cargill feed and 0.6:1.0 for the natural PCS feed. Using the scrub/deslime procedure, the minimum ratio for the Cargill feed flotation was reduced to 0.6:1.0. Equivalent rosin oil substitution for 0.2 lb. of fuel oil per ton of natural Cargill feed (25% substitution) resulted in a small increase in P2O5 recovery during rougher flotation. PCS feed responded favorably to rougher flotation using the scrub/deslime procedure and using the rosin oil partial substitution for fuel oil procedure. 1-16

Preliminary operating cost estimates were calculated utilizing hypothetical calculated amine flotation results (Crago process) required to ascertain the overall weight yield of amine concentrate obtainable using the various process modifications. When the amine concentrate weight yield and overall P2O5 recovery was greater (using rosin oil partial substitution or the scrub/deslime process) than the natural feed flotation using only fuel oil, the increased product yield was valued at more than the increased froth modifier cost and/or the extra power cost for mild scrubbing and feed desliming. Product value differences (concentrate value minus additional processing cost) were calculated using a very conservative $15/ton and also a more realistic $23/ton for the concentrate value. The positive product value difference varied from $0.020-$0.068/TF for the Cargill feed and from $0.08l-$0.275/TF for the PCS feed evaluated. These value ranges are considered to be reasonable approximations. Clean Bartow tap water was used for all flotation tests performed since the beginning of this project. If plant water containing appreciable particulate slimes would be used, the two processes for fuel oil reduction could fail to be as effective as reported herein. Plant water was not used because of possible changes that could occur (algae, solids precipitation, pH) during the 12 months of laboratory testing. Flotation of Cargill Scrubbed/Deslimed Feed Using Various Levels of Liqro GA Tall Oil at 1.0:0.6 Constant Ratio to No. 5 Fuel Oil Multiple 500 g (dry basis) samples of Cargill feed were subjected to mild 2minute attrition scrubbing at 74% solids followed by desliming at 200 mesh using the same procedure and equipment previously discussed. The resultant -200 mesh slime fraction compared favorably with previously reported results. Laboratory flotation tests were performed on the scrubbed, deslimed feed sample using various levels of Liqro GA tall oil at a constant ratio of 0.6:1.0 with No. 5 fuel oil. Tall oil levels tested ranged from 0.6 to 1.2 lb./ton of deslimed feed. Flotation material balances for all tests, including several repeats, are presented in Table 1A-11. Concentrate yields, grades, and P2O5 recoveries for these tests are illustrated graphically in Figure 1-8. The results show that about 0.9-1.0 lb. of tall oil per ton of feed was optimum to obtain at least 95% P2O5 recovery from the deslimed feed (93+% P2O5 recovery including scrub/deslime losses).

1-17

100 90 80

% by Weight

70 60 50 % P2O5 recovery Concentrate grade, % P2O5

40 30 20 10 0 0.5

0.6

0.7

0.8

0.9

1

1.1

1.2

Liqro GA Dosage, lb/Ton Feed

Figure 1-8. Collector Dosage vs. Concentrate Grade and Recovery of a Deslimed Feed. Flotation of Natural vs. Scrubbed, Deslimed Cargill Feed Using Liqro GA Tall Oil at 1.0:0.4 Ratio to No. 5 Fuel Oil with and without Rosin Oil Addition In order to determine if a combination of rosin oil partial substitution for fuel oil and feed scrubbing plus desliming would yield promising flotation results, several lab flotation tests were performed using only 0.4 lb. of fuel oil plus 1.0 lb. of tall oil per ton of Cargill feed, with and without rosin oil addition. The flotation material balances are presented in Table 1A-12. These results illustrate the very large improvement in P2O5 recovery resulting from feed scrubbing and desliming, and the beneficial effect of rosin oil addition. Test C-61 yielded 93.9% P2O5 recovery of concentrate analyzing 28.36% P2O5 and 15.23% Insol from scrubbed, deslimed feed using 0.4 lb. of fuel oil plus 0.2 lb. of rosin oil per ton of feed. Concentrate grade was also observed to increase using scrubbed, deslimed feed instead of natural feed. The overall P2O5 recovery, including slime losses, for Test C-61 was 92.5%. The minimum amount of total froth modifier, fuel oil, or fuel oil plus rosin oil, appears to be 0.6 lb./TF to obtain about 93% P2O5 recovery using 1.0 lb. of tall oil per ton of scrubbed/deslimed Cargill feed as the phosphate collector. 1-18

Flotation of Natural vs. Scrubbed, Deslimed PCS Feed Using PCS Tall Oil at 1.0:0.4 Ratio to PCS Fuel Oil with and without Rosin Oil or Extra Fuel Oil Addition Several 500 g (dry basis) samples of the same PCS feed used for previously discussed flotation testwork were subjected to the 2-minute scrubbing/deslime procedure. The slime analyzes 10% P2O5 and 47.65% Insol, and accounts for 0.89% by weight of the flotation feed and 0.9% of the total P2O5. Laboratory flotation tests were performed using the scrubbed and deslimed PCS feed in order to compare the results with those obtained from previous tests using natural feed. Several laboratory flotation tests were performed using 1.0 lb. of PCS tall oil plus 0.4 lb. and 0.6 lb. of PCS fuel oil per ton of feed. Also, similar tests were performed using 0.4 lb. of PCS fuel oil plus 0.2 lb. of rosin oil per ton of feed for comparison purposes. Flotation test material balances for these tests are presented in Table 1A-13. These results illustrate the benefits of feed scrubbing and desliming before flotation, and also show that partial substitution of rosin oil for fuel oil was possible without having a detrimental effect on flotation concentrate grade or recovery. Tests 30 and 31 produced concentrates analyzing 30.59-30.61% P2O5 and 9.11-9.29% Insol at 96.4-96.5% recovery using scrubbed, deslimed feed. Including scrubbing slime loss, the overall P2O5 recovery for these two tests exceeded 95%. Preliminary Cost Comparison Calculations for Rosin Oil Partial Substitution for Fuel Oil and for Feed Scrubbing and Desliming In order to obtain preliminary processing cost approximations for partial substitution of rosin oil for fuel oil, and for mild scrubbing plus desliming of the rougher flotation feed to compare with conventional rougher flotation, the following assumptions were used for both Cargill and PCS feed samples: • • • • • • •

Rougher concentrate and amine feed yield and grade were the same. No significant differences would result from acid scrubbing and desliming. Amine flotation P2O5 recoveries using Cargill feed and PCS feed would be set at 94% and 96%, respectively, for each set of comparison tests. Amine consumption would be the same for each set of comparison tests. Hypothetical amine concentrate % P2O5 grades would be calculated from rougher concentrate % P2O5 and % Insol analyses obtained in lab flotation tests by adjusting these values to about 5% Insol. Rosin Oil and No. 5 fuel oil costs would be $0.34/lb. and $0.07/lb., respectively. Electric power cost would be $0.04-$0.05 per kilowatt-hour. Calculated power cost estimates for scrubbing and desliming before rougher conditioning would be increased to account for scrubbing at about 74% solids. 1-19

•

Power cost estimates for scrubbing and desliming (pumping to cyclones) also would be based upon IMC’s Noralyn flotation plant vertical conditioners’ HP ratings and feed TPH processed in one fine feed circuit.

The value (production cost) of the phosphate concentrates produced was estimated at a very conservative $15.00/short ton. This figure could vary considerably for different flotation plants and/or phosphate producers. Appropriate flotation test results were selected for comparison of rougher concentrate yields, grades and P2O5 recoveries obtained using the three processing methods. Applying the previously listed assumptions, expected amine flotation results were calculated for each set of tests. Overall partial metallurgical balances were calculated for each test set in order to obtain expected overall Crago process concentrate weight yields for comparison. These calculations and results are presented in Tables 1A15 through 1A-18. Froth modifier reagent cost approximations for tests using No. 5 fuel oil and combinations of fuel oil with rosin oil are compared in Table 1A-19. Finally, power cost approximations for tests using the scrub/deslime procedure are compared with standard flotation. These results are presented in Tables 1A-20 and 1A-21. All numbers in bold print are assigned fixed values used to calculate the total flotation material balances. Table 1A-14 presents a summary of the economic analyses, with details listed in Tables 1A-15 through 1A-21. The Table 1A-14 results shown under the heading “Value Difference” are of particular interest. These values were calculated using flotation concentrate at $15/ton. Values in parenthesis are for flotation concentrate at $23/ton. When these numbers, expressed as $/T of rougher feed, were positive, the value of the extra concentrate yield exceeded the higher cost of rosin oil substitution or the additional power cost associated with feed scrubbing and desliming. Capital investment and maintenance cost increases are beyond the scope of this current work and would vary according to each plant installation of reagent distribution facilities and/or scrub/deslime circuit design.

1-20

CONCLUSIONS Fuel oil usage for phosphate flotation may be reduced by about 30% by substituting a portion of fuel oil with certain froth modifiers, with rosin oil being the most promising. The higher cost for rosin oil may be offset by improved flotation recovery. Extra desliming can also reduce fuel oil use by about 25%, with improved product grade.

1-21

REFERENCES Cooper H and others. 1985. Froths and frothers. In: Weiss NL, ed. SME mineral processing handbook. Vol. 1, Sect. 5, Chap. 6. New York: Society of Mining Engineers. p 5-33. DuRietz C. 1964. Chemisorption of collectors in surface chemistry. In: Proceedings of 2nd Scandinavian Symposium on Surface Activity, Stockholm, 1964, Academic Press, p. 21. Gruber G and others. 1995. Understanding the basics of anionic conditioning in phosphate flotation. Bartow (FL): Florida Institute of Phosphate Research. Publication nr 02-090-121. Leja J. 1982. Surface chemistry of froth flotation. New York: Plenum Press. p 577. Rosano HL, Breindel K, Schulman JH, Eydt AJ. 1966. Mechanism of ion exchange with carrier molecules through non-aqueous liquid membranes. J. Colloid Interface Science 22: 58.

1-23

FOR ADDITIONAL READING Azevedo MAD, Drelich J, Miller JD. 1997. The surface chemistry of pulping and flotation for mixed office wastepaper. In: Proceedings, 4th Research Forum on Recycling; 1997 Oct 7-9; Québec, Canada. p 125-128. Borchardt JK. 1994. Mechanistic insights into deinking. Colloids and Surfaces, A 88(1): 13-25. Laskowski JS. 1993. Frothers and flotation froth. Miner. Process. Extractive Metallur. Rev. 12: 61-89.

1-25

Appendix 1 TABLES FOR PART 1

Table 1A-1. Screen Analyses for Various Feed Samples Tested. Tyler Mesh PCS Swift Creek Feed +28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total Cargill S. Ft. Meade Feed +28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total IMC Ft. Green Feed +28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total

% Wt.

Cum. % Wt.

% P2O5

% Insol

4.47 8.99 22.11 37.21 21.93 3.82 1.04 0.43 100.00

4.47 13.46 35.57 72.78 94.71 98.53 99.57 100.00 --

16.27 11.66 12.75 10.50 7.30 8.45 10.69 10.83 10.58

49.68 63.75 61.02 62.37 78.13 73.55 66.29 63.56 65.56

0.50 1.43 14.64 29.11 34.15 14.26 3.95 1.96 7.81

1.93 16.57 45.68 79.83 94.09 98.04 100.00

19.78 6.44 7.55 8.24 8.12 5.05 6.06 7.81

40.47 79.71 76.50 74.54 74.83 83.25 74.55 75.60

18.72 8.39 4.19 3.48 4.22 3.57 3.85 6.12 4.54

43.94 73.55 86.86 89.01 86.76 88.24 86.67 72.56 85.68

2.22 7.48 30.87 35.55 17.57 5.14 0.84 0.36 100.00

1A-1

2.22 9.70 40.57 76.12 93.66 98.80 99.64 100.00

Table 1A-2. Flotation Test Results Using Various Froth Modifiers with PCS Feed. Test No.

Froth Modifier Name Lb./TF

7

Mineral Spirits

0.6

8

Mineral Spirits

0.4

5

Kerosene

0.6

6

Kerosene

0.4

3

Diesel Fuel

0.6

4

Diesel Fuel

0.4

1

No. 5 Fuel Oil (Coastal)

0.6

2

No. 5 Fuel Oil (Coastal)

0.4

9

PCS Fuel Oil

0.6

10

PCS Fuel Oil

0.4

25

IPC Fuel Oil (IMCAg)

0.6

24

IPC Fuel Oil (IMCAg)

0.4

Flotation Product % Wt. Conc. 25.5 Tail. 74.5 Feed 100.0 Conc. 22.8 Tail. 77.2 Feed 100.0 Conc. 26.7 Tail. 73.3 Feed 100.0 Conc. 24.1 Tail. 75.9 Feed 100.0 Conc. 29.8 Tail. 70.2 Feed 100.0 Conc. 26.4 Tail. 73.6 Feed 100.0 Conc. 30.0 Tail. 70.0 Feed 100.0 Conc. 25.4 Tail. 74.6 Feed 100.0 Conc. 30.7 Tail. 69.3 Feed 100.0 Conc. 24.8 Tail. 75.2 Feed 100.0 Conc. 29.3 Tail. 70.7 Feed 100.0 Conc. 23.8 Tail. 76.2 Feed 100.0

1A-2

Analysis % P2O5 % Insol 31.87 6.80 3.09 90.21 10.43 68.94 31.97 6.12 3.69 88.43 10.14 69.67 31.80 6.72 2.44 92.21 10.28 69.38 32.13 5.94 3.15 90.00 10.13 69.74 30.87 8.36 1.30 95.70 10.11 69.67 31.84 6.96 2.36 92.46 10.11 69.89 30.65 9.60 1.59 94.77 10.31 69.22 31.17 7.65 2.80 91.11 10.01 69.91 30.98 8.99 1.08 96.33 10.26 69.52 31.70 7.28 3.03 90.43 10.14 69.81 31.77 7.04 1.53 94.86 10.39 69.13 29.95 12.09 3.94 87.88 10.13 69.77

% Dist. P2O5 77.9 22.1 100.0 71.9 28.1 100.0 82.6 17.4 100.0 76.4 23.6 100.0 91.0 9.0 100.0 82.8 17.2 100.0 89.2 10.8 100.0 79.1 20.9 100.0 92.7 7.3 100.0 77.5 22.5 100.0 89.6 10.4 100.0 70.4 29.6 100.0

Table 1A-2 (Cont.). Flotation Test Results Using Various Froth Modifiers with PCS Feed. Test No.

Froth Modifier Name Lb./TF

11

Bunker C Oil

0.6

12

Bunker C Oil

0.4

13

White Mineral Oil

0.6

14

White Mineral Oil

0.4

19

Petrolatum

0.6

20

Petrolatum

0.4

15

Philflo Oil (Phillips)

0.6

16

Philflo Oil (Phillips)

0.4

17

Rosin Oil (Westvaco)

0.6

18

Rosin Oil (Westvaco)

0.4

27

(None Used)

0

28

(None Used)

0

Flotation Product % Wt. Conc. 27.0 Tail. 73.0 Feed 100.0 Conc. 19.0 Tail. 81.0 Feed 100.0 Conc. 32.0 Tail. 68.0 Feed 100.0 Conc. 25.2 Tail. 74.8 Feed 100.0 Conc. 28.2 Tail. 71.8 Feed 100.0 Conc. 20.9 Tail. 79.1 Feed 100.0 Conc. 28.1 Tail. 71.9 Feed 100.0 Conc. 23.7 Tail. 76.3 Feed 100.0 Conc. 30.0 Tail. 70.0 Feed 100.0 Conc. 23.1 Tail. 76.9 Feed 100.0 Conc. 0.3 Tail. 99.7 Feed 100.0 Conc. 3.7 Tail. 96.3 Feed 100.0

1A-3

Analysis % P2O5 % Insol 31.45 7.61 2.51 91.93 10.32 69.16 31.25 8.22 5.03 84.58 10.01 70.07 30.72 9.85 0.82 97.10 10.39 69.18 31.56 7.49 2.96 90.59 10.16 69.65 31.53 7.04 1.90 93.75 10.25 69.30 31.90 6.39 4.32 86.54 10.09 69.79 31.66 7.02 1.96 93.58 10.31 69.25 31.57 7.51 3.61 88.72 10.23 69.47 30.39 10.62 1.73 94.32 10.33 69.21 31.31 8.25 4.04 87.40 10.34 69.12

28.98 9.52 10.24

13.90 71.13 69.01

% Dist. P2O5 82.3 17.7 100.0 59.3 40.7 100.0 94.6 5.4 100.0 78.2 21.8 100.0 86.7 13.3 100.0 66.1 33.9 100.0 86.3 13.7 100.0 73.1 26.9 100.0 88.3 11.7 100.0 69.9 30.1 100.0

10.4 89.6 100.0

Table 1A-3. Flotation of PCS Feed Using PCS Tall Oil (1.0 Lb./TF) with Various Fuel Oil and Rosin Oil Additions. Test No. 21

Froth Modifier Name Lb./TF Diesel 0.4 Rosin Oil 0.2 0.6

Conc. Tail. Feed

29.8 70.2 100.0

30.87 1.30 10.11

8.36 95.70 69.67

91.0 9.0 100.0

PCS Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

32.7 67.3 100.0

30.06 0.93 10.46

11.94 96.72 68.99

94.0 6.0 100.0

PCS Fuel Oil

0.6

Conc. Tail. Feed

30.7 69.3 100.0

30.98 1.08 10.26

8.99 96.33 69.52

92.7 7.3 100.0

No. 5 Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

32.0 68.0 100.0

30.24 1.05 10.39

11.03 96.39 69.07

93.2 6.8 100.0

No. 5 Fuel Oil

0.6

Conc. Tail. Feed

30.0 70.0 100.0

30.65 1.59 10.31

9.60 94.77 69.22

89.2 10.8 100.0

IPC Oil (IMCAg) Rosin Oil

0.4 0.2

Conc. Tail. Feed

34.4 65.6 100.0

28.89 0.86 10.50

14.93 96.97 68.75

94.7 5.3 100.0

IPC Oil (IMCAg)

0.6

Conc. Tail. Feed

29.3 70.7 100.0

31.77 1.53 10.39

7.04 94.86 69.13

89.6 10.4 100.0

9

23

1

26

25

Analysis % Dist. % P2O5 % Insol P2O5 30.90 9.31 94.1 0.92 96.75 5.9 10.51 68.77 100.0

Diesel 3

22

Flotation Product % Wt. Conc. 32.0 Tail. 68.0 Feed 100.0

1A-4

Table 1A-4. Flotation of Cargill Feed Using Liqro GA Tall Oil (1.0 Lb./TF with Various No. 5 Fuel Oil and Rosin Oil Additions. Froth Modifier Name Lb./TF 0.6 No. 5 Fuel Oil C-1 (Foamy Flot.)

Test No.

Flotation Analysis % Dist. Product % Wt. % P2O5 % Insol P2O5 Conc. 29.1 24.83 25.48 91.6 Tail. 70.9 0.93 96.82 8.4 Feed 100.0 7.89 76.06 100.0

1.0

Conc. Tail. Feed

34.8 65.2 100.0

21.13 0.59 7.73

35.94 97.78 76.26

95.1 4.9 100.0

No. 5 Fuel Oil Rosin Oil C-3 (Strong Flot. & Persistent Froth)

0.6 0.4

Conc. Tail.

43.3 56.7

16.96 0.58

48.66 97.84

95.7 4.3

Feed

100.0

7.67

76.55

100.0

No. 5 Fuel Oil Rosin Oil C-4 (Good Flot. & Persistent Froth)

0.6 0.2

Conc. Tail.

32.3 67.7

22.88 0.51

31.36 98.08

95.5 4.5

Feed

100.0

7.74

76.53

100.0

No. 5 Fuel Oil N-Silicate C-5 (Less Foamy Than Test C-1)

0.6 0.4

Conc. Tail.

22.6 77.4

30.00 1.50

10.57 95.06

85.4 14.6

Feed

100.0

7.94

75.97

100.0

No. 5 Fuel Oil Rosin Oil C-6 N-Silicate (Strong Froth—Decreases After 1 Min.)

0.6 0.2

Conc. Tail.

25.5 74.5

28.87 0.82

13.76 97.15

92.3 7.7

Feed

100.0

7.97

75.89

100.0

N-Silicate 1.8 Lb./T Tall Oil Used C-7 (Foamy Froth— Subsides After 1.5 Min.—Poor Flot.)

0.4

Conc. Tail.

10.6 89.4

28.97 5.46

12.21 83.05

38.6 61.4

Feed

100.0

7.95

75.54

100.0

Rosin Oil N-Silicate C-8 (Extremely Slow Flot. About 4 Min.)

0.8 0.4

Conc. Tail.

16.4 83.6

30.60 3.50

8.46 88.67

63.1 36.9

Feed

100.0

7.95

75.52

100.0

No. 5 Fuel Oil C-2 (Improved Froth)

0.4

1A-5

Table 1A-5. Flotation of IMC Feed Using Liqro GA Tall Oil (1.0 Lb./TF with Various No. 5 Fuel Oil and Rosin Oil Additions. Froth Modifier Name Lb./TF 0.6 No. 5 Fuel Oil FG-1 (Very Foamy Flot.) Test No.

No. 5 Fuel Oil N-Silicate FG-2 (Good Froth—Flat After 1 Min.)

0.6 0.4

No. 5 Fuel Oil FG-3 N-Silicate (Flat Froth)

Flotation Analysis % Dist. Product % Wt. % P2O5 % Insol P2O5 Conc. 40.9 9.60 70.88 89.3 Tail. 59.1 0.80 97.18 10.7 Feed 100.0 4.40 86.42 100.0 Conc. Tail.

13.0 87.0

29.68 0.82

12.87 97.16

84.5 15.5

Feed

100.0

4.57

86.20

100.0

1.0 0.4

Conc. Tail. Feed

12.7 87.3 100.0

31.00 0.70 4.55

9.14 97.44 86.23

86.6 13.4 100.0

No. 5 Fuel Oil Rosin Oil FG-4 N-Silicate (Good Froth—Fast Flot.)

0.6 0.2

Conc. Tail.

14.0 86.0

29.67 0.50

13.19 98.13

90.6 9.4

0.4

Feed

100.0

4.58

86.22

100.0

No. 5 Fuel Oil N-Silicate FG-5 (Good Froth—Flat After 1 Min.)

0.8 0.4

Conc. Tail.

14.2 85.8

28.94 0.52

15.05 98.08

90.1 9.9

Feed

100.0

4.56

86.29

100.0

No. 5 Fuel Oil FG-6 (Fair Flot.—Less Foamy Than Test FG-1)

0.8

Conc. Tail. Feed

29.5 70.5 100.0

13.92 0.59 4.53

58.67 97.88 86.32

90.7 9.3 100.0

N-Silicate 1.8 Lb./T Tall Oil Used FG-7 (Very Foamy at Start— Poor Flot.)

0.4

Conc. Tail.

10.9 89.1

12.15 3.56

62.64 88.62

29.4 70.6

Feed

100.0

4.49

85.79

100.0

Rosin Oil FG-8 N-Silicate (Slow Flot.—3+ Min.)

0.8 0.4

Conc. Tail. Feed

8.4 91.6 100.0

31.34 2.04 4.50

7.38 92.47 85.36

58.4 41.6 100.0

1A-6

Table 1A-6. Results on Feed B with 1 Lb./Ton Tall Oil at Various Froth Modifier Levels. Test No. C-27A

C-27

C-21

C-20

C-24

C-23

C-29

C-28

C-31

C-30

C-22

C-4

C-26

C-25

Froth Modifier Name Lb./TF No. 5 Fuel Oil 0.8 To cell No. 5 Fuel Oil To cond.

0.8

No. 5 Fuel Oil T.B.P. To cell No. 5 Fuel Oil T.B.P. To cond. No. 5 Fuel Oil Mazu DF 160 To cell No. 5 Fuel Oil Mazu DF 160 To cond. No. 5 Fuel Oil CC6983-16B,5mol. To cell No. 5 Fuel Oil CC6983-16B,5mol. To cond. No. 5 Fuel Oil CC6983-16B,8mol. To cell No. 5 Fuel Oil CC6983-16B,8mol. To cond. No. 5 Fuel Oil Rosin Oil To cell No. 5 Fuel Oil Rosin Oil To cond. # 5 Fuel Oil Dow P-4000 To cell # 5 Fuel Oil Dow P-4000 To cond.

0.6 0.15 0.6 0.15 0.6 0.20 0.6 0.20 0.6 0.2 0.6 0.2 0.6 0.2 0.6 0.2 0.6 0.2 0.6 0.2 0.6 0.2 0.6 0.2

Flotation Product % Wt. Conc. 31.6 Tail. 68.4 Feed 100.0 Conc. 29.0 Tail. 71.0 Feed 100 Conc. 30.8 Tail. 69.2 Feed 100.0 Conc. 31.5 Tail. 68.5 Feed 100.0 Conc. 29.1 Tail. 70.9 Feed 100.0 Conc. 30.9 Tail. 69.1 Feed 100.0 Conc. 29.2 Tail. 70.8 Feed 100.0 Conc. 38.7 Tail. 61.3 Feed 100.0 Conc. 38.9 Tail. 61.1 Feed 100.0 Conc. 36.6 Tail. 63.4 Feed 100.0 Conc. 29.0 Tail. 71.0 Feed 100.0 Conc. 32.3 Tail. 67.7 Feed 100.0 Conc. 26.4 Tail. 73.6 Feed 100.0 Conc. 42.4 Tail. 57.6 Feed 100.0

1A-7

Analysis % P2O5 % Insol 22.48 31.60 0.81 97.22 7.65 76.49 25.51 22.58 0.75 97.37 7.93 75.68 24.01 26.75 0.72 97.39 7.99 75.63 23.20 29.11 0.83 97.08 7.88 75.65 25.00 24.05 0.67 97.61 7.76 76.21 23.00 29.97 0.69 97.57 7.59 76.68 25.1 23.50 0.78 97.35 7.88 75.28 19.03 41.79 0.72 97.44 7.80 75.90 19.36 40.97 0.51 98.20 7.84 75.94 20.39 37.72 0.58 97.90 7.83 75.90 24.89 24.01 0.99 96.55 7.92 75.51 22.88 31.36 0.51 98.08 7.74 76.53 27.75 15.99 0.76 97.34 7.89 75.86 16.98 48.16 0.39 98.50 7.42 77.16

% Dist. P2O5 92.8 7.2 100.0 93.3 6.7 100.0 92.6 7.4 100.0 92.8 7.2 100.0 93.8 6.2 100.0 93.7 6.3 100.0 93.0 7.0 100.0 94.4 5.6 100.0 96.0 4.0 100.0 95.3 4.7 100.0 91.2 8.8 100.0 95.5 4.5 100.0 92.9 7.1 100.0 97.0 3.0 100.0

Table 1A-7. Flotation Results Using Various Froth Modifiers with PCS (A) Feed. Test No.

Froth Modifier Name Lb./TF Mineral Spirits 0.6

7 Mineral Spirits

0.4

Kerosene

0.6

Kerosene

0.4

Diesel Fuel

0.6

Diesel Fuel

0.4

No. 5 Fuel Oil (Coastal)

0.6

1

0.4

2

No. 5 Fuel Oil (Coastal) PCS Fuel Oil

0.6

PCS Fuel Oil

0.4

0.6

25

IPC Fuel Oil (IMCAg) IPC Fuel Oil (IMCAg)

0.4

24

Bunker C Oil

0.6

Bunker C Oil

0.4

8

5

6

3

4

9

10

11

12

Flotation Product % Wt. Conc. 25.5 Tail. 74.5 Feed 100.0 Conc. 22.8 Tail. 77.2 Feed 100.0 Conc. 26.7 Tail. 73.3 Feed 100.0 Conc. 24.1 Tail. 75.9 Feed 100.0 Conc. 29.8 Tail. 70.2 Feed 100.0 Conc. 26.4 Tail. 73.6 Feed 100.0 Conc. 30.0 Tail. 70.0 Feed 100.0 Conc. 25.4 Tail. 74.6 Feed 100.0 Conc. 30.7 Tail. 69.3 Feed 100.0 Conc. 24.8 Tail. 75.2 Feed 100.0 Conc. 29.3 Tail. 70.7 Feed 100.0 Conc. 23.8 Tail. 76.2 Feed 100.0 Conc. 27.0 Tail. 73.0 Feed 100.0 Conc. 19.0 Tail. 81.0 Feed 100.0

1A-8

Analysis % P2O5 % Insol 31.87 6.80 3.09 90.21 10.43 68.94 31.97 6.12 3.69 88.43 10.14 69.67 31.80 6.72 2.44 92.21 10.28 69.38 32.13 5.94 3.15 90.00 10.13 69.74 30.87 8.36 1.30 95.70 10.11 69.67 31.84 6.96 2.36 92.46 10.11 69.89 30.65 9.60 1.59 94.77 10.31 69.22 31.17 7.65 2.80 91.11 10.01 69.91 30.98 8.99 1.08 96.33 10.26 69.52 31.70 7.28 3.03 90.43 10.14 69.81 31.77 7.04 1.53 94.86 10.39 69.13 29.95 12.09 3.94 87.88 10.13 69.77 31.45 7.61 2.51 91.93 10.32 69.16 31.25 8.22 5.03 84.58 10.01 70.07

% Dist. P2O5 77.9 22.1 100.0 71.9 28.1 100.0 82.6 17.4 100.0 76.4 23.6 100.0 91.0 9.0 100.0 82.8 17.2 100.0 89.2 10.8 100.0 79.1 20.9 100.0 92.7 7.3 100.0 77.5 22.5 100.0 89.6 10.4 100.0 70.4 29.6 100.0 82.3 17.7 100.0 59.3 40.7 100.0

Table 1A-7 (Cont.). Flotation Results Using Various Froth Modifiers with PCS (A) Feed. Test No.

Froth Modifier Name Lb./TF White Min. Oil 0.6

13 White Min. Oil

0.4

Petrolatum

0.6

Petrolatum

0.4

Philflo Oil (Phillips)

0.6

15

Philflo Oil (Phillips)

0.4

16

0.6

17

Rosin Oil (Westvaco) Rosin Oil (Westvaco)

0.4

18

(None Used)

0

(None Used) (1.6#/T. T.O. Used)

0

14

19

20

27

28

Flotation Product % Wt. Conc. 32.0 Tail. 68.0 Feed 100.0 Conc. 25.2 Tail. 74.8 Feed 100.0 Conc. 28.2 Tail. 71.8 Feed 100.0 Conc. 20.9 Tail. 79.1 Feed 100.0 Conc. 28.1 Tail. 71.9 Feed 100.0 Conc. 23.7 Tail. 76.3 Feed 100.0 Conc. 30.0 Tail. 70.0 Feed 100.0 Conc. 23.1 Tail. 76.9 Feed 100.0 Conc. 0.3 Tail. 99.7 Feed 100.0 Conc. 3.7 Tail. 96.3 Feed 100.0

Note: N/A = Not Analyzed.

1A-9

Analysis % P2O5 % Insol 30.72 9.85 0.82 97.10 10.39 69.18 31.56 7.49 2.96 90.59 10.16 69.65 31.53 7.04 1.90 93.75 10.25 69.30 31.90 6.39 4.32 86.54 10.09 69.79 31.66 7.02 1.96 93.58 10.31 69.25 31.57 7.51 3.61 88.72 10.23 69.47 30.39 10.62 1.73 94.32 10.33 69.21 31.31 8.25 4.04 87.40 10.34 69.12 N/A N/A N/A N/A N/A N/A 28.98 13.90 9.52 71.13 10.24 69.01

% Dist. P2O5 94.6 5.4 100.0 78.2 21.8 100.0 86.7 13.3 100.0 66.1 33.9 100.0 86.3 13.7 100.0 73.1 26.9 100.0 88.3 11.7 100.0 69.9 30.1 100.0

10.4 89.6 100.0

Table 1A-8. Flotation of Cargill Feed Using Liqro GA Tall Oil (1.0 Lb./TF) with Various Froth Modifier Combinations. Test No.

Froth Modifier Name Lb./TF No. 5 Fuel Oil 0.8

C-27A To Cell C-27 Avg.

No. 5 Fuel Oil

Flotation Product % Wt. Conc. 31.6 Tail. 68.4 Feed 100.0

0.8

Conc. Tail. Feed

28.5 71.5 100.0

To Cond.

Analysis % P2O5 % Insol 22.48 31.60 0.81 97.22 7.65 76.49 26.08 0.70 7.93

% Dist. P2O5 92.8 7.2 100.0

21.58 97.52 76.10

93.7 6.3 100.0

C-36

No. 5 Fuel Oil Oreprep 507 To Cell

0.6 0.2

Conc. Tail. Feed

28.4 71.6 100.0

25.75 0.73 7.83

22.32 96.65 75.54

93.4 6.6 100.0

C-35

No. 5 Fuel Oil Oreprep 507 To Cond.

0.6 0.2

Conc. Tail. Feed

29.2 70.8 100.0

23.84 0.62 7.67

27.08 96.98 76.09

90.4 5.7 100.0

C-48

No. 5 Fuel Oil Emigol To Cell

0.6 0.2

Conc. Tail. Feed

29.3 70.7 100.0

23.84 1.04 7.73

27.08 96.37 76.06

90.4 9.6 100.0

C-47

No. 5 Fuel Oil Emigol To Cond.

0.6 0.2

Conc. Tail. Feed

28.6 71.4 100.0

24.32 1.40 7.96

25.68 95.24 75.34

87.4 12.6 100.0

C-46

No. 5 Fuel Oil Liqro GA To Cell

0.6 0.2

Conc. Tail. Feed

24.7 75.3 100.0

27.03 1.31 7.67

17.53 95.49 76.23

87.1 12.9 100.0

C-45

No. 5 Fuel Oil Liqro GA To Cond.

0.6 0.2

Conc. Tail. Feed

19.0 81.0 100.0

26.05 3.34 7.66

20.36 89.41 76.29

64.6 35.4 100.0

1A-10

Table 1A-9. Flotation Material Balances Using Deslimed and Scrubbed/Deslimed Feed. Collector, Tall Oil For Deslimed Feed: 1.0 C-52 Test No.

Lb./TF Fuel Oil

Conc. 30.0 25.48 24.95 C-53 Tail. 70.0 0.55 98.00 Feed 100.0 8.03 76.09 -200M reject: 0.67% Wt., 9.67% P2O5, 53.88% Insol, 0.7% Dist. P2O5

95.1 4.9 100.0

26.69 0.95 8.06

0.8

For Scrubbed and Deslimed Feed: 1.0 0.6 C-50

C-51

27.6 72.4 100.0

% Dist. P2O5 91.4 8.6 100.0

1.0

Conc. Tail. Feed

Analysis % P2O5 % Insol 21.38 96.79 75.98

1.0

0.6

Flotation Product % Wt.

0.8

Conc. Tail. Feed

28.3 71.7 100.0

27.06 0.38 7.93

20.40 98.33 76.27

96.6 3.4 100.0

Conc. Tail. Feed

29.8 70.2 100.0

26.15 0.42 8.06

22.88 98.45 75.93

96.6 3.4 100.0

-200M reject: 0.91% Wt., 12.34% P2O5, 45.71% Insol, 1.4% Dist. P2O5

1A-11

Table 1A-10. Flotation Material Balances Using Various Degrees of Conditioner Discharge Desliming. Collector, Lb./TF Flotation Tall Oil Fuel Oil Product % Wt. Conditioner Discharge Floated Directly: 1.0 0.6 Conc. 27.9 C-1 Tail. 72.1 Avg. Feed 100.0 Test No.

Analysis % P2O5 % Insol

% Dist. P2O5

25.66 0.92 7.82

22.18 96.59 75.83

91.6 8.4 100.0

1.0

0.8

Conc. Tail. Feed

28.5 71.5 100.0

26.08 0.70 7.93

21.58 97.52 76.10

93.7 6.3 100.0

1.0

1.0

Conc. Tail. Feed

34.8 65.2 100.0

21.13 0.59 7.73

35.94 97.78 76.26

95.1 4.9 100.0

Conc. Tail. Feed

24.8 75.2 100.0

27.60 1.22 7.76

17.22 95.21 75.87

88.1 11.9 100.0

Conc. Tail. Feed

26.3 73.7 100.0

27.33 0.80 7.78

17.73 96.43 75.73

92.4 7.6 100.0

Conc. 26.8 Tail. 73.2 Feed 100.0 Conditioner Discharge Washed and Dewatered: 1.0 0.6 Conc. 24.6 C-43 Tail. 75.4 Feed 100.0

27.12 0.69 7.78

18.32 96.75 75.73

93.4 6.6 100.0

27.79 1.17 7.72

16.31 96.12 76.48

88.6 11.4 100.0

C-27 Avg.

C-2 Conditioner Discharge Dewatered: 1.0 0.6 C-41 1.0

0.8

1.0

1.0

C-39

C-40

1.0

0.8

Conc. Tail. Feed

26.2 73.8 100.0

26.22 0.82 7.48

20.40 97.14 77.03

91.8 8.2 100.0

1.0

1.0

Conc. Tail. Feed

26.4 73.6 100.0

27.31 0.89 7.86

17.64 97.01 76.06

91.7 8.3 100.0

C-42

C-44

1A-12

Table 1A-11. Flotation of Cargill Scrubbed, Deslimed Feed Using Various Levels of Liqro GA Tall Oil at 1.0:0.6 Constant Ratio to No. 5 Fuel Oil. Test No.

Collector, Tall Oil 0.6

Lb./TF Fuel Oil 0.36

0.8

0.48

Conc. Tail. Feed

24.7 75.3 100.0

28.84 1.08 7.93

14.28 96.45 76.16

89.8 10.2 100.0

0.8

0.48

Conc. Tail. Feed

23.0 77.0 100.0

29.47 1.29 7.77

10.31 95.58 75.97

87.3 12.7 100.0

0.9

0.54

Conc. Tail. Feed

29.2 70.8 100.0

25.42 0.46 7.75

22.73 98.13 76.41

95.7 4.3 100.0

0.9

0.54

Conc. Tail. Feed

25.8 74.2 100.0

28.50 0.49 7.71

13.16 98.01 96.12

95.3 4.7 100.0

1.0

0.60

Conc. Tail. Feed

28.3 71.7 100.0

27.06 0.38 7.93

20.40 98.33 76.27

96.6 3.4 100.0

1.0

0.60

Conc. Tail. Feed

29.1 70.9 100.0

25.27 0.45 7.80

23.67 98.33 76.61

95.9 4.1 100.0

1.0

0.60

Conc. Tail. Feed

29.4 70.6 100.0

25.67 0.32 7.78

22.68 98.75 76.39

97.0 3.0 100.0

1.1

0.66

Conc. Tail. Feed

31.6 68.4 100.0

24.14 0.49 7.97

28.39 98.31 76.21

95.7 4.3 100.0

1.2

0.72

Conc. Tail. Feed

35.4 64.6 100.0

20.87 0.70 7.84

37.76 97.61 76.43

94.3 5.7 100.0

1.2

0.72

Conc. Tail. Feed

36.0 64.0 100.0

20.78 0.74 7.95

36.85 97.44 75.63

94.1 5.9 100.0

C-55

C-54

C-54R

C-59

C-59R

C-50

C-50R

C-50RR

C-57

C-56

C-56R

Flotation Product % Wt. Conc. 21.6 Tail. 78.4 Feed 100.0

1A-13

Analysis % P2O5 % Insol 27.64 17.79 2.31 92.84 7.78 76.63

% Dist. P2O5 76.7 23.3 100.0

Table 1A-12. Flotation of Natural Vs. Scrubbed, Deslimed Cargill Feed Using Liqro GA Tall Oil at 1.0:0.4 Ratio to No. 5 Fuel Oil with and without Rosin Oil Addition. Flotation Lb./TF Fuel Product % Wt. Oil Using Scrubbed and Deslimed Feed: No. 5 Fuel Oil 0.4 Conc. 23.1 C-62 Tail. 76.9 Feed 100.0 Test No.

Froth Modifier Name

Analysis % P2O5

% Insol

% Dist. P2O5

29.61 1.28 7.82

11.72 95.43 76.10

87.5 12.5 100.0

No. 5 Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

26.0 74.0 100.0

28.36 0.65 7.85

15.23 97.23 75.91

93.9 6.1 100.0

Using Natural Feed: No. 5 Fuel Oil C-63

0.4

Conc. Tail. Feed

7.0 93.0 100.0

26.63 6.35 7.77

20.18 80.55 76.32

23.9 76.1 100.0

No. 5 Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

17.2 82.8 100.0

26.58 4.15 8.01

19.48 86.85 75.26

57.1 42.9 100.0

C-61

C-64

1A-14

Table 1A-13. Flotation of Natural vs. Scrubbed, Deslimed PCS Feed Using PCS Tall Oil at 1.0:0.4 Ratio to PCS Fuel Oil with and without Rosin Oil or Extra Fuel Oil Addition. Flotation Lb./TF Fuel Product % Wt. Oil Using Scrubbed and Deslimed Feed: PCS Fuel Oil 0.4 Conc. 28.0 29 Tail. 72.0 Feed 100.0 Test No.

Froth Modifier Name

Analysis

% Dist. P2O5

% P2O5

% Insol

30.79 2.15 10.17

9.00 92.83 69.36

84.8 15.2 100.0

PCS Fuel Oil

0.6

Conc. Tail. Feed

32.7 67.3 100.0

30.59 0.54 10.36

9.11 97.86 68.84

96.5 3.5 100.0

PCS Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

32.8 67.2 100.0

30.61 0.57 10.42

9.29 97.79 68.76

96.4 3.6 100.0

Using Natural Feed: PCS Fuel Oil 10

0.4

Conc. Tail. Feed

24.8 75.2 100.0

31.70 3.03 10.14

7.28 90.43 69.81

77.5 22.5 100.0

PCS Fuel Oil

0.6

Conc. Tail. Feed

30.7 69.3 100.0

30.98 1.08 10.26

8.99 96.33 69.52

92.7 7.3 100.0

PCS Fuel Oil Rosin Oil

0.4 0.2

Conc. Tail. Feed

32.7 67.3 100.0

30.06 0.93 10.46

11.94 96.72 68.99

94.0 6.0 100.0

30

31

9

22

1A-15

Table 1A-14. Summary of Preliminary Economic Calculations. Amine Concentrate % Dist. P2O5 Wt. % P2O5 Cargill Feed: Rosin Oil Substitution C-27 22.1 31.50 87.7 C-4 22.1 31.50 89.8 Test No.

Lb./T Feed Fuel Oil Rosin Oil 0.8 0.6

0 0.2

Cargill Feed: Scrub and Deslime Process C-1 21.6 31.50 86.1 C-50RR 22.2 31.50 90.4

0.6 0.6

0 0

PCS Feed: Rosin Oil Substitution 9 28.2 32.40 89.0 22 29.1 32.40 90.2

0.6 0.4

0 0.2

PCS Feed: Scrub and Deslime Process 9 28.2 32.40 89.0 30 29.7 32.40 91.8

0.6 0.6

0 0

Value Difference $/T. Ro. Feed

-0.054 (-0.054)

+0.020 (+0.068)

+0.081 (+0.153)

+0.155 (+0.275)

* Concentrate value minus processing cost. Values in ( ) are for $23.00/ton assigned concentrate value.

1A-16

Table 1A-15. Estimated Overall Flotation Balances--Cargill Feed. Rougher Flotation: Ro. Conc. Test No. % Wt. % P2O5 C-27 29.0 25.52 C-4

32.3

22.88

% Recov. P2O5 93.3

% Insol 22.58 31.36

95.5

Feed % P2O5 7.93 7.74

Lb./Ton Feed Fuel Oil Rosin Oil 0.8 0 0.6

0.2

Amine Flotation: Amine Total % Recov. Test No.

Product

% Wt.

% P2O5

Units

P2O5

P2O5

C-27

Amine Conc. Amine Tail. Amine Feed

76.2 23.8 100.0

31.50 6.43 25.52

23.99 1.53 25.52

94.0 6.0 100.0

87.7 5.6 93.3

C-4

Amine Conc. Amine Tail. Amine Feed

68.3 31.7 100.0

31.50 4.32 22.88

21.51 1.37 22.88

94.0 6.0 100.0

89.8 5.7 95.5

1A-17

Total Amine Conc. % Wt. 22.1

22.1

Table 1A-16. Estimated Overall Flotation Balances--PCS Feed. Test Ro. Conc. No. % Wt. Rougher Flotation: 9 30.7 22 32.7

Ro. Conc. % P2O5 % Insol

% Recov. P2O5

Feed % P2O5

Lb./TF Fuel Oil Rosin Oil

30.98 30.06

8.99 11.94

92.7 94.0

10.26 10.46

0.6 0.4

0.0 0.2

Product

% Wt.

% P2O5

% P2O5 Units

Recov. Amine

9

Amine Conc. Amine Tail. Amine Feed

91.8 8.2 100.0

32.40 15.12 30.98

29.74 1.24 30.98

96.0 4.0 100.0

Total Amine Conc. Total % Wt. 89.0 28.2 3.7 92.7

22

Amine Conc. Amine Tail. Amine Feed

89.1 10.9 100.0

32.40 11.01 30.06

28.86 1.20 30.06

96.0 4.0 100.0

90.2 3.8 94.0

Amine Flotation: Test No.

1A-18

29.1

Table 1A-17. Estimated Overall Flotation Balances--Cargill Feed. Test Ro. Conc. No. % Wt. Rougher Flotation: C-1 29.1 C-50RR 29.4

Ro. Conc. % P2O5 % Insol

% Recov. P2O5

Feed % P2O5

24.83 25.67

25.48 22.68

91.6 97.0

7.89 7.78

% Wt.

% P2O5

% P2O5 Units

Recov. Amine

Lb./TF Fuel Oil Rosin Oil 0.6 0.6

0.0 0.0

Amine Flotation: Test No. C-1

Product Amine Conc. Amine Tail. Amine Feed

74.1 25.9 100.0

31.50 5.75 24.83

23.34 1.49 24.83

94.0 6.0 100.0

C-50RR Amine Conc. Amine Tail. Amine Feed

76.6 23.4 100.0

31.50 6.58 25.67

24.13 1.54 25.67

94.0 6.0 100.0

Values in ( ) include scrub/desliming losses: 1.0% Wt., 1.5% P2O5 recovery loss.

1A-19

Total Amine Conc. Total % Wt. 86.1 21.6

91.2 (90.4)

22.5 (22.2)

Table 1A-18. Estimated Overall Flotation Balances--PCS Feed. Test No.

Ro. Conc. % Wt.

Rougher Flotation: 9 30.7 30 32.7

Ro. Conc. % P2O5 % Insol 30.98 30.59

8.99 9.11

% Recov. P2O5

Feed % P2O5

92.7 96.5

10.26 10.36

% P2O5 Units

Recov. Amine

Lb./TF Fuel Oil Rosin Oil 0.6 0.6

0.0 0.0

Amine Flotation: Test No.

Product

9

Amine Conc. Amine Tail. Amine Feed

91.8 8.2 100.0

32.40 15.12 30.98

29.74 1.24 30.98

96.0 4.0 100.0

30

Amine Conc. Amine Tail. Amine Feed

91.8 8.2 100.0

32.40 10.36 30.59

29.74 0.85 30.59

96.0 4.0 100.0

% Wt.

% P2O5

Values in ( ) include scrub/desliming losses: 0.9% Wt., 0.9% P2O5 recovery loss.

1A-20

Total Amine Conc. % Total Wt. 89.0 28.2

92.6 (91.8)

30.0 (29.7)

Table 1A-19. Economic Calculations (Rosin Oil Substitution). Cargill Feed: Oil Modifier, Cost/TF Test No. C-27 Fuel Oil C-4

0.8 Lb. ($0.07/Lb.) = $0.056

Fuel Oil 0.6 Lb. ($0.07/Lb.) = $0.042 Rosin Oil 0.2 Lb. ($0.34/Lb.) = $0.068 Total = $0.110 Using rosin oil substitution: $0.110 - $0.056 = $0.054 more.

Final Conc. Yield and Value/TF C-27

$15/T Conc. x 0.221T Conc./TF = $3.315

C-4

$15/T Conc. x 0.221T Conc./TF = $3.315 No change in conc. yield/value obtained. $0.054/TF reagent cost increase incurred using rosin oil.

PCS Feed: Oil Modifier, Cost/TF C-9

Fuel Oil

0.6 Lb. ($0.07/Lb.) = $0.042

C-22

Fuel Oil 0.4 Lb. ($0.07/Lb.) = $0.028 Rosin Oil 0.2 Lb. ($0.34/Lb.) = $0.068 Total = $0.096 Using rosin oil substitution: $0.096 - $0.042 = $0.054 more.

Final Conc. Yield and Value/TF C-9

$15/T Conc. x 0.282T Conc./TF = $4.230

C-22

$15/T Conc. x 0.291T Conc./TF = $4.365

$4.365 - $4.230 = $0.135 increased value using rosin oil. $0.135 - $0.054 = $0.081/TF overall value increase.

1A-21

Table 1A-20. Economic Calculations (Scrubbed vs. Unscrubbed Feed). Feed Scrub/Deslime Costs/TF (Equal Reagent Usage) Cargill Feed: Test No. C-1 No scrub/deslime – no extra power usage. C-50RR Scrubbing: 150 HP/600 TPHF x 0.746 KW/1 HP = 0.187 KW/TF Pumping To Cones: 600 HP/600 TPHF x 0.746 KW/1 HP = 0.746 KW/TF Scrubbing: 0.187 KW/TF x $0.04/KW = $0.007/TF or: 0.187 KW/TF x $0.05/KW = $0.009/TF Pumping To Cones: 0.746 KW/TF x $0.04/KW = $0.030/TF or: 0.746 KW/TF x $0.05/KW = $0.037/TF Cost Range = $0.037-$0.046/TF (Allow $0.07/TF) Final Conc. Yield and Value/TF C-1

$15/T Conc. x 0.212 T Conc./TF = $3.240

C-50RR

$15/T Conc. x 0.222T Conc./TF = $3.330 $3.330 - $3.240 = $0.090 increased value using scrub/deslime. $0.090 - $0.070 = $0.020/TF overall value increase.

1A-22

Table 1A-21. Economic Calculations (Scrubbed vs. Unscrubbed Feed). Feed Scrub/Deslime Costs/TF (Equal Reagent Usage) PCS Feed: Test No. 9 No scrub/deslime – no extra power usage. 30

Scrubbing: 150 HP/600 TPHF x 0.746 KW/1 HP = 0.187 KW/TF Pumping To Cones: 600 HP/600 TPHF x 0.746 KW/1 HP = 0.746 KW/TF Scrubbing: 0.187 KW/TF x $0.04/KW = $0.007/TF or: 0.187 KW/TF x $0.05/KW = $0.009/TF Pumping To Cones: 0.746 KW/TF x $0.04/KW = $0.030/TF or: 0.746 KW/TF x $0.05/KW = $0.037/TF Cost Range = $0.037-$0.046/TF (Allow $0.07/TF)

Final Conc. Yield and Value/TF 9

$15/T Conc. x 0.282 T Conc./TF = $4.230

30

$15/T Conc. x 0.297 T Conc./TF = $4.455 $4.455 - $4.230 = $0.225 increased value using scrub/deslime. $0.225 - $0.070 = $0.155/TF overall value increase.

1A-23

PART 2. STUDY OF PURE FATTY ACID COMPOUNDS

SUMMARY This program was designed to compare results obtained using various C12-C22 fatty acids as Florida phosphate collectors. The unsaturated C20 fatty acid, eicosenoic acid, was of particular interest since the writer was not able to find its use as a flotation reagent in a review of the technical literature. Also, preliminary laboratory flotation evaluation of an "extract" of fatty acids obtained by acidulation and washing of the comparatively cheap cottonseed soapstock sample was considered to be a worthwhile endeavor. Flotation tests were performed using the extract alone and also blended in various amounts with Liqro GA tall oil that was previously shown to be a very good phosphate collector for the Four Corners feed sample tested. A literature review of C8-C22 fatty acids properties and sources was performed in order to prepare reference tables for selection of collectors for preliminary flotation comparison testwork. Laboratory rougher flotation tests were performed on Four Corners feed using selected C12-C22 fatty acids with No. 5 fuel oil as the phosphate collector. The saturated fatty acids were found to be very poor collectors when using the standard conditioning procedure, whereas the unsaturated C16-C22 fatty acids showed fair to good phosphate collecting ability. The C18 fatty acids oleic, impure oleic, linoleic and the C20 eicosenoic acid were shown to be the best phosphate collectors with and without N-silicate addition. Flotation concentrates analyzing approximately 15-25% P2O5 at 78-87% P2O5 recovery were produced using these four fatty acid collectors. Inferior flotation results were obtained using the unsaturated C16 palmitoleic acid and the unsaturated C22 erucic acid. Two mixtures containing 15% and 25% commercial grade palmitic acid added to commercial grade oleic acid were observed to perform somewhat similar to the oleic acid as phosphate collectors. Palmitic acid was selected as the saturated fatty acid for addition to oleic acid because of its presence in most natural fatty acid mixtures produced from vegetable oils. A fatty acid extract prepared by sulfuric acid addition to a heated, rapidly stirred cottonseed soapstock solution, followed by multiple settling and washing stages, was observed to be a very poor, unselective collector for phosphate during flotation. The reason for this poor performance is presently unknown. Mixtures of the soapstock "extract" with Liqro GA tall oil performed poorly as a phosphate collector. Both concentrate grade and P2O5 recovery decreased markedly as the "extract" percentage was increased from 10% to 33% by weight. Size/assay analyses were performed on selected laboratory flotation tailings produced during tests using the C16-C22 fatty acid collectors.

2-1

Finally, several pertinent flotation references plus copies of very informative flotation test publications by TVA and other investigators were obtained during a literature search and are attached in the Appendix of this report for review. Of particular interest are the cost calculations for several potential tall oil substitute collectors that yielded excellent flotation metallurgical results but were concluded by the TVA investigators to be too costly for commercial application in 1982.

2-2

EXPERIMENTAL DESCRIPTION OF PHOSPHATE COLLECTORS EVALUATED A review of twelve literature sources was performed describing the chemical and physical characteristics, along with the natural occurrences, of the most common C8-C22 fatty acids. Tables 2A-1 and 2A-2 summarize the results found in the technical literature. The references used to prepare Tables 2A-1 and 2A-2 are listed in the reference section. The C16-C22 unsaturated fatty acids and the C12-C22 saturated fatty acids were selected for brief laboratory flotation testing in order to compare their collecting strength and selectivity with and without the use of N-brand sodium silicate depressant. The various fatty acids used for the comparison flotation tests are as follows: Fatty Acid

Producer/Supplier Unsaturated C16 Palmitoleic (98%) Sigma Aldrich, Milwaukee, WI C18 Oleic (99%) Aldrich Chem. Co., Milwaukee, WI C18 Oleic 401 (71%) Welch, Holme & Clark Co., Newark, NJ C18 Linoleic (99%) Acros Organics, Fisher Sci. Co., NJ C20 Eicosenoic (98%) Aldrich Chem. Co., Milwaukee, WI C22 Erucic (90%) (Prifac 2990) Unichema International, N.A. C12 Lauric (Prifac 2922) C14 Myristic (Prifac 2940) C16 Palmitic (Prifac 2960) C18 Stearic (Prifac 2981) C22 Behenic (Prifac 2987)

Saturated Unichema International, N.A. “ “ “ “

The unsaturated fatty acids (except for the C22 erucic acid) were liquid at room temperature. These reagents were mixed by stirring at a 1.0:0.6 ratio with No. 5 fuel oil for medicine dropper calibration in drops per gram. The solid saturated fatty acids were warmed, mixed by stirring at a 1.0:0.6 ratio with No. 5 fuel oil, and each mixture further warmed to obtain a fluid mix for dropper calibration in drops per gram. The commercial grade oleic acid 401 was reported to contain approximately 71% oleic acid, 6% palmitic acid, 10% linoleic acid and 2% linolenic acid. Other phosphate collectors used for comparison flotation testwork included two oleic acid/palmitic acid mixtures, an "extract" of fatty acids obtained by dilute, hot sulfuric acid acidulation (followed by settling and washing) of a 10% by weight of as-received cottonseed soapstock solution, and three different mixtures of the fatty acid "extract" with Liqro GA tall oil. The as-received cottonseed soapstock was previously shown to be a very unselective phosphate collector. 2-3

RESULTS AND DISCUSSION FLOTATION TESTS USING VARIOUS “PURE” FATTY ACIDS A total of eleven fatty acids were briefly tested as phosphate collectors for the IMC Four Corners plant feed described in the previous chapter. Laboratory test procedures and conditions used were also the same. Flotation tests were performed using 1.6 lb. of fatty acid and 0.96 lb. of fuel oil at a 1.0:0.6 ratio mixture as the phosphate collector, with and without the addition of N-Brand sodium silicate. Soda ash consumption for conditioning pH regulation ranged from about 1.4-1.6 lb./TF, and the resulting conditioning pH was 8.9-9.2 for these tests. Flotation test results using the unsaturated fatty acids without N-silicate and with N-silicate are presented in Table 2A-3 and Table 2A-4, respectively. These results are also shown in bar graph form in Figures 2-1 through 2-4. Figures 2-1 and 2-2 show that, when no N-silicate was used, the highest grade concentrates (15-21% P2O5) and highest P2O5 recoveries (82-87%) were obtained using the two oleic acids and the linoleic acid. Eicosenoic acid yielded results very similar to linoleic acid. Figures 2-3 and 2-4 show that, when N-silicate was used to improve selectivity, the highest grade concentrates (20-25% P2O5) and highest P2O5 recoveries (78-82%) were obtained using the linoleic acid and the eicosenoic acid. The oleic acid 401 (71%) yielded results very similar to eicosenoic acid. Flat, non-persistent froths were observed during most flotation tests using N-silicate for improving selectivity. The C12-C22 saturated fatty acids were granular, white, waxy solids at room temperature. When warmed and mixed at a 1.0:0.6 ratio with No. 5 fuel oil, the mixtures were also solid upon cooling to room temperature and required additional heating to produce fluids for dropper calibration. None of these mixtures performed as phosphate collectors when used at the standard 1.6 lb. of fatty acid plus 0.96 lb. of fuel oil per ton of feed and a conditioning pH = 9.0-9.2. The warmed, fluid C14-C22 fatty acid/fuel oil mixes did not disperse when added to the flotation conditioner. These reagent mixes separated from the flotation slurry during flotation and were observed to form small, black, sticky balls that floated at the air/pulp interface. Contact of the warm collector/fuel oil mix with the colder slurry in the conditioner apparently caused reagent agglomeration resulting in poor dispersion and probably poor saponification during conditioning. The C12 lauric acid did not produce the same visual reagent separation, but did not perform effectively as a phosphate mineral collector.

2-5

25

P2O5% in Concentrate

20

15

10

5

0

Palmitoleic Oleic Oleic Linoleic Eicosenoic Erucic (98%) C16 (99%) C18 (71%) C18 (99%) C18 (98%) C20 (90%) C22 Figure 2-1. Concentrate Grades Using Various Unsaturated C16-C22 Fatty Acids at Collector Dosage of 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil.

2-6

100 90 80

% P2O5 Recovery

70 60 50 40 30 20 10 0 Palmitoleic Oleic Oleic Linoleic Eicosenoic Erucic (98%) C16 (99%) C18 (71%) C18 (99%) C18 (98%) C20 (90%) C22 Figure 2-2. Flotation Recovery Using Various Unsaturated C16-C22 Fatty Acids at Collector Dosage of 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil.

2-7

30

P2O5 in Concentrate

25

without silicate with silicate

20

15

10

5

0 Palmitoleic Oleic (99%) Oleic (71%) Linoleic Eicosenoic Erucic (98%) C16 C18 C18 (99%) C18 (98%) C20 (90%) C22

Figure 2-3. Effect of Silicate on Concentrate Grade Using Unsaturated C16-C22 Fatty Acids at 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil and 0.5 Lb. Silicate.

2-8

100 90

without silicate with silicate

80

% P2O5 Recovery

70 60 50 40 30 20 10 0 Palmitoleic (98%) C16

Oleic (99%) C18

Oleic (71%) C18

Linoleic (99%) C18

Eicosenoic (98%) C20

Erucic (90%) C22

Figure 2-4. Effect of Silicate on Flotation Recovery Using Unsaturated C16-C22 Fatty Acids at 1.6 Lb./Ton Feed with 0.96 Lb. Fuel Oil and 0.5 Lb. Silicate.

2-9

Additional laboratory flotation tests were performed using 1.6 lb./ton of two mixed unsaturated/saturated fatty acid blends containing 85% oleic acid 401 plus 15% palmitic acid, and 75% oleic acid 401 plus 25% palmitic acid, with No. 5 fuel oil and with and without N-silicate addition. Fatty acid:fuel oil ratio remained at 1.0:0.6. The test results are compared to tests using oleic acid only as the fatty acid with No. 5 fuel oil in Table 2A-5. Very flat froths were observed particularly when N-silicate was used to improve flotation selectivity. The Table 2A-5 results were considered to be somewhat erratic; however, P2O5 recoveries of 80% or higher were obtained for most tests. The 15% palmitic acid and the 25% palmitic acid mixtures with oleic acid were waxy solids that liquefied when heated to about 29-31 °C. and 34-36 °C., respectively. The 1.0:0.6 ratio mixtures with fuel oil were fluids at 23 °C. and 25 °C., respectively. FLOTATION USING COTTONSEED SOAPSTOCK FATTY ACID EXTRACT The cottonseed soapstock fatty acid extract previously described was tested as a 1.0:0.6 ratio mixture with No. 5 fuel oil as the phosphate collector. The collector mixture was fluid at a room temperature of 25 °C. Usage levels were 1.2, 1.4 and 1.6 lb. of fatty acid extract per ton of feed. Conditioning pH was 9.0-9.1. This reagent was a very poor and unselective phosphate collector as shown by the flotation results presented in Table 2A-6. Concentrates analyzed less than 4% P2O5, and P2O5 recoveries never reached as high as 50%. Flotation concentrate silica sand appeared to be stained a light brown color when this collector was used. FLOTATION USING LIQRO GA TALL OIL/COTTONSEED FATTY ACID EXTRACT MIXTURES Three mixtures of the cottonseed soapstock fatty acid extract with Liqro GA tall oil were compared with 100% Liqro GA as the phosphate collector in this test series. The mixtures tested were 10%, 20% and 33% "extract" with Liqro GA tall oil. The mixtures were blended with No. 5 fuel oil at 1.0:0.6 ratio, and were used at the 1.4 lb. of tall oil "extract" mix plus 0.84 lb. of fuel oil per ton feed level. Each collector mix with fuel oil was fluid at room temperature. Conditioning pH was 9.0-9.2, and N-silicate was used for all tests. The flotation results are shown in Table 2A-7. The data illustrates that the addition of "extract" to Liqro GA tall oil resulted in a decrease in concentrate grade and a loss of P2O5 recovery as the percentage of "extract" was increased. Concentrate grade dropped from 24% P2O5 to as low as 10% P2O5 while P2O5 recovery decreased from 89% to about 67% when the "extract" comprised 33% of the collector mixture. SIZE/ASSAY ANALYSES OF SELECTED FLOTATION TAILS Abbreviated dry screen analyses were performed on the six selected flotation tailing samples produced using the various unsaturated fatty acids with fuel oil and N-silicate. Sizing the tailings at 28 and 35 Tyler mesh, using a 15 minute Ro-tap time, was performed. 2-10

The tailings size/assay results are shown in Table 2A-8. The Table 2A-8 results support the general trend that highest % P2O5 tailing values are present in the coarsest (+28 mesh) size fractions and the lowest % P2O5 tailing values are present in the finer (-35 mesh) size fractions for each fatty acid collector tested. Accordingly, the concentrate % P2O5 recoveries in the -35 mesh size fractions are higher than for the coarser size fractions. Linoleic acid, followed by oleic acid 401 and eicosenoic acid, were shown to be the most effective phosphate collectors for each size fraction. Table 2A-9 presents % P2O5 distribution within the flotation tailing size fractions for each of the tests listed in Table 2A8. None of the individual fatty acids tested recovered 90% or higher of the phosphate present in the -35 mesh feed size fraction, or 85% or higher of the phosphate present in the 28/35 mesh size fraction. These recovery levels were previously obtained and exceeded using Liqro GA tall oil, as shown in Part 3 of this report. The better frothing character of the Liqro GA containing some rosin acids is believed to account in part for its superior performance. RELEVANT PHOSPHATE ROUGHER FLOTATION REFERENCES Several technical literature references were found pertaining to Florida phosphate flotation using C12-C18 fatty acids, iso-stearic acid, a C18 halogenated fatty acid, a C36 dimer acid and a selected petroleum oxidate. Laboratory fatty acid comparison flotation tests results were described by Finch and Riggs (1986) of Ore Prep Chemicals, Inc. (Houston, TX). In addition, extensive laboratory and pilot plant test results comparing the four collector types cited with a selected tall oil were presented in articles by Hsieh (1982) and Hsieh and Lehr (1982) of the National Fertilizer Development Center, TVA (Muscle Shoals, AL). Of particular interest are the economic reagent cost comparisons presented in the pilot plant testing report. None of the reagents compared favorably with tall oil from a cost/usage standpoint. A brief list of these articles is shown in the References section, and other relevant sources are shown in the For Additional Reading section.

2-11

CONCLUSIONS Unsaturated fatty acids were found to be more suitable for phosphate flotation. C18 unsaturated fatty acids, such as oleic and linoleic acids perform better than other compounds. The relatively pure fatty acids are not as powerful as the tall oil type collectors commonly used by the Florida phosphate industry.

2-13

REFERENCES Finch E, Riggs WF. 1986. Fatty acid collectors—a selection guide. In: Malhotra D, Riggs WF, editors. Chemical reagents in the mineral processing industry. Littleton (CO): Society of Mining Engineers. p 95-8. Hsieh SS. 1982. Flotation studies on carboxylic acid components of tall oils. Trans. AIME 272: 2013-7. Hsieh SS, Lehr JR. 1982. Pilot plant evaluation of alternative flotation reagents. In: Proceedings of the 184th National Meeting of the American Chemical Society Division of Fertilizer and Soil Chemistry; 1982 Sep 12-17; Kansas City, MO; p 40.

2-15

FOR ADDITIONAL READING Dean JA, editor. 1967. Lange's handbook of chemistry. 10th ed. New York: McGrawHill. Ganucheau JJ. 1931. Acidulation, saponification, and distillation of cottonseed soapstock, relative to the unsaponifiable content of the distilled fatty acids. [Ch.E. thesis]. New Orleans: Tulane University. 45 p. Gunstone FD. 1958. An introduction to the chemistry of fats and fatty acids. New York: John Wiley & Sons. p 1-21, 57-67, 76-82. Jamieson GS, Baughman WF. 1920. The chemical composition of cottonseed oil. J. Am. Chem. Society 42(6): 1197-1204. Kirk RE, Othmer DF, editors. 1947. Encyclopedia of chemical technology. Vol. 6. New York: Interscience Publishers. p 20-37. Kirk RE, Othmer DF, Kroschwitz JI, Howe-Grant M, editors. 1993. Encyclopedia of chemical technology. 4th ed. Vol. 5. New York: John Wiley & Sons. p 149-50. Kirschenbauer HG. 1960. Fats and oils. 2nd ed. New York: Reinhold Publishing Corp. p 6-17; 169-71. Markley KS. 1947. Fatty acids. New York: Interscience Publishers. p 20-37. Merck & Co., editors. 1940. Merck index. 5th ed. Rahway (NJ): Merck & Co. p 92, 170, 217, 319. Pattison ES. 1959. Industrial fatty acids. New York: Rheinhold Publishing Corp. p 1-10; 29-33. Ralston AW. 1948. Fatty acids and their derivatives. New York: John Wiley & Sons. p 35; 96-150; 261-9. Zachary LG, Barjak HW, Eveline FJ. 1965. Tall oil and its uses. New York: F.W. Dodge Co., McGraw-Hill. p 25-6. Zhang P, Albarelli GR, Stewart KJ. 1999. Phosphate beneficiation bibliography. Bartow (FL): Florida Institute of Phosphate Research. Publication nr 02-114-157. p 158-9. (See #7, #8, and #10.)

2-17

Appendix 2 TABLES FOR PURE COMPOUNDS STUDY

Table 2A-1. Physical Values for Various Fatty Acids. No. C 8 10 12 14 16 16 16 18 18 18 18 18 18 20 20 22 22 22

Name Caprylic Capric Lauric Myristic Palmitic Palmitoleic Palmitolic Stearic Oleic Elaidic Linoleic Linolenic Eleaostearic Arachidic Eicosenoic Behenic Erucic Brassidic

Formula C7H15COOH C9H19COOH C11H23COOH C13H27COOH C15H31COOH C15H29COOH C15H27COOH C17H35COOH C17H33COOH C17H33COOH C17H31COOH C17H29COOH C17H31COOH C19H39COOH C19H37COOH C21H43COOH C21H41COOH C21H41COOH

M. Wt. 144.2 172.3 200.3 228.4 256.4 254.4 252.4 284.5 282.5 282.5 280.5 278.4 280.4 312.5 312.5 340.6 338.5 338.4

2A-1

Form Liq. Sol. Sol. Sol. Sol. Liq. Sol. Sol. Liq. Sol. Liq. Liq. Sol. Sol. Sol. Sol. Sol. Sol.

Saturation Sat. Sat. Sat. Sat. Sat. Unsat. Unsat. Sat. Unsat. Unsat. Unsat. Unsat. Unsat. Sat. Unsat. Sat. Unsat. Sat.

M.P., °C. 16.3-16.7 31.4 44.1 54.2 62.8 -0.5 - +0.5 42.0 69.6 14.0 51.0-57.0 -5.0 -11.0 48.0-49.0 75.0-77.0 23.0-24.0 80.0 34.0 48.0-49.0

Table 2A-2. Specific Gravity (S.G.) and Sources for Various Fatty Acids. No. C 8 10 12 14 16 16 16 18 18 18 18 18 18 20 20 22 22 22

Common Name Caprylic Capric Lauric Myristic Palmitic Palmitoleic Palmitolic Stearic Oleic Elaidic Linoleic Linolenic Eleaostearic Arachidic Eicosenoic Behenic Erucic Brassidic

Specific Gravity 0.910 0.895 0.883 0.858 0.853 0.864 -0.847 0.895 0.851 0.903 0.914 0.903 0.824 0.883 0.822 0.860 0.859

Typical Natural Sources Palm oils, milk fat Palm oils, whale head oils Palm oils, laurel family oils, milk fats Milk fats, nutmeg butter Soybean, corn, peanut, cottonseed oils Marine animal oils, amphibian and reptile fats (Synthetic) Animal and milk fats, marine oils Almost all plant and animal fats (Oleic acid stereoisomer) Almost all plant and animal fats Soybean, safflower, walnut and other seed fats Tung oil, China wood oil Peanut oil and related plants Marine oils and jojoba wax Rapeseed and peanut oils Cruciferae species (Erucic acid stereoisomer)

2A-2

Table 2A-3. Phosphate Flotation Material Balances for Tests Using Various Unsaturated C16-C22 Fatty Acid Type Collectors. Test No. FA-8

Collector, Lb./TF Fatty Acid Fuel Oil Palmitoleic (98%) 1.6 0.96 Cond. pH = 8.9

Flotation Product % Wt. Conc. 31.3 Tail. 68.7 Feed 100.0

Analysis % P2O5 % Insol 12.75 61.13 1.73 94.37 5.18 83.96

% Dist. P2O5 77.0 23.0 100.0

FA-11

Oleic (99%) 1.6 0.96 Cond. pH = 8.9-

Conc. Tail. Feed

20.8 79.2 100.0

20.81 0.90 5.04

38.17 96.88 84.67

85.9 14.1 100.0

FA-9

Oleic (71%) 1.6 0.96 Cond. pH = 9.1-

Conc. Tail. Feed

26.8 73.2 100.0

16.71 0.89 5.13

49.88 96.82 84.24

87.3 12.7 100.0

FA-7

Linoleic (99%) 1.6 0.96 Cond. pH = 8.9+

Conc. Tail. Feed

27.9 72.1 100.0

14.88 1.24 5.04

55.95 95.97 84.80

82.3 17.7 100.0

FA-10

Eicosenoic (98%) 1.6 0.96 Cond. pH = 9.1

Conc. Tail. Feed

30.9 69.1 100.0

12.91 1.21 4.83

61.38 95.99 85.40

82.6 17.4 100.0

FA-1

Erucic 1.6 0.96 Cond. pH = 9.1+

Conc. Tail. Feed

24.8 75.2 100.0

8.52 3.87 5.02

74.44 88.17 84.76

42.0 58.0 100.0

2A-3

Table 2A-4. Phosphate Flotation Material Balances for Tests Using Various Unsaturated C16-C22 Fatty Acid Type Collectors and N-Silicate. Test No. FA-8S

Collector, Lb./TF Fatty Acid Fuel Oil Palmitoleic (98%) 1.6 0.96 Cond. pH = 9.0+ + 0.5 Lb./T N-Silicate

Flotation Product % Wt. Conc. 19.9 Tail. 80.1 Feed 100.0

Analysis % P2O5 % Insol 16.39 50.85 2.08 93.50 4.93 85.01

% Dist. P2O5 66.1 33.9 100.0

FA-11S

Oleic (99%) 1.6 0.96 Cond. pH = 8.9+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

16.4 83.6 100.0

21.58 1.74 4.99

60.40 94.50 84.91

70.9 29.1 100.0

FA-9S

Oleic (71%) 1.6 0.96 Cond. pH = 9.0+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

19.4 80.6 100.0

20.31 1.36 5.04

39.53 95.63 84.75

78.2 21.8 100.0

FA-7S

Linoleic (99%) 1.6 0.96 Cond. pH = 9.0 + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

16.9 83.1 100.0

25.43 0.99 5.12

24.75 96.77 84.60

84.0 16.0 100.0

FA-10S

Eicosenoic (98%) 1.6 0.96 Cond. pH = 8.9+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

18.7 81.3 100.0

21.55 1.35 5.13

39.03 95.55 84.98

78.6 21.4 100.0

FA-1S

Erucic 1.6 0.96 Cond. pH = 9.1+ 0.5 Lb./T N-Silicate

Conc. Tail. Feed

16.4 83.6 100.0

12.85 3.55 5.08

61.58 89.13 85.10

41.5 58.5 100.0

2A-4

Table 2A-5. Flotation Material Balances Using Various Oleic/Palmitic Acid Mixes. Test No. FA-9

Collector, Lb./TF Fatty Acid Fuel Oil Oleic Only 1.6 0.96 Cond. pH = 9.1

Flotation Product % Wt. Conc. 26.8 Tail. 73.2 Feed 100.0

Analysis % P2O5 % Insol 16.71 49.88 0.89 96.82 5.13 84.24

% Dist. P2O5 87.3 12.7 100.0

FA-12

Oleic/Palmitic 85/15 1.6 0.96 Cond. pH = 8.9+

Conc. Tail. Feed

22.3 77.7 100.0

17.95 1.33 5.03

47.77 95.67 84.99

79.5 20.5 100.0

FA-13

Oleic/Palmitic 75/25 1.6 0.96 Cond. pH = 8.9+

Conc. Tail. Feed

28.8 71.2 100.0

14.78 1.05 5.01

55.98 96.47 84.81

85.0 15.0 100.0

FA-9S

Oleic Only 1.6 0.96 Cond. pH = 9.0+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

19.4 80.6 100.0

20.31 1.36 5.04

39.53 95.63 84.75

78.2 21.8 100.0

FA-12S

Oleic/Palmitic 85/15 1.6 0.96 Cond. pH = 8.9 + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

21.5 78.5 100.0

19.32 1.14 5.04

42.54 96.21 84.67

82.3 17.7 100.0

FA-13S

Oleic/Palmitic 75/25 1.6 0.96 Cond. pH = 9.1+ 0.5 Lb./T N-Silicate

Conc. Tail. Feed

20.3 79.7 100.0

20.51 1.11 5.04

39.14 96.29 84.69

82.5 17.5 100.0

2A-5

Table 2A-6. Phosphate Flotation Material Balances Using Cottonseed Soapstock Fatty Acid Extract as the Phosphate Collector.

70

Collector, Lb./TF Fatty Acid Fuel Oil 1.2 0.72 Cond. pH = 9.0-

69

1.4 0.84 Cond. pH = 9.1-

Conc. Tail. Feed

58.1 41.9 100.0

3.58 7.07 5.04

88.92 78.60 84.99

41.3 58.7 100.0

68

1.6 0.96 Cond. pH = 9.1-

Conc. Tail. Feed

64.3 35.7 100.0

3.60 7.42 4.96

88.72 77.55 84.74

46.6 53.4 100.0

Test No.

Flotation Product % Wt. Conc. 37.1 Tail. 62.9 Feed 100.0

Analysis % P2O5 % Insol 3.11 90.22 6.03 81.69 4.94 84.85

% Dist. P2O5 23.3 76.7 100.0

Table 2A-7. Phosphate Flotation Material Balances Using Various Ratios of Liqro GA Tall Oil to Cottonseed Soapstock Acids as the Collector Blend. Test No. 7

Collector, Lb./TF Tall Oil CSFA 1.4 0.84 100/0 Cond. pH = 9.1+ 0.5 Lb./T N-Silicate

Flotation Product % Wt. Conc. 19.0 Tail. 81.0 Feed 100.0

Analysis % P2O5 % Insol 24.05 28.67 0.67 97.62 5.11 84.52

% Dist. P2O5 89.4 10.6 100.0

74S

1.4 0.84 90/10 Cond. pH = 9.0+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

20.2 79.8 100.0

20.38 1.15 5.03

39.73 96.22 84.82

81.9 18.1 100.0

73S

1.4 0.84 80/20 Cond. pH = 9.1+ + 0.5 Lb./T N-Silicate

Conc. Tail. Feed

31.8 68.2 100.0

12.88 1.29 4.98

61.50 95.79 84.89

82.3 17.7 100.0

72S

1.4 0.84 67/33 Cond. pH = 9.2+ 0.5 Lb./T N-Silicate

Conc. Tail. Feed

33.9 66.1 100.0

9.90 2.43 4.97

70.16 92.46 84.90

67.6 32.4 100.0

2A-6

Table 2A-8. Detailed % P2O5 Analyses and % P2O5 Distributions from Feed for Various Flotation Tailing Size Fractions. Test No.

% Wt. Tails

FA-8S FA-11S FA-9S FA-7S FA-10S FA-1S

80.1 83.6 80.6 83.1 81.3 83.6

Test No.

% Wt. Tails

FA-8S FA-11S FA-9S FA-7S FA-10S FA-1S

80.1 83.6 80.6 83.1 81.3 83.6

Test No.

% Wt. Tails

FA-8S FA-11S FA-9S FA-7S FA-10S FA-1S

80.1 83.6 80.6 83.1 81.3 83.6

+28M % Wt. In Tails 2.1 1.8 1.7 1.7 1.8 2.3

+28M Tail. % P2O5 18.90 17.67 15.94 15.60 16.66 21.17

+28M Tail. Dist. P2O5 75.5 62.3 51.8 52.3 58.0 96.4

28/35M % Wt. In Tails 8.2 8.0 7.4 7.6 7.9 9.0

28/35M Tail. % P2O5 4.51 3.50 2.25 2.16 3.04 6.84

28/35M Tail. % Dist. P2O5 37.9 29.9 17.1 17.4 24.9 65.8

-35M % Wt. In Tails 89.7 90.2 90.9 90.7 90.3 88.7

-35M Tail. % P2O5 1.66 1.41 1.03 0.65 0.95 2.78

-35M Tail. Dist. P2O5 29.2 26.0 18.5 12.0 17.1 50.5

2A-7

% Recov. P2O5 +28M Conc. 24.5 36.8 48.2 47.7 42.0 3.60

Tot. Conc. 66.1 70.9 78.2 84.0 78.6 41.5

% Recov. P2O5 28/35M Conc. 62.1 70.1 82.9 82.6 75.1 34.1

Tot. Conc. 66.1 70.9 78.2 84.0 78.6 41.5

% Recov. P2O5 -35M Conc. 70.8 74.0 81.5 88.0 82.9 49.5

Tot. Conc. 66.1 70.9 78.2 84.0 78.6 41.5

Table 2A-9. P2O5 Losses in Various Flotation Tailing Size Fractions. Test No. FA-8S C16

% P2O5 Dist. Conc. Tail. 66.1 33.9

% P2O5 Distribution in Tail. +28M 28/35M -35M 6.0 5.6 22.3 (17.7) (16.4) (65.9)

Size Fractions Total Tail. 33.9 (100.0)

FA-11S C18

70.9

29.1

5.0 (17.1)

4.4 (15.0)

19.7 (67.9)

29.1 (100.0)

FA-9S C18

78.2

21.8

4.3 (19.6)

2.7 (12.3)

14.8 (68.1)

19.6 (100.0)

FA-7S C18

84.0

16.0

4.3 (26.5)

2.5 (15.7)

9.2 (57.8)

16.0 (100.0)

FA-10S C20

78.6

21.4

4.6 (21.4)

3.7 (17.2)

13.1 (61.4)

21.4 (100.0)

FA-1S C22

41.5

58.5

8.0 (13.7)

10.2 (17.4)

40.3 (68.9)

58.5 (100.0)

2A-8

PART 3. COMPARISON OF VARIOUS ANIONIC COLLECTORS

INTRODUCTION For at least fifty years various tall oils have been the primary collector reagents used for the rougher flotation of phosphate in Florida beneficiation plants. Cheap tall oil soap skimmings were also used from the late 1950s at IMC's Noralyn plant until they became unavailable during the late 1980s. Tall oil/pitch soap formulations have been tested and used commercially in some flotation plants and are currently used in at least one Florida beneficiation plant. The two primary reasons for the commercial acceptance of tall oil collectors include (1) the cost advantage and availability over other reagents such as vegetable fatty acids and petroleum sulfonates or oxidates, and (2) the "built in" frothing properties of rosin acids present in most tall oil collectors. Plant-scale tests using one petroleum oxidate and using a blend of tall oil with an oil-soluble petroleum sulfonate have shown that these reagents can be used in the rougher flotation stage in place of tall oil alone. No serious problems were reported for the subsequent acid "de-oiling" stage during plant trials. However, the cost of using these substitute collectors was prohibitive for immediate commercial application. The current laboratory flotation testwork described in this report is designed to further compare various potential phosphate collector reagents with a good commercial tall oil and with oleic acid in the search for less costly and/or more selective substitutes.

3-1

SUMMARY A composite sample of low-grade (approx. 5.2% P2O5) IMC Four Corners feed was subjected to preliminary laboratory rougher flotation testwork using five different anionic collectors. The feed sample contained 10.9% wt. of +35 mesh "coarse" particles representing 22.7% of the total P2O5 present in the feed. Oleic acid, Liqro GA tall oil, Petronate CR sulfonate, cottonseed soapstock and Custofloat 27AR tall oil/pitch soap were the five collectors evaluated. A mixture of Petronate CR (20%) and Liqro GA (80%) was also tested. Some of the flotation variables used at different levels included collector quantity, conditioning pH, fuel-oil-to-collector ratio, and the use of N-Brand sodium silicate for selectivity improvement. The best flotation results were obtained using Liqro GA tall oil and oleic acid. Liqro GA produced rougher concentrates analyzing 17.1-21.5% P2O5 at 91.3-87.6% P2O5 recovery, and oleic acid produced rougher concentrates analyzing 16.7-21.8% P2O5 at 87.391.2% P2O5 recovery under the best test conditions. In general, flat froths were noticed during tests using oleic acid at the lower collector levels. Liqro GA tall oil, containing a moderate level of rosin acids, appeared to produce a better flotation froth. The best test using Petronate CR produced a rougher concentrate analyzing 21.1% P2O5 at only 78.1% P2O5 recovery. The best "mixed" collector tests produced rougher concentrates analyzing 17.1-20.9% P2O5 at 88.2-83.2% P2O5 recovery. The two soap-type collectors were very unselective by comparison and did not produce rougher concentrates analyzing as high as 17-22% P2O5 at a P2O5 recovery of 80% or higher. Size/assay analyses performed on tailings obtained from selected flotation tests using Liqro GA tall oil and oleic acid as the collectors showed that P2O5 recoveries as high as 94-95% were attainable from the -35 mesh feed sizes, and as high as 86-87% were obtained from the 28/35 mesh feed sizes for some of the best tests. The highest P2O5 recovery obtained from the +28 mesh fraction was about 54% for only one test.

3-3

EXPERIMENTAL DESCRIPTION OF FLOTATION FEED SAMPLE A 150-pound composite of IMC Four Corners plant feed was prepared by thoroughly mixing (cone and quartering) individual feed samples collected during JuneSeptember, 1999. The composite sample analyzed 5.23% P2O5 and 84.04% Insol. Size/assay analyses are shown in Table 3-1. Table 3-1. Size/Assay Analyses of Test Flotation Feed. Size +20 20/28 28/35 35/48 48/65 65/100 100/150 150/200 200/325 -325 Total

% Wt. 0.6 1.4 8.9 30.9 31.3 16.7 7.8 1.7 0.6 0.1 100.0

% P2O5 27.00 18.52 8.79 5.29 4.77 3.94 2.72 3.42 4.74 5.28

% Insol 19.23 44.45 73.71 84.03 85.73 88.15 91.61 89.01 83.30 83.97

% P2O5 Dist. 3.0 4.9 14.8 30.9 28.2 12.4 4.0 1.1 0.6 100.0

The feed composite contained primarily black phosphate particles. Some siliceous "cluster" grains cemented by a brownish material (perhaps hydrated iron oxides) were observed along with minor tan-white "sugary" particles of unknown composition. The size/assay analysis also shows that 7.9% of the total feed P2O5 is present in the +28 mesh size fraction, and a total of 22.7% of the total P2O5 is coarser than 35 mesh. The presence of this much "coarse" phosphate in the feed indicates that greater than about 8890% P2O5 (rougher) flotation recovery probably will be difficult to obtain without floating excessive fine silica. PHOSPHATE FLOTATION COLLECTORS Table 3-2 shows the phosphate collectors used for the initial laboratory comparison testwork in order to determine which, if any, of the reagents perform equal to or better than oleic acid.

3-5

Table 3-2. Commercial Fatty Acid-Based Collectors Tested. Reagent Name Oleic Acid 401 (A.N. = 200) Liqro GA Tall Oil (A.N. = 154) Petronate CR Sulfonate (Petroflote 7401) Cottonseed Soapstock (50%) Custofloat 27AR (30%) (Tall Oil/Pitch Soap)

Supplier Welch, Holme & Clark Co. (Newark, NJ) Custom Chemicals (Bartow, FL) Witco Corp. (Gretna, LA) Hartville Oil Mill (Darlington, SC) Custom Chemicals (Bartow, FL)

Although the cottonseed soapstock sample was reported to contain 50% active solids, lab measurement produced approximately 80% solids for the initial sample removed from the container for lab testwork.

3-6

RESULTS AND DISCUSSION FLOTATION OF FOUR CORNERS FEED Five different anionic reagents plus one reagent mixture were briefly evaluated as phosphate collectors for the low-grade Four Corners feed. Laboratory 500g flotation tests were performed using different collector quantities at various conditioning pH levels, various fuel oil/collector ratios, and flotation with and without N-brand sodium silicate addition to improve selectivity. The standard sodium silicate addition was 0.5 lb./TF unless otherwise listed in the tables or figures. The sodium silicate, when used, was added during the final 20 seconds of the standard 2-minute conditioning period at approximately 73% solids. Laboratory tap water was used for these preliminary comparison tests. No. 5 fuel oil (extender) and soda ash (pH regulator) were also used for flotation. Fuel oil was pre-mixed with the various collectors except for the "soaps," namely, cottonseed soapstock and Custofloat 27AR. The fuel oil was added separately to the conditioner when these two collectors were evaluated. Flotation time allowed for all tests was two minutes. Oleic Acid Oleic acid was evaluated as the phosphate collector for a series of standard rougher flotation tests using fuel oil/oleic acid ratios of 0.6:1.0 and 0.8:1.0, and 0.6:1.0 ratio using 0.5 lb. of N-silicate per ton of feed. Collector levels used ranged from 1.0-1.6 lb. of oleic acid per ton of feed. Test results are tabulated in Table 3-3, and are presented graphically in Figures 3-1 through 3-3. The best results were obtained from tests using 1.6 lb. of collector per ton of feed. A 16.71% P2O5/49.88% Insol concentrate was produced at 87.3% P2O5 recovery at fuel oil/fatty acid ratio of 0.6:1.0. A 21.82% P2O5/34.92% Insol concentrate was produced at 92.1% P2O5 recovery with the higher fuel oil/oleic acid ratio of 0.8:1.0. Oleic acid was concluded to be a moderately good collector for this flotation feed sample.

3-7

30

25

% P2O5

20

15 37.5% Fuel Oil 37.5% Fuel Oil with Silicate

10

44.4% Fuel Oil

5

0 0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-1. Concentrate P2O5 vs. Oleic Acid Dosage.

3-8

1.5

1.6

1.7

60

50

% Insol

40

30

20 37.5% Fuel Oil 37.5% Fuel Oil with Silicate 44.4% Fuel Oil

10

0 0.9

1

1.1

1.2

1.3

1.4

Collector Dosage

Figure 3-2. Concentrate Insol vs. Oleic Acid Dosage.

3-9

1.5

1.6

1.7

100

90

80

% P2O5 Recovery

70

60

50

40

30 37.5% Fuel Oil 37.5% Fuel Oil with Silicate 44.4% Fuel Oil

20

10

0 0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-3. Flotation Recovery vs. Oleic Acid Dosage.

3-10

1.5

1.6

1.7

Liqro GA Tall Oil The tall oil was evaluated during a series of standard rougher flotation tests using fuel oil/tall oil ratios of 0.6:1.0, 0.8:1.0, and 0.6:1.0 using 0.5 lb. of N-silicate per ton of feed. Collector level used ranged from 1.0-1.4 lb. of tall oil per ton of feed. Test results are tabulated in Table 3-4, and presented graphically in Figures 3-4 through 3-6. The three best test results were obtained using 1.4 lb. of collector per ton of feed. A 17.14% P2O5 and 48.79% Insol concentrate was produced at 91.3% P2O5 recovery using a 0.8:1.0 fuel oil/tall oil ratio. A 21.52% P2O5/36.00% Insol concentrate was produced at 87.6% P2O5 recovery using a 1.0:1.0 fuel oil/tall oil ratio. Finally, using N-silicate, a 24.05% P2O5/28.67% Insol concentrate was achieved at 89.4% P2O5 recovery using a 0.6:1.0 fuel oil/tall oil ratio. Liqro GA tall oil was concluded to be a very good collector for this flotation feed sample. 35

30

25

% P2O5

20

15

FA:FO=1:0.6 FA:FO=1:0.6 with silicate FA:FO=1:0.8 FA:FO=1:1

10

5

0 0.8

0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-4. Concentrate P2O5 vs. Liqro GA Dosage at Different Fuel Oil Ratios.

3-11

1.5

70

60 FA:FO=1:0.6 FA:FO=1:0.6 with silicate FA:FO=1:0.8

50

FA:FO=1:1

% Insol

40

30

20

10

0 0.8

0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-5. Concentrate Insol vs. Liqro GA Dosage at Different Fuel Oil Ratios.

3-12

1.5

100

90

80

% P2O5 Recovery

70

60

50

40 FA:FO=1:0.6 FA:FO=1:0.6 with silicate

30

FA:FO=1:0.8 FA:FO=1:1

20

10

0 0.8

0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-6. Flotation Recovery vs. Liqro GA Dosage at Different Fuel Oil Ratios.

3-13

1.5

Petronate CR Sulfonate The sulfonate was tested as the phosphate collector using a fuel oil to fatty acid ratio of 0.6:1.0 with and without soda ash for pH regulation. At conditioning pH of 8.5-8.7, 0.5 lb. of N-silicate per ton of feed was also tested to improve flotation selectivity. Collector level used ranged from 1.0-1.6 lb. of petroleum sulfonate per ton of feed. Petronate CR is an oil-soluble sodium salt type reagent. Test results are tabulated in Table 3-5, and presented graphically in Figures 3-7 through 3-9. The best results were obtained using 1.6 lb. of collector per ton of feed along with 0.5 lb. of N-silicate per ton of feed. A 21.11% P2O5/37.04% Insol concentrate was obtained at only 78.1% P2O5 recovery. Petronate CR was concluded to be only a fair collector for this phosphate feed sample. Flotation selectivity was good only when % P2O5 recovery was less than about 50% unless N-silicate was also used. Using N-silicate permitted >20% P2O5 concentrates to be obtained at only 75-78% P2O5 recovery because of the difficulty floating +35 mesh phosphate particles. 35

30

25

% P2O5

20

15

10

pH 7

5

pH 8.7 pH 8.7 with silicate 0 0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

Collector Dosage, lb/Ton Feed

Figure 3-7. Concentrate % P2O5 vs. Petroleum Sulfonate Dosage with 37.5% Fuel Oil.

3-14

1.7

80

70

60

% Insol

50

pH 7 pH 8.7 pH 8.7 with silicate

40

30

20

10

0 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 3-8. Concentrate % Insol vs. Petroleum Sulfonate Dosage with 37.5% Fuel Oil.

3-15

90

80

70

% P2O5 Recovery

60

50

40

30

pH 7 pH 8.7 pH 8.7 with silicate

20

10

0 0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

1.7

Collector Dosage, lb/Ton Feed

Figure 3-9. Flotation Recovery vs. Petroleum Sulfonate Dosage with 37.5% Fuel Oil. Cottonseed Soapstock This collector failed to produce a 20+% P2O5 concentrate at 80% or higher P2O5 recovery using any of the test conditions investigated. Even the use of N-silicate failed to produce desired results. The poor selectivity exhibited by this reagent is obvious by the data in Table 3-6 and the curves shown in Figures 3-10 through 3-12. Collector level tested ranged from 1.2-2.8 lb. of "as-received" soapstock per ton of feed. Fuel oil/soap ratio was 0.63:1.0 based on 80% solids soapstock. Conditioning pH ranged from 7.4-9.1 for the various tests performed. N-silicate, when used, was at the standard 0.5 lb./TF. Cottonseed soapstock was concluded to be a poor collector for this phosphate feed sample because of the very poor selectivity shown during this testwork. 3-16

25

20

15

pH 7.5

% P2O5

pH 8.4 pH 9

10

5

0 0.5

1

1.5

2

2.5

3

Collector Dosage, lb/Ton Feed

Figure 3-10. Concentrate % P2O5 vs. Cottonseed Soap Dosage at Collector-to-Fuel-Oil Ratio of 1:0.5.

3-17

90

80

70

% Insol

60 pH 7.5 pH 8.4 pH 9

50

40

30

20 0.5

1

1.5

2

2.5

3

Collector Dosage, lb/Ton Feed

Figure 3-11. Concentrate % Insol vs. Cottonseed Soap Dosage at Collector-to-Fuel-Oil Ratio of 1:0.5.

3-18

100

90

80

% P2O5 Recovery

70

60

50 pH 7.5

40

pH 8.4 pH 9

30

20

10

0 0

0.5

1

1.5

2

2.5

3

Collector Dosage, lb/Ton Feed

Figure 3-12. Flotation Recovery vs. Cottonseed Soap Dosage at Collector-to-Fuel-Oil Ratio of 1:0.5.

3-19

Custofloat 27AR Tall Oil/Pitch Soap This collector also failed to produce a 20+% P2O5 concentrate at 80% or higher P2O5 recovery. The poor selectivity characterized by this reagent is illustrated by the results presented in Table 3-7, and the curves shown in Figures 3-13 through 3-15. This asreceived reagent was reported to contain 30% active collector, which was verified by our lab test. Collector level tested ranged from 1.33-4.00 lb. of "as-received" tall oil/pitch soap per ton of feed. The fuel oil/soap ratio was 0.66:1.00 or 1.33:1.00 based upon soap solids. Conditioning pH ranged from 7.2-8.5 for the various tests performed. N-silicate use was the normal 0.5 lb./TF and also 1.5 lb./TF (3X) as shown on Table 3-7. The tall oil/pitch soap was concluded from these flotation test results to be a poor collector choice for use with this feed because of the very poor selectivity exhibited. 25

pH 7.2;Collector:fueloil=1:0.2

20

pH 8.1;Collector:fueloil=1:0.2; with silicate pH 8.2;Collector:fueloil=1:0.4; with silicate

% P2O5

15

10

5

0 0

1

2

3

Collector Dosage, lb/Ton Feed

Figure 3-13. Concentrate % P2O5 vs. Tall Oil Pitch Soap Dosage. 3-20

4

5

90

80

70

% Insol

pH 7.2;Collector:fueloil=1:0.2 pH 8.1;Collector:fueloil=1:0.2; with silicate

60

pH 8.2;Collector:fueloil=1:0.4; with silicate

50

40

30 1

1.5

2

2.5

3

3.5

Collector Dosage, lb/Ton Feed

Figure 3-14. Concentrate % Insol vs. Tall Oil Pitch Soap Dosage.

3-21

4

4.5

100

90

80

% P2O5 recovery

70

60

50 pH 7.2;Collector:fueloil=1:0.2

40

pH 8.1;Collector:fueloil=1:0.2; with silicate pH 8.2;Collector:fueloil=1:0.4; with silicate

30

20

10

0 1

1.5

2

2.5

3

3.5

Collector Dosage, lb/Ton Feed

Figure 3-15. Flotation Recovery vs. Tall Oil Pitch Soap Dosage.

3-22

4

4.5

Petronate CR (20%) and Liqro GA Tall Oil (80%) Mixture This reagent mix was also tested as the phosphate collector using a 0.6:1.0 fuel oil/Petronate CR and tall oil mix ratio with 1.0-1.4 lb. of collector mix per ton of feed. Standard 9.0-9.2 conditioning pH was employed with and without normal N-silicate addition to the conditioner. Test results are tabulated in Table 3-8, and shown graphically in Figures 3-16 through 3-18. The best test results were obtained from using N-silicate and collector levels of 1.2 and 1.4 lb./TF. A 20.88% P2O5/38.09% Insol concentrate was produced at 83.2% P2O5 recovery using 1.2 lb. of Petronate CR and Liqro GA mixture per ton of feed. Using 1.4 lb. of this collector mixture per ton of feed, flotation produced a 17.09% P2O5/49.21% Insol concentrate at 88.2% P2O5 recovery. This collector mixture was concluded to be a reasonably good substitute for Liqro GA tall oil based upon the limited number of flotation tests performed; however, the reagent cost of using the mixed collector could easily be about $0.10 higher per ton of feed processed. 30

25 Without silicate With silicate

% P2O5

20

15

10

5

0 0.8

0.9

1

1.1

1.2

1.3

1.4

Collector Dosage

Figure 3-16. Concentrate % P2O5 vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6. 3-23

1.5

90

80

70

% Insol

60

50

40

30

Without silicate

20

With silicate

10

0 0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

Collector Dosage, lb/Ton Feed

Figure 3-17. Concentrate Insol vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6.

3-24

100

90

% P2O5 Recovery

80

70

Without silicate With silicate

60

50

40

30 0.8

0.9

1

1.1

1.2

1.3

1.4

Collector Dosage, lb/Ton Feed

Figure 3-18. Flotation Recovery vs. Collector Mixture (20% Petronate CR and 80% Liqro GA) Dosage at Collector-to-Fuel-Oil Ratio of 1:0.6.

3-25

1.5

COMPARISON OF ALL COLLECTORS Figure 3-19 shows all test data for grade versus recovery. If we set a minimum requirement of 15% P2O5 in the rougher concentrate at recovery of 80% or higher, as indicated by the arrows, only three collectors made the cut. They are oleic acid, the tall oil fatty acid, and the mixture of petroleum sulfonate and tall oil fatty acid. 100

90

80

% P2O5 recovery

70

Oleic Acid

60

Tall Oil (Liqro GA) Petro Sulfonate Cottonseed Soap Pitch Soap

50

Mixture of 20% Petro Sulfonate and 80% Liqro GA

40

30

20 0

5

10

15

20

25

30

% P2O5

Figure 3-19. Grade-Recovery Curves for All Tests of Different Collectors. 3-26

35

SIZE/ASSAY ANALYSES OF SELECTED FLOTATION TAILS Abbreviated dry screen analyses were performed on twelve selected flotation test tailings produced using either Liqro GA tall oil or oleic acid as the phosphate collector. A 15-minute screening time, using the Ro-Tap, was utilized for sizing at 28 and 35 Tyler mesh. Size/Assay results for five Liqro GA test tails and seven oleic acid test tails are presented in Tables 3-3 and 3-4, respectively. As expected, these tables illustrate the general trend that the highest % P2O5 tailing values are present in the coarsest (+28 mesh) size fraction for each test. Accordingly, the lowest % P2O5 tailing values are present in the finest (-35 mesh) size fraction for each test. The % P2O5 recoveries for the +28 mesh and 28/35 mesh size fractions are shown to be lower than for the -35 mesh size fractions for all tests. Also, % P2O5 recoveries for the +28 mesh and 28/35 mesh size fractions are always lower than for the total concentrate, and the % P2O5 recoveries are always higher for the -35 mesh concentrate size fractions compared to the total concentrate. These trends are apparent even though the lowest flotation feed grade occurs in the -35 mesh size fraction. Table 3-3. Sizing Analysis of Flotation Tails Using Liqro GA Collector for Tests with 65+% Recovery. Size, Mesh

% Wt.

% P2O5

+28 28/35 -35

1.9-2.4 8.0-9.7 87.9-90.1

16.89-19.70 1.63-5.15 0.21-1.30

% P2O5 Dist. in Tails 20.1-52.9 19.1-29.2 27.1-58.8

% P2O5 Dist. in Total Feed 4.6-6.3 1.7-6.7 2.4-18.6

Table 3-4. Sizing Analysis of Flotation Tails Using Oleic Acid Collector for Tests with 65+% Recovery. Size, Mesh

% Wt.

% P2O5

+28 28/35 -35

1.7-2.1 7.5-8.0 90.0-90.8

15.38-18.33 1.85-4.30 0.34-1.33

3-27

% P2O5 Dist. in Tails 18.2-36.6 17.0-19.7 43.7-62.8

% P2O5 Dist. in Total Feed 4.7-5.9 2.5-5.5 5.5-19.3

Appendix 3 DATA FROM EVALUATION OF ANIONIC COLLECTORS

Table 3A-1. Flotation Concentrates Analyses Using Oleic Acid Collector at pH 9. Collector/Fuel Oil, Lb./TF 1/0.6 1.2/0.72 1.4/0.84 1.6/0.96 1.2/0.72 1.4/0.84 1.6/0.96 1.2/0.96 1.4/1.12 1.6/1.28

Conditions

% Wt.

% P2O5

% Insol

No Silicate No Silicate No Silicate No Silicate Silicate Silicate Silicate Silicate Silicate Silicate

6.5 10.7 25.9 26.8 10.7 17.8 17.3 6.2 16.9 20.9

24.78 23.1 15.61 16.71 21.4 19.25 20.91 25.97 21.09 21.82

26.53 31.85 53.06 49.88 36.42 42.25 37.71 23.06 36.95 34.92

% P2O5 Recovery 33.2 48.6 81.3 87.3 46.5 69.3 72.7 32.7 72.5 92.1

Table 3A-2. Flotation Concentrates Analyses Using Liqro GA Collector at pH 9. Collector/Fuel Oil, Lb./TF 1/0.6 1.2/0.72 1.4/0.84 1/0.8 1.2/0.96 1.4/1.12 1/1 1.2/1.2 1.4/1.4 1/0.6 1.2/0.72 1.4/0.84

Conditions

% Wt.

% P2O5

% Insol

No Silicate No Silicate No Silicate No Silicate No Silicate No Silicate No Silicate No Silicate No Silicate Silicate Silicate Silicate

8.8 19.0 32.0 9.7 16.6 26.5 7.3 12.5 20.0 6.3 13.1 19.0

25.7 19.08 13.51 30.02 25.81 24.05 28.21 22.9 17.14 28.23 24.72 21.52

23.58 43.25 59.51 11.36 23.8 28.67 17.21 32.04 48.79 16.53 26.76 36

% P2O5 Recovery 44.8 73.6 87.1 36.9 68.4 89.4 52.1 78.5 91.3 42.3 64.6 87.6

Table 3A-3. Flotation Concentrates Analyses Using Petro Sulfonate Collector. Collector/Fuel Oil, Lb./TF 1/0.6 1.4/0.84 1.6/0.96 1.0/0.6 1.4/0.84 1.0/0.6 1.2/0.72 1.4/0.84 1.6/0.96

Conditions

% Wt.

% P2O5

% Insol

pH 7 pH 7 pH 7 pH 8.6 pH 8.6 pH 8.6 + Silicate pH 8.6 + Silicate pH 8.6 + Silicate pH 8.6 + Silicate

6.4 8.0 9.6 33.5 38.2 7.6 11.4 16.0 18.9

30.17 28.79 25.01 11.12 10.67 30.13 28.81 22.97 21.11

11.62 15.7 25.37 66.78 68.03 11.9 15.7 32.42 37.04

3A-1

% P2O5 Recovery 41.3 46.3 47.5 76.9 84 45.5 65.1 75.1 78.1

Table 3A-4. Flotation Concentrates Analyses Using Cottonseed Soap Collector. Collector/Fuel Oil, Lb./TF 1.2/0.6 1.6/0.8 2.0/1.0 2.4/1.2 1.2/0.6 1.6/0.8 2.0/1.0 0.8/0.4 1.2/0.6 1.6/0.8 2.0/1.0 2.8/1.4 1.2/0.6 1.6/0.8 2.0/1.0 2.4/1.2

Conditions

% Wt.

% P2O5

% Insol

pH 7.5 pH 7.5 pH 7.5 pH 7.5 pH 8.4 pH 8.4 pH 8.3 pH 9.0 pH 9.0 pH 9.0 pH 9.0 pH 9.0 pH 7.8 + Silicate pH 7.7 + Silicate pH 7.5 + Silicate pH 8.0 + Silicate

13.8 26.5 65.2 76.7 19.5 66.0 79.2 12.5 52.3 88.5 92.3 98.5 7.6 20.4 48.9 57.5

15.68 11.68 6.68 5.41 17.88 6.13 5.36 19.06 7.43 4.87 5.17 4.6 27.55 19.61 9.15 7.48

53.62 65.34 79.84 83.08 47.62 82.17 83.64 43.96 77.57 84.76 83.66 85.66 19.43 42.68 72.60 72.24

% P2O5 Recovery 42.4 63.1 83.7 85.9 67.6 84.2 88.7 47.7 78.7 90.2 93.9 95.8 39.7 79.8 87.5 88.8

Table 3A-5. Flotation Concentrates Analyses Using Tall Oil Pitch Soap Collector. Collector/Fuel Oil, Lb./TF 1.33/0.27 2.0/0.40 4.0/0.80 1.33/0.27 2.0/0.40 3.0/0.60 4.0/0.80 1.33/0.54 2.0/0.80 3.0/1.18 1.33/0.54 (3X) 2.0/0.80 (3X) 3.0/1.18 (3X)

Conditions

% Wt.

% P2O5

% Insol

pH 7.2 pH 7.2 pH 7.3 pH 8.1 + Silicate pH 8.2 + Silicate pH 8.1 + Silicate pH 8.0 + Silicate pH 8.2 + Silicate pH 8.1 + Silicate pH 8.0 + Silicate pH 8.3 + Silicate pH 8.4 + Silicate pH 8.5 + Silicate

26.6 79.6 95.4 10.6 48.7 60.6 73.2 36.0 58.4 65.7 29.9 48.3 56.7

6.69 5.81 4.94 20.59 8 6.89 6.66 11.92 7.92 7.18 13.35 9.84 8.08

80.09 82.42 85.01 39.6 76.05 79.31 80.05 64.83 76.28 78.55 60.62 70.76 75.88

3A-2

% P2O5 Recovery 35.2 91.5 95.9 45 79.1 83.4 96.1 88.5 92.8 96.1 85.4 91.7 95.4

Table 3A-6. Flotation Concentrates Analyses Using a Mixture of 20% Sulfonate and 20% Liqro GA Collector at pH 9. Collector/Fuel Oil, Lb./TF 1.0/0.6 1.2/0.72 1.4/0.84 1.0/0.6 1.2/0.72 1.4/0.84

Conditions

% Wt.

% P2O5

% Insol

+ Silicate + Silicate + Silicate

24.3 34.2 59.9 8.4 20.2 25.3

16.53 12.55 7.25 26.12 20.88 17.09

51.28 62.77 77.84 23.24 38.09 49.21

3A-3

% P2O5 Recovery 78.7 83.3 90.2 42.9 83.2 88.2

PART 4. STUDY OF ISO-ACIDS

PRELIMINARY SCREENING INTRODUCTION This test program was designed to compare flotation results obtained using Liqro GA tall oil and commercial grade Oleic Acid 401 with parallel test results using four different commercial grade isostearic/iso-oleic acids supplied by two divisions of International Paper. One isostearic acid reagent of unknown source was evaluated by TVA during 1978-1982 as a Florida phosphate collector. This reagent was found to offer better flotation performance with Florida phosphate ore than tall oil and three other types of anionic collectors. The higher cost per pound of the isostearic acid tested by TVA was concluded to prohibit commercial use at that time as a tall oil substitute, during phosphate flotation, using the Crago process. The high selectivity shown by TVA using the one isostearic acid sample indicated to this writer that further flotation evaluation of hopefully cheaper isostearic acid type reagents was warranted to determine if a 30+% P2O5 concentrate was attainable using a single-stage rougher flotation of current Florida phosphate flotation feed samples. SUMMARY Conventional laboratory rougher flotation tests were performed to compare six anionic collectors' efficiency and selectivity using a low-grade IMC feed and a higher-grade PCS feed as the test samples. Although the two samples were reported to be fine feed, each one contained more than 10% by weight of +35 mesh particles representing about 16-22% of the total feed P2O5 distribution in the "coarse" size fractions. The IMC feed sample was more difficult to process by rougher flotation than the PCS feed to obtain a 30% P2O5 concentrate at 80% P2O5 recovery or higher. Four isostearic/iso-oleic acid type fatty acid collectors, supplied by divisions of International Paper, were compared with a commercial grade oleic acid and with Liqro GA tall oil as phosphate collectors using standard laboratory conditioning and flotation procedures. The most selective collector evaluated appeared to be Century 1108. This high isostearic acid type reagent produced phosphate rougher concentrates analyzing 28% P2O5/17% Insol and 31% P2O5/7+% Insol at about 80% and 92% P2O5 recovery from the IMC/Agrico feed and the PCS feed, respectively. However, this excellent performing reagent was concluded to be too expensive at $1.25/lb. for commercial use. The overall most promising reagent was probably Century MO-5. This collector was essentially an isooleic acid/stearic acid mixture (not isostearic acid) priced at $0.35/lb. Century MO-5 produced rougher phosphate concentrates analyzing 25% P2O5/25+% Insol and 29+% P2O5/13+% Insol at about 80% and 95% P2O5 recovery from the IMC and PCS feed samples, respectively. Using N-Brand sodium silicate to improve selectivity, Century MO5 yielded phosphate rougher concentrates analyzing 29+% P2O5/13+% Insol at about 84% P2O5 recovery from the IMC feed, and 30+% P2O5/9+% Insol at about 94% P2O5 recovery 4-1

from the PCS feed. The IMC 29+% P2O5 rougher concentrate was further upgraded, using one cleaner flotation stage, to 31+% P2O5/7% Insol at an overall 75% P2O5 recovery. The Century 1108 and/or Century MO-5 consumption range required to produce the best overall concentrate grades and recoveries from these two feed samples was about 1.4-1.6 lb./TF. When used to improve selectivity, N-silicate use was about 0.6 lb./TF. A 29+% P2O5/13-% Insol phosphate rougher concentrate produced from the PCS feed at 95+% P2O5 recovery was subjected to a brief size/assay analysis. The +100 mesh fraction of the concentrate analyzed 30+% P2O5/10+% Insol and represented about 95% P2O5 recovery from the total concentrate. Size/assay analyses also were performed on selected rougher tailings obtained from four flotation tests that used two levels of Century MO-5 collector, with and without N-silicate, and IMC/Agrico feed. The results showed that concentrate P2O5 recoveries ranged from about 85-96% from the -35 mesh feed size, 55-92+% from the 28/35 mesh feed size and less than 58% for the +28 mesh feed size. EXPERIMENTAL Description of Flotation Feed Samples Two different flotation feed samples were used for the current program. In addition to the IMC Four Corners feed sample (5.2% P2O5) described in previous chapters, a sample of PCS Swift Creek feed was also used for the current collector comparison testwork. Table 4-1 shows size/assay analysis of this feed. Table 4-1. Size/Assay Analysis of the PCS Feed for Iso-Acids Evaluation. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total -28 -35

% Wt. 1.7 2.9 8.5 22.4 40.3 18.7 4.2 0.8 0.5 100.0 95.4 86.9

Cum. % Wt. 1.7 4.6 13.1 35.5 75.8 94.5 98.7 99.5 100.0 ----

19.41 13.66 11.73 13.10 9.44 7.24 7.96 10.54

38.39 57.38 64.32 60.89 71.78 77.96 75.06 66.09

% Dist.. P2O5 3.2 3.8 9.8 28.5 37.1 13.1 3.2 1.3

10.28 10.02 9.84

68.94 69.85 70.33

100.0 89.8 70.3

% P2O5

% Insol

Cum. % Dist. P2O5 3.2 7.0 16.8 45.3 82.4 95.5 98.7 100.0 ----

This PCS feed composite contained mostly light tan phosphate particles, whereas the IMC feed contained primarily black phosphate. The size/assay analysis shows that 4-2

about 7.0% of the total feed P2O5 is present in the +28 mesh size fraction, and 16.8% of the total feed P2O5 is coarser than 35 mesh. The PCS feed was well deslimed and contained less than 0.6% by weight of -200 mesh particles when sampled. Phosphate Flotation Collectors Evaluated Table 4-2 lists the fatty acid type reagents, which were subjected to laboratory rougher flotation comparison tests to determine the most selective phosphate collectors, and to ascertain the possibility of producing a 30+% P2O5 concentrate during the single-stage float process. Table 4-2. List of Collectors for Evaluation of Selective Collectors. Fatty Acid Century 1105 Century 1108 Century 1164 Century MO-5 Oleic Acid 401 (A.N. = 200) Liqro GA Tall Oil (A.N. = 154)

Producer/Supplier Arizona Chem. (Panama City, FL) Union Camp (Jacksonville, FL) Arizona Chem. (Panama City, FL) Arizona Chem. (Panama City, FL)

Cost, $/Lb. 1.24 1.25 0.87 0.35

Welch, Holme & Clark Co. (Newark, NJ)

0.72

Custom Chemicals (Bartow, FL)

0.14

Note: Arizona Chemical Co. and Union Camp Corp. are both owned and operated by International Paper.

The four "Century" fatty acids all contain appreciable isostearic and/or iso-oleic acid. Detailed compositions and physical/chemical characteristics from product data sheets for these reagents are presented in Table 4-3. Century MO-5 was the only completely nonliquid sample at room temperature, and is classified as a semi-fluid.

4-3

Table 4-3. Comparison of Century Reagent Characteristics and Compositions. Item Acid No. Sap. No. Iodine No. Titer, °C. S.G., 25°/25°C. Unsaps, %

Century 1105 182 185 6.4 4 0.900 6.0

Century 1108 181 184 6.0 5 0.906 6.0

Century 1164 174 184 74 3 (0.903) 7.1

Century MO-5 177 185 72 35 0.895 7.0

Isostearic, % Iso-oleic, % Palmitic, % Stearic, % Sat. FA, % Oleic, % Linoleic, % Comments:

High Low ---Low Low C-18 Branched & Straight Chain Fatty Acids

High Low ---Low Low C-18 Branched & Straight Chain Fatty Acids

-76 --8 11 (ppm) C-18 Mono-Unsat. Fatty Acids

-46 1 1 17 37 -C-18 Sat. & Unsat. Fatty Acids

RESULTS AND DISCUSSION Flotation of IMC Feed Using Various Fatty Acid Collectors Four "Century" fatty acid reagents, each containing appreciable amounts of isostearic acid, plus Oleic Acid 401 and Liqro GA tall oil were briefly evaluated and compared as phosphate collectors for the IMC low-grade feed. Most of the Oleic Acid 401 and Liqro GA flotation test data were previously reported in part III and are included herein for easy comparison purposes. Standard laboratory 500g. rougher flotation tests were performed using different collector quantities with 2-minute conditioning at approximately 73% solids. No. 5 fuel oil (extender) at 0.6 FO/FA ratio and soda ash (pH regulator) were used for all tests. Fuel oil was pre-mixed with the fatty acid before adding to the conditioner. Conditioning pH was usually 9.0-9.2, and flotation time allowed was 2 minutes. Tap water was used for all tests. Flotation test results obtained for these six reagents are summarized in Table 4-6, and are presented in graphical form for easier comparison in Figures 4-1 through 4-4. Since the Century isostearic acids tested are considerably more expensive than tall oil, emphasis was placed upon obtaining improved selectivity to obtain the highest possible grade concentrates (30+% P2O5) during single-stage rougher flotation. 4-4

Examination of the % P2O5 grade and recovery curves shown in Figure 1 illustrates that Liqro GA T.O., Century 1164, and Oleic Acid 401 were the strongest but least selective phosphate collectors. At about 80% P2O5 recovery, these three reagents produced concentrates analyzing about 15-20% P2O5 or less, with Century 1164 probably being the strongest of the three collectors. Collector demand for each of these three reagents to obtain 80% P2O5 recovery was 1.3-1.4 lb./ton of flotation feed. Further examination of the Figures 4-1 through 4-4 curves shows that the isostearic acid type reagents Century 1108, 1105 and MO-5 were the most selective at the 80% P2O5 recovery point. Concentrates produced at 80% P2O5 recovery analyzed about 25-28% P2O5, with Century 1108 having the best selectivity. Collector demand for these three "weaker" collectors, to obtain at least 80% P2O5 recovery, was about 1.6 lb./TF. Century MO-5, by far the least expensive iso-oleic/stearic acid reagent ($0.35/lb.), was selected for additional flotation testwork, using N-brand sodium silicate for improved selectivity, to determine if a 30% P2O5 concentrate could be produced at 80% P2O5 recovery or higher.

4-5

35

30

25

% P2O5

20

15

Century 1105 Century 1108 Century 1164 Century MO-5

10

Oleic acid Liqro GA

5

0 0.8

1

1.2

1.4

1.6

1.8

2

Collector Dosage, lb/Ton Feed

Figure 4-1. Concentrate % P2O5 vs. Dosage of Various Collectors at Collector-to-FuelOil Ratio of 1:0.6.

4-6

90

80

Century 1105

70

Century 1108 Century 1164 60

Century MO-5

% Insol

Oleic acid Liqro GA

50

40

30

20

10

0 0.8

1

1.2

1.4

1.6

1.8

2

Collector Dosage, lb/Ton Feed

Figure 4-2. Concentrate % Insol vs. Dosage of Various Collectors at Collector-to-FuelOil Ratio of 1:0.6 Using Four Corners Feed.

4-7

100

90

% P2O5 Recovery

80

70

Century 1105

60

Century 1108 Century 1164 Century MO-5 Oleic acid

50

Liqro GA

40

30 0.8

1

1.2

1.4

1.6

1.8

2

Collector Dosage, lb/Ton Feed

Figure 4-3. Flotation % P2O5 Recovery vs. Dosage of Various Collectors at Collectorto-Fuel-Oil Ratio of 1:0.6 Using Four Corners Feed.

4-8

100

90

% P2O5 Recovery

80

70

Century 1105

60

Century 1108 Century 1164 Century MO-5 Oleic acid

50

Liqro GA

40

30 0

5

10

15

20

25

Concentrate % P2O5

Figure 4-4. Concentrate Grade vs. Recovery for Various Collectors.

4-9

30

35

Flotation of IMC Feed Using Century MO-5 with N-Silicate Two rougher-cleaner flotation tests were performed using 1.8 and 1.6 lb. of Century MO-5 collector with 0.6 lb. of N-Silicate per ton of feed to determine if a 30+% P2O5 concentrate could be produced. The N-brand sodium silicate was added during the final 20 seconds of conditioning. All other flotation test conditions were the same as previously stated. Flotation material balances for these tests (FA-17S and FA-17AS) are compared with parallel tests previously performed, using no silicate, in Table 4-4. Table 4-4. Flotation Test Results Using Century MO-5 Collector Plus IMC Feed with and without N-Silicate Addition. Test No. FA-17

Collector, Lb./TF Flotation Fatty Acid Fuel Oil Product % Wt. Cent. MO-5 No. 5 Ro. Conc. 21.5 1.8 1.08 Ro. Tail. 78.5 Cond. pH = 9.0 Ro. Feed 100.0

Analysis % P2O5 % Insol 21.66 35.90 0.53 97.56 5.08 84.30

% Dist. P2O5 91.7 8.3 100.0

Cent. MO-5 No. 5 1.6 0.96 Cond. pH = 9.0-

Ro. Conc. Ro. Tail. Ro. Feed

16.3 83.7 100.0

25.36 1.19 5.12

24.95 95.43 83.94

80.7 19.3 100.0

Using N-Silicate: Cent. MO-5 No. 5 1.8 1.08 Cond. pH = 9.2FA-17S

Ro. Conc. Ro. Tail. Ro. Feed

19.6 80.4 100.0

24.23 0.49 5.14

28.88 98.27 84.67

92.4 7.6 100.0

Cl. Conc. Cl. Tail.

17.2 2.4

27.13 3.22

20.34 90.16

90.8 1.6

Ro. Conc. Ro. Tail. Ro. Feed

14.5 85.5 100.0

29.52 0.94 5.08

13.31 96.83 84.72

84.3 15.7 100.0

Cl. Conc. Cl. Tail.

12.1 2.4

31.68 18.63

7.02 44.93

75.4 8.9

FA-17A

Using N-Silicate: Cent. MO-5 No. 5 1.6 0.96 Cond. pH = 9.3 FA-17AS

Test FA-17AS produced the best rougher concentrate, analyzing 29.52% P2O5/13.31% Insol at 84.3% P2O5 recovery. Cleaner flotation of this concentrate produced a cleaner concentrate analyzing 31.68% P2O5/7.02% Insol at an overall 75.4% P2O5 recovery. The other three Table 4-4 flotation tests produced concentrates analyzing less than 29% P2O5. For Test FA-17AS, the amount of Insol present in the concentrate was only 1.01% of the flotation feed Insol. 4-10

Size/Assay Analyses of Selected IMC-Agrico Flotation Tails Abbreviated dry screen analyses were performed on four selected rougher flotation tailings. Sizing of the tailings at 28 and 35 Tyler mesh, using a 15-minute Ro-tap time, was performed for the tailings obtained from tests FA-17, FA-17A, FA-17S and FA-17AS. Tests FA-17 and FA-17A used 1.8 and 1.6 lb. of Century MO-5 per ton of feed, respectively. Tests 17S and 17AS used the same two levels of Century MO-5 collector plus 0.6 lb. of N-silicate per ton of feed for comparison. The use of N-silicate did not result in a serious loss of P2O5 recovery for these comparison tests. The size/assay results are presented in Table 4-5. The Table 4-5 test results show that the highest % P2O5 tailing analyses are present in the coarsest (+28 mesh) size fractions and the lowest % P2O5 tailing analyses occur for the finer (-35 mesh) size fractions for each flotation test performed. As expected, the concentrate % P2O5 recoveries from the -35 mesh size fraction of each test feed ranged from 85.4-96.4% and were higher than corresponding test coarser size fractions. These results can be compared with previous tailing size/assay results presented in Part 3. Finally, Table 4-6 presents % P2O5 distributions within the flotation tailing size fractions for each of the tests listed in Table 4-5.

4-11

Table 4-5. Detailed % P2O5 Analyses and % P2O5 Distributions from Feed for Various Flotation Tailings Size Fractions. Test No.

% Wt. Tails

FA-17 FA-17A FA-17S FA17-AS

78.5 83.7 80.4 85.5

Test No.

% Wt. Tails

FA-17 FA-17A FA-17S FA-17AS

78.5 83.7 80.4 85.5

Test No.

% Wt. Tails

FA-17 FA-17A FA-17S FA-17AS

78.5 83.7 80.4 85.5

+28M % Wt. In Tails 1.7 2.2 1.4 1.8

+28M Tail. % P2O5 15.79 19.15 12.78 18.28

+28M Tail. Dist. P2O5 63.7 99.8 42.5 78.1

28/35M % Wt. In Tails 7.9 8.6 7.4 7.7

28/35M Tail. % P2O5 1.47 4.14 0.84 2.79

28/35M Tail. % Dist. P2O5 14.8 45.5 7.9 27.5

-35M % Wt. In Tails 90.4 89.2 91.2 90.5

-35M Tail. % P2O5 0.22 0.67 0.16 0.50

-35M Tail. Dist. P2O5 4.9 14.6 3.6 11.1

4-12

% Recov. P2O5 +28 M Conc. 36.3 0.2 57.5 21.9

Tot. Conc. 91.7 80.7 90.8 84.3

% Recov. P2O5 28/35M Conc. 85.2 54.5 92.1 72.5

Tot. Conc. 91.7 80.7 90.8 84.3

% Recov. P2O5 -35 M Conc. 95.1 85.4 96.4 88.9

Tot. Conc. 91.7 80.7 90.8 84.3

Table 4-6. P2O5 Losses in Various Flotation Tailing Size Fractions. Test No. FA-17 FA-17A FA-17S FA-17AS

% Dist. P2O5 Conc. Tail. 91.7 8.3

% P2O5 Distribution in Tail. Size Fractions +28M 28/35M -35M Total Tail. 3.8 1.7 2.8 8.3 (45.8) (20.3) (33.9) (100.0)

80.7

19.3

5.9 (30.4)

5.0 (26.1)

8.4 (43.5)

19.3 (100.0)

90.8

9.2

4.3 (46.1)

1.4 (15.4)

3.5 (38.5)

9.2 (100.0)

84.3

15.7

5.3 (33.3)

3.5 (21.2)

7.6 (45.5)

15.7 (100.0)

Flotation of PCS Feed Using Various Fatty Acid Collectors The six fatty acid type collectors used for flotation comparison tests with IMC feed were also used with the higher-grade PCS feed for further evaluation and comparison. Flotation test procedures and conditions were the same as used with the low-grade IMC feed. Flotation test results are summarized in Table 4-10 and presented graphically for easy comparison in Figures 4-5 through 4-8.

4-13

33

32

31

30

% P2O5

29

28

27 Century 1105

26

Century 1108 Century 1164

25

Century MO-5 Oleic acid Liqro GA

24

23 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 4-5. Concentrate % P2O5 vs. Dosage of Various Collectors at Collector-to-FuelOil Ratio of 1:0.6 Using the PCS Feed.

4-14

30

25

20

Century 1105 Century 1108

% Insol

Century 1164 Century MO-5 Oleic acid

15

Liqro GA

10

5

0 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 4-6. Concentrate % Insol vs. Dosage of Various Collectors at Collector-to-FuelOil Ratio of 1:0.6 Using the PCS Feed.

4-15

110

100

90 Century 1105 Century 1108

% P2O5 Recovery

Century 1164 Century MO-5

80

Oleic acid Liqro GA

70

60

50

40 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 4-7. Flotation Recovery vs. Dosage of Various Collectors at Collector-to-FuelOil Ratio of 1:0.6 Using the PCS Feed.

4-16

100

95

90

% P2O5 Recovery

85

80

Century 1105 Century 1108 75

Century 1164 Century MO-5 Oleic acid

70

Liqro GA 65

60

55

50 25

26

27

28

29

30

31

32

33

Concentrate % P2O5

Figure 4-8. Concentrate Grade vs. Recovery for Various Collectors at Collector-toFuel-Oil Ratio of 1:0.6 Using the PCS Feed.

4-17

The Figures 4-4 through 4-8 curves show that Century 1164 and Liqro GA tall oil were again the strongest but least selective phosphate collectors. At 80-95% P2O5 recovery, these two reagents produced concentrates analyzing about 28-29% P2O5. Collector demand for these two collectors to obtain 80-95% P2O5 recovery ranged from about 1.2-1.4 lb./ton of flotation feed. Further examination of those curves shows that the isostearic acid type reagents Century 1108, 1105 and also Oleic Acid 401, followed closely by Century MO-5, were the most selective at the 85-90% (or slightly higher) P2O5 recovery level. Concentrates produced at 85-90% P2O5 recovery analyzed about 29-31% P2O5, with Century 1108 again having the best selectivity. Collector demand for these more selective collectors, to obtain 85-90% P2O5 recovery, was about 1.3-1.5+ lb./ton of flotation feed. Test PCS-9 produced a flotation concentrate analyzing 29.44% P2O5/12.83% Insol at 95.6% P2O5 recovery using 1.4 lb. of Century MO-5 per ton of feed. A brief size/assay analysis was performed using this concentrate to show Insol distribution by size fractions. Size/assay analysis of the concentrate obtained from test PCS-9 is summarized in Table 4-7. Table 4-7. Size/Assay Analysis of a Concentrate from PCS Feed Using MO-5 Collector. Size, Tyler Mesh +48 48/65 65/100 -100 Total

% Wt. P2O5 41.3 34.4 16.9 7.4 100.0

% P2O5

% Insol

32.07 30.40 26.00 20.68 29.62

5.27 10.28 23.09 37.83 12.42

% Dist. P2O5

Cum. % Wt.

Cum. % P2O5

Cum. % Insol

44.7 35.3 14.8 5.2 100.0

41.3 75.7 92.6 100.0 --

32.07 31.31 30.33 29.62 --

5.27 7.56 10.39 12.42 --

Cum. % Dist. P2O5 44.7 80.0 94.8 100.0 --

The size/assay analysis shows that the finer size fractions of the PCS-9 concentrate contain the highest % Insol content. Removal of the -100 mesh size fraction results in upgrading the final concentrate from 29.62% P2O5/12.42% Insol to 30.33% P2O5/10.39% Insol at 94.8% P2O5 recovery from the total concentrate. The least expensive iso-oleic/stearic acid type collector, Century MO-5, was again selected for additional flotation testwork, using N-Brand sodium silicate for improved selectivity, to determine if a 30% P2O5 concentrate could be produced at 90% P2O5 recovery or higher. Flotation of PCS Feed Using Century MO-5 with N-Silicate Two rougher flotation tests were performed using 1.6 and 1.4 lb. of Century MO-5 collector with 0.6 lb. of N-Silicate per ton of feed to obtain the highest grade concentrate possible at greater than 90% P2O5 recovery. No cleaner flotation stage was used. N-brand silicate was added during the last 20 seconds of rougher flotation conditioning. Flotation 4-18

material balances for these tests (PCS-9S and PCS-10S) are compared with parallel tests (PCS-9 and PCS-10) previously performed, using no silicate, in Table 4-8. Test PCS-9S yielded the best rougher concentrate, analyzing 30.82% P2O5/9.82% Insol at 93.9% P2O5 recovery. The other three Table 4-8 tests yielded higher than 95% P2O5 recovery of rougher concentrate, analyzing about 27-29% P2O5. For Test PCS-9S, the amount of Insol present in the concentrate was 4.04% of the flotation feed Insol. Table 4-8. Flotation Test Results Using Century MO-5 Collector Plus PCS Feed with and without N-Silicate Addition. Collector, Lb./TF Fatty Acid Fuel Oil Cent. MO-5 No. 5 1.6 0.96 Cond. pH = 9.1-

Flotation Product % Wt. Ro. Conc. 36.1 Ro. Tail. 63.9 Ro. Feed 100.0

No. 5 Cent. MO-5 1.4 0.84 Cond. pH = 9.1-

Ro. Conc. Ro. Tail. Ro. Feed

33.2 66.8 100.0

29.44 0.67 10.22

12.83 97.45 69.36

95.6 4.4 100.0

Using N-Silicate: Cent. MO-5 No. 5 PCS-10S 1.6 0.96 Cond. pH = 9.1-

Ro. Conc. Ro. Tail. Ro. Feed

33.4 66.6 100.0

28.50 0.44 9.81

16.38 98.33 70.96

97.0 3.0 100.0

Using N-Silicate: No. 5 Cent. MO-5 PCS-9S 1.4 0.84 Cond. pH = 9.0-

Ro. Conc. Ro. Tail. Ro. Feed

29.4 70.6 100.0

30.82 0.84 9.65

9.82 97.14 71.47

93.9 6.1 100.0

Test No. PCS-10

PCS-9

Analysis % P2O5 % Insol 27.82 17.55 0.34 98.43 10.26 69.23

% Dist. P2O5 97.8 2.2 100.0

Tables 4-9 and 4-10 show more test results using the PCS and IMC flotation feeds.

4-19

Table 4-9. Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Feed (5% P2O5). Test No. FA-13B

Collector, Lb./TF Fatty Acid Fuel Oil Cent. 1105 No. 5 1.4 0.84 Cond. pH = 9.1-

Flotation Product % Wt. Conc. 8.9 Tail. 91.1 Feed 100.0

Analysis % P2O5 % Insol 28.78 15.62 2.73 91.90 5.05 85.11

% Dist. P2O5 50.7 49.3 100.0

FA-13

Cent. 1105 No. 5 1.6 0.96 Cond. pH = 9.0+

Conc. Tail. Feed

16.6 83.4 100.0

25.41 0.94 5.02

25.05 96.79 84.68

84.4 15.6 100.0

FA-13A

Cent. 1105 No. 5 1.8 1.08 Cond. pH = 8.9+

Conc. Tail. Feed

21.2 78.8 100.0

22.01 0.45 5.02

34.30 98.23 84.68

93.0 7.0 100.0

FA-14B

Cent. 1108 No. 5 1.4 0.84 Cond. pH = 9.0+

Conc. Tail. Feed

11.5 88.5 100.0

29.03 2.01 5.12

14.55 93.69 84.59

65.2 34.8 100.0

FA-14

Cent. 1108 No. 5 1.6 0.96 Cond. pH = 9.0+

Conc. Tail. Feed

14.2 85.8 100.0

28.02 1.20 5.01

17.35 96.06 84.88

79.4 20.6 100.0

FA-14A

Cent. 1108 No. 5 1.8 1.08 Cond. pH = 8.9

Conc. Tail. Feed

18.0 82.0 100.0

23.50 1.00 5.05

30.68 96.62 84.75

83.8 16.2 100.0

FA-16B

Cent. 1164 No. 5 1.2 0.72 Cond. pH = 9.1+

Conc. Tail. Feed

14.3 85.7 100.0

22.69 1.84 4.83

33.00 93.55 84.89

67.3 32.7 100.0

FA-16A

Cent. 1164 No. 5 1.4 0.84 Cond. pH = 9.0+

Conc. Tail. Feed

27.4 72.6 100.0

16.02 0.69 4.89

52.05 97.08 84.74

89.8 10.2 100.0

FA-16

Cent. 1164 No. 5 1.6 0.96 Cond. pH = 9.0-

Conc. Tail. Feed

62.7 37.3 100.0

7.16 1.12 4.91

78.35 95.70 84.82

91.4 8.6 100.0

4-20

Table 4-9 (Cont.). Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Feed (5% P2O5). Test No. FA-17B

Collector, Lb./TF Fatty Acid Fuel Oil Cent. MO-5 No. 5 1.4 0.84 Cond. pH = 9.0+

Flotation Product % Wt. Conc. 14.6 Tail. 85.4 Feed 100.0

Analysis % P2O5 % Insol 25.04 26.23 1.36 94.97 4.82 84.93

% Dist. P2O5 75.9 24.1 100.0

FA-17A

No. 5 Cent. MO-5 1.6 0.96 Cond. pH = 9.0-

Conc. Tail. Feed

16.3 83.7 100.0

25.36 1.19 5.12

24.95 95.43 83.94

80.7 19.3 100.0

FA-17

Cent. MO-5 No. 5 1.8 1.08 Cond. pH = 9.0

Conc. Tail. Feed

21.5 78.5 100.0

21.66 0.53 5.08

35.90 97.56 84.30

91.7 8.3 100.0

52

Oleic Acid No. 5 1.2 0.72 Cond. pH = 9.1+

Conc. Tail. Feed

10.7 89.3 100.0

23.10 2.92 5.08

31.85 90.89 84.57

48.6 51.4 100.0

51

Oleic Acid No. 5 1.4 0.84 Cond. pH = 9.0

Conc. Tail. Feed

25.9 74.1 100.0

15.61 1.25 4.97

53.06 95.69 84.75

81.3 18.7 100.0

54

Oleic Acid No. 5 1.6 0.96 Cond. pH = 9.1-

Conc. Tail. Feed

26.8 73.2 100.0

16.71 0.89 5.13

49.88 96.82 84.24

87.3 12.7 100.0

1

Liqro GA No. 5 1.0 0.60 Cond. pH = 8.9

Conc. Tail. Feed

8.8 91.2 100.0

25.70 3.05 5.04

23.58 90.44 84.56

44.8 55.2 100.0

9

Liqro GA No. 5 1.2 0.72 Cond. pH = 9.0-

Conc. Tail. Feed

19.0 81.0 100.0

19.08 1.60 4.93

43.25 94.76 84.97

73.6 26.4 100.0

4

Liqro GA No. 5 1.4 0.84 Cond. pH = 8.9

Conc. Tail. Feed

32.0 68.0 100.0

13.51 0.94 4.96

59.51 96.55 84.69

87.1 12.9 100.0

FA-O

Liqro GA No. 5 1.6 0.96 Cond. pH = 9.1+

Conc. Tail. Feed

31.2 68.8 100.0

14.35 0.70 4.96

57.37 97.57 84.99

90.3 9.7 100.0

4-21

Table 4-10. Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with PCS Feed (10% P2O5). Test No. PCS-14

Collector, Lb./TF Fatty Acid Fuel Oil Cent. 1105 No. 5 1.2 0.72 Cond. pH = 9.0+

Flotation Product % Wt. Conc. 20.8 Tail. 79.2 Feed 100.0

Analysis % P2O5 % Insol 31.76 6.74 4.21 87.18 9.94 70.45

% Dist. P2O5 66.5 33.5 100.0

PCS-15

Cent. 1105 No. 5 1.4 0.84 Cond. pH = 9.1-

Conc. Tail. Feed

27.1 72.9 100.0

30.56 2.27 9.93

9.94 92.78 70.33

83.4 16.6 100.0

PCS-16

Cent. 1105 No. 5 1.6 0.96 Cond. pH = 9.0+

Conc. Tail. Feed

32.0 68.0 100.0

29.37 0.75 9.91

13.32 97.25 70.39

94.8 5.2 100.0

PCS-1

Cent. 1108 No. 5 1.0 0.60 Cond. pH = 9.2-

Conc. Tail. Feed

17.7 82.3 100.0

32.46 5.59 10.35

4.31 83.07 69.13

55.6 44.4 100.0

PCS-2

Cent. 1108 No. 5 1.2 0.72 Cond. pH = 9.1

Conc. Tail. Feed

23.6 76.4 100.0

31.74 3.62 10.26

6.16 88.83 69.32

73.0 27.0 100.0

PCS-3

Cent. 1108 No. 5 1.4 0.84 Cond. pH = 9.1+

Conc. Tail. Feed

30.3 69.7 100.0

31.18 1.23 10.31

7.65 95.79 69.08

91.7 8.3 100.0

PCS-4

Cent. 1108 No. 5 1.6 0.96 Cond. pH = 9.0

Conc. Tail. Feed

32.7 67.3 100.0

30.72 0.41 10.20

8.34 98.24 68.85

98.5 1.5 100.0

PCS-5

Cent. 1164 No. 5 1.2 0.72 Cond. pH = 9.2+

Conc. Tail. Feed

28.7 71.3 100.0

29.61 2.62 10.37

12.06 91.61 68.78

82.0 18.0 100.0

PCS-6

Cent. 1164 No. 5 1.4 0.84 Cond. pH = 9.2-

Conc. Tail. Feed

34.2 65.8 100.0

29.11 0.60 10.35

13.30 97.67 68.82

96.2 3.8 100.0

4-22

Table 4-10 (Cont.). Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with PCS Feed (10% P2O5). Test No. PCS-7

Collector, Lb./TF Fatty Acid Fuel Oil Cent. 1164 No. 5 1.6 0.96 Cond. pH = 9.1

Flotation Product % Wt. Conc. 38.9 Tail. 61.1 Feed 100.0

Analysis % P2O5 % Insol 25.23 24.45 0.37 98.31 10.04 69.58

% Dist. P2O5 97.7 2.3 100.0

PCS-8

Cent. MO-5 No. 5 1.2 0.72 Cond. pH = 9.1+

Conc. Tail. Feed

22.9 77.1 100.0

31.64 3.63 10.05

6.56 88.83 69.99

72.1 27.9 100.0

PCS-9

Cent. MO-5 No. 5 1.4 0.84 Cond. pH = 9.1-

Conc. Tail. Feed

33.2 66.8 100.0

29.44 0.67 10.22

12.83 97.45 69.36

95.6 4.4 100.0

PCS-10

No. 5 Cent. MO-5 1.6 0.96 Cond. pH = 9.1-

Conc. Tail. Feed

36.1 63.9 100.0

27.82 0.34 10.26

17.55 98.43 69.23

97.8 2.2 100.0

PCS-19

Oleic Acid No. 5 1.2 0.72 Cond. pH = 9.1+

Conc. Tail. Feed

18.9 81.1 100.0

31.85 5.25 10.28

6.12 84.20 69.45

58.6 41.4 100.0

PCS-18

Oleic Acid No. 5 1.4 0.84 Cond. pH = 9.0+

Conc. Tail. Feed

26.3 73.7 100.0

30.92 2.17 9.73

9.35 93.33 71.24

83.5 16.4 100.0

PCS-17

Oleic Acid No. 5 1.6 0.96 Cond. pH = 9.2-

Conc. Tail. Feed

32.1 67.9 100.0

29.48 1.22 10.29

12.73 95.84 69.16

91.9 8.1 100.0

PCS-11

Liqro GA No. 5 1.2 0.72 Cond. pH = 9.2-

Conc. Tail. Feed

26.1 73.9 100.0

29.78 2.96 9.96

11.91 90.71 70.04

78.0 22.0 100.0

PCS-12

Liqro GA No. 5 1.4 0.84 Cond. pH = 9.1+

Conc. Tail. Feed

33.4 66.6 100.0

28.49 0.74 10.01

15.23 97.26 69.87

95.1 4.9 100.0

PCS-13

Liqro GA No. 5 1.6 0.96 Cond. pH = 9.2-

Conc. Tail. Feed

35.4 64.6 100.0

27.58 0.53 10.10

18.24 97.90 69.70

96.6 3.4 100.0

4-23

DETAILED TESTS ON DIFFERENT FEEDS USING THE BEST ISOCOLLECTORS INTRODUCTION Previous tests showed that the iso acid collectors were generally more selective and pulled more coarse phosphate particles, with century 1108 and MO-5 being more suitable overall. Detailed tests were therefore designed to compare flotation test results obtained using the two International Paper “iso acid” reagents, Century 1108 and Century MO-5, with those obtained using Liqro GA Tall Oil and commercial Oleic Acid 401. Three different central Florida plant feed samples, including one coarse feed, were obtained and used for this testwork. Production of a 30+% P2O5 concentrate at greater than 85% P2O5 recovery during single-stage rougher flotation was the primary objective of these recent flotation tests. SUMMARY Size/assay analyses were performed on the three most recent feed samples obtained from local phosphate producers including Cargill, IMC and CF. A total of 56 rougher flotation tests, including several tests using one cleaner flotation stage, were performed comparing the four collectors described in the Introduction of this report. Overall flotation results supported previous findings for PCS and IMC fine feed samples and showed that concentrates analyzing 28-29+% P2O5/9-13% Insol at 90+% P2O5 recovery could be produced from the Cargill and CF feed samples using the two Century “iso-acid” collectors. Parallel flotation tests performed using the IMC “coarse” feed sample yielded even better results and produced rougher concentrates analyzing 3031+% P2O5/9-11% Insol at about 92-94+% P2O5 recovery. Cleaner flotation performed using N-silicate and selected test conditions with the three feeds resulted in slight further upgrading of rougher concentrates at about 3-5% P2O5 open circuit recovery loss. Dry screening of two selected 27-28% P2O5/12-13% Insol rougher concentrates (Cargill and CF) showed that the +65 or +100 mesh concentrate size fractions contained 29-30% P2O5 and about 10% Insol or less. The finer concentrate size fractions generally contained greater than 19% Insol. Further upgrading of the selected rougher concentrate -65 mesh or -100 mesh size fractions was concluded to be necessary to produce overall rougher concentrates containing less than 10% Insol. These “fine” size fractions comprised 26% by weight or less of the total flotation concentrates. Future tests will emphasize rougher concentrate sizing and cleaner flotation of only the “fines” without additional reagent usage.

4-24

EXPERIMENTAL Description of Flotation Feed Samples Three different flotation feed samples were used for the current flotation testwork summarized in this report. A sample of Cargill fine feed (5.3% P2O5) containing brown, black and white phosphate plus a small amount of dolomite. Size/assay analysis of this sample is shown in Table 4-11. Table 4-11. Size/Assay Analysis of the Flotation Feed from Cargill. Size, Tyler Mesh +28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total

0.3 1.9 12.3 24.8 32.8 15.5 10.5 1.9 100.0

Cum. % Wt. 0.3 2.2 14.5 39.3 72.1 87.6 98.1 100.0 --

-28 -35

99.7 99.8

---

% Wt.

10.98 67.46 82.73 83.19 80.34 87.17 88.09 72.98 82.62

% Dist. P2O5 1.6 3.6 12.4 24.7 37.9 11.6 6.7 1.5 100.0

Cum. % Dist. P2O5 1.6 5.2 17.6 42.3 80.2 91.8 98.5 100.0 --

82.84 83.13

98.4 94.8

---

% P2O5

% Insol

28.44 10.20 5.42 5.33 6.20 4.01 3.42 4.38 5.36 5.30 5.20

This size/assay analysis shows that only 5.2% of the total feed P2O5 was present in the +35 mesh size fraction. The Cargill feed was considered to be noticeably slimy and contained almost 2% by weight of -200 mesh particles. A sample of IMC Kingsford coarse feed (Table 4-12) containing mostly tan phosphate was tested second. This size/assay analysis reveals that almost 80% by weight, representing about 90% of the total phosphate values, was present in the +48 mesh size fractions. This IMC coarse feed was well deslimed and contained only 0.1% by weight of -200 mesh particles. Finally, a sample of CF Hardee, unsized flotation feed (Table 4-13) was tested. This feed contains mostly tan phosphate, and a small amount of dolomite.

4-25

Table 4-12. Size/Assay Analysis of the IMC Kingsford Coarse Flotation Feed. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total +35 +48

4.3 19.4 29.1 25.8 14.4 5.1 1.1 0.7 0.1 100.0

Cum. % Wt. 4.3 23.7 52.8 78.6 93.0 98.1 99.2 99.9 100.0 --

52.8 78.6

---

% Wt.

24.36 19.76 12.11 6.92 4.85 6.58 8.15 6.90

29.09 41.89 64.04 79.22 85.42 80.20 75.37 77.83

% Dist. P2O5 9.2 33.7 31.0 15.7 6.2 3.0 0.8 0.4

11.37

66.29

100.0

--

15.91 12.96

53.05 61.64

73.9 89.6

---

% P2O5

% Insol

Cum. % Dist. P2O5 9.2 42.9 73.9 89.6 95.8 98.8 99.6 100.0

Table 4-13. Size/Assay Analysis of the CF Unsized Flotation Feed. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 150/200 -200 Total -28 -35

2.0 4.3 11.8 24.1 30.7 21.0 4.9 0.9 0.3 100.0

Cum. % Wt. 2.0 6.3 18.1 42.2 72.9 93.9 98.8 99.7 100.0 --

93.7 81.9

---

% Wt.

25.18 20.75 16.37 10.70 6.54 4.89 5.15 4.38

16.78 33.29 48.52 67.05 80.09 84.81 80.56 79.49

% Dist. P2O5 5.4 9.6 20.9 27.9 21.8 11.1 2.7 0.5

9.24

70.95

100.0

--

8.38 7.23

73.83 77.48

85.0 64.1

---

% P2O5

% Insol

Cum.% Dist. P2O5 5.4 15.0 35.9 63.8 85.6 96.7 99.4 100.0

This size/assay analysis shows that the CF feed contained about 18% by weight of +35 mesh particles representing 36% of the total phosphate values present in the feed sample. The feed was considered to be fairly well deslimed and contained 0.3% by weight of -200 mesh particles. This feed, after conditioning at about 73% solids with flotation reagents, produced a peculiar yellowish-colored turbid feed slurry; this was probably the result of clay-chip breakdown.

4-26

RESULTS AND DISCUSSION Flotation of Cargill Fine Feed Using Various Fatty Acid Collectors Rougher flotation test results obtained using the Cargill fine feed sample are listed in Table 4A-1, and are presented in graphical form in Figures 4-9 through 4-12. Examination of the concentrate % P2O5 grade and % P2O5 recovery results shows that Century 1108, Century MO-5 and Oleic Acid 401 were the most selective collectors when the flotation % P2O5 recovery was at least 90%, with Century 1108 having a slight superiority. Test CA-1 concentrate analyzed 28.34% P2O5/11.37% Insol at 90.2% P2O5 recovery using 1.2 lb. of Century 1108 per ton of feed. Test CA-5 concentrate analyzed 27.92% P2O5/13.47% Insol at 90.8% P2O5 recovery using 1.2 lb. of Century MO-5 per ton of feed. Finally, Test CA-14 concentrate analyzed 27.50% P2O5/14.20% Insol at 90.7% P2O5 recovery using Oleic Acid 401, however 1.6 lb./TF was required. 32

30

% P2O5

28

26

Century 1108 Century MO-5

24

Oleic acid Liqro GA

22

20 0.8

0.9

1

1.1

1.2

1.3

1.4

1.5

1.6

1.7

Collector Dosage, lb/Ton Feed

Figure 4-9. Concentrate % P2O5 vs. Collector Dosage at pH 9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed. 4-27

30

25

% Insol

20

15

10 Century 1108 Century MO-5 Oleic acid

5

Liqro GA

0 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 4-10. Concentrate % Insol vs. Collector Dosage at pH 9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed.

4-28

100

90

80

% P2O5 Recovery

70

60

50

Century 1108 Century MO-5 Oleic acid

40

Liqro GA

30

20

10

0 0.8

1

1.2

1.4

1.6

1.8

Collector Dosage, lb/Ton Feed

Figure 4-11. Flotation Recovery vs. Collector Dosage at pH 9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed.

4-29

100

95

90

% P2O5 Recovery

85

80

75

Century 1108 Century MO-5 Oleic acid

70

Liqro GA

65

60

55

50 20

22

24

26

28

30

Concentrate % P2O5

Figure 4-12. Concentrate Grade vs. Recovery at pH 9 and Collector-to-FuelOil Ratio of 1:0.6 for Cargill Feed.

4-30

32

Test CA-5 concentrate was subjected to a brief size/assay analysis. The P2O5 and Insol analyses and distributions by size fraction are shown in Table 4-14. Table 4-14. Size/Assay Analysis of a Rougher Concentrate from Cargill Feed Using MO-5 Collector. Size, Tyler Mesh +48 48/65 65/100 -100 Total

% Wt.

% P2O5

% Insol

% Dist. P2O5

12.8 23.0 33.9 30.3 100.0

30.92 30.02 28.50 23.84 27.74

5.79 8.47 12.47 22.16 13.63

14.3 24.9 34.8 26.0 100.0

Cum. % Wt.

Cum. % P2O5

Cum. % Insol

12.8 35.8 69.7 100.0 --

30.92 30.34 29.44 27.74 --

5.79 7.51 9.93 13.63 --

Cum. % Dist. P2O5 14.3 39.2 74.0 100.0 --

The size/assay analysis shows that the finer size fractions of this concentrate contain the highest % Insol content. Removal of the -100 mesh size fraction resulted in upgrading the final concentrate from 27.74% P2O5/13.36% Insol (calculated) to 29.44% P2O5/9.93% Insol at 74.0% P2O5 recovery from the total concentrate. Flotation of Cargill Fine Feed Using Century 1108 and Century MO-5 with N-Silicate In an attempt to produce concentrates analyzing greater than 29% P2O5 at 90+% P2O5 recovery, tests were performed using 0.6 lb. of N-Silicate per ton of feed as a selectivity enhancer. A single cleaner float was performed to observe any concentrate grade improvements. Results are presented in Table 4A-2 and Figure 4-13. Test CA-4S produced a rougher concentrate analyzing 29.31% P2O5/9.75% Insol at 89.1% P2O5 recovery using 1.6 lb. of Century 1108 per ton of feed. After cleaner flotation, the concentrate analyzed 30.60% P2O5/6.14% Insol at 85.5% P2O5 recovery overall. Test CA-5S produced a rougher concentrate analyzing 27.86% P2O5/13.58% Insol at 92.7% P2O5 recovery using 1.2 lb. of the less expensive Century MO-5 per ton of feed. After cleaner flotation, the final concentrate analyzed 29.48% P2O5/8.82% Insol at 89.6% P2O5 recovery overall. In summary, cleaner flotation resulted in concentrates analyzing 2930+% P2O5 at 85-90% P2O5 recovery overall. Flotation of IMC Coarse Feed Using Various Fatty Acid Collectors Rougher flotation test results obtained using the IMC Kingsford coarse feed sample were excellent and are presented in Table 4A-3. Figures 4-14 and 4-15 summarize these results graphically for easier comparison. Examination of the concentrate % P2O5 grade vs. % P2O5 recovery results shows that all four collectors produced 30+% P2O5 concentrates at 90% or higher % P2O5 recovery. Test K-4 concentrate analyzed 31.20% P2O5/9.21% Insol at 94.9% P2O5 recovery using 2.0 lb. of Century 1108 per ton of feed. Test K-8 concentrate analyzed 30.68% P2O5/10.82% Insol 4-31

at 94.8% P2O5 recovery using 2.0 lb. of Century MO-5 per ton of feed. Best results using Oleic Acid 401 were obtained from test K-17. The test K-17 concentrate analyzed only 29.85% P2O5/13.09% Insol at 91.3% P2O5 recovery using 2.0 lb. of collector per ton of feed. Also, the best results using Liqro GA tall oil were obtained from test K-13. The Test K-13 concentrate analyzed 30.26% P2O5/11.85% Insol at 91.0% P2O5 recovery using 2.4 lb. of collector per ton of feed. 100

95

% P2O5 Recovery

90

85 Century 1108 Century MO-5 Century MO-5 with silicate Century 1108 with silicate

80

75

70 22

24

26

28

30

32

Concentrate % P2O5

Figure 4-13. Concentrate Grade vs. Recovery at pH 9 and Collector-to-Fuel-Oil Ratio of 1:0.6 for Cargill Feed with N-Silicate.

4-32

33

32

31

% P2O5

30

29

Century 1108 Century MO-5 Oleic acid

28

Liqro GA Century MO-5 with silicate

27

26 1

1.2

1.4

1.6

1.8

2

2.2

2.4

Collector Dosage

Figure 4-14. Concentrate % P2O5 vs. Collector Dosage at pH 9 and Collector-toFuel-Oil Ratio of 1:0.8 for Kingsford Coarse Feed.

4-33

2.6

20

18

Century 1108 (Insol)

16

Century MO-5 Oleic acid (Insol) Liqro GA (Insol)

14

Century MO-5 with silicate (insol)

% Insol

12

10

8

6

4

2

0 1

1.2

1.4

1.6

1.8

2

2.2

2.4

2.6

Collector Dosage

Figure 4-15. Concentrate % Insol vs. Collector Dosage at pH 9 and Collector-toFuel-Oil Ratio of 1:0.8 for Kingsford Coarse Feed.

4-34

33

32.5

Concentrate % P2O5

32

31.5

31

30.5

Century 1108

30

Century MO-5 Oleic acid Liqro GA Century MO-5 with silicate

29.5

29 0

20

40

60

80

100

120

% P2O5 Recovery

Figure 4-16. Concentrate % P2O5 vs. Recovery at pH 9 and Collector-to-Fuel-Oil Ratio of 1:0.8 for Kingsford Coarse Feed.

4-35

Flotation of IMC Coarse Feed Using Century MO-5 with N-Silicate Two rougher-cleaner flotation tests were performed using two levels of Century MO-5 collector with 0.6 lb. of N-Silicate per ton of feed for selectivity improvement. Material balances for these tests are shown in Table 4A-4. Tests K-8S and K-9S, using 2.0 and 2.4 lb. of collector, respectively, per ton of feed illustrate that rougher concentrates analyzing 29.74% P2O5/12.71% Insol at 95.0% P2O5 recovery and 29.37% P2O5/13.99% Insol at 96.2% P2O5 recovery were produced. Cleaner flotation yielded final concentrates analyzing 31+% P2O5 and less than 9% Insol at about 90-92% P2O5 recovery overall. Flotation of CF Feed Using Various Fatty Acid Collectors Rougher flotation test results obtained using the CF feed sample are shown in Table 4A-5, and are presented in graphical form in Figures 4-17 and 4-18. Material balances for these tests are shown in Table 4A-6. For a flotation % P2O5 recovery of about 90%, Century 1108, Century MO-5 and Oleic Acid 401 again appear to be the most selective collectors, with Century 1108 and Oleic Acid 401 having a slight superiority. Century MO-5 followed by Century 1108 were the strongest collectors and required 1.11.2 lb./TF for 90% flotation % P2O5 recovery, whereas Oleic Acid 401 required about 1.6 lb./TF to obtain similar results. Test CF-1 concentrate analyzed 29.49% P2O5/9.78% Insol at 91.5% P2O5 recovery using 1.2 lb. of Century 1108 per ton of feed. Test CF-5 concentrate analyzed 28.39% P2O5/12.46% Insol at 93.5% P2O5 recovery using 1.2 lb. of Century MO-5 per ton of feed. Best results using Oleic Acid 401 were obtained from Test CF-11 whose concentrate analyzed 28.56% P2O5/11.87% Insol at 90.5% P2O5 recovery using 1.6 lb. of collector per ton of feed. Finally, best results using Liqro GA tall oil were obtained from Test 13. This test concentrate analyzed 28.17% P2O5/13.35% Insol at 92.3% P2O5 recovery using 1.4 lb. of collector per ton of feed. Test CF-5 concentrate also was subjected to a brief size/assay analysis. The P2O5 and Insol analyses and distributions by size fraction are shown in Table 4-15. Table 4-15. Size/Assay Analysis of Rougher Concentrate from CF Feed Using MO-5. Size, Tyler % Wt. Mesh +48 57.4 48/65 23.5 65/100 14.0 -100 5.1 Total 100.0

% P2O5

% Insol

29.95 27.92 26.33 21.43 28.53

8.26 15.96 19.72 27.17 12.63

% Dist. P2O5

Cum. % Wt.

Cum. % P2O5

Cum. % Insol

60.3 23.0 12.9 3.8 100.0

57.4 80.9 94.9 100.0 --

29.95 29.36 28.91 28.53 --

8.26 10.49 11.85 12.63 --

Cum. % Dist. P2O5 60.3 83.3 96.2 100.0 --

This size/assay analysis again shows that the finer size fractions of the concentrate contain the highest % Insol content like the two previously-described screened 4-36

concentrates. Removal of the -100 mesh size fraction resulted in upgrading the final concentrate from 28.53% P2O5/12.63% Insol (calculated) to 28.91% P2O5/11.85% Insol at 96.2% P2O5 recovery from the total concentrate. 35

% P 2O 5

30

Century 1108 Century MO-5 Oleic acid Liqro GA Century MO-5 with silicate Century 1108 (Insol) Century MO-5 Oleic acid (Insol) Liqro GA (Insol) Century MO-5 with silicate (insol)

25

20

% Insol

15

10

5

0 0.8

1

1.2

1.4

1.6

1.8

Collector Collector Dosage Dossage

Figure 4-17. Concentrate % P2O5 and Insol vs. Collector Dosage at pH 9 and Collector-to-Fuel-Oil Ratio of 1:0.8 for CF Unsized Feed.

4-37

2

32

30

Concentrate % P2O5

28

Century 1108 Century MO-5 Oleic acid 26

Liqro GA Century MO-5 with silicate

24

22

20 80

82

84

86

88

90

92

94

96

98

100

% P2O5 Recovery

Figure 4-18. Concentrate % P2O5 vs. Recovery at pH 9 and Collector-to-Fuel-Oil Ratio of 1:0.8 for CF Unsized Feed.

4-38

Flotation of CF Feed Using Century MO-5 with N-Silicate Two rougher-cleaner flotation tests were performed using two different levels of Century MO-5 collector with 0.6 lb./ton of N-silicate per ton of feed to improve quartz depression. Material balances for these tests are presented in Table 4A-6. Tests CF-5S and CF-6S, using 1.2 and 1.4 lb. of collector per ton of feed respectively, show that rougher concentrates analyzing 29.00% P2O5/11.25% Insol at 89.9% P2O5 recovery, and 28.03% P2O5/14.02% Insol at 94.4% P2O5 recovery were obtained. Cleaner flotation yielded final concentrates analyzing near or slightly above 30% P2O5 and less than 9% Insol at about 86-91+% P2O5 recovery overall.

4-39

Appendix 4 TABLES FROM ISO-ACIDS EVALUATION

Table 4A-1. Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with Cargill Feed. Test No. CA-3

Collector, Lb./TF Fatty Acid Fuel Oil Century 1108 No. 5 1.0 0.60 Cond. pH = 9.2+

Flotation Product % Wt. Conc. 3.6 Tail. 96.4 Feed 100.0

Analysis % P2O5 % Insol 26.62 17.27 4.57 85.51 5.37 83.05

% Dist. P2O5 17.9 82.1 100.0

CA-1

Century 1108 1.2 Cond. pH = 8.9

No. 5 0.72

Conc. Tail. Feed

16.6 83.4 100.0

28.34 0.61 5.21

11.37 97.65 83.33

90.2 9.8 100.0

CA-2

Century 1108 No. 5 1.4 0.84 Cond. pH = 9.1-

Conc. Tail. Feed

17.4 82.6 100.0

28.52 0.40 5.29

11.32 98.35 83.21

93.8 6.2 100.0

CA-4

Century 1108 No. 5 1.6 0.96 Cond. pH = 9.1+

Conc. Tail. Feed

17.2 82.8 100.0

28.44 0.46 5.27

11.24 98.15 83.20

92.8 7.2 100.0

CA-5

Century MO-5 1.2 Cond. pH = 9.3

No. 5 0.72

Conc. Tail. Feed

17.0 83.0 100.0

27.92 0.58 5.23

13.47 97.81 83.47

90.8 9.2 100.0

CA-6

Century MO-5 1.4 Cond. pH = 9.3

No. 5 0.84

Conc. Tail. Feed

20.0 80.0 100.0

25.46 0.26 5.30

20.45 98.88 83.19

96.0 4.0 100.0

CA-7

Century MO-5 1.6 Cond. pH = 9.2

No. 5 0.96

Conc. Tail. Feed

20.7 79.3 100.0

24.55 0.23 5.26

22.85 99.81 83.88

96.6 3.4 100.0

4A-1

Table 4A-1 (Cont.). Flotation Test Material Balances Using Various Fatty Acid Type Collectors with Cargill Feed. Test No. CA-11

Collector, Lb./TF Fatty Acid Fuel Oil Liqro GA No. 5 1.0 0.60 Cond. pH = 9.2

Flotation Product % Wt. Conc. 16.0 Tail. 84.0 Feed 100.0

Analysis % P2O5 % Insol 27.34 14.91 1.02 96.43 5.23 83.39

% Dist. P2O5 83.6 16.4 100.0

CA-8

Liqro GA No. 5 1.0 0.72 Cond. pH = 9.2+

Conc. Tail. Feed

17.5 82.5 100.0

26.60 0.72 5.25

18.18 97.36 83.50

88.8 11.2 100.0

CA-9

Liqro GA No. 5 1.0 0.84 Cond. pH = 9.2+

Conc. Tail. Feed

20.7 79.3 100.0

23.87 0.39 5.25

25.50 98.41 83.32

94.1 5.9 100.0

CA-10

Liqro GA 1.0 Cond. pH = 9.2

No. 5 0.96

Conc. Tail. Feed

21.3 78.7 100.0

23.88 0.28 5.31

25.47 98.80 83.18

95.8 4.2 100.0

CA-12

Oleic Acid 1.2 Cond. pH = 9.2

No. 5 0.72

Conc. Tail. Feed

12.2 87.8 100.0

29.71 1.66 5.08

8.30 94.39 83.88

71.3 28.7 100.0

CA-13

Oleic Acid 1.4 Cond. pH = 9.0

No. 5 0.84

Conc. Tail. Feed

15.0 85.0 100.0

29.02 1.02 5.22

10.12 96.38 83.44

83.3 16.7 100.0

CA-14

Oleic Acid No. 5 1.6 0.96 Cond. pH = 9.1-

Conc. Tail. Feed

17.4 82.6 100.0

27.50 0.60 5.28

14.20 97.66 83.14

90.7 9.3 100.0

4A-2

Table 4A-2. Flotation Test Results Using Century MO-5 and Century 1108 Collector Plus Cargill Feed with N-Silicate Addition. Test No.

CA-S

CA-4S

CA-5S

CA-6S

CA-7S

Collector, Lb./TF Flotation Fatty Acid Fuel Oil Product % Wt. Century 1108 No. 5 Ro. Conc. 14.7 1.4 0.84 Ro. Tail. 85.3 Cond. pH = 9.3 Ro. Feed 100.0

Century 1108 1.6 Cond. pH = 9.3-

Century MO-5 1.2 Cond. pH = 9.2+

Century MO-5 1.4 Cond. pH = 9.3-

Century MO-5 1.6 Cond. pH = 9.3

No. 5 0.96

No. 5 0.72

No. 5 0.84

No. 5 0.96

Analysis % P2O5 % Insol 29.59 9.52 1.01 96.23 5.21 83.48

% Dist. P2O5 83.5 16.5 100.0

Cl. Conc. Cl. Tail.

12.9 1.8

31.10 19.10

5.55 37.87

77.0 6.5

Ro. Conc. Ro. Tail. Ro. Feed

15.9 84.1 100.0

29.31 0.68 5.23

9.75 97.15 83.25

89.1 10.9 100.0

Cl. Conc. Cl. Tail.

14.6 1.3

30.60 14.79

6.14 50.22

85.5 3.6

Ro. Conc. Ro. Tail. Ro. Feed

17.3 82.7 100.0

27.86 0.46 5.20

13.58 98.04 83.53

92.7 7.3 100.0

Cl. Conc. Cl. Tail.

15.8 1.5

29.48 10.73

8.82 63.84

89.6 3.1

Ro. Conc. Ro. Tail. Ro. Feed

18.5 81.5 100.0

26.76 0.32 5.21

16.38 98.53 83.33

95.0 5.0 100.0

Cl. Conc. Cl. Tail.

17.1 1.4

28.45 6.37

11.27 78.63

93.3 1.7

Ro. Conc. Ro. Tail. Ro. Feed

19.1 80.9 100.0

26.23 0.25 5.21

18.17 98.76 83.37

96.2 3.8 100.0

Cl. Conc. Cl. Tail.

17.7 1.4

27.96 4.45

12.89 84.87

95.0 1.2

4A-3

Table 4A-3. Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Kingsford Coarse Feed (11% P2O5). Test No. K-1

Collector, Lb./TF Fatty Acid Fuel Oil Century 1108 No. 5 1.4 1.12 Cond. pH = 8.9

Flotation Product % Wt. Conc. 15.9 Tail. 84.1 Feed 100.0

Analysis % P2O5 % Insol 32.56 5.71 6.74 80.11 10.85 68.28

% Dist. P2O5 47.7 52.3 100.0

K-2

Century 1108 1.6 Cond. pH = 9.0

No. 5 1.28

Conc. Tail. Feed

30.4 69.6 100.0

32.47 1.76 11.09

5.85 94.07 67.25

89.0 11.0 100.0

K-3

Century 1108 1.8 Cond. pH = 8.9

No. 5 1.44

Conc. Tail. Feed

31.0 69.0 100.0

32.41 1.49 11.08

6.45 94.28 67.05

90.7 9.3 100.0

K-4

Century 1108 2.0 Cond. pH = 8.9

No. 5 1.60

Conc. Tail. Feed

33.7 66.3 100.0

31.20 0.85 11.07

9.21 96.64 67.17

94.9 5.1 100.0

K-5

Century 1108 2.4 Cond. pH = 8.9

No. 5 1.92

Conc. Tail. Feed

33.9 66.1 100.0

31.07 0.75 11.03

9.71 97.05 67.44

95.5 4.5 100.0

K-6

Century MO-5 1.6 Cond. pH = 8.9

No. 5 1.28

Conc. Tail. Feed

29.9 70.1 100.0

31.76 2.19 11.04

8.02 92.88 67.51

86.1 13.9 100.0

K-7

Century MO-5 1.8 Cond. pH = 8.9

No. 5 1.44

Conc. Tail. Feed

30.1 69.9 100.0

31.79 2.10 11.04

7.82 93.10 67.43

86.7 13.3 100.0

K-8

Century MO-5 2.0 Cond. pH = 8.9

No. 5 1.60

Conc. Tail. Feed

34.4 65.6 100.0

30.68 0.89 11.13

10.82 96.59 67.08

94.8 5.2 100.0

K-9

Century MO-5 2.4 Cond. pH = 8.9

No. 5 1.92

Conc. Tail. Feed

36.4 63.6 100.0

29.57 0.53 11.10

13.85 97.53 67.07

96.9 3.1 100.0

4A-4

Table 4A-3 (Cont.). Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with IMC Kingsford Coarse Feed (11% P2O5). Test No. K-10

Collector, Lb./TF Fatty Acid Fuel Oil Liqro GA No. 5 1.6 1.28 Cond. pH = 9.1+

Flotation Product % Wt. Conc. 10.9 Tail. 89.1 Feed 100.0

Analysis % P2O5 % Insol 31.72 7.98 8.28 75.54 10.84 68.18

% Dist. P2O5 31.9 68.1 100.0

K-11

Liqro GA 1.8 Cond. pH = 9.2

No. 5 1.44

Conc. Tail. Feed

24.9 75.1 100.0

31.77 4.30 11.14

8.10 87.01 67.36

71.0 29.0 100.0

K-12

Liqro GA 2.0 Cond. pH = 9.2-

No. 5 1.60

Conc. Tail. Feed

27.6 72.4 100.0

31.26 3.39 11.08

9.35 89.48 67.37

77.9 22.1 100.0

K-13

Liqro GA 2.4 Cond. pH = 9.0-

No. 5 1.92

Conc. Tail. Feed

33.8 66.2 100.0

30.26 1.53 11.24

11.85 94.81 66.77

91.0 9.0 100.0

K-14

Oleic Acid 1.6 Cond. pH = 9.0+

No. 5 1.28

Conc. Tail. Feed

10.3 89.7 100.0

30.44 8.56 10.82

12.10 74.65 68.21

29.0 71.0 100.0

K-15

Oleic Acid 1.8 Cond. pH = 8.9-

No. 5 1.44

Conc. Tail. Feed

24.7 75.3 100.0

31.78 4.02 10.88

8.06 87.22 67.67

72.2 27.8 100.0

K-17

Oleic Acid 2.0 Cond. pH = 8.9-

No. 5 1.60

Conc. Tail. Feed

34.2 65.8 100.0

29.85 1.47 11.18

13.09 94.58 67.71

91.3 8.7 100.0

K-16

Oleic Acid 2.4 Cond. pH = 8.9+

No. 5 1.92

Conc. Tail. Feed

35.1 64.9 100.0

29.45 1.02 11.00

17.46 95.75 68.27

94.0 6.0 100.0

4A-5

Table 4A-4. Flotation Test Results Using Century MO-5 Collector Plus IMC Kingsford Coarse Feed with N-Silicate Addition. Test No.

K-8S

K-9S

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 2.0 1.60 Cond. pH = 9.1

Century MO-5 2.4 Cond. pH = 9.1+

No. 5 1.92

Flotation Product % Wt. Ro. Conc. 35.1 Ro. Tail. 64.9 Ro. Feed 100.0

Analysis % P2O5 % Insol 29.74 12.71 0.85 96.62 10.99 67.17

% Dist. P2O5 95.0 5.0 100.0

Cl. Conc. Cl. Tail.

31.3 3.8

31.52 15.09

7.65 54.36

89.8 5.2

Ro. Conc. Ro. Tail. Ro. Feed

36.3 63.7 100.0

29.37 0.67 11.09

13.99 97.11 66.96

96.2 3.8 100.0

Cl. Conc. Cl. Tail.

32.4 3.9

31.45 11.91

8.09 63.20

91.9 4.3

4A-6

Table A4-5. Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with CF Feed (9% P2O5). Test No. CF-1

Collector, Lb./TF Fatty Acid Fuel Oil Century 1108 No. 5 1.2 0.96 Cond. pH = 9.2

Flotation Product % Wt. Conc. 28.2 Tail. 71.8 Feed 100.0

Analysis % P2O5 % Insol 29.49 9.78 1.07 95.54 9.09 71.36

% Dist. P2O5 91.5 8.5 100.0

CF-2

Century 1108 1.4 Cond. pH = 9.1+

No. 5 1.12

Conc. Tail. Feed

29.8 70.2 100.0

28.70 0.74 9.07

12.31 96.81 71.63

94.3 5.7 100.0

CF-3

Century 1108 1.6 Cond. pH = 9.2

No. 5 1.28

Conc. Tail. Feed

31.4 68.6 100.0

27.96 0.46 9.10

14.05 97.76 71.47

96.5 3.5 100.0

CF-4

Century 1108 1.8 Cond. pH = 9.1

No. 5 1.44

Conc. Tail. Feed

30.5 69.5 100.0

28.35 0.55 9.09

12.99 97.54 71.75

95.8 4.2 100.0

CF-8

Century MO-5 1.0 Cond. pH = 9.2+

No. 5 0.80

Conc. Tail. Feed

26.2 73.8 100.0

29.69 1.64 8.99

9.49 94.03 71.86

86.5 13.5 100.0

CF-5

Century MO-5 1.2 Cond. pH = 9.2

No. 5 0.96

Conc. Tail. Feed

29.6 70.4 100.0

28.39 0.82 8.98

12.46 96.61 71.70

93.5 6.5 100.0

CF-6

Century MO-5 1.4 Cond. pH = 9.1+

No. 5 1.12

Conc. Tail. Feed

34.3 65.7 100.0

25.95 0.28 9.08

19.65 98.41 71.40

98.0 2.0 100.0

CF-7

Century MO-5 1.6 Cond. pH = 9.1+

No. 5 1.28

Conc. Tail. Feed

35.5 64.5 100.0

24.80 0.24 8.96

23.50 98.35 71.78

98.2 1.8 100.0

4A-7

Table 4A-5 (Cont.). Flotation Test Material Balances Using Various Fatty-Acid Type Collectors with CF Feed (9% P2O5). Test No. CF-9

Collector, Lb./TF Fatty Acid Fuel Oil Oleic Acid 401 No. 5 1.2 0.96 Cond. pH = 9.2+

Flotation Product % Wt. Conc. 10.7 Tail. 89.3 Feed 100.0

Analysis % P2O5 % Insol 30.89 5.79 6.20 80.17 8.85 72.21

% Dist. P2O5 37.4 62.6 100.0

CF-10

Oleic Acid 401 1.4 Cond. pH = 9.2

No. 5 1.12

Conc. Tail. Feed

23.5 76.5 100.0

29.38 2.58 8.87

9.67 89.20 70.51

77.8 22.2 100.0

CF-11

Oleic Acid 401 1.6 Cond. pH = 9.2

No. 5 1.28

Conc. Tail. Feed

28.3 71.7 100.0

28.56 1.19 8.93

11.87 95.58 71.89

90.5 9.5 100.0

CF-12

Oleic Acid 401 1.8 Cond. pH = 9.1

No. 5 1.44

Conc. Tail. Feed

31.3 68.7 100.0

27.94 0.67 9.21

13.58 97.15 70.99

95.0 5.0 100.0

CF-13

Liqro GA 1.2 Cond. pH = 9.2+

No. 5 0.96

Conc. Tail. Feed

24.6 75.4 100.0

28.55 2.25 8.74

12.63 92.32 72.72

80.3 19.7 100.0

CF-14

Liqro GA 1.4 Cond. pH = 9.2

No. 5 1.12

Conc. Tail. Feed

29.4 70.6 100.0

28.17 0.98 8.97

13.35 96.17 71.82

92.3 7.7 100.0

CF-15

Liqro GA 1.6 Cond. pH = 9.2-

No. 5 1.28

Conc. Tail. Feed

31.0 69.0 100.0

27.56 0.73 9.04

15.31 96.92 71.62

94.5 5.5 100.0

CF-16

Liqro GA 1.8 Cond. pH = 9.1+

No. 5 1.44

Conc. Tail. Feed

33.9 66.1 100.0

25.56 0.47 8.97

20.94 97.69 71.67

96.5 3.5 100.0

4A-8

Table 4A-6. Flotation Test Results Using Century MO-5 Collector Plus CF Feed with N-Silicate Addition. Test No.

CF-5S

CF-6S

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.2 0.96 Cond. pH = 9.3

Century MO-5 1.4 Cond. pH = 9.2

No. 5 1.12

Flotation Product % Wt. Ro. Conc. 28.0 Ro. Tail. 72.0 Ro. Feed 100.0

Analysis % P2O5 % Insol 29.00 11.25 1.26 95.16 9.03 71.66

% Dist. P2O5 89.9 10.1 100.0

Cl. Conc. Cl. Tail.

25.5 2.5

30.37 15.14

7.28 51.50

85.7 4.2

Ro. Conc. Ro. Tail. Ro. Feed

30.1 69.9 100.0

28.03 0.71 8.94

14.02 96.17 71.44

94.4 5.6 100.0

Cl. Conc. Cl. Tail.

27.5 2.6

29.87 8.73

8.62 71.21

91.8 2.6

4A-9

PART 5. DEVELOPMENT OF SINGLE-COLLECTOR (FIPR/SAPR) FLOTATION PROCESSES

SUMMARY The FIPR/SAPR process is FIPR’s third approach to developing a viable alternative to the Crago “Double Float” process for phosphate flotation. SAPR stands for Single-collector, All-anionic Phosphate Recovery. The FIPR/SAPR process offers a universal flowsheet for any anionic reagent system and flotation feed of varying sizes. For an unsized or fine flotation feed, the FIPR/SAPR process consists of the following steps: (1) high-solids conditioning with an anionic collector; (2) anionic rougher flotation, with the rougher concentrate sized at 48 (or 65) mesh and the +48 mesh recovered as a final product; and (3) cleaning flotation of the -48 mesh fraction from Step 2. In a variation of Step 2, the rougher concentrate from the first two cells may be collected as a final product, and the rougher concentrate from the last two cells sized at 48 or 65 mesh. The new process was tested with a blend of anionic collectors, achieving single-digit Insol at 85+% recoveries. Pilot testing obtained concentrates of about 63% BPL and 10-11% Insol at around 88% recovery. Sizing of the rougher concentrate (reagentized material) proved to be challenging on pilot scale. In another all-anionic flowsheet, rougher flotation is conducted under “reagent starvation” conditions so that a low-Insol rougher concentrate can be achieved that would not require further cleaning. The rougher tail is then sized at 48 mesh. The coarser (+48 mesh) fraction of the tail is subject to scavenging flotation, while the -48 fraction is discarded. This rougher-scavenger flowsheet achieved excellent results on lab scale, but required fine tuning of fatty acid dosage in rougher flotation. Recognizing some of the limitations of the above-discussed flowsheets, another conceptual flowsheet was proposed. In this process, the flotation feed is first sized at 48 mesh (or somewhere between 35 and 48 mesh). The coarse feed is subject to one-step flotation, while the finer feed is processed using a straight rougher-cleaner flowsheet. To achieve low-Insol product, the coarser fraction may also be floated using the roughercleaner approach. This process was not tested extensively in the lab. However, a brief pilot testing showed great potential for this process. One pilot test run achieved concentrate analyzing 64.4% BPL and 10.6% Insol at a flotation recovery of 89.7%. It must be pointed out that this single-shot test was far from optimized.

5-1

INTRODUCTION THE RESERVE SHORTAGE AND RECOVERY ISSUE It is estimated that the Florida phosphate reserves that can be economically processed with available technology may only last for about 20 to 30 years at the current mining rate. While development of a viable dolomite separation process is critical to extending Florida's phosphate reserve, improvement in P2O5 recovery from the currently mined siliceous phosphates is equally important. Phosphate recoveries from the flotation feeds in most plants in Florida do not exceed 85%, with 30% P2O5 were obtained for 13 tests, and containing 20 million lb. per year of the mixture would be currently available if the demand existed. Experimental Phosphate Flotation Collectors Tested The fatty-acid type phosphate collectors investigated during this current work are summarized as follows: Reagent Name Century MO-5 Sylfat FA-11 Sylfat FA-12 Liqro GA Tall Oil Ariz. 2122 T.O. Heads Century MO-5/Sylfat FA-11 (1:1) Century MO-5/Sylfat FA-12 (1:1) Century MO-4/Liqro GA (1:1) Ariz. 2122/Sylfat FA-11 (1:1)

Supplier International Paper Co. Arizona Chem. Division Arizona Chem. Division Custom Chemicals Arizona Chem. Division Int. Paper/Ariz. Chem. Div. Int. Paper/Ariz. Chem. Div. Int. Paper/Custom Chem. Arizona Chem. Division

Approx. $/Lb. 0.32 0.25 0.25 0.15 0.14 0.28 0.28 0.23 0.19

Major Component Acids Iso-oleic & Stearic Oleic & Linoleic Oleic & Linoleic Oleic & Linoleic Oleic & Palmitic Iso-oleic, Stearic, Oleic Iso-oleic, Stearic, Oleic Iso-oleic, Stearic, Palmitic Oleic, Linoleic, Palmitic

The “high purity” fatty acids Century MO-5, Sylfat FA-11 and Sylfat FA-12 have acid number ranges of 166-177, 188-192 and 186-190, respectively. The lower purity tall oil fatty-acid mixtures, Liqro GA and Arizona 2122 “heads”, have lower acid numbers ranging from 150 down to about 135 and are considerably less expensive per pound. The current price for Arizona 2122 “heads” is $0.14 per pound delivered to central Florida. The two Sylfat fatty acids and the Liqro GA tall oil reagent are oily liquids at room temperature (74o F.). Century MO-5 is semi-fluid containing some dispersed solids, 5-27

whereas Arizona 2122 “heads” is a waxy semi-solid at room temperature. When these reagents are mixed at a 1.0 FA/0.6 FO ratio using No. 5 fuel oil, the mixtures are fluid; except for the mixtures containing Arizona 2122 “heads.” The “heads”/Sylfat FA-11/fuel oil mix used during the flotation testwork required warming to assure the reagent was fluid enough to be easily and accurately added dropwise to the laboratory conditioner. Lab Flotation Test Procedure As described earlier, standard 500g. rougher flotation tests were performed using a 2-minute conditioning time at about 73% solids, with soda ash as the pH regulator plus collector/fuel oil mix and N-silicate, followed by 2-minute phosphate flotation. The rougher flotation was performed in duplicate, and the two froth products were combined and crudely wet hand screened at 48 or 65 mesh to produce a finished “coarse” concentrate product and a “fine” product to be re-floated in a cleaner stage with no further reagent addition. As usual, tap water was used for all tests, No. 5 fuel oil : collector ratio was 0.6:1, and N-silicate added during the final 20 seconds of conditioning was 0.6 lb./TF. Test Results and Discussion Laboratory flotation test results obtained using the six different fatty-acid collectors, including mixtures, are shown in Tables 5A-12 through 5A-17. An abbreviated summary of the results is presented in Table 5A-6 for easier comparison of the data. A brief discussion of the results using each specific collector formulation follows: Using Century MO-5 Collector (Acid No. = >166) Detailed flotation results obtained using Century MO-5 collector are shown in Table 5A-12, Appendix 5. The data illustrates that 1.4 lb./ton (of feed) of this collector was required to obtain >90% P2O5 recovery, and that a final concentrate analyzing 31.8% P2O5/6.1% Insol was obtained when the rougher concentrate sizing step was performed at 48 mesh. When the collector level used was slightly less than 1.4 lb./TF, P2O5 recovery decreased rapidly. The subsequent flotation tests that follow in the next section were performed in an attempt to use less expensive collector formulations that would produce equivalent results and provide a greater supply source of effective fatty collector. Using Sylfat FA-12 and FA-11 (Acid No. = >186, >188) The performance of these two Sylfat oleic acid/linoleic acid mixtures is shown in Table 5A-13, Appendix 5. The results illustrate that >90% P2O5 recovery is attainable for final concentrates analyzing about 30.1% P2O5/11.3% Insol using 65 mesh rougher 5-28

concentrate, and that both reagents performed very similarly as expected from their similar compositions. The cost of both of these reagents is about $0.07/lb. less than for Century MO-5 and probably could be used for “blending”, thereby lowering overall collector cost. Using Liqro GA Tall Oil (Acid No. = 148) Table 5A-14 in Appendix 5 shows that Liqro GA tall oil possessed very good selectivity and produced a final concentrate analyzing about 31.5% P2O5/7.2% Insol at 90% P2O5 recovery when its use was increased to 1.5 lb./TF, using sizing at 65 mesh. Having a lower acid value than the previously described collectors, this comparatively cheap ($0.15/lb.) reagent should be further evaluated in a mixture with Century MO-5 in order to take advantage of the possibility of creating a strong and selective reagent combination having a lower cost than Century MO-5 alone. Using Century MO-5/Sylfat FA-11 Mixture (1:1) (Acid No. = >176) The flotation results obtained using a 1:1 mixture of Century MO-5 with Sylfat FA-11 (to improve fluidity) are summarized in Table 5A-15, Appendix 5. This reagent mixture, at a cost of about $0.28/lb., showed excellent performance and yielded final concentrates analyzing about 30.6-31.4% P2O5/9.7-7.4% Insol at >94% P2O5 recovery using either 48 mesh or 65 mesh rougher concentrate sizing before the fines cleaner flotation stage. Using Century MO-5/Liqro GA Mixture (1:1) (Acid No. = >157) Table 5A-16 in Appendix 5 presents the flotation results obtained using a 1:1 mixture of Century MO-5/Liqro GA tall oil collector. Both 48 mesh and 65 mesh rougher concentrate sizing were compared in the two tests performed. Final concentrates analyzed 31.1-31.3% P2O5 and 6.2-5.1% Insol at >93% P2O5 recovery. These are considered to be excellent results considering this fluid collector mixture cost is about $0.23/lb. From an overall cost/performance standpoint, this collector formulation is considered to be the most promising of all reagents tested to date. Using Arizona 2122 Heads/Sylfat FA-11 Mixture (1:1) (Acid No. = >160) A 1:1 mixture of the waxy semi-solid Arizona 2122 heads with Sylfat FA-11 liquid fatty acids, as previously mentioned, required warming to assure fluidity. This collector mixture’s flotation performance is illustrated in Table 5A-17 in Appendix 5. Final concentrates, using 48 mesh or 65 mesh rougher concentrate sizing, analyzed 31.732.7% P2O5 and 7.0-3.8% Insol; however, overall P2O5 recovery was only 86-84%. Selectivity was considered to be very good; however, collecting strength was lower than 5-29

any of the other collectors that contained Century MO-5 and used at the 1.4 lb./TF level. Loss of coarse phosphate in the rougher flotation tails was easily observed during these two laboratory tests. At about $0.19/lb., this heads mixture was the least expensive of any of the collector formulations tested. General Comments An abbreviated summary of all rougher flotation test results is present in Table 5A-18 in Appendix 5. Rougher flotation tests that were repeated (for concentrate screening at different mesh sizes), using 1.4 lb. of different collectors per ton of feed, are shown in bold type for a visual comparison of test reproducibility. With the probable exceptions of tests PCSX-1A and PCSX-1, the reproducibility of the various rougher floats was considered to be good to excellent. Of the list of collector reagent mixtures presented at the beginning of this section, the 1:1 mixture of Century MO-5/Sylfat FA-12 was observed to be a fluid at room temperature; however, because of its close similarity to the mixture using Sylfat FA-11, it was not subjected to flotation testing. PILOT TEST INDICATIONS Results Using the FIPR/SAPR Flowsheet This flowsheet was evaluated on two plant feeds, 5 runs on feed #1 and 2 runs on feed #2. The results are shown in Tables 5-9 through 5-15. These data indicate that lowInsol concentrate is difficult to achieve using the basic FIPR/SAPR flowsheet. The inefficient sizing of rough concentrate is the primary reason for high-Insol product. The sizer oversize fractions contain 25-70% -48 mesh material, indicating obvious inefficient sizing. Table 5-9. Pilot Test Run #1 Using the FIPR/SAPR Process on Feed #1 at 2.40 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.6 Lb. Fuel Oil, and 0.25 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 19.72 4.48 61.39 59.10 63.57 62.99 6.97 63.29

% Insol 71.10 92.50 12.59 15.71 9.64 10.06 91.46 9.84 5-30

% >48 Mesh 47.81 44.78 56.06 36.67 74.43 38.88 7.01 57.78

% BPL Distribution 100.00 16.62 83.38 39.04 44.34 38.72 0.32 83.06

Table 5-10. Pilot Test Run #2 Using the FIPR/SAPR Process on Feed #1 at 2.24 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.6 Lb. Fuel Oil, and 0.24 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 19.14 3.87 60.61 58.52 62.98 62.00 6.20 62.47

% Insol 71.69 92.98 13.86 16.16 11.24 11.45 87.12 11.35

% >48 Mesh 45.52 43.31 51.50 30.84 75.07 32.46 6.42 53.05

% BPL Distribution 100.00 14.79 85.21 43.84 41.37 43.55 0.29 84.92

Table 5-11. Pilot Test Run #3 Using the FIPR/SAPR Process on Feed #1 at 1.34 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.81 Lb. Fuel Oil, and 0.24 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 20.15 3.12 62.25 61.65 63.72 63.32 6.50 63.44

% Insol 70.74 94.65 11.63 12.24 10.14 9.87 90.77 9.94

% >48 Mesh 48.30 42.18 63.43 54.40 85.90 55.73 10.61 53.05

% BPL Distribution 100.00 11.02 88.98 62.88 26.10 62.69 0.19 88.78

Table 5-12. Pilot Test Run #4 Using the FIPR/SAPR Process on Feed #1 at 1.36 Lb. of Collector (1:1 Mixture of MO-5 and Liqro GA), 0.81 Lb. Fuel Oil, and 0.32 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 20.43 3.15 61.26 60.88 62.74 63.55 11.30 63.38

% Insol 70.81 94.89 13.89 14.52 11.47 10.94 81.04 11.05

5-31

% >48 Mesh 47.78 42.97 59.13 56.47 69.50 58.13 25.50 60.55

% BPL Distribution 100.00 10.85 89.15 70.51 18.64 69.84 0.67 88.48

Table 5-13. Pilot Test Run #5 Using the FIPR/SAPR Process on Feed #1 at 1.46 Lb. of Collector (FA12), 0.88 Lb. Fuel Oil, and 0.61 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 21.48 2.75 62.04 61.61 63.29 64.43 23.94 64.12

% Insol 69.33 95.47 12.74 12.96 12.07 9.21 63.27 9.97

% >48 Mesh 47.56 42.43 58.69 55.60 67.78 56.86 38.73 59.78

% BPL Distribution 100.00 8.75 91.25 67.66 23.59 65.84 1.83 89.42

Table 5-14. Pilot Test Run #1 Using the FIPR/SAPR Process on Feed #2 at 1.02 Lb. of Collector (FA12), 0.26 Lb. Fuel Oil and 0.39 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 21.53 2.31 57.36 54.22 63.02 65.11 19.76 64.32

% Insol 70.03 95.88 20.95 24.93 13.20 10.22 71.38 11.49

% >48 Mesh 13.74 15.42 10.61 0.12 29.57 0.01 0.48 12.47

% BPL Distribution 100.0 7.0 93.0 56.6 36.4 51.6 5.0 88.1

Table 5-15. Pilot Test Run #2 Using the FIPR/SAPR Process on Feed #2 at 1.28 Lb. of Collector (FA12), 0.14 Lb. Fuel Oil, and 0.44 Lb. Silicate per Ton of Feed. Stream Feed Rougher Tail Rougher Concentrate Sizer Undersize Sizer Oversize Cleaner Concentrate Cleaner Tail Total Concentrate

% BPL 17.90 1.21 58.75 54.54 64.91 60.58 23.07 62.52

% Insol 73.92 97.39 16.45 22.22 8.00 13.72 66.50 11.16

5-32

% >48 Mesh 21.13 23.13 16.22 0.56 39.16 0.27 2.03 17.72

% BPL Distribution 100.0 4.8 95.2 52.5 42.7 48.9 3.6 91.6

Results Using All-Anionic Flowsheet #2 The flowsheet could generally achieve lower Insol than the basic flowsheet, but at lower total flotation recovery, Tables 5-16 and 5-17. Delicate control is required in both the rougher and scavenger flotation steps to achieve the optimal balance between recovery and grade. However, mechanical cell flotation on the coarse scavenger feed is a major factor for the low recovery. It is widely accepted that mechanical cells may achieve recoveries of 50-60% for coarse feed on commercial application. The application of columns is called for if this process is ever considered for commercial application. It is expected that a recovery improvement of 5% could be achieved using columns. Table 5-16. Pilot Test Run #1 Using All-Anionic Flowsheet #2 on Feed #2 at 0.61 Lb. of Collector (1:1 Mixture of FA12 and CC41601), 0.50 Lb. Fuel Oil, and 0.64 Lb. Silicate per Ton of Feed. Stream Feed Rougher Concentrate Rougher Tail -48 Mesh Tail Scavenger Feed Scavenger Concentrate Scavenger Tail Total Concentrate

% BPL 17.65 64.09 9.05 5.71 11.06 63.49 6.12 64.00

% Insol 75.00 7.80 87.45 89.96 85.94 9.57 93.13 8.20

% >48 Mesh 21.41 13.29 22.91 1.00 36.10 28.16 36.85 16.62

% BPL Distribution 100.0 56.8 43.2 10.2 33.0 16.3 16.7 73.1

Table 5-17. Pilot Test Run #2 Using All-Anionic Flowsheet #2 on Feed #2 at 1.43 Lb. of Collector (1:1 Mixture of FA12 and CC41601), 0.89 Lb. Fuel Oil, and 0.93 Lb. Silicate per Ton of Feed. Stream Feed Rougher Concentrate Rougher Tail -48 Mesh Tail Scavenger Feed Scavenger Concentrate Scavenger Tail Total Concentrate

% BPL 18.11 64.99 6.10 4.67 7.25 56.17 1.60 63.4

% Insol 73.83 7.46 90.84 93.37 88.80 21.68 96.55 10.10

% >48 Mesh 21.76 15.74 23.30 0.30 41.84 43.91 41.60 20.95

% BPL Distribution 100.0 73.2 26.8 9.2 17.6 14.1 3.5 87.3

Results Using All-Anionic Flowsheet #3 It must be pointed out that this flowsheet was not investigated in any details in the lab, and was only tested in single-shot pilot testing. Yet, the results look quite promising; see Tables 5-18 through 5-22. By combining Test Run #1 on the fine fraction and Test Run #2 on the coarse fraction, a total recovery of 89.7% was achieved, with the 5-33

concentrate analyzing 64.4% BPL and 10.7% Insol. Again, sizing was not optimized in this pilot testing, with the coarse fraction containing 25.6% -48 material. The ideal cut size should actually be somewhere between 35 and 48 mesh. Table 5-18. Feed Sizing for the All-Anionic Flowsheet #3 on Feed #1. Stream Feed #1 Coarse Fraction Fine Fraction

Weight, Lb. 851 520 331

% BPL 19.66 26.32 9.19

% Insol 72.10 63.39 85.79

% >48 Mesh 46.58 74.07 3.40

% BPL Distribution 100.00 81.81 18.19

Table 5-19. Pilot Test Run #1 Using the All-Anionic Flowsheet #3 on the Fine Fraction of Feed #1 at 1.65 Lb. of Collector (FA12) and 0.99 Lb. Fuel Oil per Ton of Feed. Stream Fine Feed Rougher Tail Rougher Concentrate Cleaner Tail Cleaner Concentrate

% BPL 9.45 0.53 47.33 6.17 57.37

% Insol 85.91 98.44 32.67 87.58 19.28

% >48 Mesh 3.91 3.21 6.90 3.78 7.67

% BPL Distribution 100.00 4.58 95.42 2.44 92.98

Table 5-20. Pilot Test Run #1 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.81 Lb. of Collector (FA12) and 1.09 Lb. Fuel Oil per Ton of Feed. Stream Coarse Feed Rougher Tail Rougher Concentrate Cleaner Tail Cleaner Concentrate

% BPL 26.65 5.37 52.10 1.09 61.70

% Insol 62.01 90.96 27.38 99.82 13.76

% >48 Mesh 77.55 82.57 71.53 44.48 76.62

% BPL Distribution 100.00 10.98 89.02 0.29 88.73

Table 5-21. Pilot Test Run #2 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.34 Lb. of Collector (FA12) and 0.80 Lb. Fuel Oil per Ton of Feed. Stream Coarse Feed Rougher Tail Rougher Concentrate Cleaner Tail Cleaner Concentrate

% BPL 26.42 4.65 58.34 2.92 66.33

% Insol 63.11 93.18 19.05 93.29 8.33

5-34

% >48 Mesh 71.04 72.72 68.57 29.51 74.21

% BPL Distribution 100.00 10.45 89.55 0.57 88.98

Table 5-22. Pilot Test Run #3 Using the All-Anionic Flowsheet #3 on the Coarse Fraction of Feed #1 at 1.15 Lb. of Collector and 0.69 Lb. or Fuel Oil per Ton of Feed. Stream Coarse Feed Rougher Tail Rougher Concentrate Cleaner Tail Cleaner Concentrate

% BPL 24.38 2.95 59.30 8.28 66.11

% Insol 65.98 95.82 17.35 85.50 8.26

5-35

% >48 Mesh 68.49 68.18 69.01 34.46 73.62

% BPL Distribution 100.00 7.50 92.50 1.52 90.98

CONCLUSIONS • • • • • •

FIPR/SAPR could achieve concentrate Insol of 6-9% at 85-96% recovery. Feed size distribution is an important factor. The iso-fatty acids are more selective. Silicate is of significant help in improving concentrate grade. Sizing the rougher concentrate improves recovery. The optimal cut size for cleaner flotation is feed specific.

5-37

REFERENCES Anthes RJ, Kremer RA, inventors; Mobil Oil Corporation, assignee. beneficiating ores. 1985 Jul 30. US patent 4,532,033.

Method for

Gao Z, Gu Z. 1998. Plant practice of phosphate beneficiation in China. In: Zhang P, ElShall, H, Wiegel R, editors. Beneficiation of phosphates: advances in research and practice. Littleton (CO): SME. Gieseke EW, inventor. Froth flotation of nonmetallic ores with black liquor soap in acid circuit. 1949 Apr 12. US patent 2,466,671. Haseman JF, inventor. Phosphate flotation. 1968 Jan 2. US patent 3,361,257. Hirsch HE, Bushell CHG, inventors; Cominco Ltd., assignee. 1969 Aug 19. Phosphate flotation process. US patent 3,462,017. Hodges WA, inventor; Swift & Company, assignee. Flotation of siliceous impurities from mineral-bearing material. 1952 June 10. US patent 2,599,530. Hollingsworth CA, Sapp BL, inventors; Borden, Inc., assignee. Phosphate flotation. 1969 Jul 8. US patent 3,454,159. Hsieh SS, Brooks DG, inventors; Tennessee Valley Authority, assignee. flotation with tribasic acids. 1981 Aug 4. US patent 4,282,089.

Phosphate

Johnston DL, inventor; Cominco Ltd., assignee. Phosphate rock flotation. 1974 Apr 30. US patent 3,807,556. Jones DA, inventor; U.S. Department of Agriculture, assignee. Flotation beneficiation of phosphate ores. 1975 Jan 21. US patent 3,862,028. Nagaraj DR, Rothenberg AS, Lambert AS, inventors; American Cyanamid Co., assignee. Flotation beneficiation process for non-sulfide minerals. 1988 Jan 19. US patent 4,720,339. Ray CL, Baarson RE, Jonaitis CW, Treweek HB, inventors. Phosphate ore flotation process. 1963 Jul 23. US patent 3,098,817. Zellars-Williams Company. 1989. Anionic flotation of Florida phosphate. Bartow (FL): Florida Institute of Phosphate Research. Publication nr 02-063-071.

5-39

FOR ADDITIONAL READING El-Shall H, Yu Y, Moudgil BM. 1996. Scavenging for better recovery of phosphates. Minerals and Metallurgical Processing 13(2): 58-60. Floyd JE, Hodges WA, inventors. Froth flotation of phosphate values involving pH control. 1954 Jun 29. US patent 2,682,337. Orphy MK, Yousef AA, Hanna HS, Bibawy TA. 1969. Anionic flotation of Nile Valley phosphate ores. Mining Magazine 12(3): 183-91. Sharma MK, O’Neill GJ, Moudgil BM, inventors; Eastman Kodak Co., assignee. Phosphate flotation using sulfo-polyesters. 1994 May 24. US patent 5,314,073.

5-41

Appendix 5 TEST DATA FOR FIPR/SAPR FLOWSHEET DEVELOPMENT

Table 5A-1. Flotation Test Material Balances Using Century MO-5 Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

PCS -9S1

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.4 0.84 Cond. pH = 9.3

Flotation Product Stream % Wt. +65M Ro. Conc. 23.3 -65M Cl. Conc. 4.6

Analysis % P2O5 % Insol 32.70 6.61 29.82 12.49

% Dist. P2O5 75.8 13.6

-65M Cl. Tail. Ro. Tail. Feed

1.1 71.0 100.0

11.57 1.32 10.06

65.19 95.40 70.56

1.3 9.3 100.0

Total Conc. Total Tail.

27.9 72.1

32.22 1.48

7.56 94.94

89.4 10.6

-65M Cl. Feed

5.7

26.32

22.63

14.9

Total Ro. Conc.

29.0

31.45

9.76

90.7

5A-1

Table 5A-2. Flotation Test Material Balances Using Century MO-5 Collector Plus Cargill S. Ft. Meade Fine Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.2 0.72 Cond. pH = 9.3-

CA5S1

Total Conc. Total Tail.

Century MO-5 1.4 Cond. pH = 9.2-

CA6S1

Flotation Product Stream % Wt. +65M Ro. Conc. 9.8 -65M Cl. Conc. 4.7 -65M Cl. Tail. 1.6 Ro. Tail. 83.9 Feed 100.0

No. 5 0.84

Analysis % P2O5 % Insol 30.25 8.24 30.34 7.52 16.30 44.55 0.89 95.29 5.40 81.82

% Dist. P2O5 54.8 26.5 4.8 13.9 100.0

14.5 85.5

30.28 1.18

8.00 94.34

81.3 18.7

-65M Cl. Feed

6.3

26.83

16.83

31.3

Total Ro. Conc.

16.1

28.88

11.30

86.1

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

9.6 5.9 2.6 81.9 100.0

29.29 29.21 14.26 0.44 5.26

10.44 10.02 50.66 97.60 82.84

53.4 32.7 7.0 6.9 100.0

Total Conc. Total Tail.

15.5 84.5

29.23 0.86

10.26 96.15

86.1 13.9

-65M Cl. Feed

8.5

24.88

22.74

39.7

Total Ro. Conc.

18.1

27.07

16.07

93.1

5A-2

Table 5A-3. Flotation Test Material Balances Using Century MO-5 Collector Plus CF Industries Hardee Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.2 0.96 Cond. pH = 9.3

CF5S1

Total Conc. Total Tail.

Century MO-5 1.2 Cond. pH = 9.2+

CF5S2

Flotation Product Stream % Wt. +65M Ro. Conc. 24.5 -65M Cl. Conc. 3.3 -65M Cl. Tail. 0.7 Ro. Tail. 71.5 Feed 100.0

No. 5 0.96

Analysis % P2O5 % Insol 29.34 10.16 30.56 6.87 9.28 68.18 0.99 96.02 8.97 71.85

% Dist. P2O5 80.2 11.2 0.7 7.9 100.0

27.7 72.3

29.60 1.07

9.82 95.62

91.4 8.6

-65M Cl. Feed

4.0

26.75

17.75

11.9

Total Ro. Conc.

28.5

28.98

11.23

92.1

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

19.7 8.8 1.4 70.1 100.0

29.30 28.14 4.89 0.85 8.92

10.40 9.71 82.63 96.98 72.04

64.7 27.8 0.8 6.7 100.0

Total Conc. Total Tail.

28.5 71.5

28.95 0.94

10.17 96.70

92.5 7.5

-48M Cl. Feed

10.2

25.00

19.70

28.6

Total Ro. Conc.

29.9

27.82

13.58

93.3

5A-3

Table 5A-4. Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Fine Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.4 0.84 Cond. pH = 9.2+

4C2S1

Total Conc. Total Tail.

Century MO-5 1.4 Cond. pH = 9.2

4C3S1

Flotation Product Stream % Wt. +65M Ro. Conc. 18.8 -65M Cl. Conc. 5.9 -65M Cl. Tail. 1.9 Ro. Tail. 73.4 Feed 100.0

No. 5 0.84

Analysis % P2O5 % Insol 28.30 18.27 30.74 10.43 2.24 92.23 0.35 98.47 7.43 78.07

% Dist. P2O5 71.6 24.4 0.5 3.5 100.0

24.7 75.3

28.87 0.40

16.40 98.30

96.0 4.0

-65M Cl. Feed

7.8

23.72

30.38

24.9

Total Ro. Conc.

26.6

26.88

21.80

96.5

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

7.5 15.4 3.0 74.1 100.0

30.86 31.38 2.20 0.29 7.42

10.80 9.53 91.51 98.63 78.11

31.1 65.1 0.9 2.9 100.0

Total Conc. Total Tail.

22.9 77.1

31.18 0.36

9.96 98.35

96.2 3.8

-48M Cl. Feed

18.4

26.63

22.93

66.0

Total Ro. Conc.

25.9

27.84

19.42

97.1

5A-4

Table 5A-4 (Cont.). Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Fine Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.2 0.72 Cond. pH = 9.2+

4C6S1

Total Conc. Total Tail.

Century MO-5 1.2 Cond. pH = 9.3+

4C6S2

Flotation Product Stream % Wt. +65M Ro. Conc. 13.6 -65M Cl. Conc. 8.2 -65M Cl. Tail. 1.7 Ro. Tail. 76.5 Feed 100.0

No. 5 0.96

Analysis % P2O5 % Insol 30.98 10.84 32.10 7.65 6.65 79.25 0.55 98.00 7.37 78.42

% Dist. P2O5 57.1 35.7 1.5 5.7 100.0

21.8 78.2

31.38 0.68

9.63 97.60

92.8 7.2

-65M Cl. Feed

9.9

27.68

20.00

37.2

Total Ro. Conc.

23.5

29.57

14.68

94.3

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

12.1 8.6 1.4 77.9 100.0

31.74 32.49 8.50 0.89 7.44

8.44 6.55 73.09 97.01 78.17

51.6 37.5 1.6 9.3 100.0

Total Conc. Total Tail.

20.7 79.3

32.03 1.02

7.63 96.58

89.1 10.9

-65M Cl. Feed

10.0

29.10

15.80

39.1

Total Ro. Conc.

22.1

30.54

11.76

90.7

5A-5

Table 5A-4 (Cont.). Flotation Test Material Balances Using Century 1108 Collector Plus IMC Four Corners Fine Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century 1108 No. 5 1.4 0.84 Cond. pH = 9.2+

4C4S1

Total Conc. Total Tail.

Century 1108 1.6 Cond. pH = 9.2-

4C5S1

Flotation Product Stream % Wt. +65M Ro. Conc. 13.4 -65M Cl. Conc. 7.4 -65M Cl. Tail. 1.0 Ro. Tail. 78.2 Feed 100.0

No. 5 0.96

Analysis % P2O5 % Insol 31.92 7.82 32.33 6.30 12.26 62.16 0.64 97.65 7.29 78.50

% Dist. P2O5 58.7 32.8 1.6 6.9 100.0

20.8 79.2

32.07 0.78

7.31 97.20

91.5 8.5

-65M Cl. Feed

8.4

29.88

12.98

34.4

Total Ro. Conc.

21.8

31.15

9.82

93.1

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

14.2 7.5 1.3 77.0 100.0

31.42 32.15 11.57 0.48 7.39

8.23 7.02 65.05 98.13 78.10

60.4 32.6 2.0 5.0 100.0

Total Conc. Total Tail.

21.7 78.3

31.66 0.66

7.83 97.57

93.0 7.0

-65M Cl. Feed

8.8

29.09

15.57

34.6

Total Ro. Conc.

23.0

30.52

11.04

95.0

5A-6

Table 5A-4 (Cont.). Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Fine Feed with and without N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.2 0.72 Cond. pH = 9.1

4C8R

Total Conc. Total Tail.

Century MO-5 1.2 Cond. pH = 9.2 No N-Silicate Used 4C-9

Flotation Product Stream % Wt. +65M Ro. Conc. 11.6 -65M Cl. Conc. 8.3 -65M Cl. Tail. 0.9 Ro. Tail. 79.2 Feed 100.0

No. 5 0.72

Analysis % P2O5 % Insol 33.00 5.72 32.24 6.59 8.89 73.40 1.20 96.01 7.54 77.91

% Dist. P2O5 50.8 35.5 1.1 12.6 100.0

19.9 80.1

32.71 1.28

6.08 95.76

86.3 13.7

-65M Cl. Feed

9.2

30.00

13.15

36.6

Total Ro. Conc.

20.8

31.68

8.99

87.4

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

13.4 9.2 2.7 74.7 100.0

30.86 30.74 1.11 0.59 7.43

10.72 11.71 95.69 97.75 78.12

55.6 38.1 0.4 5.9 100.0

Total Conc. Total Tail.

22.6 77.4

30.80 0.61

11.15 97.67

93.7 6.3

-65M Cl. Feed

11.9

24.03

30.76

38.5

Total Ro. Conc.

25.3

27.63

20.16

94.1

5A-7

Table 5A-5. Flotation Test Material Balances Using Century MO-5 Collector Plus IMC Four Corners Coarse Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Century MO-5 No. 5 1.6 1.28 Cond. pH = 9.4+

4CC -3S

Total Conc. Total Tail.

Century MO-5 1.6 Cond. pH = 9.4+

4CC -4S

Flotation Product Stream % Wt. +65M Ro. Conc. 24.7 -65M Cl. Conc. 2.4 -65M Cl. Tail. 1.1 Ro. Tail. 71.8 Feed 100.0

No. 5 1.28

Analysis % P2O5 % Insol 30.74 9.93 27.90 16.32 2.39 91.17 0.50 97.97 8.65 74.18

% Dist. P2O5 87.7 7.8 0.3 4.2 100.0

27.1 72.9

30.48 0.53

10.48 97.86

95.5 4.5

-65M Cl. Feed

3.5

20.00

39.71

8.1

Total Ro. Conc.

28.2

29.40

13.62

95.8

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

20.7 6.2 1.1 72.0 100.0

31.41 28.36 1.29 0.63 8.72

7.49 16.44 95.07 96.79 73.31

74.5 20.2 0.1 5.2 100.0

Total Conc. Total Tail.

26.9 73.1

30.71 0.63

9.55 96.77

94.7 5.3

-48M Cl. Feed

7.3

24.25

28.36

20.3

Total Ro. Conc.

28.0

29.54

12.93

94.8

5A-8

Table 5A-6. Summary of Anionic Flotation/Sizing Process Results.

Table No. 1 2 3

4

5

Feed Sample PCS Swift Creek Cargill S. Ft. Meade (+ Dolo.) CF Chem. Hardee (+ Dolo.) IMC Four Corners (Fine) No Silicate (+ Rinse) (No Silicate) IMC Four Corners (Coarse)

Test No.

Century Collector No.

PCS-9S1

Lb./Ton Feed

Ro. Conc. Sizing, Tyler Mesh

Total Conc.

Total Conc. % Recov. P2O5

Total Tail

Ro. Feed

% P2O5

% Insol

% P2O5

% Insol

89.4

1.48

94.94

10.06

70.56

8.00

81.3

1.18

94.34

5.40

81.82

29.23

10.26

86.1

0.86

96.15

5.26

82.84

65

29.60

9.82

91.4

1.07

95.62

8.97

71.85

0.96

48

28.95

10.17

92.5

0.94

96.70

8.92

72.04

1.4 1.4 1.2 1.2 1.4 1.6

0.84 0.84 0.72 0.96 0.84 0.96

65 48 65 65 65 65

28.87 31.18 31.38 32.03 32.07 31.66

16.40 9.96 9.63 7.63 7.31 7.83

96.0 96.2 92.8 89.1 91.5 93.0

0.40 0.36 0.68 1.02 0.78 0.66

98.30 98.35 97.60 96.58 97.20 97.57

7.43 7.42 7.37 7.44 7.29 7.39

78.07 78.11 78.42 78.17 78.50 78.10

MO-5

1.2

0.72

65

32.71

6.08

86.3

1.28

95.76

7.54

77.91

4C-9

MO-5

1.2

0.72

65

30.80

11.15

93.7

0.61

97.67

7.43

78.12

4CC-3S

MO-5

1.6

1.28

65

30.48

10.48

95.5

0.53

97.86

8.65

74.18

4CC-4S

MO-5

1.6

1.28

48

30.71

9.55

94.7

0.63

96.77

8.72

73.31

Collector

F.O.

% P2O5

% Insol

MO-5

1.4

0.84

65

32.22

7.56

CA-5S1

MO-5

1.2

0.72

65

30.28

CA-6S1

MO-5

1.4

0.84

65

CF-5S1

MO-5

1.2

0.96

CF-5S2

MO-5

1.2

4C-2S1 4C-3S1 4C-6S1 4C-6S2 4C-4S1 4C-5S1

MO-5 MO-5 MO-5 MO-5 1108 1108

4C-8R

5A-9

Table 5A-7. Summary of Flotation Concentrate and Middling Yields, Grades and P2O5 Recoveries. From Total Feed, Wt. % IMC Four Corners Coarse Feed: Primary Concentrate 26.4 Total Mids -48 Mesh 3.8 Rougher Concentrate 30.2 Flotation Product

Analysis % P2O5 % Insol

From Total Feed, % Dist. P2O5

29.20 16.05 27.58

13.18 51.84 18.01

90.1 7.1 97.2

IMC Four Corners Fine Feed: Primary Concentrate Total Mids -65 Mesh Rougher Concentrate

17.6 4.4 22.0

31.42 22.50 29.64

9.55 35.23 14.68

74.6 13.4 88.0

CF Chem. Hardee Feed: Primary Concentrate Total Mids -48 Mesh Rougher Concentrate

25.4 5.2 30.6

28.94 22.50 27.81

10.87 31.15 13.95

81.5 13.1 94.6

PCS Swift Creek Feed: Primary Concentrate Total Mids -65 Mesh Rougher Concentrate

27.0 2.6 29.6

29.33 20.00 28.51

15.19 40.77 17.43

86.2 5.7 91.9

5A-10

Table 5A-8. Detailed Flotation Material Balances for IMC Four Corners Coarse Feed—Timed Floats. Test No. C-1 C-2 C-3 C-4 T-4

Feed

Analysis % P2O5

% Insol

% Dist. P2O5

13.5 4.2 (17.7) 7.1 2.6 (9.7) 1.3 0.6 (1.9) 0.3 0.6 (0.9) 36.2 33.6 (69.8)

30.87 23.60 (29.15) 29.68 19.69 (27.01) 28.90 13.15 (24.21) 24.18 3.09 (10.00) 0.62 0.03 (0.33)

8.82 28.47 (13.45) 11.63 41.37 (19.59) 14.45 60.42 (28.95) 28.30 89.10 (67.78) 97.65 99.28 (99.44)

48.7 11.6 (60.3) 24.6 6.0 (30.6) 4.4 0.9 (5.3) 0.8 0.2 (1.0) 2.6 0.1 (2.7)

58.4 41.6 100.0

11.90 3.87 (8.56)

64.45 87.76 (74.15)

81.2 18.8 (100.0)

Product

% Wt.

+48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total

Cum. % Wt. 13.5 4.2 (17.7) 20.6 6.8 (27.4) 21.9 22.5 (29.3) 22.2 23.1 (30.2) 58.4 41.6 (100.0)

5A-11

Cumulative Analysis % P2O5

% Insol

30.87 23.60 (29.15) 30.48 22.06 (28.39) 30.41 21.35 (28.12) 30.32 20.00 (27.58)

8.82 28.37 (13.45) 9.81 33.24 (15.62) 10.09 35.41 (16.48) 10.31 39.38 (18.01)

Cumulative %P2O5 Dist. From Total From Feed Feed Size Fraction 48.7 60.0 11.6 61.5 (60.3) (60.3) 73.3 90.3 17.5 93.2 (90.9) (90.9) 77.7 95.8 18.4 98.1 (96.2) (96.2) 78.5 96.8 18.6 99.4 (97.2) (97.2)

Table 5A-9. Detailed Flotation Material Balances for IMC Four Corners Fine Feed—Timed Floats. Test No. C-1 C-2 C-3 C-4 T-4

Feed

Analysis % P2O5

% Insol

% Dist. P2O5

7.0 7.5 (14.5) 2.3 3.1 (5.4) 0.5 0.7 (1.2) 0.3 0.6 (0.9) 40.0 38.0 (78.0)

33.01 30.51 (31.72) 31.28 25.37 (27.96) 29.15 21.21 (25.00) 21.18 8.24 (12.22) 1.96 0.25 (1.13)

5.04 12.23 (8.76) 9.91 26.69 (19.63) 15.65 38.22 (29.17) 34.18 74.89 (61.11) 93.72 98.74 (96.17)

31.2 30.9 (62.1) 9.7 10.7 (20.4) 2.0 2.0 (4.0) 0.8 0.7 (1.5) 10.5 1.4 (11.9)

50.1 49.9 100.0

8.02 6.77 (7.40)

76.35 80.14 (78.24)

54.3 45.7 (100.0)

Product

% Wt.

+65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total

Cum. % Wt. 7.0 7.5 (14.5) 9.3 10.6 (19.9) 9.8 11.3 (21.1) 10.1 11.9 (22.0) 50.1 49.9 (100.0)

5A-12

Cumulative Analysis % P2O5

% Insol

33.01 30.51 (31.72) 32.58 29.06 (30.70) 32.45 28.58 30.38 32.08 27.56 (29.64)

5.04 12.23 (8.76) 6.24 16.51 (11.71) 6.94 17.88 (12.70) 7.52 20.76 (14.68)

Cum. %P2O5 Dist. From Total From Feed Feed Size Fraction 31.2 57.5 30.9 67.8 (62.1) (62.1) 40.9 75.4 41.6 91.1 (82.5) (82.5) 42.9 79.1 43.6 95.6 (86.5) (86.5) 43.7 80.5 44.3 97.0 (88.0) (88.0)

Table 5A-10. Detailed Flotation Material Balances for CF Chemicals Hardee Feed—Timed Floats. Test No. C-1 C-2 C-3 C-4 T-4

Feed

Analysis % P2O5

% Insol

% Dist. P2O5

10.9 7.8 (18.7) 5.0 3.5 (8.5) 1.3 1.1 (2.4) 0.4 0.6 (1.0) 22.3 47.1 (69.4)

30.01 27.91 (29.14) 28.99 25.12 (27.29) 27.81 21.40 (25.00) 22.22 8.65 (14.00) 1.77 0.21 (1.06)

7.40 14.49 (10.37) 10.24 23.30 (15.65) 14.34 34.23 (23.75) 30.88 71.58 (55.00) 93.13 96.18 (95.20)

36.3 24.2 (60.5) 16.0 9.8 (25.8) 4.0 2.7 (6.7) 1.0 0.6 (1.6) 4.3 1.1 (5.4)

39.9 60.1 100.0

12.93 5.74 (9.00)

56.14 79.97 (70.46)

61.6 38.4 (100.0)

Product

% Wt.

+48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total +48 -48 Total

Cum. % Wt. 10.9 7.8 (18.7) 15.9 11.3 (27.2) 17.2 12.4 (29.6) 17.6 13.0 (30.6) 39.9 60.1 (100.0)

5A-13

Cumulative Analysis % P2O5

% Insol

30.01 27.91 (29.14) 29.62 27.08 (28.57) 29.48 26.61 (28.28) 29.32 25.85 (27.81)

7.40 14.49 (10.37) 8.30 17.26 (12.02) 8.80 18.79 (12.97) 9.26 21.23 (13.95)

Cumulative %P2O5 Dist. From Total From Feed Feed Size Fraction 36.3 58.9 24.2 63.0 (60.5) (60.5) 52.3 84.9 34.0 88.4 (86.3) (86.3) 56.3 91.4 36.7 95.4 (93.0) (93.0) 57.3 93.0 37.3 97.1 (94.6) (94.6)

Table 5A-11. Detailed Flotation Material Balances for PCS Swift Creek Feed—Timed Floats. Test No. C-1 C-2 C-3 C-4 T-4

Feed

Analysis % P2O5

% Insol

% Dist. P2O5

15.4 5.0 (20.4) 5.5 2.1 (7.6) 0.7 0.3 (1.0) 0.4 0.2 (0.6) 51.4 19.0 (70.4)

30.87 23.28 (29.02) 31.08 21.06 (28.29) 30.65 18.46 (27.00) 18.88 9.53 (16.67) 1.19 0.67 (1.05)

10.96 31.79 (16.08) 10.15 37.75 (17.76) 11.30 44.75 (21.00) 44.84 69.42 (53.33) 95.84 96.85 (96.11)

51.7 12.7 (64.4) 18.6 4.8 (23.4) 2.3 0.7 (3.0) 0.9 0.2 (1.1) 6.7 1.4 (8.1)

73.4 26.6 100.0

10.03 6.84 (9.18)

70.53 79.14 (72.82)

80.2 19.8 (100.0)

Product

% Wt.

+65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total +65 -65 Total

Cum. % Wt. 15.4 5.0 (20.4) 20.9 7.1 (28.0) 21.6 7.4 (29.0) 22.0 7.6 (29.6) 73.4 26.6 (100.0)

5A-14

Cumulative Analysis % P2O5

% Insol

30.87 23.28 (29.02) 30.91 22.68 (28.82) 30.88 22.27 (28.76) 30.68 22.24 (28.51)

10.96 31.79 (16.08) 10.77 33.52 (16.54) 10.79 33.92 (16.69) 11.41 34.87 (17.43)

Cum. %P2O5 Dist. From Total From Feed Feed Size Fraction 51.7 64.5 12.7 64.3 (64.4) (64.4) 70.4 87.8 17.5 88.5 (87.9) (87.9) 72.7 90.6 18.2 91.8 (90.9) (90.9) 73.5 91.7 18.4 92.9 (91.9) (91.9)

Table 5A-12. Flotation Test Material Balances Using Century MO-5 Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Flotation Product Fatty Acid Fuel Oil Stream % Wt. 24.9 Century MO-5 No. 5 +65M Ro. Conc. 1.4 0.84 -65M Cl. Conc. 3.4 Cond. pH = 9.0+ -65M Cl. Tail. 3.4 Ro. Tail. 68.3 Feed 100.0

PCS X-1

Total Conc. Total Tail.

Century MO-5 No. 5 1.3 0.78 Cond. pH = 9.0+

PCS X-3

Analysis % P2O5 % Insol 29.10 14.90 30.08 11.67 10.10 69.45 0.74 97.25 9.11 72.89

% Dist. P2O5 79.6 11.2 3.7 5.5 100.0

28.3 71.7

29.22 1.17

14.52 95.93

90.8 9.2

-65M Cl. Feed

6.8

20.00

40.59

14.9

Total Ro. Conc.

31.7

27.16

20.41

94.5

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

21.4 2.4 2.8 73.4 100.0

30.97 31.23 18.56 1.48 8.99

9.78 8.73 45.01 95.14 73.39

73.8 8.3 5.8 12.1 100.0

Total Conc. Total Tail.

23.8 76.2

31.01 2.11

9.66 93.29

82.1 17.9

-65M Cl. Feed

5.2

24.42

28.27

14.1

Total Ro. Conc.

26.6

29.70

13.38

87.9

5A-15

Table 5A-12 (Cont.). Flotation Test Material Balances Using Century MO-5 Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Flotation Product Fatty Acid Fuel Oil Stream % Wt. Century MO-5 No. 5 +65M Ro. Conc. 14.4 1.2 0.72 -65M Cl. Conc. 2.8 Cond. pH = 9.1+ -65M Cl. Tail. 1.9 Ro. Tail. 80.9 Feed 100.0

PCS X-2

Total Conc. Total Tail.

Century MO-5 No. 5 1.4 0.84 Cond. pH = 9.1+ PCS X1A

Analysis % P2O5 % Insol 30.95 9.74 30.18 11.54 16.10 52.50 3.90 88.15 8.77 74.03

% Dist. P2O5 50.9 9.7 3.4 36.0 100.0

17.2 82.8

30.87 4.18

10.00 87.33

60.6 39.4

-65M Cl. Feed

4.7

24.47

28.09

13.1

Total Ro. Conc.

19.1

29.37

14.24

64.0

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

15.7 13.0 2.7 68.6 100.0

31.58 32.04 8.96 0.47 9.68

6.69 5.30 72.63 97.99 70.92

51.2 43.0 2.5 3.3 100.0

Total Conc. Total Tail.

28.7 71.3

31.78 0.79

6.06 97.03

94.2 5.8

-48M Cl. Feed

15.7

28.02

16.88

45.5

Total Ro. Conc.

31.4

29.81

11.78

96.7

5A-16

Table 5A-13. Flotation Test Material Balances Using Sylfat FA-12 and 11 Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Sylfat FA-12

No. 5

1.4 Cond. pH = 9.0-

0.84

PCS X-4

No. 5

1.4 0.84 Cond. pH = 9.0+

Analysis % P2O5 % Insol

% Dist. P2O5

30.12

11.54

77.5

30.48 5.93 0.88 9.17

9.94 80.38 96.81 72.57

14.3 1.5 6.7 100.0

27.9 72.1

30.18 1.04

11.29 96.28

91.8 8.2

-65M Cl. Feed

6.6

21.97

34.55

15.8

Total Ro. Conc.

30.2

28.34

16.56

93.3

Total Conc. Total Tail.

Sylfat FA-11

PCS X-5

Flotation Product Stream % Wt. +65M Ro. 23.6 Conc. -65M Cl. Conc. 4.3 -65M Cl. Tail. 2.3 Ro. Tail. 69.8 Feed 100.0

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

24.7

30.01

11.87

80.6

3.7 2.8 68.8 100.0

30.97 10.29 0.50 9.19

8.75 68.91 97.88 72.52

12.5 3.2 3.7 100.0

Total Conc. Total Tail.

28.4 71.6

30.14 0.88

11.44 96.75

93.1 6.9

-65M Cl. Feed

6.5

22.15

34.62

15.7

Total Ro. Conc.

31.2

28.37

16.60

96.3

5A-17

Table 5A-14. Flotation Test Material Balances Using Liqro GA T.O. Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil Liqro GA T.O.

No. 5

1.4 0.84 Cond. pH = 9.1+ PCS X-6

PCS X-7

Flotation Product Stream % Wt. +65M Ro. 19.1 Conc. -65M Cl. Conc. 4.2 -65M Cl. Tail. 0.9 Ro. Tail. 75.8 Feed 100.0

No. 5

1.5 Cond. pH = 9.2

0.9

% Dist. P2O5

32.57

4.18

65.2

30.69 14.45 2.51 9.54

8.66 56.05 92.02 71.41

13.5 1.4 19.9 100.0

23.3 76.7

32.23 2.65

4.98 91.59

78.7 21.3

-65M Cl. Feed

5.1

27.84

16.86

14.9

Total Ro. Conc.

24.2

31.57

6.86

80.1

Total Conc. Total Tail.

Liqro GA T.O.

Analysis % P2O5 % Insol

+65M Ro. Conc. -65M Cl. Conc. -65M Cl. Tail. Ro. Tail. Feed

21.9

31.83

6.31

74.1

5.0 1.5 71.6 100.0

30.10 5.25 1.20 9.41

11.07 82.81 95.76 71.73

15.9 0.9 9.1 100.0

Total Conc. Total Tail.

26.9 73.1

31.49 1.29

7.17 95.49

90.0 10.0

-65M Cl. Feed

6.5

24.31

27.54

16.8

Total Ro. Conc.

28.4

30.11

11.16

90.9

5A-18

Table 5A-15. Flotation Test Material Balances Using Century MO-5/Sylfat FA-11 Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil MO-5/FA-11

No. 5

1.4 Cond. pH = 9.2

0.84

PCS X-8

PCS X8A

Flotation Product Stream % Wt. +65M Ro. 25.6 Conc. -65M Cl. Conc. 5.1 -65M Cl. Tail. 1.1 Ro. Tail. 68.2 Feed 100.0

No. 5

1.4 Cond. pH = 9.2-

0.84

% Dist. P2O5

30.79

9.38

79.8

29.95 5.79 0.59 9.87

11.20 81.36 97.58 70.41

15.5 0.6 4.1 100.0

30.7 69.3

30.65 0.66

9.67 97.32

95.3 4.7

-65M Cl. Feed

6.2

25.65

23.55

16.1

Total Ro. Conc.

31.8

29.78

12.14

95.9

Total Conc. Total Tail.

MO-5/FA-11

Analysis % P2O5 % Insol

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

15.4

31.51

7.02

49.9

13.9 2.3 68.4 100.0

31.27 5.61 0.59 9.73

7.79 82.53 97.78 70.94

44.7 1.3 4.1 100.0

Total Conc. Total Tail.

29.3 70.7

31.40 0.75

7.37 97.28

94.6 5.4

-48M Cl. Feed

16.2

27.65

18.40

46.0

Total Ro. Conc.

31.6

29.53

12.85

95.9

5A-19

Table 5A-16. Flotation Test Material Balances Using Century MO-5/Liqro GA Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil MO-5/L. GA

No. 5

1.4 0.84 Cond. pH = 9.2+ PCS X-9

PCS X9A

Flotation Product Stream % Wt. +65M Ro. 24.4 Conc. -65M Cl. Conc. 4.9 -65M Cl. Tail. 0.9 Ro. Tail. 69.8 Feed 100.0

No. 5

1.4 Cond. pH = 9.2-

0.84

% Dist. P2O5

31.13

5.94

78.2

30.81 11.69 0.73 9.72

7.46 63.36 97.06 70.14

15.5 1.0 5.3 100.0

29.3 70.7

31.09 0.86

6.21 96.63

93.7 6.3

-65M Cl. Feed

5.8

27.76

16.21

16.5

Total Ro. Conc.

30.2

30.50

7.91

94.7

Total Conc. Total Tail.

MO-5/L. GA

Analysis % P2O5 % Insol

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

13.5

31.59

4.44

43.1

15.9 1.0 69.6 100.0

31.15 9.24 0.84 9.88

5.69 70.83 96.57 69.42

50.1 0.9 5.9 100.0

Total Conc. Total Tail.

29.4 70.6

31.33 0.95

5.10 96.20

93.2 6.8

-48M Cl. Feed

16.9

29.82

9.53

51.0

Total Ro. Conc.

30.4

30.59

7.27

94.1

5A-20

Table 5A-17. Flotation Test Material Balances Using Ariz. 2122/Sylfat FA-11 Mix Collector Plus PCS Swift Creek Feed with N-Silicate Addition. Test No.

Collector, Lb./TF Fatty Acid Fuel Oil A-2122/FANo. 5 11 1.4 0.84 Cond. pH = 9.2-

PCS X-10

Analysis % P2O5 % Insol

% Dist. P2O5

31.71

7.04

72.0

31.67 14.29 1.78 10.13

7.05 57.54 94.17 69.83

14.4 1.1 12.5 100.0

27.6 72.4

31.70 1.91

7.03 93.77

86.4 13.6

-65M Cl. Feed

5.4

29.07

14.44

15.5

Total Ro. Conc.

28.4

31.20

8.45

87.5

Total Conc. Total Tail.

A-2122/FANo. 5 11 1.4 0.84 Cond. pH = 9.2+ PCS X10A

Flotation Product Stream % Wt. +65M Ro. 23.0 Conc. -65M Cl. Conc. 4.6 -65M Cl. Tail. 0.8 Ro. Tail. 71.6 Feed 100.0

+48M Ro. Conc. -48M Cl. Conc. -48M Cl. Tail. Ro. Tail. Feed

11.8

32.89

3.33

38.4

14.2 1.5 72.5 100.0

32.60 19.30 1.79 10.10

4.12 43.10 94.14 69.88

45.8 2.9 12.9 100.0

Total Conc. Total Tail.

26.0 74.0

32.73 2.15

3.77 93.11

84.2 15.8

-48M Cl. Feed

15.7

31.34

7.90

48.7

Total Ro. Conc.

27.5

32.00

5.93

87.1

5A-21

Table 5A-18. Summary of Laboratory Rougher Flotation Test Results. Test No. CFX-7 CFX-6 CFX-2 CFX-4 CFX-5

Collector Name Century MO-5 75% Century MO-5/25% Liqro GA 50% Century MO-5/50% Liqro GA 25% Century MO-5/75% Liqro GA Liqro GA

Lb./Ton Feed Collector Fuel Oil 1.2 0.72 1.2 0.72 1.2 0.72 1.2 0.72 1.2 0.72

Ro. Conc. Sizing, Tyler Mesh 48 48 48 48 48

Rougher Conc. % P2O5 % Insol 26.38 21.76 26.38 21.63 26.50 21.45 26.93 19.91 27.66 18.01

Rougher Conc. % P2O5 Recovery 97.3 96.4 96.4 95.8 93.6

CFX-10 Century MO-5 CFX-9 Century MO-5

1.0 1.1

0.60 0.66

48 48

30.11 27.86

11.49 17.67

90.4 93.6

CFX-3 CFX-1

50% Century MO-5/50% Liqro GA 50% Century MO-5/50% Liqro GA

1.1 1.3

0.66 0.78

48 48

28.84 25.11

14.95 25.15

91.3 97.2

CFX-8

Liqro GA

1.3

0.78

48

25.71

24.16

98.0

5A-22

Table 5A-18 (Cont.). Summary of Laboratory Rougher Flotation Test Results. Lb./Ton Feed Collector Fuel Oil 1.4 0.84 1.4 0.84 1.3 0.78 1.2 0.72

Rougher Conc. % P2O5 % Insol 29.81 11.78 27.16 20.41 29.70 13.38 29.37 14.24

Test No. PCSX-1A PCSX-1 PCSX-3 PCSX-2

Century MO-5 Century MO-5 Century MO-5 Century MO-5

PCSX-4 PCSX-5

Sylfat FA-12 Sylfat FA-11

1.4 1.4

0.84 0.84

65 65

28.34 28.37

16.56 16.60

93.3 96.3

PCSX-6 PCSX-7

Liqro GA Tall Oil Liqro GA Tall Oil

1.4 1.5

0.84 0.90

65 65

31.57 30.11

6.86 11.16

80.1 90.9

PCSX-8A PCSX-8

Century MO-5/Sylfat FA-11 (1:1) Century MO-5/Sylfat FA-11 (1:1)

1.4 1.4

0.84 0.84

48 65

29.53 29.78

12.85 12.14

95.9 95.9

PCSX-9A PCSX-9

Century MO-5/Liqro GA (1:1) Century MO-5/Liqro GA (1:1)

1.4 1.4

0.84 0.84

48 65

30.59 30.50

7.27 7.91

94.1 94.7

PCSX-10A PCSX-10

Ariz. 2122/Sylfat FA-11 (1:1) Ariz. 2122/Sylfat FA-11 (1:1)

1.4 1.4

0.84 0.84

48 65

32.00 31.20

5.93 8.45

87.1 87.5

Collector Name

5A-23

Ro. Conc. Sizing, Tyler Mesh 48 65 65 65

Rougher Conc. % P2O5 Recovery 96.7 94.5 87.9 64.0

PART 6. AMINE STUDY

SUMMARY, CONCLUSIONS AND RECOMMENDATIONS This research has studied the performance of six types of amines; primary, secondary, tertiary, quaternary, ether, and condensate on the cleaning step of the rougher concentrates for the Crago process, and the effect of particle size on the performance of each type of amine. The research also studied the effect of slimes (tolerance) of these six types of amines and Perco 90L polymer addition on the amine flotation step of the Reverse Crago process. The flotation results shown in this report are influence by the type, origin, and characteristics of the amine flotation feed and/or flotation feed sample used for the tests. Moreover, two different samples from the same plant that were taken at different occasions show different flotation results. Thus, absolute values of grades and recoveries changed, but the trends were still valid. In addition, it should be taken into consideration that the data shown in the report does not correspond to optimum flotation conditions with respect to any variable. The characterization studies conducted on Plant I, Unsized Amine Feed; Plant II, Course and Fine Amine Feeds; and Plant III, Unsized Flotation Feed showed that these samples represent typical Florida phosphate products. Plant I, Unsized Amine Feed analyzed 28.18% P2O5 and 16.48% Insol with a d50 of 331 µm; Plant II, Coarse Amine Feed, 30.62% P2O5 and 9.78% Insol with a d50 of 400 µm; Plant II, Fine Amine Feed, 26.88% P2O5 and 20.17% Insol with a d50 of 200 µm; and Plant III, Unsized Flotation Feed, 6.82% P2O5 and 78.38% Insol with a d50 of 221 µm. For the evaluation of the different types of amines; the Selectivity Index, SI; the ratio of Insol rejection to the tailings weight percentage, R*; the shape of the RecoveryGrade curve (Selectivity Curve) represented by the tangent (Tang) at the keen of the curve; the Tree Analysis results; and Locked Cycle tests were used. Even though the Tree Analysis technique was not able to describe the whole locus of the Recovery-Grade curve due to an improper distribution of the amine addition during the different steps of the test, this technique was able to obtain results close to those obtained by several batch flotation tests. The Tree analysis eliminates the effect of feed grade variation on each batch flotation test, and requires less time, effort, and amount of material to obtain the Selectivity Curve. More work is recommended to develop this technique for phosphate ores. The best flotation results obtained using Armeen HT primary amine on the cleaning step of the Crago process required 0.4 lb./ton of amine addition. At this amine addition, a 32.88% P2O5 and 2.05% Insol concentrate was obtained with a P2O5 recovery of 97.56% and an Insol rejection of 89.15%. The cleaning step of the Crago process using Armeen HT primary Amine had an average R* of 5.07, SI of 252.7, and a Tang of 2.11. 6-1

The cleaning step of the Crago process using Armeen 2HT secondary amine showed a poor flotation performance due to the insoluble nature of the amine. The best test required 2.8 lb./ton of Armeen 2HT secondary amine addition to obtain a 30.81% P2O5 and 8.50% Insol concentrate with 99.04% P2O5 recovery and 52.35% Insol rejection. An average R* of 3.88 and SI of 22.0 were obtained. It is recommended to request to the manufacturers a new secondary amine with a tallow hydrocarbon chain and one methyl group. This will make the amine more soluble and will follow a nice amine series, which only one HT in their structure. The best results of the cleaning step flotation of the Crago process obtained for Plant I, Unsized Amine Feed using Armeen DMHTD Tertiary amine are obtained at 0.4 lb./ton of amine addition. The concentrate analyzed 32.73% P2O5 and 3.93% Insol with a P2O5 recovery of 97.59% and an Insol rejection of 79.60%. Average R* of 4.91, SI of 139.7, and Tang of 0.88 were obtained. When Arquad 2HT-75 Quaternary amine was used in the cleaning step of the Crago process, 0.3 lb./ton amine was added to obtain the best flotation results; 32.66% P2O5 and 3.46 Insol concentrate with P2O5 recovery of 98.72% and Insol rejection of 81.37%. The use of the Arquad 2HT-75 Quaternary amine in the cleaning step of the Crago process produces an average R* of 5.08, SI of 290.5, and a Tang of 1.33. In the case of using Adogen 185 Ether amine acetate in the cleaning flotation step of the Crago process, 0.2 lb./ton of amine addition was required to obtain the best flotation test results. Under these conditions, a 33.39% P2O5 and 2.54% Insol concentrate with P2O5 recovery of 97.96 and an Insol rejection of 86.48% was obtained. The average values of the evaluating indices are: R* of 4.46, SI of 171.8, and Tang of 1.60. The cleaning step of the Crago process in the presence of 0.4 lb./ton of Arr-Maz condensate amine render the best flotation results. This test produces a concentrate analyzing 33.30% P2O5 and 2.54% Insol with P2O5 recovery of 97.98% and Insol rejection of 86.83%. The average indices for this amine correspond to a R* of 4.90, SI of 232.2, and Tang of 1.06. The comparison of the flotation results of the batch tests of the cleaning step of the Crago process for Plant I, Unsized Amine Feed generates the following rank from the most selective to the least selective amine: Quaternary > Primary = Tertiary = Condensate > Ether > Secondary (?). For similar flotation results, the strength of the amine addition for this feed, from the strongest to the weakest follows: Ether > Quaternary > Primary = Tertiary = Condensate > Secondary (?).

6-2

A similar comparison was carried out for the corresponding Locked Cycle tests for each type of amine used. The ranking of the selectivity of these amines from the most selective to the least selective follows: Quaternary > Primary = Tertiary > Ether > Condensate > Secondary (?). These Locked Cycle tests could be also an indication of the tolerance of each amine tested to the presence of slimes (effect of slimes). By evaluating the increase in amine consumption to achieve quasi-steady state conditions, the tolerance can be inferred. The rank form the most tolerant to the least tolerant follows: Primary > Tertiary = Condensate > Ether > Quaternary. The effect of particle size on the performance of all six types of amines in the cleaning step of the Crago process was evaluated by screen assays of the concentrates and tailings of the best batch flotation tests performed. For this purpose, the P2O5 and Insol weight frequency and distribution as a function of particle size were used. In addition, batch flotation tests on Plant II, Coarse Amine Feed and Plant II, Fine Amine Feed were carried out. However, the flotation results were strongly affected by the change in the type of feed. Two indices were designed to compare the data, R and D. R correspond to the ratio of Insol distribution at a given particle size to the P2O5 distribution at the same particle size (specificity of the amine for the Insol). D corresponds to the difference between the Insol weight frequency to that of the plain weight frequency (selectivity to reject Insol) for each size fraction. The results indicate that the primary amine is more efficient in the 65 x 200-mesh particle size range, secondary amine in the 100 x 150-mesh range, tertiary in the 35 x 200-mesh range, quaternary and ether amine acetate in the 65 x 200-mesh range, and condensate amine in the 100 x 200-mesh particle size fraction. The distribution of P2O5 and Insol in the concentrate and tailings of each particle size fraction studied for the best tests using all six types of amines were evaluated based on the PInsol50. This parameter corresponds to the particle size at which an Insol particle has 50% of probability to be report in the concentrate or tailings. PInsol50 for the primary amine was 410 µm; for the secondary amine, 230 µm (?); for the tertiary and quaternary amines, 333 µm; for the ether amine acetate, 370 µm; and for the condensate amine, 400 µm. Apparently, the flotation rank from coarser to finer Insol based on the batch flotation tests conducted on Plant I, Unsized Amine Feed and Plant II, Coarse and Fine Amine Feeds follows: Primary > Ether = Condensate > Tertiary > Quaternary. The effect of slimes on the amine flotation step of the Reverse Crago process was studied using Plant III, Unsized Flotation Feed, but using the dosage determine for the best test for each type of the six amines for Plant I, Unsized Amine Feed. The Reverse 6-3

Crago process was developed under a different FIPR in-house project. In this process, the sands are floated first with an amine plus an anionic polymer to “blind” the slime, followed by fatty acid flotation. In general, it was observed that the effect of slimes was complex since slimes affect the water quality, surface of silica and phosphate particles, and amine consumption by increasing the specific surface area available for amine adsorption. In addition, the use of scrubbing in the experimental procedure to generate slimes contributes to the complexity of the effect of slimes by altering the composition of them; clay, fine silica and phosphate. Again, the results were analyzed in a relative basis using the Relative Insol rejection, Relative P2O5 losses (rejection) and the selectivity ratio, [R]. When using Armeen HT primary amine, a maximum in Relative Insol rejection, P2O5 losses and selectivity ratio, [R], was observed at 0.32% of slimes content. Using Armeen 2HT secondary amine and Armeen DMHTD Tertiary amine showed a maximum at 0.42% of slimes content. For Arquad 2HT-75 Quaternary amine and Adogen 185 Ether amine acetate a maximum in the Relative Insol rejection was shown at 0.46% and 0.48% of slimes content, respectively. Arr-Maz condensate amine showed no maximum in the Relative Insol rejection, Relative P2O5 losses, and selectivity ratio, [R]. In general, the presence of the maximum in the Relative Insol rejection and Relative P2O5 losses is related to the slimes composition. The relative increase in clay over fine silica and phosphate particles at low slimes content may be responsible for the decrease in Relative Insol rejection and Relative P2O5 losses. At slimes content above the maximum, the large amount of clay, fine silica and phosphate increases the overall specific surface area for amine adsorption (decrease in amine adsorption density) depressing the systems. The behavior of the selectivity ratio, [R], is related to the rate at which the Relative Insol rejection changes with respect to that of the Relative P2O5 losses as the slimes content increases; thus, the selectivity of the amine for silica for Plant III, Unsized Flotation Feed. This selectivity ratio presented a maximum at the same slimes content at which a maximum for the Relative Insol rejection and Relative P2O5 losses appeared with the exception of Armeen DMHTD Tertiary amine, Arquad 2HT-75 Quaternary amine, and Arr-Maz condensate amine. In the case of Armeen DMHTD Tertiary amine the selectivity ratio decreased continuously as the slimes content increased, showing high sensitivity to slimes and poor selectivity. The selectivity ratio in the presence of Arquad 2HT-75 Quaternary amine showed that the selectivity ratio, [R], did not decrease significantly as the slimes content increased. This indicated the high selectivity of this amine. Arr-Maz condensate amine showed an apparent sharp increase in selectivity at high slimes content, which was related to the depression of the system and the poor selectivity of this amine. Condensate amine showed poor selectivity over low and medium slimes content. The rank from most selective to least selective amine for Plant III, Unsized Flotation Feed seems to be: 6-4

Quaternary > Ether > Primary > Tertiary > Secondary > Condensate. The effect of Percol 90L polymer addition on the amine flotation step of the reverse Crago process for Plant III, Unsized Flotation Feed was also evaluated on a relative basis for this type of feed since no optimization of the amine dosage was carried out on any of the six types of amines tested. Insol rejection, P2O5 losses (rejection) and selectivity ratio, [R], were used to evaluate the effect of Percol 90L polymer. In general, the Insol rejection increases to a maximum as the Percol 90L polymer addition increases. At this Percol 90L polymer addition, the P2O5 losses also increase, decreasing the selectivity ratio, [R]. Further increase in Percol 90L polymer addition depresses the system, the Insol rejection, P2O5 losses, and selectivity ratio decreasing. This optimum in Pecol 90L Polymer addition corresponded to 0.024 lb./ton in the presence of Armeen HT primary amine; 0.016 lb./ton in the presence of Armeen DMHTD Tertiary amine, Arquad 2HT-75 Quaternary amine, Adogen 185 Ether amine acetate, and Arr-Maz condensate amine; and 0.031 lb./ton in the presence of Armeen 2HT secondary amine. Locked Cycle tests carried out in the presence of Arr-Maz condensate amine confirmed this behavior. The amine and the Percol 90L polymer additions have to be doubled in this case to obtain the maximum in Insol rejection due to the increase in slimes in the water as the number of cycles increased. As in the case of batch flotation tests, an increase in Percol 90L polymer over 0.032 lb./ton depressed the system. The data obtained for all six types of amines can be interpreted according to the following mechanism proposed. In the absence of Percol 90L polymer, the presence of slimes (large specific surface area) may consume the amine in the bulk, reducing the flotation of silica particles. As Percol 90L polymer addition increases, this highmolecular weight (MW) anionic polymer flocculates the slimes, mainly clay. Flocs are formed, reducing the overall specific surface area available for amine adsorption, thus increasing the amine adsorption density. Therefore, the Insol rejection increases. These flocs may grow as the polymer addition further increases, fine silica and phosphate particles being entrapped and/or adsorbed (unselectively). Under these conditions, the specific surface area available for the amine to adsorb increases again (highly negatively charged flocs), reducing the overall amine adsorption density. Thus, the system is depressed. If we add the effect of the selectivity of a given amine, the depression of the system and lost of selectivity may be enhanced for a poor selective amine or decreased for a more selective one. Therefore, it is expected that an optimum balance of polymer and amine should be obtained to achieve the best Insol rejection and selectivity. Consequently, choosing the appropriate polymer and preparing a condensate amine more selective for a given feed is of utmost importance for the amine flotation of the Reverse Crago process. Apparently, a low MW polymer that produces smaller flocs, avoiding entrapment and/or adsorption of fine silica and phosphate particles would benefits the process. Also, a condensate amine with an increase in quaternary amine in its composition could be beneficial for the amine flotation step of the Reverse Crago process. 6-5

INTRODUCTION Since its broad adoption in the early 1940s, flotation has been the workhorse for phosphate beneficiation in Florida, with the Crago “Double Float” process dominating every plant. In the “Double Float” process, deslimed flotation feed is dewatered and conditioned at 70 percent or higher solids with fatty acid/fuel oil at pH about 9 for three minutes, and then the phosphate is floated. The rougher concentrate goes through a dewatering cyclone, an acid scrubber, and a wash box to remove the reagents from phosphate surfaces, followed by amine flotation (Crago 1950). Although extensive research has been done on fatty acid flotation of phosphate, limited information is available on amine flotation of quartz from phosphate. This is attributed to three major reasons. First, since amine is very selective, flotation recoveries in most plants are at the high 90s, unless the deoiling circuit is messed up. The second reason is the small amount of amine flotation feed, accounting for about one third of the fatty acid flotation feed. Finally, amine flotation is so simple, at neutral pH without conditioning, that not many factors other than slime could cause significant harm (Wiegel 1999; Klimpel 1999). However, understanding of amine flotation will become more important, as the industry encounters leaner phosphate ore, does away with deep well water for amine flotation, and searches for more environmentally friendly flotation processes (Zhang 1997).

6-7

LITERATURE REVIEW Bleier and others (1976) conducted systematic investigation on the influence of collector structure on the amine (RNH2, R=alkyl) flotation of quartz. Although definitive effects were detected of chain length, branching in the alkyl group, polyfunctionality of the collector molecule and alkyl substitution on the nitrogen atom, the authors admitted the complexity of the effects. The effectiveness of amines at pH 8 was ranked as follows: quaternary>primary>secondary>tertiary; while at pH 10 the ranking differed: primary>secondary>quaternary>tertiary. Christmann (1945) patented a mixture of polyethylenepolyamine containing predominantly diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, achieving efficient separation of silica from phosphate. Ellis (1945) conducted testing of several amine collectors from different producers, and found that the optimal size range is 20 by 100 mesh for amine flotation of sand from phosphate. Soto and Iwasaki (1985) studied different amines as phosphate collectors in separating apatite from calcareous ores. The most informative review on amine collectors was probably given by Gefvert (1988). The author first discussed the processes for manufacturing different types of amines and the basic chemical and physical properties of each type. The paper then presented some rule-of-the-thumb selection criteria for amine collectors, according to particle size, water chemistry, and water temperature. The major conclusions included the following: (1) for very coarse feed, primary amine or long-chained condensates are more suitable; while ether amines or diamines work better for finer particles because of their better selectivity; (2) pH is not important as long as it is below 10, while increasing water hardness decreases the effectiveness of cationic flotation due to increased competition for the negative sites on the particle; (3) anions will reduce the floating power of some cationic collectors, because they react with the positive collector ions to form insoluble salts, but condensates seem to be less likely to react with the anions than either the primary amines or ether amines; and (4) higher temperature reduces the effectiveness because of the increased solubility of amines in hot water. Another important research on amine flotation is the use of phosphate depressant. Nagaraj and others (1987) disclosed development of modified polymers as phosphate depressant in amine flotation of silica. The addition of this modifier at dosages of 5-20 grams per ton of feed resulted in significant increase in phosphate recovery. Other phosphate depressants investigated in silica flotation include starches (Allen 1982; Lange 1933; Leal Filho 1993;), orthophosphoric, diphosphonic, and hydrofluosilicic acids (Prasad and others 1995; Suarez and others 1997), and sodium tripolyphosphate (Snow 1988). Most early development work on silica collectors was carried out by American Cyanamid Co. (Jayne and others 1943, 1944a and 1944b). Day and others (1944) developed a class of new collectors/promoters other than amines derived from tall oil fatty acids. These reagents included higher alkyl substituted guanidines, biguanides, guanylthioureas, guanylureas, and salts thereof. Flotation tests using these reagents on a 6-9

35 by 200 mesh deslimed phosphate sample achieved silica removal of more than 95%. The same group of people (1943) also developed another class of silica collectors, consisting of higher alkyl and acyl derivatives of N-aminoethyl morpholine and salts of such derivatives. In yet another patent, Day and others (1943) disclosed a different class of silica collectors, which was derived by reacting a sulfonic acid salt of an alkylol amine with a higher fatty acid at high temperature. Hanna (1975) compared two types of quaternary amine salts and two primary amine salts in terms of adsorption and flotation performance in separating silica from phosphate. Quaternary amine salts were found to be more effective.

6-10

INFORMATION GAPS As can be seen from the above literature review, several gaps exist in the understanding of amine flotation of silica from phosphate. They include inconsistent information on selectivity, the effect of particle size, and slime tolerance level of different amines. In 1996, FIPR launched a multi-year research project to fill these gaps. The flotation results shown in this report are influenced by type, origin, and characteristics of the amine flotation feed used for the tests. Thus, absolute values of grades and recoveries changed with each sample floated, but the trends stayed the same. In addition, it should be pointed out that the data shown in the report does not correspond to optimum flotation conditions with respect to any variable. Moreover, custom designed amine for a given amine flotation feed is usually prepared in industrial practice (Yap 1999), which is modified according to changes in the characteristics of the amine flotation feed. The amines used in this study were not specific for the material tested. Therefore, trends and relative indices should be used to compare the selectivity of these amines.

6-11

OBJECTIVES The aim of this research program was to evaluate six types of amines on the cleaning step of the Crago process and on the amine flotation step of the Reverse Crago process. The unsized amine flotation feeds samples were obtained from Plant I, whereas the sized amine flotation feeds both coarse and fine were obtained from Plant II. The unsized rougher flotation feed was obtained from Plant III. These samples were submitted to screen analysis, batch and Locked Cycle flotation tests, and Tree Analysis procedure to fulfill the research work plan proposed. Specifically, this research is aimed at determining the following: i. The performance of six types of amines used for the cleaning step of rougher concentrates of the Crago process. For this purpose, primary, secondary, tertiary, and quaternary amines as well as ether amine acetate and condensate amine were tested. ii. The effect of particle size determined by the particle range to be floated by each type of amine, and the performance of these types of amines on coarse and fine amine flotation feeds. iii. The effect of slimes (tolerance) on the amine flotation step of the Reverse Crago process using the six types of amines at different slimes contents. iv. The effect of Percol 90L polymer dosage on the amine flotation step of the Reverse Crago using the six types of amines.

6-13

MATERIALS AND METHODS FLOTATION FEEDS Four types of amine flotation feeds were used during this investigation: Plant I unsized amine feed, Plant II coarse amine feed, and Plant II fine amine feed for the cleaning step of the Crago process. ocess. For the amine flotation step of the Reverse Crago process, Plant III flotation tation feed was used. Table 66-1 1 and Figure 61 summarize the characterization data obtained for these samples. Detailed sizing analyses of these samples are shown in Appendix 6A. A. Table 6-1. Basic Properties of Test Samples. Sample Plant I U.A.F. Plant II Coarse A.F. Plant II Fine A.F. Plant III Flotation F.

Grade % P2O5 % Insol 28.18 16.48 30.62 9.78 26.88 20.17 6.82 78.38

Particle Size Distribution, µm m d90 d50 d10 600 331 152 631 400 171 427 200 113 422 221 123

Figure 6-1. Particle Size Distribution for A All Feeds. 6-15

REAGENTS The reagents selected for this research are presented in Table 6-2. All of these amines were 75% neutralized with acetic acid and mixed with 25% of 2-ethylhexanol frother. They represent the three major groups of amines used as collectors: fatty acid amines (the first four amines tested), ether amines and amine condensates. Unfortunately, a secondary amine with one methyl group was not available to complete the series. Table 6-2. Amines Tested. Brand Name Armeen HT Armeen 2HT Armeen DMHTD Arquad 2HT-75 Adogen 185 Arr-Maz

Description Hydrogenated Tallow Alkylamine Dihydrogenated Tallow Alkylamine Dimethylhydrogenated Tallow Alkylamine Distilled Dihydrogenated Tallow Alkyl-dimethyl Ammonium Chloride Ether Amine Acetate Condensate Amine

6-16

Type Primary Secondary

State S S

Tertiary

L

Quaternary

S

Ether Condensate

L L

EXPERIMENTAL RESULTS AND DISCUSSION EVALUATION OF DIFFERENT TYPES OF AMINES As an example of these selectivity studies, eight dosage levels of the six types of amines were tested using the unsized amine flotation feed from Plant I. For the evaluation of the different types of amines, the following parameters were used: the Selectivity Index as defined by Gaudin (1957), the ratio of Insol rejection to the tailings weight percentage, and the shape of the Recovery-Grade curve (selectivity curve) represented by the tangent (Tang) at the keen of the curve. In addition, the Tree Analysis procedure (Pratten and others 1957) was conducted for the best reagent dosage for each type of amine to determine the locus of the Recovery-Grade curve. Tree analysis is a standard procedure to determine the best possible separation under standard test conditions. Even though this technique was not able to fully describe the whole locus of the Recovery-Grade curve due to an improper distribution of the amine addition during the different steps of the test, this technique was able to obtain results close to those obtained by several batch flotation tests. The Tree Analysis procedure eliminates the effect of feed grade variation on the batch flotation tests, and requires less time, effort and material to obtain the selectivity curve. Finally, a locked cycle flotation test was carried out based on the best conditions for each type of amine to determine the effect of recycle water on the reagent dosage and product quality. The results of the batch flotation tests are summarized in Tables 6-3 to 6-8 and in Figures 6-2 to 6-12. Appendix 6B contains the complete set of results obtained. The effect of each amine on the flotation of Plant I, Unsized Amine Feed was evaluated using the Selectivity Index, SI, and the ratio of Insol rejection to the tailings weight percentage, R*, for all amines tested. The results of batch flotation tests using Armeen HT primary amine are shown in Table 6-3. This table shows that the best results were obtained at 0.4 lb./ton amine addition based on the selectivity, concentrate grade, and recovery. Figure 6-2 shows that at this amine addition, a 2% Insol in the concentrate with 97.6% P2O5 recovery was obtained. Further addition of this primary amine did not decrease the Insol grade in the concentrate. Probably, Armeen HT primary amine was not able to float coarse silica particles. Figure 6-3 presents the recovery of P2O5 as a function of Insol grade in the concentrate (Selectivity Curve). This figure shows a sharp decrease in the P2O5 recovery without any decrease in the Insol grade in the concentrate. These results were confirmed with the Tree Analysis procedure. Even though it was not possible to characterize the whole locus of the Recovery-Grade curve due to an improper distribution of the amine addition for each step, this technique is able to obtain results close to those obtained by several batch flotation tests. The Tree Analysis procedure eliminates the effect of feed grade variation on the batch flotation tests, and requires less time, effort and material to obtain the Selectivity curve. Tree analysis results for all amines are shown in Appendix 6C.

6-17

Table 6-3. Armeen HT Primary Amine Series. Dosage cc

Lb./Ton

2.5 2.5 5.0 7.5 7.5 10.0 12.5 15.0

0.198 0.198 0.395 0.586 0.591 0.779 0.988 1.195

Concentrate % % % Wt. P2O5 Insol 85.16 32.50 3.13 87.10 32.20 4.04 83.70 32.88 2.05 82.48 32.99 1.92 84.04 33.09 2.00 80.95 32.82 2.14 79.11 32.97 1.84 75.43 32.96 1.84

Distribution % % P2O5 Insol 98.52 16.52 99.20 22.52 97.56 10.85 96.34 9.99 97.75 10.79 94.60 10.74 92.27 9.27 87.66 8.97

Reject. % Insol 83.48 77.48 89.15 90.01 89.21 89.26 90.73 91.03

R*

SI

5.62 6.01 5.47 5.14 5.59 4.69 4.34 3.70

335.5 427.5 328.1 237.3 358.4 145.6 116.9 72.1

ecovery and Insol Grade in the C Concentrate as a Function of Figure 6-2. P2O5 Recovery Armeen HT Primary A Amine Addition ddition for Plant I, Unsized Amine Feed.

6-18

Figure 6-3. P2O5 Recovery as a F Function of Insol Grade in the Concentrate for Plant I, Unsized Amine Feed U Using Armeen HT Primary Amine with Tree Analysis Results Shown for Comparison. 6 The flotation results using Armeen 2HT secondary amine are shown in Table 6-4 and Figure 6-4. 4. No conclusion can be drawn from this data due to limitations in the solubility of this amine. This amine is so insoluble that it requires to be warmed to prepare an emulsion. However, once in contact with the flotation slurry in the cell, the emulsion collapse, and little collector is dispersed. Under these conditions, poor flotation takes place at reasonable reagent additions. No tests over 22.8 lb./ton on amine addition were carried out (see Figure 6-4). 4). A secondary amine with only one tallow hydrocarbon chain and one methyl group was requested from the manufacturers. However, it was not obtained. Future work requires test testing this type of moree soluble amine. In addition, this type of amine will suit better to the series tested. Table 6-4. Armeen 2HT Secondary Amine Series. Dosage cc

Lb./Ton

2.5 5.0 7.5 10.0 12.5 15.0 17.5 35.0

0.204 0.405 0.605 0.813 1.015 1.216 1.423 2.846

Concentrate % % % Wt. P2O5 Insol 99.41 28.23 16.49 99.13 28.54 15.84 98.97 28.61 15.97 98.84 28.16 16.94 99.19 28.24 15.85 98.82 28.27 15.76 98.11 28.38 15.76 90.61 30.81 8.50

6-19

Distribution % % P2O5 Insol 99.76 97.77 99.66 96.62 99.58 96.31 99.43 96.24 99.57 97.38 99.47 95.75 99.33 92.17 99.04 47.65

Reject. % Insol 2.23 3.38 3.69 3.76 2.62 4.25 7.83 52.35

R*

SI

3.78 3.89 3.58 3.24 3.23 3.60 4.14 5.58

9.3 10.2 9.2 6.9 6.2 8.4 12.6 113.0

Figure 6-4. P2O5 Recovery and d Insol Grade in the Concentrate as a F Function n of Armeen 2HT Secondary Amine Addition ddition for Plant I, Unsized Amine Feed. flotation results for Armeen DMHTD tertiary ertiary amine. Table 6-5 presents the batch flot The best results were obtained at 0.4 lb./ton amine addition with 97.6% of P2O5 recovery and 3.9% Insol nsol in the concentrate. Figure 66-5 5 shows that tertiary amine requires large amounts to float as coarse silica as primary amine since 2% Insol in the concentrate is obtained at 1.1 lb./ton on tertiary amine addition. Similar to the case of the primary amine, amine an increase in tertiary amine addition over that of the best batch flotation test decreased decrease the recovery significantly, losing sing selectivity. T This can be clearly seen in the Selectivity electivity curve shown in Figure 6-6. 6. This curve includes also the Tree Analysi Analysiss results, which falls over the same locus of the Recovery Recovery-Grade Grade curve. As in the case of primary amine, the incremental addition of tertiary amine was not properly selected. As a consequence, the data only describes a small portion of the Selectivity cu curve. rve. Further investigation of this flotation procedure should be considered. The flotation results of Arquad 2HT 2HT-75 Quaternary ary amine are shown in Table 6-6 6 and Figures 6-7 and 6-8. 8. This amine seems to be very selective for the Plant I, Unsized Amine Feed ed floated. The best results were obtained at 0.2 lb./ton on quaternary amine addition. At this level of addition, 98.7% P2O5 was recovered with the concentrate containing 3.5% Insol. At 0.4 lb lb./ton on of quaternary amine addition, the Insol in the concentratee dropped to about 2% (see Figure 66-7). 7). As the quaternary amine addition increased over 0.4 lb./ton, on, the Insol grade of the concentrate did not drop further down, and the recovery decreased slightly. These indicate a better selectivity than both the primary ary and tertiary amines. Figure 66-7 shows that the Recovery Grade curve for Plant I, Unsized Amine Feed, using this quaternary amine was almost horizontal until about 2% Insol in the concentrate; thus, the amine was highly selective. The Tree Analysis results re

6-20

are also shown in Figure 6-7. 7. This data only describes a short segment of the Selectivity curve due the distribution of the amine addition selected. More research on this technique should be carried out. Table 6-5. Armeen DMHTD Tertiary Amine Ser Series. Dosage cc

Lb./Ton

1.25 2.00 2.50 2.50 3.00 3.50 5.00 7.50

0.182 0.292 0.364 0.364 0.440 0.513 0.727 1.092

Concentrate % % % Wt. P2O5 Insol 97.59 29.15 13.70 84.35 32.39 3.97 87.39 31.77 5.13 85.48 32.42 3.86 84.32 32.73 3.93 82.61 32.68 3.36 78.90 32.65 2.57 67.51 32.77 2.13

Distribution % % P2O5 Insol 99.87 85.44 97.07 20.38 99.09 27.76 98.09 20.54 97.59 20.40 95.51 17.07 91.50 12.71 79.26 8.80

Reject. % Insol 14.56 79.62 72.24 79.46 79.60 82.93 87.29 91.20

R*

SI

6.04 5.09 5.73 5.47 5.24 4.97 4.14 2.81

128.9 129.4 283.8 198.5 160.1 103.4 74.0 7 39.6

Figure 6-5. P2O5 Recovery and Insol in the Concentrate as a F Function unction of Armeen DMHTD Tertiary Amine A Addition ddition for Plant I, Unsized Amine Feed.

6-21

Figure 6-6. P2O5 Recovery as a F Function of Insol in the Concentrate for or Plant I, Unsized Amine Feed Using Armeen DMHTD Tertiary Amine with Tree T Analysis Results Shown hown for Comparison. Table 6-6. Arquad 2H-75 75 Quaternary Amine Series. Dosage cc

Lb./Ton

1.25 1.25 2.50 2.50 4.00 5.00 6.00 7.50

0.101 0.101 0.203 0.202 0.322 0.404 0.485 0.607

Concentrate % % % Wt. P2O5 Insol 91.48 30.91 8.49 91.43 30.78 9.13 89.25 31.46 6.77 88.20 32.66 5.57 85.83 32.66 3.46 82.96 33.11 2.24 83.16 33.04 2.38 81.99 33.08 2.19

6-22

Distribution % % P2O5 Insol 99.74 48.51 99.72 50.00 99.44 37.20 99.26 30.70 98.72 18.63 96.84 11.53 96.72 12.41 95.67 11.16

Reject. % Insol 51.49 50.00 62.80 69.30 81.37 88.47 87.59 88.84

R*

SI

6.04 5.83 5.84 5.87 5.74 5.19 5.20 4.93

405.0 357.0 302.0 304.3 337.6 235.0 207.9 175.8

Figure 6-7. P2O5 Recovery ecovery and Insol Grade in the C Concentrate as a Function on of Arquad 2HT-75 75 Quaternary Amine A Addition for Plant I, Unsized Amine Feed.

Figure 6-8. P2O5 Recovery as a Function of Insol Grade in the Concentrate oncentrate for f Plant I, Unsized Amine Feed U Using Arquad 2HT-75 Quaternary Amine with Tree Analysis Results Shown for Comparison.

6-23

Similar to the case of previous amines, the Adogen 185 Ether amine acetate was evaluated. It was found that a 98% P2O5 recovery with 2.5% Insol in the concentrate was obtained with an addition of 0.163 lb./ton ether amine acetate. For the Plant I, Unsized Amine Feed used, the ether amine was able to pull some coarse silica and reduced the Insol content in the concentrate to 1.7%. However, P2O5 recovery decreased as the ether amine acetate increased. Thus, poor selectivity was obtained by using this amine (see Table 6-7 and Figure 6-9). Table 6-7. Adogen 185 Ether Amine Acetate Series. Dosage cc

Lb./Ton

1.25 2.00 2.50 3.00 4.00 4.50 5.00 7.50

0.102 0.163 0.204 0.245 0.325 0.366 0.408 0.612

% Wt. 87.37 84.34 83.29 82.27 78.89 76.79 74.38 57.17

Concentrate % % P2O5 Insol 32.61 4.78 33.39 2.54 33.34 2.43 33.74 2.05 33.58 1.88 33.82 1.38 33.62 1.68 33.43 1.70

Distribution % % P2O5 Insol 99.08 26.36 97.96 13.52 96.99 12.69 96.17 10.60 92.03 9.38 89.49 6.93 86.85 7.97 66.67 6.11

Reject. % Insol 73.64 86.48 87.31 89.40 90.62 93.07 92.03 93.89

R*

SI

5.83 5.52 5.23 5.04 4.29 4.00 3.59 2.19

301.4 306.8 221.5 211.7 111.5 114.3 76.3 30.7

The Selectivity curve and the Tree Analysis procedure results are presented in Figure 6-10. This figure clearly shows that the P2O5 recovery sharply decreased without decreasing the Insol grade in the concentrate. Again poor selectivity was observed. The Tree Analysis procedure follows the same locus of the Selectivity curve obtained by using batch flotation tests. In the case of Arr-Maz condensate amine, the best results were obtained at 0.4 lb./ton amine addition. At this level of amine addition, a 98% P2O5 recovery with 2.54% Insol grade in the concentrate was obtained. Even though the decrease in the recovery as the Insol grade in the concentrate decreased to 1.6% was not as sharp as that for the ether amine acetate, the data indicated poor selectivity (see Table 6-8 and Figure 6-11). The Recovery-Grade curve is shown in Figure 6-12. As can be seen, the selectivity decreased sharply when the Insol grade in the concentrate was lower than 2%. Tree Analysis results followed the locus of the Selectivity curve over the range studied. However, a better distribution of the amine addition was required to cover the whole range from the highest recovery-highest Insol grade in the concentrate to the lowest recovery-lowest Insol grade.

6-24

ecovery and Insol Grade in th thee Concentrate as a Function of Figure 6-9. P2O5 Recovery Adogen 185 Ether Amine Acetate A Addition ddition for Plant I, Unsized Amine Feed.

Figure 6-10. P2O5 Recovery as a Function of Insol Grade in the Concentrate oncentrate for Plant I, Unsized Amine Feed U Using Adogen 185 Ether Amine Acetate, with Tree Analysis Results Shown for C Comparison.

6-25

Table 6-8. Arr-Maz Condensate Amine Series. Dosage cc

Lb./Ton

2.50 4.00 5.00 6.00 7.50 8.00 10.00 12.50

0.202 0.323 0.405 0.485 0.605 0.645 0.811 1.011

Concentrate % % % Wt. P2O5 Insol 88.58 32.05 6.04 84.92 33.09 3.04 83.96 33.30 2.54 82.77 33.30 1.79 81.09 33.41 2.12 80.51 33.51 2.32 78.56 33.50 1.93 74.52 33.39 1.64

Distribution % % P2O5 Insol 99.51 33.04 98.44 16.00 97.98 13.17 96.96 9.50 95.22 10.50 94.43 11.41 91.90 9.50 87.32 7.68

Reject. % Insol 66.96 84.00 86.83 90.50 89.50 88.59 90.50 92.32

R*

SI

5.86 5.57 5.41 5.25 4.73 4.54 4.22 3.62

408.6 331.6 320.3 303.5 169.9 131.6 108.1 82.7

To compare the results of the batch flotation tests, the amine consumption for the best tests; the average ratio tio of Insol rejection to the weight percentage of tailings, R*; the Selectivity Index, SI; and the tangent to the keen of the Selectivity curve were evaluated and the results sults are presented in Table 66-9.

Figure 6-11. P2O5 Recovery and Insol Grade as a Function of Arr-Maz Condensate Amine Addition ddition for Plant I, Unsized Amine Feed.

6-26

Figure 6-12. P2O5 Recovery as a F Function of Insol Grade in the Concentrate oncentrate for Plant I, Unsized Amine Feed Using Arr-Maz Condensate Amine, with w Tree Analysis Results Shown for Comparison. Table 6-9.. Summary of Batch Flotation Test Tests. Amine Type Primary Secondary Tertiary Quaternary Ether Condensate

Best Test Lb./Ton 0.4 2.8 0.4 0.3 0.2 0.4

R* 5.07 3.88 4.91 5.58 4.46 4.90

Average SI Tang. 252.7 2.11 22.0 -139.7 0.88 290.5 1.33 171.8 1.60 232.2 1.06

R* 2 6 3 1 5 4

Rank SI Tang. 2 5 6 6 5 1 1 3 4 4 3 2

Overall 3.0 6.0 3.0 .0 1.7 4.3 3.0

This table indicates that the quaternary amine seems to be the most selective one follow by the tertiary, condensate, and primary amine, which behave similarly. Finally, the secondary amine is the last in the series because it was not possible to evaluate it. Observation of the tests indicates that the ether amine acetate is the strongest of the amine tested for the sample of Plantt I, Unsized Amine Feed, followed by the primary, tertiary, and condensate amines. The Locked Cycle tests results are summarized in Table 6-10 and nd the data shown in Appendix 6D.. These tests evaluate the influence of slimes on the performance of these amines ines and the selectivity obtainable at quasi quasi-steady steady state conditions for Plant I, Unsized Amine Feed. For this purpose, the ratio of Insol/100 Insol/100-concentrate concentrate weight, R*; the

6-27

Selectivity Index, SI; and the relative increase in amine consumption for quasi-steady state conditions were used to evaluate the Locked Cycle tests. Table 6-10. Summary of Locked Cycle Tests. Amine Type Primary Secondary Tertiary Quaternary Ether Condensate

Dosage, Lb./Ton Init. Final ∆, % 0.4 0.2 -50 ---0.4 0.5 +25 0.3 0.5 +67 0.2 0.2 +50 0.4 0.5 +25

Grade, % P2O5 Insol 32.84 2.11 --32.59 3.18 32.77 2.77 32.74 2.60 32.94 1.84

Dist., % P2O5 Insol 96.90 10.98 --97.36 16.61 98.65 14.72 96.21 13.30 92.88 9.16

R*

SI

5.22 -5.30 5.73 4.98 4.42

284 -203 422 167 130

Rank R* SI 3 2 -- -2 3 1 1 4 4 5 5

Total 2.5 -2.5 1.0 4.0 5.0

This summary table clearly shows that the most selective amine was the quaternary amine, but it was also the amine most affected by the presence of slimes (increase in amine consumption). Primary and tertiary amines had similar selectivity. However, tertiary amine was affected by slimes, whereas primary amine was able to perform better in the presence of slimes (reduction of amine consumption). Ether amine acetate was not very selective, and was strongly affected by slimes. The least selective amine for this amine feed was the condensate amine. However, it floated more Insol and was not strongly affected by slimes. EFFECT OF PARTICLE SIZE The evaluation of the effect of particle size on the performance of the amine tests was carried out using the screen assays of the tailings and concentrates of the best batch flotation tests performed. The data is presented as weight frequency of P2O5 and Insol, and P2O5 and Insol distribution as a function of particle size. In addition, flotation tests for Plant II, Coarse Amine Feed and Plant II, Fine Amine Feed were performed based on the amine additions used in the best tests for each amine for the Plant I, Unsized Amine Feed. Since the dosages used for the flotation of the Plant II samples were not adequate for these types of new feeds, the results were analyzed only on a relative basis. The data are presented in Appendix 6E, Figures 6-13 through 6-24, and summarized in Tables 6-11 and 6-12. For this purpose, two types of indices were developed; R and D, and shown in Table 6-12. R corresponds to the ratio between the Insol distribution at a given particle size to the P2O5 distribution at the same particle size for the tailings (see Appendix 6F and Figures 6-3 through 6-7). Therefore, R could be related to the specificity of the amine for the Insol at the stated particle size. If R is less or equal to one, it is indicating that losses in P2O5 are greater (R1, the amine specifically adsorbs onto the silica surfaces, the silica particles floating preferentially.

6-28

Table 6-11. Summary of Screen Assays for Tailings Using the Relative Effect on Distributions; R, D. Amine Primary Secondary Tertiary Quaternary Ether Condensate

Index R D R D R D R D R D R D

35 0.39 -1.02 --1.25 +0.02 0.53 -0.23 0.41 -0.60 0.35 -0.83

Mesh 65 1.21 +0.56 0.33 -1.02 1.08 +0.23 1.07 +0.17 1.21 +0.54 0.81 -0.41

48 0.56 -1.97 0.33 -1.07 1.22 +0.21 0.79 -0.46 0.73 -0.88 0.67 -1.11

100 1.57 +1.61 1.61 +1.99 0.77 -1.13 1.08 +0.27 1.17 +0.62 1.56 +1.61

150 1.46 +0.83 1.09 +0.21 1.19 +0.50 1.13 +0.24 1.14 +0.30 1.38 +0.66

200 1.05 -0.02 0.85 -0.11 1.65 +0.17 1.16 +0.01 1.12 +0.02 1.33 +0.08

The index D is calculated by comparing the plain weight frequency with the Insol weight frequency (see Figures 6-13 through 6-17) in the tailings. The purpose of this index is to determine if the reagent is able to alter the weight distribution by selectively rejecting Insol at a given size fraction. A positive number indicates that the weight frequency has being altered by floating more Insol at the stated size fraction. A zero or negative value indicates that no or less Insol was floated from that size fraction. Table 6-11 presents the specificity for Insol of each amine. Primary amine is more efficient in the 65 x 150-mesh particle size range, secondary amine in the 100 x 150-mesh range, tertiary amine in the 35 x 200-mesh particle size range, quaternary amine in the 65 x 200-mesh range, ether amine acetate in the 65 x 200-mesh particle size range, and condensate amine in the 100 x 200-mesh range. Appendix G also presents the material balance for each particle size fraction studied for Plant I, Unsized Amine Feed using six types of amines. Figures 6-19 through 6-23 show the distribution of both P2O5 and Insol in the concentrates and tailings as a function of particle size for the primary, secondary, tertiary, quaternary, ether, and condensate amines, respectively. These figures clearly show the particle size at which the Insol has 50% of probability to report in the tailings or the concentrate (PInsol 50). A coarser PInsol 50 indicates that the amine was able to float coarser particles. Thus, PInsol 50 was used in Table 6-12 as an index to evaluate the effect of particle size on the different types of amines.

6-29

Table 6-12. Summary of Semi-Q Quantitative uantitative Evaluation of the Effect of Particle Size. Amine Primary Secondary Tertiary Quaternary Ether Condensate

PInsol 50 µm 410 230 333 333 370 400

Plant II Insol Rejec. Coarse Fine 81.92 94.87 --61.74 61.91 57.60 63.50 58.71 61.57 69.61 81.05

Specificity Size Range 65 x 150M 100 x 150M 35 x 200M 65 x 200M 65 x 200M 100 x 200M

Ratio Insol Rejec. Coarse/Fine 0.86 -1.00 0.91 0.95 0.86

Overall Rank 1 N.D. 3 4 2 2

Note: N.D. = not defined.

Figure 6-13. Weight Frequency D Distributions for Insol and P2O5 of Tailings ailings and Concentrates oncentrates for Pla Plant I, Unsized Amine Feed as a Function of Particle Size Using sing Armeen HT Primary A Amine.

6-30

Distributions for Insol and P2O5 of Tailings ailings and Figure 6-14. Weight Frequency D Concentrates oncentrates for Plant I, Unsized Amine Feed as a Function of Particle article Size Using sing Armeen 2HT Second Secondary Amine.

Figure 6-15. Weight Frequency D Distributions for Insol and P2O5 of Tailings ailings and Concentrates oncentrates for Plant I, Unsized Amine Feed as a Function of Particle article Size Using sing Armeen DMHTD Tertiary Amine.

6-31

Figure 6-16. Weight Frequency Distributions ffor Insol and P2O5 of Tailings and nd Concentrates for Plant II, Unsized Amine Feed as a Function off Particle Size Using Arquad 2HT 2HT-75 Quaternary Amine.

Figure 6-17. Weight Frequency Distributions ffor Insol and P2O5 of Tailings and nd Concentrates for Plant II, Unsized Amine Feed as a Function off Particle Size Using Adogen 185 Ether Amine Acetate.

6-32

Figure 6-18. Weight Frequency Distributions ffor Insol and P2O5 of Tailings and nd Concentrates for Plant II, Unsized Amine Feed as a Function off Particle Size Using Arr-Maz Maz Condensate Amine.

Figure 6-19. 9. Distributions of Insol and P2O5 in Both Tailings and Concentrates oncentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen HT Primary A Amine. 6-33

Figure 6-20.. Distributions of Insol and P2O5 in Both Tailings and Concentrates oncentrates for Plant ant I, Unsized Amine Feed as a Function of Particle Size U Using Armeen 2HT Secondary A Amine.

Figure 6-21. Distributions of Insol and P2O5 in Both Tailings and nd Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Armeen DMHTD Tertiary Amine.

6-34

f Figure 6-22. Distributions of Insol and P2O5 in Both Tailings and Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Arquad 2HT-75 Quaternary Amine.

Figure 6-23. Distributions of Insol and P2O5 in Both Tailings and nd Concentrates for Plant I, Unsized Amine Feed as a Function of Particle Size Using Adogen 185 Ether Amine Acetate Acetate.

6-35

Figure 6-24.. Distributions of Insol and P2O5 in Both Tailings and Concentrates oncentrates for Plant I, Unsized Amine Feed as a F Function of Particle Size Using ArrArr Maz Condensate Amine. mine. Apparently, the flotation rank from coarse to fine Insol is as follows: Primary > Ether = Condensate > Tertiary > Quaternary for the flotation results of Plant I, Unsized Amine Feed and Plant II, Coarse and Fine Amine Feeds. EFFECT OF SLIMES ON THE AMINE FLOTATION STEP OF THE REVERSE CRAGO PROCESS For these studies, Plant III, Unsized Flotation Feed was used. In general, it was observed that the effect of slimes was complex since slimes affect the water quality, surface of the silica and phosphate particles, and amine consumption by increasing the total specific surface area available for amine adsorption. To evaluate the effect of slimes, the Plant III, Unsized Flotation Feed was scrubbed for one and three minutes, and washed over a 200 mesh (75 µm) to reduce the slimes content. The base line test was performed on a sample without scrubbing, and the highest slime content was obtained by scrubbing the sample for three minu minutes tes without washing it. The slimes content was measured bby drying and weighing the -200-mesh mesh size fraction generated after scrubbing for different periods of time. For the samples that were washed the weight was subtracted to that of the unscrubbed sampl sample. e. If the samples were 6-36

not washed the equivalent weight of the three minutes scrubbed sample was added to the slimes weight of the unscrubbed sample. This procedure to generate slimes by scrubbing contributes to the complexity of the effect of slimes since scrubbing generates fine particles (-200 M) of silica and phosphate besides clay. Since the amines dosages used for these tests were based on Plant I, Unsized Amine Feed tests, and the amine addition depends on the type of phosphate feed, the results were analyzed on a relative basis to determine trends. Thus, all data are related to the corresponding results of the unscrubbed test (baseline). The results of these tests are presented in Appendix VI-G and summarized in Tables 115-120. Table 6-13 presents the results of the amine flotation step of the Reverse Crago Process for Plant III, Unsized Flotation Feed using Armeen HT primary amine. The results indicated that at 0.32% of slimes content the relative Insol rejection reached a maximum, as well as the relative phosphate losses and the selectivity ratio, R. As the slimes content increased, the indices decreased due to the depression of the amine flotation system. Thus, the phosphate losses and the Insol rejection (or floated fraction) decreased, the latter decreasing at a higher rate. Therefore, the selectivity ratio, R, decreased. At lower slimes content the results were also lower than those obtained at 0.32% slimes content. Apparently, at lower than 0.32% slimes content more clay was present in the slimes than fine phosphate and silica, slightly reducing the flotation efficiency. At higher than 0.32% slimes content, large amount of clay as well as fine phosphate and silica increased the overall specific surface area for amine adsorption (decreased in amine adsorption density); thus, depressing the system. The effect of slimes on the amine flotation step of the Reverse Crago process using Armeen 2HT secondary amine is summarized in Table 6-14. Similar to the Armeen HT primary amine, a maximum at 0.42% of slimes content was observed, even though flotation was poor because Armeen 2HT secondary amine was not properly dispersed. As slimes content increased, the amine flotation system was depressed. Table 6-13. Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen HT Primary Amine. Slimes Cont. Gram 2.50 1.60 1.40 3.60

% 0.50 0.32 0.28 0.72

Dosage, Lb./Ton 0.099 0.099 0.100 0.098

% Wt. 13.91 20.76 18.45 1.30

Tailings % P2O5 0.42 0.32 0.31 2.05

% Insol 97.97 98.30 98.38 92.88

Distribution % % P2O5 Insol 0.84 17.80 0.94 26.47 0.87 22.97 0.39 1.54

6-37

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 64.0 11.90 49.55 56.0 3.57 29.77 144.0 -53.57 -91.30

R 21.07 28.16 26.40 3.95

Table 6-14. Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen 2HT Secondary Amine. Slimes Cont. Gram 2.50 2.10 1.60 3.40

% 0.50 0.42 0.32 0.68

Dosage, Lb./Ton 1.598 1.595 1.592 1.604

% Wt. 7.03 7.38 3.96 0.98

Tailings % P2O5 0.46 0.46 0.85 2.31

% Insol 98.06 98.09 96.55 91.97

Distribution % % P2O5 Insol 0.47 8.89 0.48 9.31 0.49 4.88 0.33 1.16

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 84.0 2.13 4.72 64.0 4.26 -45.11 136.0 -29.79 -86.95

R 18.91 19.90 9.95 3.51

The results for Plant III, Unsized Flotation Feed floated using Armeen DMHTD Tertiary amine in the amine flotation step of the Reverse Crago process are presented in Table 6-15. Similar to the case of Armeen HT primary amine and Armeen 2HT secondary amine, a maximum was observed at 0.42% of slimes content for the relative Insol rejection and the relative P2O5 losses. However, the selectivity ratio, R, decreased continuously over the whole range of slimes content studied. This index indicated that the rate of Insol rejection decreased faster than the rate of P2O5 losses (loss of selectivity) since the flotation of silica was depressed by slimes. Apparently, the maximum in relative Insol rejection and P2O5 losses is related to the slimes composition. The relative increase in clay over fine silica and phosphate at lower slimes content may be responsible for the decrease in relative Insol rejection and relative P2O5 losses with respect to that at 0.42% of slimes content. As the total amount of slimes increased over 0.42% of slimes content, the amine flotation system is depressed. Table 6-15. Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Armeen DMHTD Tertiary Amine. Slimes Cont. Gram 2.50 2.10 1.70 3.30

% 0.50 0.42 0.34 0.66

Dosage, Lb./Ton 0.284 0.283 0.285 0.287

% Wt. 40.32 50.17 33.73 1.76

Tailings % P2O5 0.37 0.35 0.25 0.70

% Insol 98.48 98.43 98.88 97.29

Distribution % % P2O5 Insol 2.15 50.49 2.50 62.94 1.20 42.66 0.19 2.17

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 84.0 16.28 24.66 68.0 -44.19 -15.51 132.0 -91.16 -95.70

R 23.48 25.18 35.25 11.42

Table 6-16 summarizes the effect of slimes on the amine flotation step of the Reverse Crago process for Plant III, Unsized Flotation Feed using Arquad 2HT-75 quaternary amine. This type of amine proves to be the most selective amine in the case of Plant I, Unsized Amine Feed. Apparently, this high selectivity is also shown in the case of Plant III, Unsized Flotation Feed since the selectivity ratio, R, did not decrease significantly as the slimes content increased. This indicates that the rate at which the Insol rejection decreased was almost the same of that of the P2O5 losses decreased as the slimes content increased. The selectivity of this amine towards silica can be also observed by the absence of a maximum in the relative Insol rejection. This showed that at low slimes content, the quaternary amine would preferentially adsorbs onto silica 6-38

particles rather than onto clay. In the case of relative P2O5 losses a maximum was still present at 0.46% of slimes content. As in the case of previous amines tested, this maximum may be related to the relative content of clay, fine silica and phosphate in the slimes. At high slimes content, the system was depressed as in the case of primary, secondary, and tertiary amines. Table 6-16. Summary of the Effect of Slimes on the Amine Flotation Step of the the Reverse Crago Using Arquad 2HT-75 Quaternary Amine. Slimes Cont. Gram 2.50 2.30 1.90 3.10

% 0.50 0.46 0.38 0.62

Dosage, Lb./Ton 0.198 0.197 0.197 0.200

% Wt. 40.41 45.30 46.62 4.43

Tailings % P2O5 0.32 0.34 0.30 0.40

% Insol 98.54 98.48 98.68 98.10

Distribution % % P2O5 Insol 1.83 50.76 2.18 56.95 1.96 58.78 0.25 5.64

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 92.0 19.13 12.20 76.0 7.10 15.80 124.0 -86.34 -81.89

R 27.74 26.12 29.99 22.56

The effect of slimes on the flotation behavior of Plant III, Unsized Flotation Feed in the presence of Adogen 185 Ether amine acetate in the amine flotation step of the Reverse Crago process is summarized in Table 6-17. Even though Adogen 185 Ether amine acetate showed poor selectivity in the case of Plant I, Unsized Amine Feed; this amine showed better selectivity in the case of Plant III, Unsized Flotation Feed. The selectivity Ratio, R, presented a maximum at 0.40% of slimes content, decreasing only slightly at lower or higher slimes content. Thus, the decrease in Insol rejection with respect to that of P2O5 losses was not significantly affected by the increase or decrease in slimes content. As in the case of the quaternary amine, ether amine acetate showed a maximum for the relative Insol rejection as a function of slimes content. This indicates the selectivity of this amine for silica particles. The presence of a maximum in the relative P2O5 losses may be related to the slimes composition at 0.48% of slimes content. Further increase in the slimes content depressed the system decreasing both the relative Insol rejection and the relative P2O5 losses. Table 6-18 presents the summary of the effect of slimes on the amine flotation step of the Reverse Crago process for Plant III, Unsized Flotation Feed using Arr-Maz condensate amine. This amine presented an apparent sharp increase in the selectivity at high slimes content. This effect is related to the fast rate of decrease in relative P2O5 losses at high slimes content in comparison with that of the relative Insol rejection in the presence of high condensate amine addition (0.4 lb./ton). At this high slimes content, fine silica and clay may adsorb preferentially the amine. The absence of a maximum in both the relative Insol rejection and the relative P2O5 losses also indicated that the flotation in the presence of condensate amine is strongly affected by the presence of slimes. Arr-Maz condensate amine seemed to be unselective since at low and medium slimes content, high relative P2O5 losses were observed along with low selectivity ratios. However, the high condensate amine addition may contribute to the poor selectivity shown as low and medium slimes content.

6-39

The rank from most selective to least selective amine for Plant III, Unsized flotation Feed could be given as: Quaternary > Ether > Primary > Tertiary > Secondary > Condensate. Table 6-17. Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Adogen 185 Ether Amine Acetate. Slimes Cont. Gram 2.50 2.40 1.60 3.40

% 0.50 0.48 0.32 0.68

Dosage, Lb./Ton 0.158 0.157 0.157 0.159

% Wt. 41.01 53.76 63.73 1.89

Tailings % P2O5 0.40 0.38 0.51 0.66

% Insol 98.24 98.20 97.92 97.36

Distribution % % P2O5 Insol 2.35 51.45 3.08 66.22 4.56 79.69 0.17 2.40

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 96.0 31.06 27.71 64.0 9.40 54.89 136.0 -92.77 -95.34

R 21.89 21.50 17.48 14.12

Table 6-18. Summary of the Effect of Slimes on the Amine Flotation Step of the Reverse Crago Using Arr-Maz Condensate Amine. Slimes Cont. Gram % 2.50 0.50 2.10 0.42 2.00 0.40 3.00 0.60

Dosage, Lb./Ton 0.393 0.394 0.393 0.398

% Wt. 69.26 77.19 78.91 24.47

Tailings % P2O5 0.55 0.99 1.04 0.15

% Insol 97.85 93.43 96.25 98.87

Distribution % % P2O5 Insol 5.35 86.22 10.55 95.26 11.51 96.90 0.62 37.64

Relative Effect % % % Clay ∆P2O5 ∆Insol 100.0 0.00 0.00 84.0 97.20 10.48 80.0 115.14 12.39 120.0 -88.41 -56.34

R 16.12 9.03 8.42 60.71

EFFECT OF PERCOL 90L POLYMER ON THE AMINE FLOTATION STEP OF THE REVERSE CRAGO PROCESS The results of the amine flotation step of the Reverse Crago process for Plant III, Unsized Flotation Feed using six types of amines in the absence and presence of Percol 90L addition are presented in Appendix 6G. As in the case of the effect of slimes, Plant III, Unsized Flotation Feed was scrubbed for three minutes without washing and floated using the six types of amines in the absence and presence of Percol 90L polymer additions. Since the amine dosage for each type was that used to float Plant I, Unsized Amine Feed, the data are being compared on a relative basis, and summarized in Tables 6-19 through 6-24 and Figures 6-25 through 6-30. Table 6-19 and Figure 6-25 present the relative effect of Percol 90L addition on the amine flotation step of the Reverse Crago process using 0.1 Lb./Ton of Armeen HT primary amine. As can be seen in Figure 6-25, the Insol rejection increases to a maximum as Percol 90L addition increases to 0.2 lb./ton. At this Percol addition, P2O5 losses (rejection) also increases, decreasing the selectivity ratio, R. Further increase in Percol addition depresses the system, the Insol rejection, P2O5 losses, and selectivity ratio

6-40

decreasing. In the absence of Percol 90L polymer, the presence of slimes (large specific surface area) may consume the amine in the bulk, reducing the floatability of silica particles. This high molecular weight (MW) anionic polymer flocculated the slimes, mainly clays. Flocs are formed reducing the overall specific surface area available for amine adsorption; thus, increasing the amine adsorption density. As a consequence, Insol rejection increases. These flocs may grow as the polymer addition increases entrapping and/or adsorbing (unselectively) fine silica and phosphate particles. Under these conditions, the specific surface area available for the amine to adsorb increases again (high-negative charged flocs), reducing the overall amine adsorption density. Thus, the system is depressed. If we add the low selectivity of the Armeen HT primary amine, the depression of the system and the lost of selectivity is enhanced at high Percol 90L polymer dosage. Therefore, it is expected that an optimum balance of polymer and amine should be obtained to achieve the best Insol rejection and selectivity. Consequently, choosing the appropriate polymer (of lower molecular weight) and a selective amine is of utmost importance for the amine flotation step of the Reverse Crago process. Apparently, a low molecular weight polymer that produces smaller flocs than a large molecular weight polymer reduces or avoids entrapment and/or adsorption of the fine silica and phosphate, benefiting the process. The effect of Percol 90L polymer addition on the amine flotation step of the Reverse Crago process using Armeen 2HT secondary amine is presented in Table 16-20 and Figure 6-26. Even though Armeen 2HT secondary amine was not dispersed properly due to its insolubility in water, partial flotation was possible under the low residual concentration available in the bulk. For the Percol 90L polymer additions studied, Table 6-20 and Figure 6-26 showed that no maximum Insol rejection and P2O5losses (rejection) were obtained. However, the selectivity ratio, R, showed a maximum at 0.016 lb./ton of Percol 90L addition. This indicates that further increase in Percol 90L addition would increase the ratio of P2O5 losses with respect to the rate of Insol rejection. It seems that this eventually caused the depression of the system at higher than 0.032 lb./ton of Percol 90L addition.

6-41

Table 6-19. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Armeen HT Primary Amine. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032 0.032

0.098 0.099 0.099 0.100 0.100

1.30 9.81 29.81 13.76 18.31

Tailings % P2O5 2.05 0.56 0.61 0.74 0.84

% Insol 92.88 97.74 97.52 97.15 96.70

Distribution % % P2O5 Insol 0.39 1.54 0.77 12.43 2.70 36.98 1.47 17.18 2.13 21.34

Relative Effect % % ∆P2O5 ∆Insol 0.00 0.00 97.44 707.14 592.31 2031.30 276.15 1015.58 446.15 1285.71

R 3.95 16.14 13.70 11.68 10.01

Table 6-20. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Armeen 2HT Secondary Amine. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032

1.604 1.600 1.602 1.608

0.98 10.96 10.59 17.44

Tailings % P2O5 2.31 0.72 0.89 1.00

% Insol 91.97 97.19 95.50 96.22

Distribution % % P2O5 Insol 0.33 1.16 1.17 13.53 1.33 13.03 2.43 21.67

Relative Effect % % ∆Insol ∆P2O5 0.00 0.00 254.54 1066.38 303.03 1023.28 636.36 1768.10

R 3.52 11.56 9.80 8.91

In the case of the effect of Percol 90L polymer addition using Armeen DMHTD Tertiary amine on the amine flotation step of the Reverse Crago process, the results are summarized in Table 6-21 and Figure 6-27. Similar behavior as that described for Armeen 2HT secondary amine is observed. An increased Percol 90L polymer addition to 0.016 lb./ton in the presence of 0.3 lb./ton Armeen DMHTD Tertiary amine increased the Insol rejection without an increase in P2O5 losses; thus, a significant increase in the selectivity ratio, R. Further increase in Percol 90L addition leveled off the Insol rejection, but increased the P2O5 losses. This caused a sharp decrease in the selectivity ratio. As in the case of Armeen HT primary amine, these effects may be related to the nature of the polymer used (high MW anionic polymer), the entrapping of the fine silica and phosphate particles in the large flocs formed, the loss of inselectivity of the tertiary amine, and changes in the specific surface area available for the amine to adsorb in the system (change in adsorption density of the amine).

6-42

P2O5 Losses

y Ratio as a Function of Figure 6-25. Insol Rejection, P2O5 Losses, and Selectivity Percol 90L Polymer Addition in the P Presence of 0.1 Lb./Ton Armeen HT Primary Amine. mine.

P2O5 Losses

Figure 6-26. Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function unction of Percol 90L Polymer A Addition at 1.6 Lb./Ton Armeen 2HT Secondary Amine.

6-43

Table 6-21.. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step off the Reverse Crago U Using sing Armeen DMHTD Tertiary Amine. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032

0.287 0.287 0.288 0.288

1.76 18.41 21.23 21.62

Tailings % P2O5 0.70 0.20 0.37 0.76

% Insol 97.29 98.25 98.15 97.02

Distribution % % P2O5 Insol 0.19 2.17 0.49 23.77 1.14 26.83 2.06 27.25

Relative Effect % % ∆P2O5 ∆Insol 0.00 0.00 157.89 995.39 500.00 1136.41 1089.47 1155.76

R 11.42 48.51 23.54 12.06

P2O5 Losses

n of Figure 6-27. Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function Percol 90L Polymer A Addition Using 0.3 Lb./Ton Armeen DMHTD Tertiary Amine. The results of Percol 90L ppolymer olymer addition on the amine flotation step of the Reverse Crago process in the presence of 0.2 lb./ton Arquad 2HT-75 75 Quaternary amine are summarized in Table 6-22 22 and Figure 66-28. In the absence of Percol 90L polymer olymer addition, silica flotation is poor, but selective. Similar to the flotation behavior observed in the presence of the tertiary amine, the Insol rejection increased up to 0.016 lb./ton of Percol 90L addition with little increase in the P2O5 losses (rejection); thus, increasing slightly the selectivity ratio.. Above 0.016 lb./ton of Percol 90L addition, the Insol rejection leveled off whereas the P2O5 losses increased. Therefore, the selectivity ctivity ratio, ratio R,, decreased. The lost of selectivity even with this selective quaternary amine, the level off of the Insol rejection, and the increase in P2O5 losses (rejection) may be also related to the same mechanism; nature of the polymer used, entrap entrapping ping of fine silica and phosphate 6-44

particles in large flocs, and changes in the specific surface area available for the amine to adsorb in the system. Table 6-23 and Figure 6-29 present the summary of the results of the effect of Percol 90L polymer addition in the amine flotation step of the Reverse Crago process using 0.16 lb./ton Adogen 185 ether amine acetate. The results showed no maximum in both Insol rejection and P2O5 losses (rejection) as Percol 90L addition increased. However, a maximum in the selectivity ratio was observed at 0.016 lb./ton of Percol 90L addition. The same mechanism previously described could explain the flotation behavior of Plant III, Unsized Flotation Feed in the presence of 0.016 lb./ton of Adogen 185 Ether amine acetate as a function of Percol 90L polymer addition. It is likely that above 0.032 lb./ton Percol 90L addition, the system was depressed. Table 6-22. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Arquad 2HT-75 Quaternary Amine. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032

0.200 0.200 0.200 0.200

4.43 36.59 31.63 36.62

Tailings % P2O5 0.40 0.40 0.46 0.66

% Insol 98.10 97.87 97.76 97.16

Distribution % % P2O5 Insol 0.25 5.64 2.00 46.63 1.99 40.20 3.34 46.15

Relative Effect % % ∆Insol ∆P2O5 0.00 0.00 700.00 726.77 696.00 612.77 1236.00 718.26

R 22.56 23.32 20.20 13.82

Table 6-23. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Step of the Reverse Crago Using Adogen 185 Ether Amine Acetate. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032

0.159 0.159 0.159 0.159

1.89 28.28 34.06 42.05

Tailings % P2O5 0.66 0.37 0.45 0.75

% Insol 97.36 98.04 97.90 96.88

Distribution % % P2O5 Insol 0.17 2.40 1.40 36.23 2.07 43.26 4.33 52.68

Relative Effect % % ∆P2O5 ∆Insol 0.00 0.00 723.53 1409.58 1117.65 1702.50 2447.06 2095.00

R 14.12 25.87 20.90 12.17

The effect of Percol 90L polymer addition on the amine flotation step of the Reverse Crago process for Plant III, Unsized Flotation Feed in the presence of 0.4 lb./ton Arr-Maz condensate amine is presented in Table 6-24 and Figure 6-30. In addition, Appendix 6D presents the results of Locked Cycle tests that were carried out for Plant III, Unsized Flotation Feed after three minutes scrubbing in the presence of this condensate amine. However, a different sample of this flotation feed was used for the Locked Cycle tests. This new feed contained more slimes and was of a lower grade than the previous sample (see Appendix 4). Table 6-24 and Figure 6-30 show that in the presence of 0.4 lb./ton of Arr-Maz condensate amine and in the absence of Percol 90L polymer, the Insol rejection is significantly higher than that of the other five types of amines tested. Thus, Arr-Maz condensate amine seems to be strong enough to float sand even in the presence of slimes. As the addition of Percol 90L polymer increased up to 0.016 lb./ton, both the 6-45

Insol rejection and the P2O5 losses (rejection) increased, decreasing the selectivity ty ratio continuously. As in the case of previous amines tested, the Insol rejection leveled off, whereas the P2O5 losses slightly increased. Apparently, the flotation behavior could be also explained by the mechanism proposed. The sharp drop of the selectivity ectivity ratio, ratio R, may indicate the poor selectivity of this type of amine for this flotation feed. It is expected that the Insol rejection decreased at higher than 0.032 lb./ton of Percol 90L polymer addition due to the depression of the system. Table 6-24.. Summary of the Effect of Percol 90L Polymer on the Amine Flotation Flotation tion Step of the Reverse Crago U Using Arr-Maz Condensate Amine. Percol 90L, Lb./Ton

Amine, Lb./Ton

% Wt.

0.000 0.016 0.024 0.032

0.398 0.398 0.398 0.397

29.47 65.97 68.23 67.73

Tailings % P2O5 0.15 0.49 0.74 0.80

% Insol 98.87 97.58 96.80 96.63

Distribution % % P2O5 Insol 0.62 37.64 4.38 83.31 6.72 85.86 7.35 84.67

Relative Effect % % ∆P2O5 ∆Insol 0.00 0.00 606.45 121.33 983.87 128.11 1085.48 124.95

R 60.91 19.02 12.78 11.52 11.

P2O5 Losses

Figure 6-28. Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function unction of Percol 90L Polymer A Addition Using 0.2 Lb./Ton Arquad 2HT-75 Quaternary Amine. mine.

6-46

P2O5 Losses

unction of Figure 6-29. Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function Percol ol 90L Polymer A Addition Using 0.2 Lb./Ton Adogen 185 Ether Amine Acetate.

P2O5 Losses

Figure 6-30. Insol Rejection, P2O5 Losses, and Selectivity Ratio as a Function unction of Percol 90L Polymer A Addition Using 0.4 Lb./Ton Arr-Maz Condensate Amine. 6-47

Locked Cycle tests confirmed these expectations. Since the sample used for the Locked Cycle tests contained more slimes and had lower P2O5 grade, 0.4 lb./ton of ArrMaz condensate amine along with 0.016 lb./ton of Percol 90L addition were not able to float sand (6% Insol rejection). Furthermore, the increase in slimes in the recycled water due to the three minutes scrubbing of the Plant III, Unsized Flotation Feed required the use of 0.8 lb./ton amine to obtain an increase in Insol rejection to a maximum of 24% in the presence of 0.032 lb./ton of Percol 90L polymer addition. As in the case of the batch tests performed, an increase in the addition of Percol 90L to 0.01 lb./ton decreased the Insol rejection to 17-22%.

6-48

REFERENCES Allen HL, inventor; W.R. Grace & Co., assignee. Phosphate flotation. 1983 Mar 22. US patent 4,377,472. Bleier A, Goddard ED, Kulkarni RD. 1976. The structural effects of amine collectors on the flotation of quartz. In: Fuerstenau MC, editor. Flotation, A.M. Gaudin Memorial Volume. Vol. 1. New York: AIME. p 117-47. Christmann LJ, inventor. Removal of silica from nonmetallic ores by froth flotation. 1945 Feb 6. US patent 2,368,968. Crago A. 1950. Three new steps in treating Florida phosphate rocks. Engineering and Mining Journal 151(11): 78-83. Day HM, Gieseke EW, Jayne DW Jr, inventors. Beneficiation of acidic minerals. 1943 Dec 7. US patent 2,336,015. Day HM, Gieseke EW, Jayne DW Jr, inventors. Beneficiation of acidic minerals. 1944 Dec 12. US patent 2,365,084. Ellis EJ, inventor. Separating quartz sand from phosphate rock. 1945 Sep 18. US patent 2,384,825. Erickson SE, Jayne DW Jr, Day HM, inventors. Process for concentrating ore materials. 1943 Mar 2. US patent 2,312,414. Gaudin AM. 1957. Flotation. 2nd ed. New York: McGraw Hill. 573 p. Gefvert DL. 1988. Product and process update. Choosing a cationic collector. Mining Magazine 158(6): 513-7. Hanna HS. 1975. Role of cationic surfactants in the selective flotation of phosphate ore constituents. Powder Technology 12(1): 57-64. Jayne DW Jr, Day HM, Gieseke EW, inventors. Beneficiation of acidic minerals. 1943 Dec 7. US patent 2,336,015. Jayne DW Jr, Day HM, Gieseke EW, inventors. Process for concentrating ore materials. 1943 Mar 2. US patent 2,312,414. Jayne DW Jr, Day HM, Gieseke EW, inventors. Beneficiation of minerals. 1944 Dec 12. US patent 2,365,084.

6-49

Klimpel RR. 1999 A review of amine chemicals used in the flotation of silica. In: Zhang P, El-Shall H, Wiegel R, editors. Beneficiation of phosphate: advances in research and practice. Littleton (CO): SME. Chapter 6. p 65-74 Lange LH, inventor, General Engineering Company, assignee. phosphate-bearing material. 1933 Jun 20. US Patent 1,914,694.

Concentration of

Leal Filho LS, Assis SM, Araujo AC, Chaves AP. 1993. Process mineralogy studies for optimizing the flotation performance of two refractory phosphate ores. Minerals Engineering 6(8-10): 907-16. Nagaraj DR, Rothenberg AS, Lipp DW, Panzer HP. 1987. Low molecular weight polyacrylamide based polymers as modifiers in phosphate beneficiation. International Journal of Mineral Processing 20(3-4): 291-308. Prasad M, Majmudar AK, Rao GM, Rao TC. 1995. Flotation studies on a low-grade, cherty-calcareous rock phosphate ore from Jhabua, India. Minerals & Metallurgical Processing 12(2): 92-6. Pratten SJ, Bensley CN, Nicol SK. 1989. An investigation of the flotation response of coals. International Journal of Minerals Processing 27(3-4): 243-62. Snow RE, inventor; International Minerals and Chemical Corp., assignee. Flotation process for recovery of phosphate values from ore. 1988 Apr 12. US patent 4,737,273. Soto H, Iwasaki I. 1985. Flotation of apatite from calcareous ores with primary amines. Minerals and Metallurgical Processing 2(3): 160-6. Suarez MV, Suarez J, Miranda S. 1997. Reverse froth flotation of phosphatic sand ores using cationic collectors. Información Tecnológica 8(4): 133-9. Wiegel RL. 1999. Phosphate rock beneficiation practice in Florida. In: Zhang P, ElShall H, Wiegel R, editors. Beneficiation of phosphate: advances in research and practice. Littleton (CO): SME. Chapter 23, p 271-5. Yap S, inventor; ARR-MAZ Products, L.P., assignee. Phosphate beneficiation process using polymers as slime flocculants. 1999 Jan 12. US Patent 5,858,214. Zhang P, Yu Y, Bogan M. 1997. Challenging the “Crago” double float process II. Amine-fatty acid flotation of siliceous phosphates. Minerals Engineering 10(9): 983-94.

6-50

Appendix 6A SCREEN ANALYSIS OF TEST FEEDS

Table 6A-1A. Screen Analysis for Fort Green Amine Feed Unsized. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 1.10 4.70 33.70 94.00 148.90 86.80 51.60 20.00 2.70 0.50 444.00

Weight % 0.25 1.06 7.59 21.17 33.54 19.55 11.62 4.50 0.61 0.11 100.00

Retained % 0.25 1.31 8.90 30.07 63.60 83.15 94.77 99.28 99.89 100.00

Passing % 99.75 98.69 91.10 69.93 36.40 16.85 5.23 0.72 0.11 0.00

Table 6A-1B. Screen Analysis for Fort Green Amine Feed Unsized. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 1.00 3.90 33.60 91.60 143.50 84.60 50.30 19.40 2.90 0.40 431.20

Weight % 0.23 0.90 7.79 21.24 33.28 19.62 11.67 4.50 0.67 0.09 100.00

6A-1

Retained % 0.23 1.14 8.93 30.17 63.45 83.07 94.74 99.23 99.91 100.00

Passing % 99.77 98.86 91.07 69.83 36.55 16.93 5.26 0.77 0.09 0.00

Table 6A-2A. Screen Analysis for Four Corners Coarse Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 1.60 5.40 46.80 132.10 136.30 54.20 36.60 15.80 4.00 1.40 434.20

Weight % 0.37 1.24 10.78 30.42 31.39 12.48 8.43 3.64 0.92 0.32 100.00

Retained % 0.37 1.61 12.39 42.81 74.21 86.69 95.12 98.76 99.68 100.00

Passing % 99.63 98.39 87.61 57.19 25.79 13.31 4.88 1.24 0.32 0.00

Table 6A-2B. Screen Analysis for Four Corners Coarse Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 1.70 4.90 47.20 130.20 135.00 53.50 37.60 15.20 4.90 1.90 432.10

Weight % 0.39 1.13 10.92 30.13 31.24 12.38 8.70 3.52 1.13 0.44 100.00

6A-2

Retained % 0.39 1.53 12.45 42.58 73.83 86.21 94.91 98.43 99.56 100.00

Passing % 99.61 98.47 87.55 57.42 26.17 13.79 5.09 1.57 0.44 0.00

Table 6A-3A. Screen Analysis for Four Corners Fine Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 0.20 0.80 6.30 26.80 70.40 80.20 130.00 76.90 19.00 5.50 416.10

Weight % 0.05 0.19 1.51 6.44 16.92 19.27 31.24 18.48 4.57 1.32 100.00

Retained % 0.05 0.24 1.75 8.20 25.11 44.39 75.63 94.11 98.68 100.00

Passing % 99.95 99.76 98.25 91.80 74.89 55.61 24.37 5.89 1.32 0.00

Table 6A-3B. Screen Analysis for Four Corners Fine Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 0.20 0.80 6.30 26.50 69.70 85.70 125.80 75.50 18.80 7.00 416.30

Weight % 0.05 0.19 1.51 6.37 16.74 20.59 30.22 18.14 4.52 1.68 100.00

6A-3

Retained % 0.05 0.24 1.75 8.12 24.86 45.45 75.67 93.80 98.32 100.00

Passing % 99.95 99.76 98.25 91.88 75.14 54.55 24.33 6.20 1.68 0.00

Table 6A-4A. Screen Analysis for CF Industries, Inc. Flotation Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 2.20 2.30 11.50 36.50 88.50 92.60 125.30 59.30 10.90 2.30 431.40

Weight % 0.51 0.53 2.67 8.46 20.51 21.46 29.04 13.75 2.53 0.53 100.00

Retained % 0.51 1.04 3.71 12.17 32.68 54.15 83.19 96.94 99.47 100.00

Passing % 99.49 98.96 96.29 87.83 67.32 45.85 16.81 3.06 0.53 0.00

Table 6A-4B. Screen Analysis for CF Industries, Inc. Flotation Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm) 1.90 2.00 10.80 38.40 92.20 95.50 129.90 60.60 10.70 2.10 444.10

Weight % 0.43 0.45 2.43 8.65 20.76 21.50 29.25 13.65 2.41 0.47 100.00

6A-4

Retained % 0.43 0.88 3.31 11.96 32.72 54.22 83.47 97.12 99.53 100.00

Passing % 99.57 99.12 96.69 88.04 67.28 45.78 16.53 2.88 0.47 0.00

Appendix 6B DATA FOR DIFFERENT AMINES ON UNSIZED AMINE FEED

Table 6B-1. Armeen HT Primary Amine Series. 1.1

DOSAGE: 2.5 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed 1.2

Weight Weight (Gm) % 100.00 429.80 85.16 74.90 14.84 504.70 100.00

% P2O5 28.18 32.50 2.81 28.09

% Insol 16.48 3.13 90.79 16.14

1.3

Weight Weight (Gm) % 100.00 424.10 83.70 82.60 16.30 506.70 100.00

% P2O5 28.18 32.88 4.23 28.21

% Insol 16.48 2.05 86.52 15.82

1.4

Content P2O5 Insol Units Units 28.18 16.48 27.52 1.72 0.69 14.10 28.21 15.82

Distribution % % P2O5 Insol 100.00 100.00 97.56 10.85 2.44 89.15 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.21 1.58 1.03 14.28 28.24 15.86

Distribution % % P2O5 Insol 100.00 100.00 96.34 9.99 3.66 90.01 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Distribution % % P2O5 Insol 100.00 100.00 98.52 16.52 1.48 83.48 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 27.68 2.67 0.42 13.47 28.09 16.14

% Weight Weight P2O5 (Gm) % 100.00 28.18 422.40 82.48 32.99 89.70 17.52 5.90 512.10 100.00 28.24

% Insol 16.48 1.92 81.50 15.86

DOSAGE: 10.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 415.50 80.95 Tailings 97.80 19.05 Cal. Feed 513.30 100.00

Grades % % P2O5 Insol 28.18 16.48 32.82 2.14 7.96 75.58 28.08 16.13

6B-1

Content P2O5 Insol Units Units 28.18 16.48 26.57 1.73 1.52 14.40 28.08 16.13

Distribution % % P2O5 Insol 100.00 100.00 94.60 10.74 5.40 89.26 100.00 100.00

Table 6B-1 (Cont.). Armeen HT Primary Amine Series. 1.5

DOSAGE: 12.5 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 400.40 79.11 Tailings 105.70 20.89 Cal. Feed 506.10 100.00 1.6

Grades % % P2O5 Insol 28.18 16.48 32.97 1.84 10.46 68.24 28.27 15.71

1.7

Weight Weight % (Gm) % P2O5 100.00 28.18 378.90 75.43 32.96 123.40 24.57 14.25 502.30 100.00 28.36

% Insol 16.48 1.84 57.37 15.48

1.8

Weight Weight (Gm) % 100.00 439.60 87.10 65.10 12.90 504.70 100.00

% P2O5 28.18 32.20 1.75 28.27

% Insol 16.48 4.04 93.86 15.63

Distribution % % P2O5 Insol 100.00 100.00 87.66 8.97 12.34 91.03 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.05 3.52 0.23 12.11 28.27 15.63

Distribution % % P2O5 Insol 100.00 100.00 99.20 22.52 0.80 77.48 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.81 1.68 0.64 13.90 28.45 15.58

Distribution % % P2O5 Insol 100.00 100.00 97.75 10.79 2.25 89.21 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 24.86 1.39 3.50 14.09 28.36 15.48

DOSAGE: 2.5 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Distribution % % P2O5 Insol 100.00 100.00 92.27 9.27 7.73 90.73 100.00 100.00

DOSAGE: 15.0 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 26.08 1.46 2.18 14.25 28.27 15.71

Weight Weight % (Gm) % P2O5 100.00 28.18 426.60 84.04 33.09 81.00 15.96 4.02 507.60 100.00 28.45

% Insol 16.48 2.00 87.09 15.58

6B-2

Table 6B-2. Armeen 2HT Secondary Amine Series. 2.1

DOSAGE: 2.5 cc @ 2% Solution Grades

Weight Weight Product (Gm) % Feed 100.00 Concent. 488.50 99.41 Tailings 2.90 0.59 Cal. Feed 491.40 100.00 2.2

% P2O5 28.18 28.23 11.63 28.13

% Insol 16.48 16.49 63.49 16.77

Weight Weight Product (Gm) % Feed 100.00 Concent. 489.60 99.13 Tailings 4.30 0.87 Cal. Feed 493.90 100.00

% P2O5 28.18 28.54 11.21 28.39

% Insol 16.48 15.84 63.16 16.25

Content P2O5 Insol Units Units 28.18 16.48 28.29 15.70 0.10 0.55 28.39 16.25

Distribution % % P2O5 Insol 100.00 100.00 99.66 96.62 0.34 3.38 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.32 15.81 0.12 0.61 28.43 16.41

Distribution % % P2O5 Insol 100.00 100.00 99.58 96.31 0.42 3.69 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.83 16.74 0.16 0.65 27.99 17.40

Distribution % % P2O5 Insol 100.00 100.00 99.43 96.24 0.57 3.76 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution

Grades % % Weight Weight Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 490.90 98.97 28.61 15.97 Tailings 5.10 1.03 11.53 58.96 Cal. Feed 496.00 100.00 28.43 16.41 2.4

Distribution % % P2O5 Insol 100.00 100.00 99.76 97.77 0.24 2.23 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution Grades

2.3

Content P2O5 Insol Units Units 28.18 16.48 28.06 16.39 0.07 0.37 28.13 16.77

DOSAGE: 10.0 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 486.40 98.84 28.16 16.94 Tailings 5.70 1.16 13.70 56.50 Cal. Feed 492.10 100.00 27.99 17.40

6B-3

Table 6B-2 (Cont.). Armeen 2HT Secondary Amine Series. 2.5

DOSAGE: 12.5 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 488.70 99.19 28.24 15.85 Tailings 4.00 0.81 14.86 52.11 Cal. Feed 492.70 100.00 28.13 16.14 2.6

Product Feed Concent. Tailings Cal. Feed 2.8

Distribution % % P2O5 Insol 100.00 100.00 99.57 97.38 0.43 2.62 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.94 15.65 0.15 0.69 28.09 16.35

Distribution % % P2O5 Insol 100.00 100.00 99.47 95.75 0.53 4.25 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.84 15.46 0.19 1.31 28.03 16.78

Distribution % % P2O5 Insol 100.00 100.00 99.33 92.17 0.67 7.83 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.92 7.70 0.27 8.46 28.19 16.16

Distribution % % P2O5 Insol 100.00 100.00 99.04 47.65 0.96 52.35 100.00 100.00

DOSAGE: 15.0 cc @ 2% Solution

Grades % Weight Weight % (Gm) % Insol Product P2O5 Feed 100.00 28.18 16.48 Concent. 487.80 98.82 28.27 15.84 Tailings 5.80 1.18 12.63 59.14 Cal. Feed 493.60 100.00 28.09 16.35 2.7

Content P2O5 Insol Units Units 28.18 16.48 28.01 15.72 0.12 0.42 28.13 16.14

DOSAGE: 17.5 cc @ 2% Solution Grades % Weight Weight % (Gm) % Insol P2O5 100.00 28.18 16.48 482.70 98.11 28.38 15.76 9.30 1.89 9.90 69.52 492.00 100.00 28.03 16.78 DOSAGE: 35.0 cc @ 2% Solution Grades

Weight Weight % Product P2O5 (Gm) % Feed 100.00 28.18 Concent. 445.80 90.61 30.81 Tailings 46.20 9.39 2.89 Cal. Feed 492.00 100.00 28.19

% Insol 16.48 8.50 90.10 16.16

6B-4

Table 6B-3. Armeen DMHTD Tertiary Amine Series. 3.1

DOSAGE: 2.5 cc @ 2% Solution Grades

Weight Weight % Product (Gm) % P2O5 Feed 100.00 28.18 Concent. 431.90 87.39 31.77 Tailings 62.30 12.61 2.02 Cal. Feed 494.20 100.00 28.02 3.2

% Insol 16.48 5.13 92.57 16.15

Weight Weight Product (Gm) % Feed 100.00 Concent. 390.80 78.90 Tailings 104.50 21.10 Cal. Feed 495.30 100.00

% P2O5 28.18 32.65 11.34 28.15

% Insol 16.48 2.57 66.02 15.96

Content P2O5 Insol Units Units 28.18 16.48 25.76 2.03 2.39 13.93 28.15 15.96

Distribution % % P2O5 Insol 100.00 100.00 91.50 12.71 8.50 87.29 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 22.12 1.44 5.79 14.89 27.91 16.33

Distribution % % P2O5 Insol 100.00 100.00 79.26 8.80 20.74 91.20 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.45 13.37 0.04 2.28 28.48 15.65

Distribution % % P2O5 Insol 100.00 100.00 99.87 85.44 0.13 14.56 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution Grades

Weight Weight Product (Gm) % Feed 100.00 Concent. 333.70 67.51 Tailings 160.60 32.49 Cal. Feed 494.30 100.00 3.4

Distribution % % P2O5 Insol 100.00 100.00 99.09 27.76 0.91 72.24 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution Grades

3.3

Content P2O5 Insol Units Units 28.18 16.48 27.77 4.48 0.25 11.67 28.02 16.15

% P2O5 28.18 32.77 17.82 27.91

% Insol 16.48 2.13 45.84 16.33

DOSAGE: 1.25 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 481.50 97.59 29.15 13.70 Tailings 11.90 2.41 1.56 94.50 Cal. Feed 493.40 100.00 28.48 15.65

6B-5

Table 6B-3 (Cont.). Armeen DMHTD Tertiary Amine Series. 3.5

DOSAGE: 2.0 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) P2O5 % Insol Feed 100.00 28.18 16.48 Concent. 416.60 84.35 32.39 3.97 Tailings 77.30 15.65 5.27 83.61 Cal. Feed 493.90 100.00 28.15 16.43 3.6

Content P2O5 Insol Units Units 28.18 16.48 27.32 3.35 0.82 13.09 28.15 16.43

Distribution % % P2O5 Insol 100.00 100.00 97.07 20.38 2.93 79.62 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.71 3.30 0.54 12.76 28.25 16.06

Distribution % % P2O5 Insol 100.00 100.00 98.09 20.54 1.91 79.46 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.76 3.33 0.68 13.01 28.45 16.34

Distribution % % P2O5 Insol 100.00 100.00 97.59 20.40 2.41 79.60 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.00 2.78 1.27 13.49 28.27 16.26

Distribution % % P2O5 Insol 100.00 100.00 95.51 17.07 4.49 82.93 100.00 100.00

DOSAGE: 2.5 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 422.20 85.48 32.42 3.86 Tailings 71.70 14.52 3.72 87.93 Cal. Feed 493.90 100.00 28.25 16.06 3.7

DOSAGE: 3.0 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Grades Weight Weight % % (Gm) % P2O5 Insol 100.00 28.18 16.48 416.30 84.82 32.73 3.93 74.50 15.18 4.51 85.71 490.80 100.00 28.45 16.34

3.8

DOSAGE: 3.5 cc @ 2% Solution Grades

Weight Weight % Product (Gm) % P2O5 Feed 100.00 28.18 Concent. 405.80 82.61 32.68 Tailings 85.40 17.39 7.30 Cal. Feed 491.20 100.00 28.27

% Insol 16.48 3.36 77.58 16.26

6B-6

Table 6B-4. Arquad 2HT-75 Quaternary Amine Series. 4.1

DOSAGE: 2.5 cc @ 2% Solution Grades

Weight Weight % Product (Gm) % P2O5 Feed 100.00 28.18 Concent. 440.00 89.25 31.46 Tailings 53.00 10.75 1.46 Cal. Feed 493.00 100.00 28.23 4.2

% Insol 16.48 6.77 94.89 16.24

Weight Weight % Product (Gm) % P2O5 Feed 100.00 28.18 Concent. 454.30 91.48 30.91 Tailings 42.30 8.52 0.87 Cal. Feed 496.60 100.00 28.35

% Insol 16.48 8.49 96.77 16.01

4.4

Content P2O5 Insol Units Units 28.18 16.48 28.28 7.77 0.07 8.24 28.35 16.01

Distribution % % P2O5 Insol 100.00 100.00 99.74 48.51 0.26 51.49 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.47 1.86 0.90 14.25 28.36 16.11

Distribution % % P2O5 Insol 100.00 100.00 96.84 11.53 3.16 88.47 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.16 4.91 0.21 11.09 28.37 16.00

Distribution % % P2O5 Insol 100.00 100.00 99.26 30.70 0.74 69.30 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution Grades

Product Feed Concent. Tailings Cal. Feed

Distribution % % P2O5 Insol 100.00 100.00 99.44 37.20 0.56 62.80 100.00 100.00

DOSAGE: 1.25 cc @ 2% Solution Grades

4.3

Content P2O5 Insol Units Units 28.18 16.48 28.08 6.04 0.16 10.20 28.23 16.24

% Insol 16.48 2.24 83.64 16.11

Weight Weight % (Gm) % P2O5 100.00 28.18 410.40 82.96 33.11 84.30 17.04 5.26 494.70 100.00 28.36

DOSAGE: 2.5 cc @ 2% Solution Grades

Weight Weight % Product (Gm) % P2O5 Feed 100.00 28.18 Concent. 436.40 88.20 31.93 Tailings 58.40 11.80 1.77 Cal. Feed 494.80 100.00 28.37

% Insol 16.48 5.57 93.97 16.00

6B-7

Table 6B-4 (Cont.). Arquad 2HT-75 Quaternary Amine Series. 4.5

DOSAGE: 1.25 cc @ 2% Solution

Grades Weight Weight % % Product P2O5 (Gm) % Insol Feed 100.00 28.18 16.48 Concent. 453.50 91.43 30.78 9.13 Tailings 42.50 8.57 0.92 97.43 Cal. Feed 496.00 100.00 28.22 16.70 4.6

Content P2O5 Insol Units Units 28.18 16.48 28.03 2.97 0.36 12.97 28.40 15.94

Distribution % % P2O5 Insol 100.00 100.00 98.72 18.63 1.28 81.37 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.48 1.98 0.93 13.97 28.41 15.95

Distribution % % P2O5 Insol 100.00 100.00 96.72 12.41 3.28 87.59 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.12 1.80 1.23 14.30 28.35 16.10

Distribution % % P2O5 Insol 100.00 100.00 95.67 11.16 4.33 88.84 100.00 100.00

DOSAGE: 6.0 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 411.80 83.16 33.04 2.38 Tailings 83.40 16.84 5.54 82.96 Cal. Feed 495.20 100.00 28.41 15.95 4.8

Distribution % % P2O5 Insol 100.00 100.00 99.72 50.00 0.28 50.00 100.00 100.00

DOSAGE: 4.0 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 425.90 85.83 32.66 3.46 Tailings 70.30 14.17 2.56 91.56 Cal. Feed 496.20 100.00 28.40 15.94 4.7

Content P2O5 Insol Units Units 28.18 16.48 28.14 8.35 0.08 8.35 28.22 16.70

DOSAGE: 7.5 cc @ 2% Solution

Grades Weight Weight % % Product P2O5 (Gm) % Insol Feed 100.00 28.18 16.48 Concent. 405.50 81.99 33.08 2.19 Tailings 89.10 18.01 6.82 79.38 Cal. Feed 494.60 100.00 28.35 16.10

6B-8

Table 6B-5. Adogen 185 Ether Amine Acetate Series. 5.1

Product Feed Concent. Tailings Cal. Feed 5.2

DOSAGE: 2.5 cc @ 2% Solution Grades Weight Weight % % (Gm) % P2O5 Insol 100.00 28.18 16.48 408.30 83.29 33.34 2.43 81.90 16.71 5.16 83.32 490.20 100.00 28.63 15.94

Content P2O5 Insol Units Units 28.18 16.48 25.01 1.25 3.79 14.44 28.79 15.69

Distribution % % P2O5 Insol 100.00 100.00 86.85 7.97 13.15 92.03 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 19.11 0.97 9.56 14.94 28.67 15.91

Distribution % % P2O5 Insol 100.00 100.00 66.67 6.11 33.33 93.89 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.49 4.18 0.26 11.67 28.75 15.84

Distribution % % P2O5 Insol 100.00 100.00 99.08 26.36 0.92 73.64 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 280.30 57.17 33.43 1.70 Tailings 210.00 42.83 22.31 34.88 Cal. Feed 490.30 100.00 28.67 15.91 5.4

Distribution % % P2O5 Insol 100.00 100.00 96.99 12.69 3.01 87.31 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 364.60 74.38 33.62 1.68 Tailings 125.60 25.62 14.78 56.35 Cal. Feed 490.20 100.00 28.79 15.69 5.3

Content P2O5 Insol Units Units 28.18 16.48 27.77 2.02 0.86 13.92 28.63 15.94

DOSAGE: 1.25 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 429.40 87.37 32.61 4.78 Tailings 62.10 12.63 2.09 92.33 Cal. Feed 491.50 100.00 28.75 15.84

6B-9

Table 6B-5 (Cont.). Adogen 185 Ether Amine Acetate Series. 5.5

DOSAGE: 2.0 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 412.70 84.34 33.39 2.54 Tailings 76.60 15.66 3.75 87.52 Cal. Feed 489.30 100.00 28.75 15.84 5.6

Content P2O5 Insol Units Units 28.18 16.48 27.76 1.69 1.11 14.23 28.86 15.92

Distribution % % P2O5 Insol 100.00 100.00 96.17 10.60 3.83 89.40 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 26.49 1.48 2.29 14.32 28.79 15.81

Distribution % % P2O5 Insol 100.00 100.00 92.03 9.38 7.97 90.62 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 25.97 1.06 3.05 14.22 29.02 15.28

Distribution % % P2O5 Insol 100.00 100.00 89.49 6.93 10.51 93.07 100.00 100.00

DOSAGE: 4.0 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 388.00 78.89 33.58 1.88 Tailings 103.80 21.11 10.87 67.87 Cal. Feed 491.80 100.00 28.79 15.81 5.8

Distribution % % P2O5 Insol 100.00 100.00 97.96 13.52 2.04 86.48 100.00 100.00

DOSAGE: 3.0 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 403.30 82.27 33.74 2.05 Tailings 86.90 17.73 6.24 80.27 Cal. Feed 490.20 100.00 28.86 15.92 5.7

Content P2O5 Insol Units Units 28.18 16.48 28.16 2.14 0.59 13.70 28.75 15.84

DOSAGE: 4.5 cc @ 2% Solution

Grades Weight Weight % % P2O5 Product (Gm) % Insol Feed 100.00 28.18 16.48 Concent. 378.10 76.79 33.82 1.38 Tailings 114.30 23.21 13.14 61.28 Cal. Feed 492.40 100.00 29.02 15.28

6B-10

Table 6B-6. Arr-Maz Condensate Amine Series. 6.1

DOSAGE: 2.5 cc @ 2% Solution

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 438.20 88.58 32.05 6.04 Tailings 56.50 11.42 1.23 94.94 Cal. Feed 494.70 100.00 28.53 16.19 6.2

Content P2O5 Insol Units Units 28.18 16.48 27.96 2.13 0.58 14.06 28.54 16.20

Distribution % % P2O5 Insol 100.00 100.00 97.98 13.17 2.02 86.83 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.09 1.72 1.36 14.66 28.45 16.38

Distribution % % P2O5 Insol 100.00 100.00 95.22 10.50 4.78 89.50 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 26.32 1.52 2.32 14.44 28.63 15.96

Distribution % % P2O5 Insol 100.00 100.00 91.90 9.50 8.10 90.50 100.00 100.00

DOSAGE: 7.5 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 402.20 81.09 33.41 2.12 Tailings 93.80 18.91 7.19 77.51 Cal. Feed 496.00 100.00 28.45 16.38 6.4

Distribution % % P2O5 Insol 100.00 100.00 99.51 33.04 0.49 66.96 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 414.70 83.96 33.30 2.54 Tailings 79.20 16.04 3.59 87.71 Cal. Feed 493.90 100.00 28.54 16.20 6.3

Content P2O5 Insol Units Units 28.18 16.48 28.39 5.35 0.14 10.84 28.53 16.19

DOSAGE: 10.0 cc @ 2% Solution Grades

Weight Weight Product (Gm) % Feed 100.00 Concent. 387.60 78.56 Tailings 105.80 21.44 Cal. Feed 493.40 100.00

% P2O5 28.18 33.50 10.81 28.63

% Insol 16.48 1.93 67.34 15.96

6B-11

Table 6B-6 (Cont.). Arr-Maz Condensate Amine Series. 6.5

DOSAGE: 12.5 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 368.60 74.52 Tailings 126.00 25.48 Cal. Feed 494.60 100.00 6.6

Grades % % P2O5 Insol 28.18 16.48 33.39 1.64 14.19 57.64 28.50 15.91

Weight Weight Product (Gm) % Feed 100.00 Concent. 421.30 84.92 Tailings 74.80 15.08 Cal. Feed 496.10 100.00

% P2O5 28.18 33.09 2.95 28.55

% Insol 16.48 3.04 89.87 16.13

Content P2O5 Insol Units Units 28.18 16.48 28.10 2.58 0.44 13.55 28.55 16.13

Distribution % % P2O5 Insol 100.00 100.00 98.44 16.00 1.56 84.00 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.56 1.48 0.86 14.11 28.43 15.59

Distribution % % P2O5 Insol 100.00 100.00 96.96 9.50 3.04 90.50 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 26.98 1.87 1.59 14.50 28.57 16.37

Distribution % % P2O5 Insol 100.00 100.00 94.43 11.41 5.57 88.59 100.00 100.00

DOSAGE: 6.0 cc @ 2% Solution Grades

Weight Weight Product (Gm) % Feed 100.00 Concent. 409.80 82.77 Tailings 85.30 17.23 Cal. Feed 495.10 100.00 6.8

Distribution % % P2O5 Insol 100.00 100.00 87.32 7.68 12.68 92.32 100.00 100.00

DOSAGE: 4.0 cc @ 2% Solution Grades

6.7

Content P2O5 Insol Units Units 28.18 16.48 24.88 1.22 3.61 14.68 28.50 15.91

% P2O5 28.18 33.30 5.02 28.43

% Insol 16.48 1.79 81.90 15.59

DOSAGE: 8.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 399.50 80.51 Tailings 96.70 19.49 Cal. Feed 496.20 100.00

Grades % % P2O5 Insol 28.18 16.48 33.51 2.32 8.17 74.41 28.57 16.37

6B-12

Appendix 6C TREE ANALYSIS

Table 6C-1. Tree Analysis Using Armeen HT Primary Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

5 cc @ 2% Solution Weight (Gm) 79.9 414.9 3.3 411.6 2.3 409.3 1.6 407.7 494.8

Weight % 16.14 83.85 0.66 83.18 0.46 82.72 0.32 82.39 100.00

Grade % P2O5 % Insol 4.86 85.54 33.13 2.96 12.61 62.42 33.29 2.49 21.24 37.40 33.36 2.29 24.68 26.49 33.40 2.20 28.56 16.30

FEED: Distribution % P2O5 % Insol 2.74 84.73 97.25 15.26 0.29 2.55 96.95 12.71 0.34 1.06 96.61 11.64 0.27 0.52 96.33 11.12 100.00 100.00

6C-1

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 4.86 85.54 5.16

84.62

5.59

83.35

5.95 28.56

82.31 16.30

Cum. Distribution % P2O5 % Insol 2.74 84.73 100.00 100.00 3.04 87.28 100.00 100.00 3.38 88.35 100.00 100.00 3.66 88.88 100.00 100.00

Table 6C-1 (Cont.). Tree Analysis Using Armeen HT Primary Amine. DOSAGE Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

6.5cc @ 2% Solution Weight (Gm) 80.4 420.8 2.4 418.4 7.9 410.5 4.3 406.2 501.2

Weight % 16.04 83.95 0.47 83.47 1.57 81.90 0.85 81.04 100.00

Grade % P2O5 % Insol 3.03 87.94 32.81 2.57 21.05 36.05 32.87 2.38 26.96 19.85 32.99 2.05 30.28 10.47 33.02 1.96 28.03 16.27

FEED: Distribution % P2O5 % Insol 1.73 86.70 98.26 13.29 0.35 1.01 97.90 12.23 1.51 1.92 96.39 10.31 0.92 0.55 95.46 9.76 100.00 100.00

6C-2

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 3.03 87.94 3.55

86.43

5.59

80.63

6.70 28.03

77.46 16.27

Cum. Distribution % P2O5 % Insol 1.73 86.70 100.00 100.00 2.09 87.76 100.00 100.00 3.61 89.68 100.00 100.00 4.53 90.23 100.00 100.00

Table 6C-2. Tree Analysis Using Armeen DMHTD Tertiary Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

3 cc @ 2% Solution Weight (Gm) 37.4 454.0 0.6 453.4 0.9 452.5 1.5 451.0 491.4

Weight % 7.61 92.38 0.12 92.26 0.18 92.08 0.30 91.77 100.00

Grade % P2O5 % Insol 1.08 97.32 30.69 9.63 20.44 40.08 30.71 9.59 20.44 40.08 30.73 9.53 19.64 42.80 30.77 9.42 28.44 16.30

FEED: Distribution % P2O5 % Insol 0.28 45.42 99.71 54.57 0.08 0.30 99.62 54.27 0.13 0.45 99.49 53.82 0.21 0.80 99.28 53.02 100.00 100.00

6C-3

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 1.08 97.32 1.38

96.41

1.82

95.11

2.48 28.44

93.17 16.30

Cum. Distribution % P2O5 % Insol 0.28 45.42 100.00 100.00 0.37 45.72 100.00 100.00 0.51 46.17 100.00 100.00 0.72 46.97 100.00 100.00

Table 6C-2 (Cont.). Tree Analysis Using Armeen DMHTD Tertiary Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

4.5 cc @ 2% Solution Weight (Gm) 38.8 435.5 0.7 434.8 0.6 434.2 1.9 432.3 474.3

Weight % 8.18 91.81 0.14 91.67 0.12 91.54 0.40 91.14 100.00

Grade % P2O5 % Insol 1.02 95.00 30.24 9.75 20.58 38.99 30.26 9.71 20.58 38.99 30.27 9.66 20.73 38.22 30.32 9.54 27.85 16.72

FEED: Distribution % P2O5 % Insol 0.29 46.46 99.70 53.53 0.11 0.34 99.59 53.19 0.09 0.29 99.49 52.89 0.29 0.91 99.19 51.98 100.00 100.00

6C-4

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 1.02 95.00 1.36

94.01

1.65

93.18

2.51 27.85

90.69 16.72

Cum. Distribution % P2O5 % Insol 0.29 46.46 100.00 100.00 0.41 46.80 100.00 100.00 0.50 47.10 100.00 100.00 0.80 48.02 100.00 100.00

Table 6C-3. Tree Analysis Using Arquad 2HT-75 Quaternary Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

5 cc @ 2% Solution Weight (Gm) 53.6 435.9 4.7 431.2 1.5 429.7 1.9 427.8 489.5

Weight % 10.95 89.05 0.96 88.08 0.31 87.78 0.38 87.39 100.00

Grade % P2O5 % Insol 1.07 96.42 31.97 6.17 17.15 49.27 32.13 5.70 8.22 75.42 32.22 5.45 27.08 20.50 32.24 5.39 28.58 16.05

FEED: Distribution % P2O5 % Insol 0.41 65.77 99.59 34.22 0.57 2.94 99.01 31.28 0.08 1.44 98.92 29.84 0.36 0.49 98.55 29.34 100.00 100.00

6C-5

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 1.07 96.42 2.36

92.62

2.51

92.18

3.26 28.58

89.97 16.05

Cum. Distribution % P2O5 % Insol 0.41 65.77 100.00 100.00 0.98 68.72 100.00 100.00 1.07 70.15 100.00 100.00 1.44 70.65 100.00 100.00

Table 6C-3 (Cont.). Tree Analysis Using Arquad 2HT-75 Quaternary Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

6.5 cc @ 2% Solution Weight (Gm) 51.6 440.1 3.1 437.0 1.8 435.2 2.9 432.3 491.7

Weight % 10.49 89.51 0.63 88.87 0.36 88.51 0.58 87.92 100.00

Grade % P2O5 % Insol 1.17 94.69 31.30 7.22 8.61 73.58 31.46 6.75 17.68 47.45 31.52 6.58 18.11 46.21 31.61 6.32 28.14 16.40

FEED: Distribution % P2O5 % Insol 0.43 60.57 99.56 39.42 0.19 2.83 99.37 36.59 0.23 1.05 99.14 35.53 0.37 1.66 98.76 33.87 100.00 100.00

6C-6

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 1.17 94.69 1.59

93.49

2.10

92.02

2.88 28.14

89.78 16.40

Cum. Distribution % P2O5 % Insol 0.43 60.57 100.00 100.00 0.63 63.41 100.00 100.00 0.85 64.46 100.00 100.00 1.24 66.12 100.00 100.00

Table 6C-4. Tree Analysis Using Adogen 185 Ether Amine Acetate. DOSAGE:

Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

2 cc @ 2% Solution

Weight (Gm) 50.6 439.1 2.7 436.4 0.6 435.8 0.9 434.9 489.7

Weight % 10.33 89.66 0.55 89.12 0.12 88.99 0.18 88.81 100.00

Grade % P2O5 % Insol 0.96 96.71 31.94 6.95 3.38 88.62 32.12 6.44 24.72 27.55 32.13 6.41 24.72 27.55 32.15 6.37 28.74 16.22

FEED:

Fort Green Unsized Amine Feed

Distribution % P2O5 % Insol 0.34 61.59 99.65 38.40 0.06 3.01 99.59 35.39 0.10 0.21 99.48 35.18 0.16 0.31 99.32 34.87 100.00 100.00

6C-7

Cum. Grade % P2O5 % Insol 0.96 96.71 1.08

96.30

1.34

95.53

1.73 28.74

94.42 16.22

Cum. Distribution % P2O5 % Insol 0.34 61.59 100.00 100.00 0.41 64.61 100.00 100.00 0.51 64.81 100.00 100.00 0.67 65.12 100.00 100.00

Table 6C-4 (Cont). Tree Analysis Using Adogen 185 Ether Amine Acetate. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

3.5 cc @ 2% Solution Weight (Gm) 54.1 432.3 3.8 428.5 0.6 427.9 1.3 426.6 486.4

Weight % 11.12 88.87 0.78 88.09 0.12 87.97 0.27 87.70 100.00

Grade % P2O5 % Insol 0.90 95.60 31.71 6.18 2.52 91.32 31.96 5.42 22.49 33.04 31.98 5.38 22.49 33.04 32.01 5.30 28.28 16.12

FEED: Distribution % P2O5 % Insol 0.35 65.94 99.64 34.05 0.07 4.42 99.57 29.63 0.09 0.25 99.47 29.37 0.21 0.54 99.26 28.83 100.00 100.00

6C-8

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 0.90 95.60 1.01

95.32

1.22

94.68

1.68 28.28

93.34 16.12

Cum. Distribution % P2O5 % Insol 0.35 65.94 100.00 100.00 0.42 70.37 100.00 100.00 0.52 70.62 100.00 100.00 0.73 71.17 100.00 100.00

Table 6C-5. Tree Analysis Using Arr-Maz Condensate Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

5 cc @ 2% Solution Weight (Gm) 51.7 438.9 1.4 437.5 0.6 436.9 1.0 435.9 490.6

Weight % 10.54 89.46 0.28 89.17 0.12 89.05 0.20 88.85 100.00

Grade % P2O5 % Insol 0.80 96.62 31.75 6.63 8.01 75.76 31.82 6.41 19.87 47.01 31.84 6.35 19.87 47.01 31.87 6.26 28.48 16.11

FEED:

Fort Green Unsized Amine Feed

Distribution % P2O5 % Insol 0.29 63.18 99.70 36.81 0.08 1.34 99.62 35.46 0.08 0.35 99.54 35.11 0.14 0.59 99.39 34.52 100.00 100.00

6C-9

Cum. Grade % P2O5 % Insol 0.80 96.62 0.99

96.07

1.20

95.52

1.54 28.48

94.63 16.11

Cum. Distribution % P2O5 % Insol 0.29 63.18 100.00 100.00 0.37 64.53 100.00 100.00 0.46 64.88 100.00 100.00 0.60 65.48 100.00 100.00

Table 6C-5 (Cont.). Tree Analysis Using Arr-Maz Condensate Amine. DOSAGE: Product Tailings 1 Concen. 1 Tailings 2 Concen. 2 Tailings 3 Concen. 3 Tailings 4 Concen. 4 Cal. Head

6.5 cc @ 2% Solution Weight (Gm) 48.5 439.8 4.5 435.3 3.0 432.3 3.2 429.1 488.3

Weight % 9.93 90.06 0.92 89.14 0.61 88.53 0.65 87.87 100.00

Grade % P2O5 % Insol 0.63 96.54 31.34 7.24 2.37 91.87 31.64 6.36 3.75 87.71 31.84 5.80 8.78 72.97 32.01 5.30 28.29 16.11

FEED: Distribution % P2O5 % Insol 0.22 59.52 99.77 40.47 0.07 5.25 99.70 35.22 0.08 3.34 99.62 31.87 0.20 2.96 99.42 28.91 100.00 100.00

6C-10

Fort Green Unsized Amine Feed Cum. Grade % P2O5 % Insol 0.63 96.54 0.77

96.14

0.93

95.69

1.36 28.29

94.46 16.11

Cum. Distribution % P2O5 % Insol 0.22 59.52 100.00 100.00 0.29 64.77 100.00 100.00 0.37 68.12 100.00 100.00 0.58 71.08 100.00 100.00

Appendix 6D DETAILED RESULTS FROM LOCKED CYCLE TESTS

Table 6D-1. Armeen HT Primary Amine Series. 1.1 DOSAGE: 5.0 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Weight Weight (Gm) % 100.00 230.20 46.69 262.80 53.31 493.00 100.00

Grades % % P2O5 Insol 28.18 16.48 32.63 2.31 23.76 29.03 27.90 16.55

1.2 DOSAGE: 2.0 cc @ 2% Solution

Weight Weight % Product (Gm) Feed 100.00 Concent. 410.90 83.30 Tailings 82.40 16.70 Cal. Feed 493.30 100.00

Grades % % Insol P2O5 28.18 16.48 32.80 2.15 4.60 84.25 28.09 15.86

1.3 DOSAGE: 3.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 364.40 73.57 Tailings 130.90 26.43 Cal. Feed 495.30 100.00

Grades % % Insol P2O5 28.18 16.48 32.79 1.91 15.01 54.50 28.09 15.81

1.4 DOSAGE: 2.5 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Weight Weight (Gm) % 100.00 331.30 67.35 160.60 32.65 491.90 100.00

Grades % % P2O5 Insol 28.18 16.48 32.74 1.89 18.13 45.43 27.97 16.11

6D-1

CYCLE NUMBER: Content P2O5 Insol Units Units 28.18 16.48 15.24 1.08 12.67 15.47 27.90 16.55 CYCLE NUMBER: Content P2O5 Insol Units Units 28.18 16.48 27.32 1.79 0.77 14.07 28.09 15.86 CYCLE NUMBER: Content P2O5 Insol Units Units 28.18 16.48 24.12 1.41 3.97 14.40 28.09 15.81 CYCLE NUMBER: Content P2O5 Insol Units Units 28.18 16.48 22.05 1.27 5.92 14.83 27.97 16.11

1 Distribution % % P2O5 Insol 100.00 100.00 54.61 6.52 45.39 93.48 100.00 100.00 2 Distribution % % P2O5 Insol 100.00 100.00 97.26 11.29 2.74 88.71 100.00 100.00 3 Distribution % % P2O5 Insol 100.00 100.00 85.88 8.89 14.12 91.11 100.00 100.00 4 Distribution % % P2O5 Insol 100.00 100.00 78.84 7.90 21.16 92.10 100.00 100.00

Table 6D-1 (Cont.). Armeen HT Primary Amine Series. 1.5 DOSAGE: 2.5 cc @ 2% Solution CYCLE NUMBER:

Weight Weight Product (Gm) % Feed 100.00 Concent. 410.50 82.95 Tailings 84.40 17.05 Cal. Feed 494.90 100.00

Grades % % P2O5 Insol 28.18 16.48 32.90 2.01 4.88 83.99 28.12 15.99

Content P2O5 Insol Units Units 28.18 16.48 27.29 1.67 0.83 14.32 28.12 15.99

1.6 DOSAGE: 2.5 cc @ 2% Solution CYCLE NUMBER: Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 410.70 82.99 32.79 2.22 Tailings 82.90 16.75 4.41 85.20 Cal. Feed 493.60 99.74 27.95 16.11

6D-2

Content P2O5 Insol Units Units 28.18 16.48 27.21 1.84 0.74 14.27 27.95 16.11

5 Distribution % % P2O5 Insol 100.00 100.00 97.04 10.43 2.96 89.57 100.00 100.00 6 Distribution % % P2O5 Insol 100.00 100.00 96.76 11.52 2.63 89.25 99.39 100.77

Table 6D-2. Armeen 2HT Secondary Amine Series. 2.1 DOSAGE: 2.5 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 488.50 99.41 Tailings 2.90 0.59 Cal. Feed 491.40 100.00

Grades % % P2O5 Insol 28.18 16.48 28.23 16.49 11.63 63.49 28.13 16.77

Content P2O5 Insol Units Units 28.18 16.48 28.06 16.39 0.07 0.37 28.13 16.77

Distribution % % P2O5 Insol 100.00 100.00 99.76 97.77 0.24 2.23 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.29 15.70 0.10 0.55 28.39 16.25

Distribution % % P2O5 Insol 100.00 100.00 99.66 96.62 0.34 3.38 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 28.32 15.81 0.12 0.61 28.43 16.41

Distribution % % P2O5 Insol 100.00 100.00 99.58 96.31 0.42 3.69 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.83 16.74 0.16 0.65 27.99 17.40

Distribution % % P2O5 Insol 100.00 100.00 99.43 96.24 0.57 3.76 100.00 100.00

2.2 DOSAGE: 5.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 489.60 99.13 Tailings 4.30 0.87 Cal. Feed 493.90 100.00

Grades % % Insol P2O5 28.18 16.48 28.54 15.84 11.21 63.16 28.39 16.25

2.3 DOSAGE: 7.5 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 490.90 98.97 Tailings 5.10 1.03 Cal. Feed 496.00 100.00

Grades % % P2O5 Insol 28.18 16.48 28.61 15.97 11.53 58.96 28.43 16.41

1.4 DOSAGE: 10.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 486.40 98.84 Tailings 5.70 1.16 Cal. Feed 492.10 100.00

Grades % % P2O5 Insol 28.18 16.48 28.16 16.94 13.70 56.50 27.99 17.40

6D-3

Table 6D-2 (Cont.). Armeen 2HT Secondary Amine Series. 2.5 DOSAGE: 12.5 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 488.70 99.19 Tailings 4.00 0.81 Cal. Feed 492.70 100.00

Grades % % P2O5 Insol 28.18 16.48 28.24 15.85 14.86 52.11 28.13 16.14

Content P2O5 Insol Units Units 28.18 16.48 28.01 15.72 0.12 0.42 28.13 16.14

Distribution % % P2O5 Insol 100.00 100.00 99.57 97.38 0.43 2.62 100.00 100.00

Content P2O5 Insol Units Units 28.18 16.48 27.94 15.65 0.15 0.69 28.09 16.35

Distribution % % P2O5 Insol 100.00 100.00 99.47 95.75 0.53 4.25 100.00 100.00

2.6 DOSAGE: 15.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 487.80 98.82 Tailings 5.80 1.18 Cal. Feed 493.60 100.00

Grades % % Insol P2O5 28.18 16.48 28.27 15.84 12.63 59.14 28.09 16.35

6D-4

Table 6D-3. Armeen DMHTD Tertiary Amine Series. 3.1 DOSAGE: 3.0 cc @ 2% Solution CYCLE NUMBER:

Weight Product (Gm) Feed Concent. 410.80 Tailings 79.50 Cal. Feed 490.30

Grades Weight % % % P2O5 Insol 100.00 28.18 16.48 83.79 32.49 3.58 16.21 5.99 80.90 100.00 28.19 16.12

Content P2O5 Insol Units Units 28.18 16.48 27.22 3.00 0.97 13.12 28.19 16.12

3.2 DOSAGE: 3.0 cc @ 2% Solution CYCLE NUMBER: Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 414.70 84.86 32.54 3.42 Tailings 74.00 15.14 5.90 85.97 Cal. Feed 488.70 100.00 28.51 15.92 3.3 DOSAGE: 3.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 416.30 85.15 Tailings 72.60 14.85 Cal. Feed 488.90 100.00

Grades % % P2O5 Insol 28.18 16.48 32.49 3.59 3.47 88.97 28.18 16.27

3.4 DOSAGE: 3.5 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Weight Weight (Gm) % 100.00 407.20 83.27 81.80 16.73 489.00 100.00

Grades % % P2O5 Insol 28.18 16.48 32.64 2.99 5.89 81.84 28.17 16.18

6D-5

Content P2O5 Insol Units Units 28.18 16.48 27.61 2.90 0.89 13.02 28.51 15.92

1 Distribution % % P2O5 Insol 100.00 100.00 96.56 18.61 3.44 81.39 100.00 100.00 2 Distribution % % P2O5 Insol 100.00 100.00 96.87 18.23 3.13 81.77 100.00 100.00

CYCLE NUMBER:

3

Content P2O5 Insol Units Units 28.18 16.48 27.67 3.06 0.52 13.21 28.18 16.27

Distribution % % P2O5 Insol 100.00 100.00 98.17 18.79 1.83 81.21 100.00 100.00

CYCLE NUMBER:

4

Content P2O5 Insol Units Units 28.18 16.48 27.18 2.49 0.99 13.69 28.17 16.18

Distribution % % P2O5 Insol 100.00 100.00 96.50 15.39 3.50 84.61 100.00 100.00

Table 6D-3 (Cont.). Armeen DMHTD Tertiary Amine Series. 3.5 DOSAGE: 3.5 cc @ 2% Solution

Weight Weight (Gm) Product % Feed 100.00 Concent. 418.70 85.14 Tailings 73.10 14.86 Cal. Feed 491.80 100.00

Grades % % P2O5 Insol 28.18 16.48 32.54 3.38 3.37 89.20 28.20 16.14

6D-6

CYCLE NUMBER:

5

Content P2O5 Insol Units Units 28.18 16.48 27.70 2.88 0.50 13.26 28.20 16.14

Distribution % % P2O5 Insol 100.00 100.00 98.22 17.83 1.78 82.17 100.00 100.00

Table 6D-4. Arquad 2HT-75 Quaternary Amine Series. 4.1 DOSAGE: 4.0 cc @ 2% Solution

Weight Weight (Gm) Product % Feed 100.00 Concent. 421.20 86.21 Tailings 67.40 13.79 Cal. Feed 488.60 100.00

Grades % % P2O5 Insol 28.18 16.48 32.33 4.12 2.44 91.58 28.21 16.18

4.2 DOSAGE: 4.5 cc @ 2% Solution Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 420.50 85.71 32.59 3.28 Tailings 70.10 14.29 2.02 93.16 Cal. Feed 490.60 100.00 28.22 16.12 4.3 DOSAGE: 5.0 cc @ 2% Solution Grades % Weight Weight % Product % Insol (Gm) P2O5 Feed 100.00 28.18 16.48 Concent. 419.60 85.35 32.64 3.12 Tailings 72.00 14.65 2.27 92.23 Cal. Feed 491.60 100.00 28.19 16.17 4.4 DOSAGE: 6.0 cc @ 2% Solution Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 417.80 85.09 32.86 2.73 Tailings 73.20 14.91 2.61 91.48 Cal. Feed 491.00 100.00 28.35 15.96

6D-7

CYCLE NUMBER: Content P2O5 Insol Units Units 28.18 16.48 27.87 3.55 0.34 12.63 28.21 16.18

1 Distribution % % P2O5 Insol 100.00 100.00 98.81 21.94 1.19 78.06 100.00 100.00

CYCLE NUMBER:

2

Content P2O5 Insol Units Units 28.18 16.48 27.93 2.81 0.29 13.31 28.22 16.12

Distribution % % P2O5 Insol 100.00 100.00 98.98 17.44 1.02 82.56 100.00 100.00

CYCLE NUMBER:

3

Content P2O5 Insol Units Units 28.18 16.48 27.86 2.66 0.33 13.51 28.19 16.17

Distribution % % P2O5 Insol 100.00 100.00 98.82 16.47 1.18 83.53 100.00 100.00

CYCLE NUMBER:

4

Content P2O5 Insol Units Units 28.18 16.48 27.96 2.32 0.39 13.64 28.35 15.96

Distribution % % P2O5 Insol 100.00 100.00 98.63 14.55 1.37 85.45 100.00 100.00

Table 6D-4 (Cont.). Arquad 2HT-75 Quaternary Amine Series. 4.5 DOSAGE: 6.0 cc @ 2% Solution Grades Weight Weight % % (Gm) Product P2O5 % Insol Feed 100.00 28.18 16.48 Concent. 420.60 85.14 32.68 2.81 Tailings 73.40 14.86 2.53 92.02 Cal. Feed 494.00 100.00 28.20 16.07

6D-8

CYCLE NUMBER:

5

Content P2O5 Insol Units Units 28.18 16.48 27.82 2.39 0.38 13.67 28.20 16.07

Distribution % % P2O5 Insol 100.00 100.00 98.67 14.89 1.33 85.11 100.00 100.00

Table 6D-5. Adogen 185 Ether Amine Acetate Series. 5.1 DOSAGE: 2.0 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Weight Weight (Gm) % 100.00 418.50 84.41 77.30 15.59 495.80 100.00

Grades % % P2O5 Insol 28.18 16.48 32.56 2.94 3.69 87.49 28.06 16.12

5.2 DOSAGE: 2.0 cc @ 2% Solution

Weight Weight Product % (Gm) Feed 100.00 Concent. 419.70 84.55 Tailings 76.70 15.45 Cal. Feed 496.40 100.00

Grades % % Insol P2O5 28.18 16.48 32.53 3.02 3.47 88.02 28.04 16.15

5.3 DOSAGE: 2.5 cc @ 2% Solution

Weight Weight Product % (Gm) Feed 100.00 Concent. 416.10 83.74 Tailings 80.80 16.26 Cal. Feed 496.90 100.00

Grades % % Insol P2O5 28.18 16.48 32.66 2.68 4.85 83.99 28.14 15.90

5.4 DOSAGE: 3.0 cc @ 2% Solution

Weight Weight (Gm) Product % Feed 100.00 Concent. 408.70 82.12 Tailings 89.00 17.88 Cal. Feed 497.70 100.00

Grades % % P2O5 Insol 28.18 16.48 32.76 2.50 6.68 78.79 28.10 16.14

6D-9

CYCLE NUMBER:

1

Content P2O5 Insol Units Units 28.18 16.48 27.48 2.48 0.58 13.64 28.06 16.12

Distribution % % P2O5 Insol 100.00 100.00 97.95 15.39 2.05 84.61 100.00 100.00

CYCLE NUMBER:

2

Content P2O5 Insol Units Units 28.18 16.48 27.50 2.55 0.54 13.60 28.04 16.15

Distribution % % P2O5 Insol 100.00 100.00 98.09 15.81 1.91 84.19 100.00 100.00

CYCLE NUMBER:

3

Content P2O5 Insol Units Units 28.18 16.48 27.35 2.24 0.79 13.66 28.14 15.90

Distribution % % P2O5 Insol 100.00 100.00 97.20 14.11 2.80 85.89 100.00 100.00

CYCLE NUMBER:

4

Content P2O5 Insol Units Units 28.18 16.48 26.90 2.05 1.19 14.09 28.10 16.14

Distribution % % P2O5 Insol 100.00 100.00 95.75 12.72 4.25 87.28 100.00 100.00

Table 6D-5 (Cont.). Adogen 185 Ether Amine Acetate Series. 5.5 DOSAGE: 3.0 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Weight Weight (Gm) % 100.00 412.90 83.06 84.20 16.94 497.10 100.00

CYCLE NUMBER:

Grades % % P2O5 Insol 28.18 16.48 32.73 2.71 5.53 82.43 28.12 16.21

6D-10

Content P2O5 Insol Units Units 28.18 16.48 27.19 2.25 0.94 13.96 28.12 16.21

5 Distribution % % P2O5 Insol 100.00 100.00 96.67 13.88 3.33 86.12 100.00 100.00

Table 6D-6. Arr-Maz Condensate Amine Series. 6.1 DOSAGE: 5.0 cc @ 2% Solution

CYCLE NUMBER:

Grades Weight Weight % % (Gm) Product % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 413.50 83.20 32.82 2.04 Tailings 83.50 16.80 4.55 85.02 Cal. Feed 497.00 100.00 28.07 15.98 6.2 DOSAGE: 5.0 cc @ 2% Solution

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 27.31 1.70 0.76 14.28 28.07 15.98

Distribution % % P2O5 Insol 100.00 100.00 97.28 10.62 2.72 89.38 100.00 100.00

CYCLE NUMBER:

2

Content P2O5 Insol Units Units 28.18 16.48 27.02 1.75 1.00 14.58 28.02 16.34

Distribution % % P2O5 Insol 100.00 100.00 96.43 10.72 3.57 89.28 100.00 100.00

CYCLE NUMBER:

3

Content P2O5 Insol Units Units 28.18 16.48 26.71 1.65 1.41 14.45 28.12 16.10

Distribution % % P2O5 Insol 100.00 100.00 94.99 10.24 5.01 89.76 100.00 100.00

Grades % % Weight Weight % Insol P2O5 (Gm) 100.00 28.18 16.48 410.00 82.21 32.87 2.13 88.70 17.79 5.62 82.00 498.70 100.00 28.02 16.34

6.3 DOSAGE: 5.5 cc @ 2% Solution

Weight Weight Product % (Gm) Feed 100.00 Concent. 403.30 81.18 Tailings 93.50 18.82 Cal. Feed 496.80 100.00

1

Grades % % Insol P2O5 28.18 16.48 32.90 2.03 7.48 76.79 28.12 16.10

6.4 DOSAGE: 6.0 cc @ 2% Solution CYCLE NUMBER: Grades Content Weight Weight % % P2O5 Insol Product (Gm) % P2O5 Insol Units Units Feed 100.00 28.18 16.48 28.18 16.48 Concent. 396.00 79.84 32.97 1.82 26.32 1.45 Tailings 100.00 20.16 9.47 71.08 1.91 14.33 Cal. Feed 496.00 100.00 28.23 15.78 28.23 15.78

6D-11

4 Distribution % % P2O5 Insol 100.00 100.00 93.24 9.21 6.76 90.79 100.00 100.00

Table 6D-6 (Cont.). Arr-Maz Condensate Amine Series. 6.5 DOSAGE: 6.0 cc @ 2% Solution CYCLE NUMBER: 5 Grades Content Distribution Weight Weight % % P2O5 Insol % % (Gm) Product % P2O5 Insol Units Units P2O5 Insol Feed 100.00 28.18 16.48 28.18 16.48 100.00 100.00 Concent. 396.40 79.00 32.90 1.85 25.99 1.46 92.53 9.10 Tailings 105.40 21.00 9.99 69.51 2.10 14.60 7.47 90.90 Cal. Feed 501.80 100.00 28.09 16.06 28.09 16.06 100.00 100.00

6D-12

Table 6D-7. Arr-Maz Condensate Amine Series—Reverse Crago Process. 7.1 DOSAGE: 5.0 cc @ 2% Solution CYCLE NUMBER: 1 PERCOL 90L: 4.0 cc @ 0.1% Solution SCRUBBING: 3 minutes Grades Content Distribution Weight Weight % % P2O5 Insol % % (Gm) Product % P2O5 Insol Units Units P2O5 Insol Feed 100.00 6.82 78.38 28.18 16.48 100.00 100.00 Concent. 471.70 97.44 5.56 82.44 5.42 80.33 99.19 97.13 Tailings 12.40 2.56 1.73 92.72 0.04 2.37 0.81 2.87 Cal. Feed 484.10 100.00 5.46 82.70 5.46 82.70 100.00 100.00 7.2 DOSAGE: 6.0 cc @ 2% Solution PERCOL 90L: 6.0 cc @ 0.1% Solution

Weight Weight % Product (Gm) Feed 100.00 Concent. 463.20 95.37 Tailings 22.50 4.63 Cal. Feed 485.70 100.00 7.3

CYCLE NUMBER: SCRUBBING:

Grades % % P2O5 Insol 6.82 78.38 5.64 82.36 1.00 95.93 5.43 82.99

Content P2O5 Insol Units Units 28.18 16.48 5.38 78.54 0.05 4.44 5.43 82.99

2 3 minutes Distribution % % P2O5 Insol 100.00 100.00 99.15 94.65 0.85 5.35 100.00 100.00

DOSAGE: 8.0 cc @ 2% Solution CYCLE NUMBER: 3 PERCOL 90L: 8.0 cc @ 0.1% Solution SCRUBBING: 3 minutes

Weight Weight Product (Gm) % Feed 100.00 Concent. 420.70 86.67 Tailings 64.70 13.33 Cal. Feed 485.40 100.00

Grades % % P2O5 Insol 6.82 78.38 6.12 80.47 0.60 97.46 5.38 82.73

6D-13

Content P2O5 Insol Units Units 28.18 16.48 5.30 69.74 0.08 12.99 5.38 82.73

Distribution % % P2O5 Insol 100.00 100.00 98.51 84.30 1.49 15.70 100.00 100.00

Table 6D-7 (Cont.). Arr-Maz Condensate Amine Series—Reverse Crago Process. 7.4

DOSAGE: 10.0 cc @ 2% Solution CYCLE NUMBER: 4 PERCOL 90L: 10.0 cc @ 0.1% Solution SCRUBBING: 3 minutes

Weight Weight Product (Gm) % Feed 100.00 Concent. 414.20 85.45 Tailings 70.50 14.55 Cal. Feed 484.70 100.00 7.5

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 5.41 68.04 0.10 14.17 5.51 82.20

Distribution % % P2O5 Insol 100.00 100.00 98.26 82.77 1.74 17.23 100.00 100.00

DOSAGE: 6.0 cc @ 2% Solution CYCLE NUMBER: 5 PERCOL 90L: 10.0 cc @ 0.1% Solution SCRUBBING: 3 minutes

Weight Weight (Gm) % Product Feed 100.00 Concent. 461.20 94.64 Tailings 26.10 5.36 Cal. Feed 487.30 100.00 7.6

Grades % % P2O5 Insol 6.82 78.38 6.33 79.62 0.66 97.39 5.51 82.20

Grades % % P2O5 Insol 6.82 78.38 5.68 81.71 1.33 95.14 5.45 82.43

Content P2O5 Insol Units Units 28.18 16.48 5.38 77.33 0.07 5.10 5.45 82.43

Distribution % % P2O5 Insol 100.00 100.00 98.69 93.82 1.31 6.18 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution CYCLE NUMBER: PERCOL 90L: 4.0 cc @ 0.1% Solution SCRUBBING: None

Weight Weight (Gm) % 100.00 452.40 93.45 31.70 6.55 484.10 100.00

Grades % % P2O5 Insol 6.82 78.38 5.53 81.66 1.05 95.28 5.24 82.55

6D-14

Content P2O5 Insol Units Units 28.18 16.48 5.17 76.31 0.07 6.24 5.24 82.55

6

Distribution % % P2O5 Insol 100.00 100.00 98.69 92.44 1.31 7.56 100.00 100.00

Table 6D-7 (Cont.). Arr-Maz Condensate Amine Series—Reverse Crago Process. 7.7

DOSAGE: 10.0 cc @ 2% Solution CYCLE NUMBER: PERCOL 90L: 8.0 cc @ 0.1% Solution SCRUBBING: None

Weight Weight Product (Gm) % Feed 100.00 Concent. 388.80 79.44 Tailings 100.60 20.56 Cal. Feed 489.40 100.00 7.8

Product Feed Concent. Tailings Cal. Feed

Grades % % P2O5 Insol 6.82 78.38 6.46 78.87 0.71 96.20 5.28 82.43

Content P2O5 Insol Units Units 28.18 16.48 5.13 62.66 0.15 19.77 5.28 82.43

Distribution % % P2O5 Insol 100.00 100.00 97.23 76.01 2.77 23.99 100.00 100.00

DOSAGE: 10.0 cc @ 2% Solution CYCLE NUMBER: PERCOL 90L: 10.0 cc @ 0.1% Solution SCRUBBING: None

Weight Weight (Gm) % 100.00 399.00 81.56 90.20 18.44 489.20 100.00

Grades % % Insol P2O5 6.82 78.38 6.58 78.43 0.71 96.13 5.50 81.69

6D-15

Content P2O5 Insol Units Units 28.18 16.48 5.37 63.97 0.13 17.72 5.50 81.69

7

8

Distribution % % P2O5 Insol 100.00 100.00 97.62 78.30 2.38 21.70 100.00 100.00

Appendix 6E TESTS ON PARTICLE SIZE EFFECT

Table 6E-1. Armeen HT Primary Amine Series. 1.1

Product Feed Concent. Tailings Cal. Feed 1.2

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION: Grades Weight Weight % % P2O5 (Gm) % Insol 100.00 28.18 16.48 144.19 96.77 32.73 2.87 4.82 3.23 8.94 71.51 149.01 100.00 31.96 5.09

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 151.91 90.11 Tailings 16.67 9.89 Cal. Feed 168.58 100.00 1.3

Grades % % Insol P2O5 28.18 16.48 33.01 2.33 6.70 78.17 30.41 9.83

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 29.75 2.10 0.66 7.73 30.41 9.83

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 52.89 74.74 33.28 2.04 Tailings 17.88 25.26 3.56 88.87 Cal. Feed 70.77 100.00 25.77 23.98 1.4

Content P2O5 Insol Units Units 28.18 16.48 31.67 2.78 0.29 2.31 31.96 5.09

Content P2O5 Insol Units Units 28.18 16.48 24.87 1.52 0.90 22.45 25.77 23.98

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 65.06 71.98 25.33 28.02 90.39 100.00

Grades % P2O5 28.18 33.38 2.80 24.81

% Insol 16.48 2.04 91.24 27.04

6E-1

Content P2O5 Insol Units Units 28.18 16.48 24.03 1.47 0.78 25.57 24.81 27.04

+ 35 M Distribution % % P2O5 Insol 100.00 100.00 99.10 54.56 0.90 45.44 100.00 100.00 35X48 M Distribution % % P2O5 Insol 100.00 100.00 97.82 21.36 2.18 78.64 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 96.51 6.36 3.49 93.64 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 96.84 5.43 3.16 94.57 100.00 100.00

Table 6E-1 (Cont.). Armeen HT Primary Amine Series. 1.5

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 10.05 35.97 Tailings 17.89 64.03 Cal. Feed 27.94 100.00

Grades % % P2O5 Insol 28.18 16.48 31.78 7.68 3.14 89.88 13.44 60.31

6E-2

Content P2O5 Insol Units Units 28.18 16.48 11.43 2.76 2.01 57.55 13.44 60.31

100X150 M Distribution % % P2O5 Insol 100.00 100.00 85.04 4.58 14.96 95.42 100.00 100.00

Table 6E-2. Armeen 2HT Secondary Amine Series. 2.1

DOSAGE: 35.0 cc @ 2% Solution SIZE FRACTION: + 48 M

Weight Weight Product (Gm) % Feed 100.00 Concent. 304.26 99.00 Tailings 3.08 1.00 Cal. Feed 307.34 100.00 2.2

Grades % % P2O5 Insol 28.18 16.48 31.74 6.51 7.52 76.15 31.50 7.21

DOSAGE: 35.0 cc @ 2% Solution SIZE FRACTION:

Grades % Weight Weight % Product P2O5 (Gm) % Insol Feed 100.00 28.18 16.48 Concent. 79.93 96.29 29.70 13.10 Tailings 3.08 3.71 7.56 76.87 Cal. Feed 83.01 100.00 28.88 15.47 2.3

Content P2O5 Insol Units Units 28.18 16.48 28.60 12.61 0.28 2.85 28.88 15.47

DOSAGE: 35.0 cc @ 2% Solution SIZE FRACTION:

Grades % % Weight Weight Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 50.33 66.95 30.54 11.69 Tailings 24.85 33.05 1.91 93.99 Cal. Feed 75.18 100.00 21.08 38.89 2.4

Content P2O5 Insol Units Units 28.18 16.48 31.42 6.44 0.08 0.76 31.50 7.21

Content P2O5 Insol Units Units 28.18 16.48 20.45 7.83 0.63 31.07 21.08 38.89

DOSAGE: 35.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 11.28 42.61 Tailings 15.19 57.39 Cal. Feed 26.47 100.00

Grades % % P2O5 Insol 28.18 16.48 27.78 19.38 2.83 90.88 13.46 60.41

6E-3

Content P2O5 Insol Units Units 28.18 16.48 11.84 8.26 1.62 52.15 13.46 60.41

Distribution % % P2O5 Insol 100.00 100.00 99.76 89.41 0.24 10.59 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 99.03 81.56 0.97 18.44 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 97.00 20.12 3.00 79.88 100.00 100.00 100X150 M Distribution % % P2O5 Insol 100.00 100.00 87.94 13.67 12.06 86.33 100.00 100.00

Table 6E-3. Armeen DMHTD Tertiary Amine Series. 3.1

DOSAGE: 3.0 cc @ 2% Solution SIZE FRACTION: + 35 M

Weight Weight Product (Gm) % Feed 100.00 Concent. 141.00 98.31 Tailings 2.42 1.69 Cal. Feed 143.42 100.00 3.2

Grades % % P2O5 Insol 28.18 16.48 32.55 3.26 3.62 86.69 32.06 4.67

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 30.17 3.14 0.28 6.46 30.45 9.60

DOSAGE: 3.0 cc @ 2% Solution SIZE FRACTION:

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 62.49 79.06 32.81 3.38 Tailings 16.55 20.94 4.21 87.11 Cal. Feed 79.04 100.00 26.82 20.91 3.4

Distribution % % P2O5 Insol 100.00 100.00 99.81 68.66 0.19 31.34 100.00 100.00

DOSAGE: 3.0 cc @ 2% Solution SIZE FRACTION: 35x48 M

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 149.16 92.61 32.58 3.39 Tailings 11.91 7.39 3.75 87.34 Cal. Feed 161.07 100.00 30.45 9.60 3.3

Content P2O5 Insol Units Units 28.18 16.48 32.00 3.20 0.06 1.46 32.06 4.67

Content P2O5 Insol Units Units 28.18 16.48 25.94 2.67 0.88 18.24 26.82 20.91

DOSAGE: 3.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 52.91 66.84 26.25 33.16 79.16 100.00

Grades % % P2O5 Insol 28.18 16.48 32.54 5.05 5.63 83.47 23.62 31.05

6E-4

Content P2O5 Insol Units Units 28.18 16.48 21.75 3.38 1.87 27.68 23.62 31.05

Distribution % % P2O5 Insol 100.00 100.00 99.09 32.71 0.91 67.29 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 96.71 12.78 3.29 87.22 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 92.09 10.87 7.91 89.13 100.00 100.00

Table 6E-3 (Cont.). Armeen DMHTD Tertiary Amine Series. 3.5

DOSAGE: 3.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 10.74 38.22 Tailings 17.36 61.78 Cal. Feed 28.10 100.00

Grades % % P2O5 Insol 28.18 16.48 28.35 17.38 3.74 88.72 13.15 61.45

6E-5

Content P2O5 Insol Units Units 28.18 16.48 10.84 6.64 2.31 54.81 13.15 61.45

100X150 M Distribution % % P2O5 Insol 100.00 100.00 82.42 10.81 17.58 89.19 100.00 100.00

Table 6E-4. Arquad 2HT-75 Quaternary Amine Series. 4.1

DOSAGE: 4.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 142.51 98.47 Tailings 2.21 1.53 Cal. Feed 144.72 100.00 4.2

Product Feed Concent. Tailings Cal. Feed 4.4

Content P2O5 Insol Units Units 28.18 16.48 31.90 3.35 0.07 1.30 31.96 4.65

Distribution % % P2O5 Insol 100.00 100.00 99.79 72.03 0.21 27.97 100.00 100.00

DOSAGE: 4.0 cc @ 2% Solution SIZE FRACTION: 35x48 M

Weight Weight Product (Gm) % Feed 100.00 Concent. 151.15 92.83 Tailings 11.68 7.17 Cal. Feed 162.83 100.00 4.3

Grades % % P2O5 Insol 28.18 16.48 32.39 3.40 4.37 85.12 31.96 4.65

+35 M

Grades % % P2O5 Insol 28.18 16.48 32.41 3.17 3.08 89.34 30.31 9.35

Content P2O5 Insol Units Units 28.18 16.48 30.09 2.94 0.22 6.41 30.31 9.35

DOSAGE: 4.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 68.57 79.09 18.13 20.91 86.70 100.00

Grades % % Insol P2O5 28.18 16.48 32.81 2.76 2.37 92.48 26.44 21.52

Content P2O5 Insol Units Units 28.18 16.48 25.95 2.18 0.50 19.34 26.44 21.52

DOSAGE: 4.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 51.79 70.81 Tailings 21.35 29.19 Cal. Feed 73.14 100.00

Grades % % P2O5 Insol 28.18 16.48 32.73 3.91 2.36 92.68 23.86 29.82

6E-6

Content P2O5 Insol Units Units 28.18 16.48 23.18 2.77 0.69 27.05 23.86 29.82

Distribution % % P2O5 Insol 100.00 100.00 99.27 31.47 0.73 68.53 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 98.13 10.14 1.87 89.86 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 97.11 9.28 2.89 90.72 100.00 100.00

Table 6E-4 (Cont.). Arquad 2HT-75 Quaternary Amine Series. 4.5

DOSAGE: 4.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 11.88 41.25 Tailings 16.92 58.75 Cal. Feed 28.80 100.00

Grades % % P2O5 Insol 28.18 16.48 30.34 11.43 2.24 92.82 13.83 59.25

6E-7

Content P2O5 Insol Units Units 28.18 16.48 12.52 4.71 1.32 54.53 13.83 59.25

100X150 M Distribution % % P2O5 Insol 100.00 100.00 90.49 7.96 9.51 92.04 100.00 100.00

Table 6E-5. Adogen 185 Ether Amine Acetate Series. 5.1

DOSAGE: 2.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 139.49 97.70 Tailings 3.28 2.30 Cal. Feed 142.77 100.00 5.2

Grades % % P2O5 Insol 28.18 16.48 32.92 2.81 7.67 76.00 32.34 4.49

Product Feed Concent. Tailings Cal. Feed 5.4

Distribution % % P2O5 Insol 100.00 100.00 99.46 61.13 0.54 38.87 100.00 100.00

DOSAGE: 2.0 cc @ 2% Solution SIZE FRACTION: 35x48 M

Grades % Weight Weight % Product (Gm) % Insol P2O5 Feed 100.00 28.18 16.48 Concent. 148.37 91.30 33.05 2.35 Tailings 14.13 8.70 4.86 84.27 Cal. Feed 162.50 100.00 30.60 9.47 5.3

Content P2O5 Insol Units Units 28.18 16.48 32.16 2.75 0.18 1.75 32.34 4.49

+35 M

Content P2O5 Insol Units Units 28.18 16.48 30.18 2.15 0.42 7.33 30.60 9.47

DOSAGE: 2.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 47.58 70.54 19.87 29.46 67.45 100.00

Grades % % P2O5 Insol 28.18 16.48 33.52 1.82 3.15 90.34 24.57 27.90

Content P2O5 Insol Units Units 28.18 16.48 23.65 1.28 0.93 26.61 24.57 27.90

DOSAGE: 2.0 cc @ 2% Solution SIZE FRACTION:

Grades Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 28.18 16.48 Concent. 67.19 74.21 33.66 2.34 Tailings 23.35 25.79 3.24 90.25 Cal. Feed 90.54 100.00 25.81 25.01

6E-8

Content P2O5 Insol Units Units 28.18 16.48 24.98 1.74 0.84 23.28 25.81 25.01

Distribution % % P2O5 Insol 100.00 100.00 98.62 22.65 1.38 77.35 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 96.22 4.60 3.78 95.40 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 96.76 6.94 3.24 93.06 100.00 100.00

Table 6E-5 (Cont.). Adogen 185 Ether Amine Acetate Series. 5.5

DOSAGE: 2.0 cc @ 2% Solution SIZE FRACTION:

Grades Weight Weight % % Product P2O5 Insol (Gm) % Feed 100.00 28.18 16.48 Concent. 10.03 38.58 31.91 7.68 Tailings 15.97 61.42 3.32 89.80 Cal. Feed 26.00 100.00 14.35 58.12

6E-9

Content P2O5 Insol Units Units 28.18 16.48 12.31 2.96 2.04 55.16 14.35 58.12

100X150 M Distribution % % P2O5 Insol 100.00 100.00 85.79 5.10 14.21 94.90 100.00 100.00

Table 6E-6. Arr-Maz Condensate Amine Series. 6.1

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight Product (Gm) % Feed 100.00 Concent. 141.83 97.36 Tailings 3.84 2.64 Cal. Feed 145.67 100.00 6.2

Product Feed Concent. Tailings Cal. Feed 6.4

Product Feed Concent. Tailings Cal. Feed

Content P2O5 Insol Units Units 28.18 16.48 32.18 2.60 0.23 1.93 32.41 4.53

Distribution % % P2O5 Insol 100.00 100.00 99.30 57.36 0.70 42.64 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION: 35x48 M

Weight Weight Product (Gm) % Feed 100.00 Concent. 147.68 90.81 Tailings 14.95 9.19 Cal. Feed 162.63 100.00 6.3

Grades % % P2O5 Insol 28.18 16.48 33.05 2.67 8.62 73.31 32.41 4.53

+35 M

Grades % % P2O5 Insol 28.18 16.48 33.34 1.88 5.17 83.23 30.75 9.36

Content P2O5 Insol Units Units 28.18 16.48 30.28 1.71 0.48 7.65 30.75 9.36

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 56.28 80.38 13.74 19.62 70.02 100.00

Grades % % P2O5 Insol 28.18 16.48 33.63 1.58 4.45 86.32 27.90 18.21

Content P2O5 Insol Units Units 28.18 16.48 27.03 1.27 0.87 16.94 27.90 18.21

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Weight Weight (Gm) % 100.00 59.10 67.47 28.49 32.53 87.59 100.00

Grades % % P2O5 Insol 28.18 16.48 33.77 1.75 2.47 92.36 23.59 31.22

6E-10

Content P2O5 Insol Units Units 28.18 16.48 22.79 1.18 0.80 30.04 23.59 31.22

Distribution % % P2O5 Insol 100.00 100.00 98.45 18.24 1.55 81.76 100.00 100.00 48X65 M Distribution % % P2O5 Insol 100.00 100.00 96.87 6.97 3.13 93.03 100.00 100.00 65X100 M Distribution % % P2O5 Insol 100.00 100.00 96.59 3.78 3.41 96.22 100.00 100.00

Table 6E-6 (Cont.). Arr-Maz Condensate Amine Series. 6.5

DOSAGE: 5.0 cc @ 2% Solution SIZE FRACTION:

Grades Content Weight Weight % % P2O5 Insol Product P2O5 Insol (Gm) % Units Units Feed 100.00 28.18 16.48 28.18 16.48 Concent. 9.83 35.09 32.64 6.02 11.45 2.11 Tailings 18.18 64.91 2.78 91.26 1.80 59.23 Cal. Feed 28.01 100.00 13.26 61.35 13.26 61.35

6E-11

100X150 M Distribution % % P2O5 Insol 100.00 100.00 86.39 3.44 13.61 96.56 100.00 100.00

Appendix 6F SCREEN ANALYSIS OF FLOTATION TAILS

Table 6F-1A. Screen Analysis for Flotation Tailings—Armeen HT Primary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 0.00 0.00 2.40 8.30 8.90 12.60 7.50 1.40 0.00 41.10

0.00 0.00 0.00 5.84 20.19 21.65 30.66 18.25 3.41 0.00 100.00

0.00 0.00 0.00 5.84 26.03 47.69 78.35 96.59 100.00 100.00

100.00 100.00 100.00 94.16 73.97 52.31 21.65 3.41 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

Cum. Distribution % % P2O5 Insol

8.94 6.70 3.56 2.80 2.99 3.95

71.51 78.17 88.87 91.24 90.59 86.11

12.48 32.33 18.42 20.51 13.04 3.22

4.82 18.22 22.21 32.28 19.08 3.39

8.94 7.20 5.55 4.47 4.19 4.18

12.48 44.81 63.23 83.75 96.78 100.00

4.18

86.64

100.00

100.00

6F-1

71.51 76.68 82.21 85.75 86.66 86.64

4.82 23.04 45.25 77.53 96.61 100.00

Table 6F-1B. Screen Analysis for Flotation Concentrate—Armeen HT Primary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 2.80 15.90 42.90 64.90 22.60 27.80 4.30 0.00 0.00 181.20

0.00 1.55 8.77 23.68 35.82 12.47 15.34 2.37 0.00 0.00 100.00

0.00 1.55 10.32 34.00 69.81 82.28 97.63 100.00 100.00 100.00

100.00 98.45 89.68 66.00 30.19 17.72 2.37 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

Cum. Distribution % % P2O5 Insol

32.30 32.76 32.75 33.01 33.28 33.38 31.78

4.30 3.12 2.69 2.33 2.04 2.21 7.68

1.51 8.72 23.51 35.85 12.59 15.53 2.29

2.57 10.58 24.61 32.25 9.83 13.10 7.04

32.30 32.69 32.73 32.87 32.94 33.01 32.98

1.51 10.23 33.74 69.60 82.18 97.71 100.00

32.98

2.59

100.00

100.00

6F-2

4.30 3.30 2.87 2.59 2.51 2.46 2.59

2.57 13.15 37.76 70.02 79.85 92.96 100.00

Table 6F-2A. Screen Analysis for Flotation Tailings—Armeen 2HT Secondary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm)

Weight %

Retained %

Passing %

0.00 0.00 0.00 0.00 1.50 1.50 12.10 6.40 1.00 0.00 22.50

0.00 0.00 0.00 0.00 6.67 6.67 53.78 28.44 4.44 0.00 100.00

0.00 0.00 0.00 0.00 6.67 13.33 67.11 95.56 100.00 100.00

100.00 100.00 100.00 100.00 93.33 86.67 32.89 4.44 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

Cum. Distribution % % P2O5 Insol

7.52 7.56 1.91 2.75 3.37

76.15 76.87 93.99 91.29 88.25

16.91 17.00 34.65 26.39 5.05

5.60 5.65 55.77 28.65 4.33

7.52 7.54 3.03 2.95 2.96

16.91 33.91 68.56 94.95 100.00

2.96

90.64

100.00

100.00

6F-3

76.15 76.51 90.52 90.75 90.64

5.60 11.26 67.02 95.67 100.00

Table 6F-2B. Screen Analysis for Flotation Concentrate—Armeen 2HT Secondary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 2.80 15.40 42.90 68.30 34.00 21.40 4.80 0.00 0.00 189.60

0.00 1.48 8.12 22.63 36.02 17.93 11.29 2.53 0.00 0.00 100.00

0.00 1.48 9.60 32.23 68.25 86.18 97.47 100.00 100.00 100.00

100.00 98.52 90.40 67.77 31.75 13.82 2.53 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

32.78 32.56 32.32 31.14 29.70 30.54 27.78

4.19 3.94 4.88 8.20 13.10 11.69 19.38

1.55 8.49 23.49 36.03 17.11 11.07 2.26

0.72 3.72 12.84 34.35 27.32 15.34 5.71

32.78 32.59 32.40 31.74 31.31 31.22 31.14

31.14

8.60

100.00

100.00

6F-4

Cum. Distribution % % P2O5 Insol

4.19 1.55 3.98 10.05 4.61 33.54 6.51 69.56 7.88 86.67 8.32 97.74 8.60 100.00

0.72 4.44 17.28 51.63 78.95 94.29 100.00

Table 6F-3A. Screen Analysis for Flotation Tailings—Armeen DMHTD Tertiary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm)

Weight %

Retained %

Passing %

0.00 0.00 0.00 1.20 5.90 8.20 13.00 7.30 1.30 0.00 36.90

0.00 0.00 0.00 3.25 15.99 22.22 35.23 19.78 3.52 0.00 100.00

0.00 0.00 0.00 3.25 19.24 41.46 76.69 96.48 100.00 100.00

100.00 100.00 100.00 96.75 80.76 58.54 23.31 3.52 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

Cum. Distribution % % P2O5 Insol

3.62 3.75 4.21 5.63 3.89 2.87

86.69 87.34 87.11 83.47 88.42 90.43

2.61 13.30 20.76 44.01 17.07 2.24

3.27 16.20 22.45 34.10 20.29 3.69

3.62 3.73 3.99 4.74 4.57 4.51

2.61 15.92 36.67 80.68 97.76 100.00

4.51

86.23

100.00

100.00

6F-5

86.69 87.23 87.17 85.47 86.07 86.23

3.27 19.47 41.91 76.02 96.31 100.00

Table 6F-3B. Screen Analysis for Flotation Concentrate—Armeen DMHTD Tertiary Amine, Plant I, Unsized Amine Feed. Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 3.00 15.40 42.10 64.00 26.80 22.70 4.60 0.00 0.00 178.60

0.00 1.68 8.62 23.57 35.83 15.01 12.71 2.58 0.00 0.00 100.00

0.00 1.68 10.30 33.87 69.71 84.71 97.42 100.00 100.00 100.00

100.00 98.32 89.70 66.13 30.29 15.29 2.58 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

32.37 32.46 32.60 32.58 32.81 32.54 28.35

4.44 3.48 3.09 3.39 3.38 5.05 17.38

1.67 8.61 23.65 35.93 15.15 12.73 2.25

1.91 7.67 18.61 31.03 12.96 16.40 11.44

32.37 32.45 32.55 32.57 32.61 32.60 32.49

32.49

3.91

100.00

100.00

6F-6

Cum. Distribution % % P2O5 Insol

4.44 1.67 3.64 10.29 3.26 33.94 3.32 69.87 3.33 85.02 3.56 97.75 3.91 100.00

1.91 9.57 28.18 59.21 72.17 88.56 100.00

Table 6F-4A. Screen Analysis for Flotation Tailings—Arquad 2HT-75 Quaternary Amine, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm)

Weight %

Retained %

Passing %

0.00 0.00 0.00 1.10 5.80 9.00 10.60 7.20 1.20 0.00 34.90

0.00 0.00 0.00 3.15 16.62 25.79 30.37 20.63 3.44 0.00 100.00

0.00 0.00 0.00 3.15 19.77 45.56 75.93 96.56 100.00 100.00

100.00 100.00 100.00 96.85 80.23 54.44 24.07 3.44 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

4.37 3.08 2.37 2.36 2.25 2.17

85.12 89.34 92.48 92.68 92.92 92.25

5.47 20.34 24.29 28.49 18.45 2.97

2.92 16.16 25.96 30.64 20.87 3.45

4.37 3.29 2.77 2.60 2.53 2.52

2.52

91.87 100.00

100.00

6F-7

Cum. Distribution % % P2O5 Insol

85.12 5.47 88.67 25.82 90.83 50.10 91.57 78.59 91.86 97.03 91.87 100.00

2.92 19.08 45.04 75.68 96.55 100.00

Table 6F-4B. Screen Analysis for Flotation Concentrate—Arquad 2HT-75 Quaternary Amine, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 3.00 15.70 42.40 64.80 29.40 22.20 5.10 0.00 0.00 182.60

0.00 1.64 8.60 23.22 35.49 16.10 12.16 2.79 0.00 0.00 100.00

0.00 1.64 10.24 33.46 68.95 85.05 97.21 100.00 100.00 100.00

100.00 98.36 89.76 66.54 31.05 14.95 2.79 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

32.52 32.46 32.36 32.41 32.81 32.73 30.34

3.59 3.38 3.39 3.17 2.76 3.91 11.43

1.65 8.60 23.16 35.44 16.28 12.26 2.61

1.68 8.30 22.49 32.14 12.69 13.58 9.12

32.52 32.47 32.39 32.40 32.48 32.51 32.45

32.45

3.50

100.00

100.00

6F-8

Cum. Distribution % % P2O5 Insol

3.59 1.65 3.41 10.25 3.40 33.40 3.28 68.85 3.18 85.13 3.27 97.39 3.50 100.00

1.68 9.99 32.47 64.61 77.30 90.88 100.00

Table 6F-5A. Screen Analysis for Flotation Tailings—Adogen 185 Ether Amine Acetate, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm)

Weight %

Retained %

Passing %

0.00 0.00 0.00 1.60 6.90 9.70 11.40 6.80 1.00 0.00 37.40

0.00 0.00 0.00 4.28 18.45 25.94 30.48 18.18 2.67 0.00 100.00

0.00 0.00 0.00 4.28 22.73 48.66 79.14 97.33 100.00 100.00

100.00 100.00 100.00 95.72 77.27 51.34 20.86 2.67 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

7.67 4.86 3.15 3.24 3.32 3.33

76.00 84.27 90.34 90.25 89.93 88.95

8.82 24.09 21.95 26.53 16.22 2.39

3.68 17.57 26.48 31.10 18.48 2.69

7.67 5.39 4.20 3.83 3.73 3.72

3.72

88.47 100.00

100.00

6F-9

Cum. Distribution % % P2O5 Insol

76.00 8.82 82.71 32.91 86.78 54.86 88.12 81.39 88.45 97.61 88.47 100.00

3.68 21.25 47.73 78.83 97.31 100.00

Table 6F-5B. Screen Analysis for Flotation Concentrate—Adogen 185 Ether Amine Acetate, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 2.90 15.30 41.60 63.60 20.40 28.80 4.30 0.00 0.00 176.90

0.00 1.64 8.65 23.52 35.95 11.53 16.28 2.43 0.00 0.00 100.00

0.00 1.64 10.29 33.80 69.76 81.29 97.57 100.00 100.00 100.00

100.00 98.36 89.71 66.20 30.24 18.71 2.43 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

32.27 32.86 32.99 33.05 33.52 33.66 31.91

4.85 2.93 2.62 2.35 1.82 2.34 7.68

1.60 8.58 23.41 35.86 11.67 16.54 2.34

3.09 9.85 23.96 32.86 8.16 14.82 7.26

32.27 32.77 32.92 32.99 33.06 33.16 33.13

33.13

2.57

100.00

100.00

6F-10

Cum. Distribution % % P2O5 Insol

4.85 1.60 3.24 10.17 2.81 33.59 2.57 69.45 2.47 81.12 2.44 97.66 2.57 100.00

3.09 12.95 36.91 69.76 77.93 92.74 100.00

Table 6F-6A. Screen Analysis for Flotation Tailings—Arr-Maz Condensate Amine, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns) 1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

Weight (Gm)

Weight %

Retained %

Passing %

0.00 0.00 0.00 1.90 7.40 6.80 14.10 7.60 1.40 0.00 39.20

0.00 0.00 0.00 4.85 18.88 17.35 35.97 19.39 3.57 0.00 100.00

0.00 0.00 0.00 4.85 23.72 41.07 77.04 96.43 100.00 100.00

100.00 100.00 100.00 95.15 76.28 58.93 22.96 3.57 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

8.62 5.17 4.45 2.47 2.77 2.83

73.31 83.23 86.32 92.36 91.42 90.36

11.32 26.43 20.91 24.06 14.55 2.74

8.62 5.87 5.27 3.96 3.72 3.69

3.69

88.41 100.00 100.00

6F-11

4.02 17.77 16.94 37.58 20.05 3.65

Cum. Distribution % % P2O5 Insol

73.31 11.32 81.20 37.75 83.36 58.66 87.56 82.72 88.34 97.26 88.41 100.00

4.02 21.79 38.73 76.30 96.35 100.00

Table 6F-6B. Screen Analysis for Flotation Concentrate—Arr-Maz Condensate Amine, Plant I, Unsized Amine Feed.

Mesh +16 16x20 20x28 28x35 35x48 48x65 65x100 100x150 150x200 -200

Opening (Microns)

Weight (Gm)

Weight %

Retained %

Passing %

1000.00 840.00 590.00 420.00 297.00 210.00 149.00 105.00 74.00

0.00 2.80 15.90 41.80 63.00 24.00 25.20 4.20 0.00 0.00 176.90

0.00 1.58 8.99 23.63 35.61 13.57 14.25 2.37 0.00 0.00 100.00

0.00 1.58 10.57 34.20 69.81 83.38 97.63 100.00 100.00 100.00

100.00 98.42 89.43 65.80 30.19 16.62 2.37 0.00 0.00 0.00

Grade % % P2O5 Insol

Distribution % % P2O5 Insol

Cum. Grade % % P2O5 Insol

32.78 33.02 33.08 33.34 33.63 33.77 32.64

4.05 2.88 2.50 1.88 1.58 1.75 6.02

1.56 8.91 23.46 35.63 13.69 14.44 2.33

2.93 11.82 26.98 30.57 9.79 11.38 6.53

32.78 32.98 33.05 33.20 33.27 33.34 33.32

33.32

2.19

100.00

100.00

6F-12

Cum. Distribution % % P2O5 Insol

4.05 1.56 3.06 10.46 2.67 33.92 2.27 69.55 2.16 83.24 2.10 97.67 2.19 100.00

2.93 14.75 41.72 72.30 82.09 93.47 100.00

Appendix 6G EFFECT OF SLIME ON REVERSE CRAGO

Table 6G-1. Armeen HT Primary Amine Series—Clay Effect—Reverse Crago. 1.1 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. Feed, As Received Grade Weight Product (Gm) Feed Concent. 433.20 Tailings 70.00 Cal. Feed 503.20

Weight % 100.00 86.09 13.91 100.00

% P2O5 6.82 7.99 0.42 6.94

% Insol 78.38 73.60 97.97 76.99

Content P2O5 Insol Units Units 28.18 16.48 6.88 63.36 0.06 13.63 6.94 76.99

Distribution % % P2O5 Insol 100.00 100.00 99.16 82.30 0.84 17.70 100.00 100.00

1.2 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 1 min. Scrub Grade Weight Product (Gm) Feed Concent. 398.60 Tailings 104.40 Cal. Feed 503.00

Weight % 100.00 79.24 20.76 100.00

% P2O5 6.82 8.82 0.32 7.06

% Insol 78.38 71.53 98.30 77.09

Content P2O5 Insol Units Units 28.18 16.48 6.99 56.68 0.07 20.40 7.06 77.09

Distribution % % P2O5 Insol 100.00 100.00 99.06 73.53 0.94 26.47 100.00 100.00

1.3 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 409.30 92.60 501.90

Weight % 100.00 81.55 18.45 100.00

% P2O5 6.82 7.95 0.31 6.54

% Insol 78.38 74.66 98.38 79.04

6G-1

Content P2O5 Insol Units Units 28.18 16.48 6.48 60.89 0.06 18.15 6.54 79.04

Distribution % % P2O5 Insol 100.00 100.00 99.13 77.03 0.87 22.97 100.00 100.00

Table 6G-2. Armeen 2HT Secondary Amine Series—Clay Effect—Reverse Crago. 2.1 DOSAGE: 20 cc @ 2% Solution Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 465.40 35.20 500.60

Weight % 100.00 92.97 7.03 100.00

% P2O5 6.82 7.31 0.46 6.83

% Insol 78.38 76.02 98.06 77.57

2.2 DOSAGE: 20 cc @ 2% Solution Grade Weight Product (Gm) Feed Concent. 464.50 Tailings 37.00 Cal. Feed 501.50

Weight % 100.00 92.62 7.38 100.00

% P2O5 6.82 7.67 0.46 7.14

% Insol 78.38 76.11 98.09 77.73

2.3 DOSAGE: 20 cc @ 2% Solution Grade Weight Product (Gm) Feed Concent. 482.50 Tailings 19.90 Cal. Feed 502.40

Weight % 100.00 96.04 3.96 100.00

% P2O5 6.82 7.19 0.85 6.94

% Insol 78.38 77.70 96.55 78.45

6G-2

FEED: Plant III, U. F. Feed, As Received

Content P2O5 Insol Units Units 28.18 16.48 6.80 70.67 0.03 6.90 6.83 77.57

Distribution % % P2O5 Insol 100.00 100.00 99.53 91.11 0.47 8.89 100.00 100.00

FEED: Plant III, U. F. F., 1 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 7.10 70.49 0.03 7.24 7.14 77.73

Distribution % % P2O5 Insol 100.00 100.00 99.52 90.69 0.48 9.31 100.00 100.00

FEED: Plant III, U. F. F., 3 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 6.91 74.62 0.03 3.82 6.94 78.45

Distribution % % P2O5 Insol 100.00 100.00 99.51 95.12 0.49 4.88 100.00 100.00

Table 6G-3. Armeen DMHTD Tertiary Amine Series—Clay Effect—Reverse Crago. 3.1 DOSAGE: 2.0 cc @ 2% Solution Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 302.60 204.40 507.00

Weight % 100.00 59.68 40.32 100.00

% P2O5 6.82 11.37 0.37 6.94

% Insol 78.38 65.22 98.48 78.63

3.2 DOSAGE: 2.0 cc @ 2% Solution

Weight Product (Gm) Feed Concent. 253.70 Tailings 255.40 Cal. Feed 509.10

Weight % 100.00 49.83 50.17 100.00

Grade % % P2O5 Insol 6.82 78.38 13.76 58.35 0.35 98.43 7.03 78.46

3.3 DOSAGE: 2.0 cc @ 2% Solution Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 335.00 170.50 505.50

Weight % 100.00 66.27 33.73 100.00

% P2O5 6.82 10.49 0.25 7.04

% Insol 78.38 67.65 98.88 78.18

6G-3

FEED: Plant III, U. F. F., As Received

Content P2O5 Insol Units Units 28.18 16.48 6.79 38.93 0.15 39.70 6.94 78.63

Distribution % % P2O5 Insol 100.00 100.00 97.85 49.51 2.15 50.49 100.00 100.00

FEED: Plant III, U. F. F., 1 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 6.86 29.08 0.18 49.38 7.03 78.46

Distribution % % P2O5 Insol 100.00 100.00 97.50 37.06 2.50 62.94 100.00 100.00

FEED: Plant III, U. F. F., 3 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 6.95 44.83 0.08 33.35 7.04 78.18

Distribution % % P2O5 Insol 100.00 100.00 98.80 57.34 1.20 42.66 100.00 100.00

Table 6G-4. Arquad 2HT-75 Quaternary Amine Series—Clay Effect—Reverse Crago. 4.1 DOSAGE: 2.5 cc @ 2% Solution

FEED: Plant III, U. F. F., As Received

Grade Weight Weight % Product (Gm) Feed 100.00 Concent. 300.80 59.59 Tailings 204.00 40.41 Cal. Feed 504.80 100.00

% P2O5 6.82 11.61 0.32 7.05

Content % P2O5 Insol Insol Units Units 78.38 28.18 16.48 64.84 6.92 38.64 98.54 0.13 39.82 78.46 7.05 78.46

4.2 DOSAGE: 2.5 cc @ 2% Solution

FEED: Plant III, U. F. F., 1 min. Scrub

Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm)

Weight % 100.00 277.80 54.70 230.10 45.30 507.90 100.00

% P2O5 6.82 12.63 0.34 7.06

Content % P2O5 Insol Insol Units Units 78.38 28.18 16.48 61.67 6.91 33.73 98.48 0.15 44.62 78.35 7.06 78.35

4.3 DOSAGE: 2.5 cc @ 2% Solution Grade Weight Product (Gm) Feed Concent. 271.20 Tailings 236.90 Cal. Feed 508.10

Weight % 100.00 53.38 46.62 100.00

% P2O5 6.82 13.13 0.30 7.15

Distribution % % P2O5 Insol 100.00 100.00 97.82 43.05 2.18 56.95 100.00 100.00

FEED: Plant III, U. F. F., 3 min. Scrub

Content % P2O5 Insol Insol Units Units 78.38 28.18 16.48 60.46 7.01 32.27 98.68 0.14 46.01 78.28 7.15 78.28

6G-4

Distribution % % P2O5 Insol 100.00 100.00 98.17 49.24 1.83 50.76 100.00 100.00

Distribution % % P2O5 Insol 100.00 100.00 98.04 41.22 1.96 58.78 100.00 100.00

Table 6G-5. Adogen 185 Ether Amine Acetate Series—Clay Effect—Reverse Crago. 5.1 DOSAGE: 2.0 cc @ 2% Solution

Weight Product (Gm) Feed Concent. 298.90 Tailings 207.80 Cal. Feed 506.70

Weight % 100.00 58.99 41.01 100.00

Grade % % P2O5 Insol 28.18 16.48 11.55 64.45 0.40 98.24 6.98 78.31

5.2 DOSAGE: 2.0 cc @ 2% Solution

FEED: Plant III, U. F. Feed, As Received

Content P2O5 Insol Units Units 28.18 16.48 6.81 38.02 0.16 40.29 6.98 78.31

FEED: Plant III, U. F. F., 1 min. Scrub

Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm)

Weight % 100.00 235.20 46.24 273.50 53.76 508.70 100.00

% P2O5 28.18 13.89 0.38 6.63

Content % P2O5 Insol Insol Units Units 16.48 28.18 16.48 58.24 6.42 26.93 98.20 0.20 52.80 79.72 6.63 79.72

5.3 DOSAGE: 2.0 cc @ 2% Solution Grade Weight Weight % % P2O5 Product (Gm) Feed 100.00 28.18 Concent. 184.80 36.27 18.76 Tailings 324.70 63.73 0.51 Cal. Feed 509.50 100.00 7.13

Distribution % % P2O5 Insol 100.00 100.00 96.92 33.78 3.08 66.22 100.00 100.00

FEED: Plant III, U. F. F., 3 min. Scrub

Content % P2O5 Insol Insol Units Units 16.48 28.18 16.48 43.86 6.80 15.91 97.92 0.33 62.40 78.31 7.13 78.31

6G-5

Distribution % % P2O5 Insol 100.00 100.00 97.65 48.55 2.35 51.45 100.00 100.00

Distribution % % P2O5 Insol 100.00 100.00 95.44 20.31 4.56 79.69 100.00 100.00

Table 6G-6. Arr-Maz Modified 1054 Condensate Amine Series—Clay Effect— Reverse Crago. 6.1 DOSAGE: 5.0 cc @ 2% Solution Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 156.60 352.90 509.50

Weight % 100.00 30.74 69.26 100.00

% P2O5 28.18 21.91 0.55 7.12

% Insol 16.48 35.25 97.85 78.61

6.2 DOSAGE: 5.0 cc @ 2% Solution

Weight Weight Product (Gm) % Feed 100.00 Concent. 115.90 22.81 Tailings 392.30 77.19 Cal. Feed 508.20 100.00

Grade % % P2O5 Insol 28.18 16.48 28.42 16.24 0.99 96.43 7.25 78.14

6.3 DOSAGE: 5.0 cc @ 2% Solution Grade Product Feed Concent. Tailings Cal. Feed

Weight (Gm) 107.40 401.80 509.20

Weight % 100.00 21.09 78.91 100.00

% P2O5 28.18 29.90 1.04 7.13

% Insol 16.48 11.52 96.25 78.38

6G-6

FEED: Plant III, U. F. Feed, As Received

Content P2O5 Insol Units Units 28.18 16.48 6.73 10.83 0.38 67.77 7.12 78.61

Distribution % % P2O5 Insol 100.00 100.00 94.65 13.78 5.35 86.22 100.00 100.00

FEED: Plant III, U. F. F., 1 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 6.48 3.70 0.76 74.44 7.25 78.14

Distribution % % P2O5 Insol 100.00 100.00 89.45 4.74 10.55 95.26 100.00 100.00

FEED: Plant III, U. F. F., 3 min. Scrub

Content P2O5 Insol Units Units 28.18 16.48 6.31 2.43 0.82 75.95 7.13 78.38

Distribution % % P2O5 Insol 100.00 100.00 88.49 3.10 11.51 96.90 100.00 100.00

Appendix 6H EFFECT OF PERCOL ON REVERSE CRAGO

Table 6H-1. Armeen HT Primary Amine Series—Percol 90L Effect—Reverse Crago. 1.1 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Grade Weight Weight (Gm) Product % Feed 100.00 Concent. 501.50 98.70 Tailings 6.60 1.30 Cal. Feed 508.10 100.00

% P2O5 6.82 6.90 2.05 6.84

% Insol 78.38 77.90 92.88 78.09

Content P2O5 Insol Units Units 28.18 16.48 6.81 76.89 0.03 1.21 6.84 78.09

Distribution % % P2O5 Insol 100.00 100.00 99.61 98.46 0.39 1.54 100.00 100.00

1.2 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Grade Weight Weight % Product (Gm) Feed 100.00 Concent. 457.70 90.19 Tailings 49.80 9.81 Cal. Feed 507.50 100.00

% P2O5 6.82 7.86 0.56 7.14

% Insol 78.38 74.91 97.74 77.15

Content P2O5 Insol Units Units 28.18 16.48 7.09 67.56 0.05 9.59 7.14 77.15

Distribution % % P2O5 Insol 100.00 100.00 99.23 87.57 0.77 12.43 100.00 100.00

1.3 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 6.0 cc Percol 90L @ 0.1% Sol. Grade Weight Weight % Product (Gm) Feed 100.00 Concent. 353.60 70.19 Tailings 150.20 29.81 Cal. Feed 503.80 100.00

% P2O5 6.82 9.33 0.61 6.73

% Insol 78.38 70.58 97.52 78.61

6H-1

Content P2O5 Insol Units Units 28.18 16.48 6.55 49.54 0.18 29.07 6.73 78.61

Distribution % % P2O5 Insol 100.00 100.00 97.30 63.02 2.70 36.98 100.00 100.00

Table 6H-1 (Cont.). Armeen HT Primary Amine Series—Percol 90L Effect—Reverse Crago. 1.4 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol.

Weight Weight (Gm) Product % Feed 100.00 Concent. 432.30 86.24 Tailings 69.00 13.76 Cal. Feed 501.30 100.00

Grade % % P2O5 Insol 6.82 78.38 7.92 74.73 0.74 97.15 6.93 77.82

Content P2O5 Insol Units Units 28.18 16.48 6.83 64.44 0.10 13.37 6.93 77.82

Distribution % % P2O5 Insol 100.00 100.00 98.53 82.82 1.47 17.18 100.00 100.00

1.5 DOSAGE: 1.25 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol. Grade Weight Weight Product % (Gm) Feed 100.00 Concent. 407.30 81.69 Tailings 91.30 18.31 Cal. Feed 498.60 100.00

% P2O5 6.82 8.64 0.84 7.21

% Insol 78.38 79.92 96.70 82.99

6H-2

Content P2O5 Insol Units Units 28.18 16.48 7.06 65.29 0.15 17.71 7.21 82.99

Distribution % % P2O5 Insol 100.00 100.00 97.87 78.66 2.13 21.34 100.00 100.00

Table 6H-2. Armeen 2HT Secondary Amine Series—Percol 90L Effect—Reverse Crago. 2.1 DOSAGE: 20 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 0.0 cc Percol 90L @ 0.1% Sol.

Weight Weight (Gm) Product % Feed 100.00 Concent. 493.80 99.02 Tailings 4.90 0.98 Cal. Feed 498.70 100.00 2.2

Grade % % P2O5 Insol 6.82 78.38 6.97 78.02 2.31 91.97 6.92 78.16

Distribution % % P2O5 Insol 100.00 100.00 99.67 98.84 0.33 1.16 100.00 100.00

DOSAGE: 20 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Grade

Weight Weight Product (Gm) % Feed 100.00 Concent. 445.20 89.04 Tailings 54.80 10.96 Cal. Feed 500.00 100.00 2.3

Content P2O5 Insol Units Units 28.18 16.48 6.90 77.25 0.02 0.90 6.92 78.16

% P2O5 6.82 7.51 0.72 6.77

% Insol 78.38 76.44 97.19 78.71

Content P2O5 Insol Units Units 28.18 16.48 6.69 68.06 0.08 10.65 6.77 78.71

Distribution % % P2O5 Insol 100.00 100.00 98.83 86.47 1.17 13.53 100.00 100.00

DOSAGE: 20 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 6.0 cc Percol 90L @ 0.1% Sol. Grade

Weight Weight Product (Gm) % Feed 100.00 Concent. 446.50 89.41 Tailings 52.90 10.59 Cal. Feed 499.40 100.00

% P2O5 6.82 7.81 0.89 7.08

% Insol 78.38 75.49 95.50 77.61

6H-3

Content Distribution P2O5 Insol % % Units Units P2O5 Insol 28.18 16.48 100.00 100.00 6.98 67.49 98.67 86.97 0.09 10.12 1.33 13.03 7.08 77.61 100.00 100.00

Table 6H-2 (Cont.). Armeen 2HT Secondary Amine Series—Percol 90L Effect— Reverse Crago. 2.4

Product Feed Concent. Tailings Cal. Feed

DOSAGE: 20 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol.

Weight Weight (Gm) % 100.00 410.80 82.56 86.80 17.44 497.60 100.00

Grade % % P2O5 Insol 6.82 78.38 8.48 73.48 1.00 96.22 7.18 77.45

6H-4

Content Distribution P2O5 Insol % % Units Units P2O5 Insol 28.18 16.48 100.00 100.00 7.00 60.66 97.57 78.33 0.17 16.78 2.43 21.67 7.18 77.45 100.00 100.00

Table 6H-3. Armeen DMHTD Tertiary Amine Series—Percol 90L Effect—Reverse Crago. 3.1

Product

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 0.0 cc Percol 90L @ 0.1% Sol. Wt. (Gm)

% Wt.

Feed 100.00 Concent. 492.30 98.24 Tailings 8.80 1.76 Cal. Feed 501.10 100.00 3.2

Product

Product

Content P2O5 Insol Units Units 28.18 16.48 6.56 76.98 0.01 1.71 6.57 78.69

Distribution % % P2O5 Insol 100.00 100.00 99.81 97.83 0.19 2.17 100.00 100.00

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Wt. (Gm)

% Wt.

Feed 100.00 Concent. 409.90 81.59 Tailings 92.50 18.41 Cal. Feed 502.40 100.00 3.3

Grade % % P2O5 Insol 6.82 78.38 6.68 78.36 0.70 97.29 6.57 78.69

Grade % P2O5 6.82 9.15 0.20 7.50

% Insol 78.38 71.10 98.25 76.10

Content Distribution P2O5 Insol % % Units Units P2O5 Insol 28.18 16.48 100.00 100.00 7.47 58.01 99.51 76.23 0.04 18.09 0.49 23.77 7.50 76.10 100.00 100.00

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol.

Wt. (Gm)

% Wt.

Feed 100.00 Concent. 394.40 78.77 Tailings 106.30 21.23 Cal. Feed 500.70 100.00

Grade % P2O5 6.85 8.62 0.37 6.87

% Insol 78.38 72.16 98.15 77.68

6H-5

Content P2O5 Insol Units Units 28.18 16.48 6.79 56.84 0.08 20.84 6.87 77.68

Distribution % % P2O5 Insol 100.00 100.00 98.86 73.17 1.14 26.83 100.00 100.00

Table 6H-3 (Cont.). Armeen DMHTD Tertiary Amine Series—Percol 90L Effect— Reverse Crago. 3.4

Product

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol. Wt. (Gm)

% Wt.

Feed 100.00 Concent. 391.80 78.38 Tailings 108.10 21.62 Cal. Feed 499.90 100.00

Grade % P2O5 6.82 9.08 0.76 7.28

% Insol 78.38 71.46 97.02 76.99

6H-6

Content P2O5 Insol Units Units 28.18 16.48 7.12 56.01 0.16 20.98 7.28 76.99

Distribution % % P2O5 Insol 100.00 100.00 97.74 72.75 2.26 27.25 100.00 100.00

Table 6H-4. Arquad 2HT-75 Quaternary Amine Series—Percol 90L Effect—Reverse Crago. 4.1

Product

DOSAGE: 2.5 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 0.0 cc Percol 90L @ 0.1% Sol. Wt. (Gm)

% Wt.

Feed 100.00 Concent. 477.10 95.57 Tailings 22.10 4.43 Cal. Feed 499.20 100.00 4.2

Product

Content P2O5 Insol Units Units 28.18 16.48 7.13 72.68 0.02 4.34 7.15 77.03

Distribution % % P2O5 Insol 100.00 100.00 99.75 94.36 0.25 5.64 100.00 100.00

DOSAGE: 2.5 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Wt. (Gm)

% Wt.

Feed 100.00 Concent. 317.80 63.41 Tailings 183.40 36.59 Cal. Feed 501.20 100.00 4.3

Grade % % P2O5 Insol 6.82 78.38 7.46 76.05 0.40 98.10 7.15 77.03

Grade % P2O5 6.82 11.33 0.40 7.33

% Insol 78.38 64.65 97.87 76.81

Content P2O5 Insol Units Units 28.18 16.48 7.18 40.99 0.15 35.81 7.33 76.81

Distribution % % P2O5 Insol 100.00 100.00 98.00 53.37 2.00 46.63 100.00 100.00

DOSAGE: 2.5 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 6.0 cc Percol 90L @ 0.1% Sol. Grade

% Weight Weight Product (Gm) % P2O5 Feed 100.00 6.82 Concent. 341.10 68.37 10.48 Tailings 157.80 31.63 0.46 Cal. Feed 498.90 100.00 7.31

% Insol 78.38 67.27 97.76 76.91

6H-7

Content P2O5 Insol Units Units 28.18 16.48 7.17 45.99 0.15 30.92 7.31 76.91

Distribution % % P2O5 Insol 100.00 100.00 98.01 59.80 1.99 40.20 100.00 100.00

Table 6H-4 (Cont.). Arquad 2HT-75 Quaternary Amine Series—Percol 90L Effect— Reverse Crago. 4.4

DOSAGE: 2.5 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol.

Grade Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 6.82 78.38 Concent. 317.60 63.38 11.02 65.51 Tailings 183.50 36.62 0.66 97.16 Cal. Feed 501.10 100.00 7.23 77.10

6H-8

Content P2O5 Insol Units Units 28.18 16.48 6.98 41.52 0.24 35.58 7.23 77.10

Distribution % % P2O5 Insol 100.00 100.00 96.66 53.85 3.34 46.15 100.00 100.00

Table 6H-5. Adogen 185 Ether Amine Acetate Series—Percol 90L Effect—Reverse Crago. 5.1

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 0.0 cc Percol 90L @ 0.1% Sol.

Weight Weight Product (Gm) % Feed 100.00 Concent. 492.80 98.11 Tailings 9.50 1.89 Cal. Feed 502.30 100.00 5.2

Grade % % P2O5 Insol 6.82 78.38 7.50 76.27 0.66 97.36 7.37 76.67

Weight Weight % Product (Gm) % P2O5 Feed 100.00 6.82 Concent. 360.70 71.72 10.24 Tailings 142.20 28.28 0.37 Cal. Feed 502.90 100.00 7.45

% Insol 78.38 68.02 98.04 76.51

Content P2O5 Insol Units Units 28.18 16.48 7.34 48.79 0.10 27.72 7.45 76.51

Distribution % % P2O5 Insol 100.00 100.00 98.60 63.77 1.40 36.23 100.00 100.00

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 6.0 cc Percol 90L @ 0.1% Sol. Grade

Product Feed Concent. Tailings Cal. Feed

Distribution % % P2O5 Insol 100.00 100.00 99.83 97.60 0.17 2.40 100.00 100.00

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Grade

5.3

Content P2O5 Insol Units Units 28.18 16.48 7.36 74.83 0.01 1.84 7.37 76.67

% Weight Weight (Gm) % P2O5 100.00 6.82 331.70 65.94 11.00 171.30 34.06 0.45 503.00 100.00 7.41

% Insol 78.38 66.32 97.90 77.07

6H-9

Content P2O5 Insol Units Units 28.18 16.48 7.25 43.73 0.15 33.34 7.41 77.07

Distribution % % P2O5 Insol 100.00 100.00 97.93 56.74 2.07 43.26 100.00 100.00

Table 6H-5 (Cont.). Adogen 185 Ether Amine Acetate Series—Percol 90L Effect— Reverse Crago. 5.4

DOSAGE: 2.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol.

Grade Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 6.82 78.38 Concent. 291.60 57.95 12.03 63.15 Tailings 211.60 42.05 0.75 96.88 Cal. Feed 503.20 100.00 7.29 77.33

6H-10

Content Distribution P2O5 Insol % % Units Units P2O5 Insol 28.18 16.48 100.00 100.00 6.97 36.59 95.67 47.32 0.32 40.74 4.33 52.68 7.29 77.33 100.00 100.00

Table 6H-6. Arr-Maz Condensate Amine Series—Percol 90L Effect—Reverse Crago. 6.1

DOSAGE: 5.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 0.0 cc Percol 90L @ 0.1% Sol. Grade

Weight Weight % Product P2O5 (Gm) % Feed 100.00 6.82 Concent. 354.60 70.53 10.11 Tailings 148.20 29.47 0.15 Cal. Feed 502.80 100.00 7.17 6.2

% Insol 78.38 68.47 98.87 77.43

Distribution % % P2O5 Insol 100.00 100.00 99.38 62.36 0.62 37.64 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 4.0 cc Percol 90L @ 0.1% Sol. Grade

Weight Weight Product (Gm) % Feed 100.00 Concent. 170.70 34.03 Tailings 330.90 65.97 Cal. Feed 501.60 100.00 6.3

Content P2O5 Insol Units Units 28.18 16.48 7.13 48.29 0.04 29.14 7.17 77.43

% P2O5 6.82 20.74 0.49 7.38

% Insol 78.38 37.89 97.58 77.27

Content P2O5 Insol Units Units 28.18 16.48 7.06 12.89 0.32 64.37 7.38 77.27

Distribution % % P2O5 Insol 100.00 100.00 95.62 16.69 4.38 83.31 100.00 100.00

DOSAGE: 5.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 6.0 cc Percol 90L @ 0.1% Sol.

Weight Weight Product (Gm) % Feed 100.00 Concent. 159.70 31.77 Tailings 342.90 68.23 Cal. Feed 502.60 100.00

Grade % % P2O5 Insol 6.82 78.38 22.07 34.23 0.74 96.80 7.52 76.92

6H-11

Content P2O5 Insol Units Units 28.18 16.48 7.01 10.88 0.50 66.04 7.52 76.92

Distribution % % P2O5 Insol 100.00 100.00 93.28 14.14 6.72 85.86 100.00 100.00

Table 6H-6 (Cont.). Arr-Maz Condensate Amine Series—Percol 90L Effect—Reverse Crago. 6.4

DOSAGE: 5.0 cc @ 2% Solution FEED: Plant III, U. F. F., 3 min. Scrub 8.0 cc Percol 90L @ 0.1% Sol.

Grade Weight Weight % % Product (Gm) % P2O5 Insol Feed 100.00 6.82 78.38 Concent. 162.40 32.27 21.16 36.71 Tailings 340.80 67.73 0.80 96.63 Cal. Feed 503.20 100.00 7.37 77.29

6H-12

Content P2O5 Insol Units Units 28.18 16.48 6.83 11.85 0.54 65.44 7.37 77.29

Distribution % % P2O5 Insol 100.00 100.00 92.65 15.33 7.35 84.67 100.00 100.00

PART 7. SELECTIVITY ENHANCEMENT IN ALL-ANIONIC FLOTATION OF FLORIDA PHOSPHATES

ABSTRACT As presented in Part 5, in its continued efforts to develop a simpler, more efficient and environmentally friendlier flowsheet than the conventional "double float" process for phosphate flotation, the Florida Institute of Phosphate Research (FIPR) has invented several all-anionic flowsheets. These flowsheets are based on fatty acid rougher-cleaner flotation, with sizing of flotation feed, rougher concentrate, or rougher tails to reduce coarse phosphate loss. The key to success using these flowsheets is to achieve relatively low-Insol products while maintaining high P2O5 recovery. Numerous flotation modifiers were evaluated for improving selectivity. Tested modifiers included sodium silicate, lignosulfonates, calcium complexing agents, and ground phosphate rock. Proper sizing also enhanced selectivity.

7-1

INTRODUCTION The rational for developing an alternative to the Crago “Double Float” process has been elaborated in some of our previous publications and presentations (Zhang and Snow 2002; Zhang and others 2004). The Crago process involves anionic (fatty acid) rougher flotation, acid scrubbing/washing (de-oiling) of the rougher concentrate, and cationic (amine) flotation. Our current research effort focuses on developing flotation processes with anionic reagents only, thus eliminating the de-oiling and amine flotation steps. One major problem with most of the previously developed anionic flotation processes for phosphate is the conflict between recovery and concentrate grade. Although this conflict exists in all flotation processes, it is more remarkable in anionic flotation of phosphate. For example, to reduce the Insol in the concentrate from 10% to 6% would generally sacrifice recovery by up to 10%. Coarse phosphate particles are the main reason for the big gap between recovery and grade. Over-reagentizing in rougher flotation could ensure better recovery of coarse phosphate particles, but would make it impossible to achieve low Insol product in cleaner flotation. On the other hand, if reagent starvation were practiced in rougher flotation, coarse phosphate particles would not float readily in cleaner flotation. Another problem with some of the previous processes is the high cost for purer and more expensive collectors. Recognizing the above problems, FIPR extended the research project “An Investigation of Flotation Reagents” (FIPR #97-02-125), and conducted the program “Optimizing Single-Collector Flotation of Florida Phosphates” (FIPR #02-02-158). The extension project was designed to optimize the four all-anionic flowsheets developed under the previous project with a focus on selectivity enhancement. Table 7-1 summarizes laboratory performance of the new flowsheets. These results are extremely encouraging. However, Insol level of around 10% is not the current industry norm, even though it is regularly accepted by some fertilizer plants. To further reduce Insol while maintaining recovery of 90% or higher, one has to improve selectivity. The following selectivity enhancement methods were tested in this study: 1. Addition of collector-absorbing powders, such as ground phosphate rock and CaHPO4 to take up the extra fatty acids 2. Removal of detrimental Ca++ ions using complexing agent oxalic acid 3. Discharge (“rinse”) of conditioning liquid to remove secondary slime and residual fatty acid 4. Comparison of flotation modifiers focusing on silica depressants sodium silicate and lignosulfonate 5. Proper sizing of flotation feed, rougher concentrate, and tailings. 7-3

Table 7-1. Some Laboratory Testing Results Using Various Flowsheets. Flowsheet #1, Unsized Feed #1, Fine Feed #1, Coarse Feed #2, Coarse Feed #2, Fine Feed #3, Coarse & Fine Combined #3, Unsized Feed #3, Fine Feed

Product Grade % P2O5 % Insol 29.60 9.82 30.28 8.00 30.71 9.55 32.61 7.10 31.59 10.10 30.20 9.98 29.66 9.41 30.06 9.88

7-4

% P2O5 Recovery 91.4 81.3 94.7 94.7 91.1 90.7 84.9 92.7

EXPERIMENTAL MATERIALS AND REAGENTS Flotation Collectors Unless noted, flotation tests were performed using 0.6 lb./TF of N-silicate as usual, a blend of the 1:1 Century MO-5 to Liqro GA fatty acid collector mixed at a 1.0:0.6 ratio with No. 5 fuel oil. Flotation Feed Samples Three flotation feed samples were tested, with two collected from CF Industries’ Hardee plant and one from IMC’s South Fort Meade mine. Tables 7-2 through 7-4 show size distribution and assay of the three samples. Table 7-2. Size Distribution and Analysis of the CF Feed #1. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 -150 Total

% Wt.

% Cum. Wt.

% P2O5

% Insol

2.2 2.9 8.0 21.4 34.3 22.8 6.8 1.6 100.0

2.2 5.1 13.1 34.5 68.8 91.6 98.4 100.0 --

22.64 19.48 13.57 9.18 6.46 5.66 4.83 3.96 7.98

24.56 37.52 57.75 71.94 80.45 83.34 85.12 84.17 75.41

Table 7-3. Size Distribution and Analysis of the CF Feed #2. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 -150 Total

% Wt.

% Cum. Wt.

% P2O5

% Insol

0.8 1.6 5.3 18.2 39.3 25.3 8.3 1.2 100.0

0.8 2.4 7.7 25.9 65.2 90.5 98.8 100.0 --

22.61 19.42 13.41 8.60 5.84 5.00 4.56 4.00 6.76

22.61 37.12 56.92 71.72 80.33 83.77 85.22 85.19 77.69

7-5

Table 7-4. Size Distribution and Analysis of the IMC Feed. Size, Tyler Mesh +20 20/28 28/35 35/48 48/65 65/100 100/150 -150 Total

% Wt.

% Cum. Wt.

% P2O5

% Insol

0.4 0.5 2.2 11.4 27.8 35.5 17.8 4.4 100.0

0.4 0.9 3.1 14.5 42.3 77.8 95.6 100.0 --

-23.53 14.44 9.81 8.78 10.66 9.51 7.72 9.91

-23.80 53.16 69.01 70.21 67.40 70.44 72.01 68.41

Flotation Modifiers Eight flotation modifiers were selected for initial screening of their effectiveness in improving selectivity in rougher (fatty acid) flotation of phosphate. Test modifiers are listed in Table 7-5. Table 7-5. Flotation Modifiers Tested. Modifier Solution Concentration pH Ca lignosulfonate (Lignotech D-712) 5% 4.22 Na lignosulfonate (Lignotech D-750) 5% 8.11 Na thiosulfate (LabChem 25150-1) (cont’s. Na2CO3 2.0 N 9.76 Na silicate (N-Brand 3.22:1) 11.70 36° Be Na hypochlorite (Clorox) 6.15% 9.65 Sulfonated oleic acid (Na salt – Tenn. Corp. OA-5) 5% 3.93 Oreprep 606 Pure -Tergitol NP-10 5% 6.64 Collector Adsorbing Powers The first ground phosphate additive was prepared by wet ball milling and wet screening a sample of laboratory CF flotation concentrate. The product contained 100% -48 mesh particles and had the following size/assay profile: Product +200 M -200 M Total

% Wt. 34.3 65.7 100.0

% P2O5 30.59 30.95 30.82 7-6

% Insol 9.68 6.83 7.81

% Dist. P2O5 42.5 57.5 100.0

The second phosphate concentrate additive was prepared by further wet grinding and screening at 325 mesh. A laboratory grade CaHPO4 and an activated carbon were purchased from Fisher Scientific. TEST PROCEDURES Rougher Flotation Standard laboratory 500g rougher flotation tests were performed in a Denver cell using different collector quantities with 2-minute conditioning at approximately 73% solids. No. 5 fuel oil at a 0.6 ratio of fuel oil to fatty acid, and soda ash (pH regulator) were used for all tests. Fuel oil was pre-mixed with the fatty acid before adding to the conditioner. Conditioning pH was usually 9.0-9.2 and flotation time was two minutes. Tap water was used for all tests. Sizing and Cleaner Flotation Sizing of the rougher concentrate at either 48 or 65 mesh was conducted manually using lab size Tyler screens. The fine fractions from two rougher flotation floats were combined for cleaner flotation with a flotation time of up to a minute without adding new reagents. Addition of Sodium Silicate N-silicate was used in many of the tests, and was added during the final 20 seconds of conditioning, usually at 0.6 lb./TF. Addition of Modifiers The various flotation modifiers were added to the feed before fatty acid conditioning. Flotation Procedure with Solid Powder Additives Flotation conditioning (approx. 73% solids) with soda ash and 1:1 Century MOS/Liqro GA mix plus No. 5 fuel oil at a 0.6:1.0 ratio with the fatty acid blend was performed for 1.5 minutes. Next, the ground phosphate rock “additive” slurry (at 65% 7-7

solids) was added and conditioning continued for 0.5 minute. In the case of CaHPO4, it was added as a powder. Finally, 0.6 lb./TF of N-silicate was added and conditioning continued for 0.5 minute. Total conditioning time was 2.5 minutes. Subsequent rougher flotation was performed for 2 minutes. The froth product, after drying, was dry screened (Ro-Tap) for 10 minutes using Tyler 48 mesh as the coarse and fine concentrate split size. Total rougher concentrate yield, grades, and P2O5 recovery were calculated from the coarse and fine concentrate data.

7-8

RESULTS AND DISCUSSION EFFECT OF LIGNOSULFONATES Flotation tests were performed using varying levels of collector plus 0.6 lb./TF of Ca lignosulfonate or Na lignosulfonate added with stirring for 30 seconds before standard conditioning. The primary objective of these tests was to block active clay particle sites and/or tie up cations such as Ca+2 that could consume collector. The results for these tests are presented in Figures 7-1 through 7-3. Figure 7-1 indicates significant recovery improvement by adding lignosulfonates. The benefit of lignosulfonate is more remarkable at lower collector dosages. For example, at a collector dosage of 1 lb./TF, flotation recovery was improved by over 20% with D-750 (sodium lignosulfonate) and about 10% with D-712 (calcium lignosulfonate). Not only did lignosulfonates increase phosphate recovery, they also enhanced selectivity, as is shown in Figure 7-2. For example, at a low collector dosage of 0.9 lb./ton, the rougher concentrate analyzed nearly 31% P2O5, with an Insol of less than 8%, when the sodium lignosulfonate was used. It may also be seen that Insol content in the rougher concentrate increases faster with collector dosage without lignosulfonates.

7-9

95

90

% P2O5 Recovery

85

80

75

None

70

D-750 D-712

65

60

55

50 0.8

0.9

1

1.1

1.2

Collector Dosage, lb/Ton Feed

Figure 7-1. Effect of Lignosulfonates on Flotation Recovery.

7-10

1.3

1.4

35

% P2O5

30

25

None D-750

20

D-712 None D-750 D-712

% Insol

15

10

5

0 0.6

0.7

0.8

0.9 1 1.1 Collector Dosage

Figure 7-2. Effect of Lignosulfonates on Concentrate Grade.

7-11

1.2

1.3

1.4

30 29 28 C o n c. % P 2 O 5

27 26

"N" Process Ligno D-748 Ligno D-905 Ligno D-777

25 24 23 22 21 20 90

92

94 96 % P2O5 Recovery

98

100

Figure 7-3. Selectivity Comparison of Silicate with Lignosulfonates. Sodium silicate is widely used in minerals flotation to improve selectivity as a depressant for silica. Silicate is also used at some phosphate beneficiation plants in Florida because of its low price and its effectiveness in depressing sands. In Figure 7-3, the test points with lignosulfonates are all above the selectivity curve for sodium silicate in the high recovery range from 92-96%. Therefore, lignosulfonates are more selective silica depressants than silicate. EFFECT OF FROTHERS Two exploratory float/size tests were performed, using the standard 1.0 lb./TF of collector, wherein a small quantity of frother Oreprep M-600 was added at the start of rougher flotation or Tergitol NP-10 was added during the final 15 seconds of rougher flotation. Final concentrates analyzed 31.57% P2O5/6.34% Insol at 64.8% P2O5 recovery, and 31.98% P2O5/6.10% Insol at 73.3% P2O5 recovery, respectively, for these two tests. No truly significant improvement resulted in either final concentrate grade or P2O5 recovery compared to the standard test in which no frother was used. The P2O5 recovery 7-12

differences observed were probably the result of experimental error encountered using minimal collector. Two preliminary float/size tests were also performed in which 0.5 lb./TF of additional fuel oil, either No. 5 or the aromatic Philflo, was added to the conditioning stage, using 1.0 lb./TF of collector at a 1.0:0.6 ratio with No. 5 fuel oil, to determine if increased P2O5 recovery was possible with no serious decrease in final concentrate grade. The use of additional No. 5 fuel oil resulted in a final concentrate analyzing 30.89% P2O5/7.49% Insol at 79.4% P2O5 recovery. These results represent an apparent possible increase of about 10% in overall P2O5 recovery over the comparison standard, with very little drop in final concentrate grade, and are believed to be significant. When Philflo oil was used, the final concentrate analyzed 30.98% P2O5/8.14% Insol at 74.3% P2O5 recovery. EFFECTIVENESS OF VARIOUS SOLID POWDERS Twenty two laboratory rougher flotation tests were performed to compare the concentrate grades and P2O5 recoveries obtained with and without additions of ground phosphate concentrate (65% -200 mesh) or finer ground (100% -325 mesh), and/or monocalcium phosphate powder during high-solids conditioning. Rougher concentrates produced analyzed >30% P2O5 29.8% P2O5