Heat of combustion. (HHV), BTU/lb. Average heat of combustion. BTU/lb. 0.357 ... Methyl linoleate. (wt%). Methyl oleate. (wt%). Methyl stearate. (wt%). Total.
Production of biodiesel from crude tall oil (CTO)
S. Marda, S.Omori, S. Shastri and S. G. Chatterjee Paper and Bioprocess Engineering SUNY-ESF Syracuse, NY Date: February 14, 2007
Overview Introduction Production of biodiesel from crude tall oil Characterization of biodiesel Conclusions Future work
Introduction
Introduction What is biodiesel? Why biodiesel? Depletion of resources
Half of the world’s oil resources will be exhausted by 2025 (EIA) Global oil production will peak in next 10 years
Environmental concerns Advantages of biodiesel
Biodegradable Renewable Non-toxic, thus safe handling and transporttion Reduction of greenhouse gas emissions Reduction in particulates Can produce domestically High cetane number
Disadvantages of biodiesel
Increase in NOx emissions
Introduction Objective
Investigate the feasibility of producing biodiesel from CTO
Relevance of study
Annual global production of tall oil was 1.6 million metric tonnes in 2000 Conventionally converted to tall oil rosin, varnishes, tall oil fatty acids by tall oil fractionators Recently inventory build-up at fractionators due to weak demand of products derived from CTO Very viscous, malodorous and sticky Makes transportation very cumbersome
CTO sells at very low price( ~ $0.10- 0.35 per kg)
Production of biodiesel from crude tall oil
Production of biodiesel from crude tall oil
Introduction With both Northern CTO (NCTO) and Southern CTO (SCTO) Using acetyl chloride and methanol in closed vessel Using sulfuric acid and methanol in closed vessel Using sulfuric acid and methanol by the condenser method With molecular sieve Without molecular sieve
Production of biodiesel from crude tall oil
By the acetyl chloride-methanol method Experiment 150 g of SCTO/NCTO Varying amount of methanol Different molar ratios of acetyl chloride to fatty acids
Assumed molecular weight of 290 Temperature 55 C
Extraction With ethyl acetate
Vacuum distillation Under pressure of 2 mm Hg
Quantification Weight % - By direct weighing
Production of biodiesel from crude tall oil
By the acetyl chloride-methanol method Yield
of
biodiesel
produced
from
NCTO
and
SCTO
by
the
acetyl
chloride-methanol
method
Source
Amount of acetyl chloride (ml)
Amount of methanol (ml)
Reaction time (hours)
Temperature ( C)
Yield of biodiesel (wt %)
NCTO (Na)
100
600
24
25
29.9
NCTO (Na)
100
600
1
55
25.2
NCTO (Na)
100
600
6
55
36.9
SCTO
100
600
1
25
52.7
SCTO
100
600
6
25
52.7
SCTO
100
600
1
55
65.9
SCTO
100
600
6
55
66.0
SCTO
10
350
1
55
60.6
SCTO
10
350
6
55
55.7
SCTO
10
350
0.5
55
56.1
SCTO
3
350
1
55
56.8
SCTO
3
150
1
55
55.9
SCTO
1
50
1
55
54.9
VO
100
350
1
55
88.5
Production of biodiesel from crude tall oil
By the sulfuric acid-methanol method Yield of biodiesel produced from NCTO and SCTO using H2SO4 and methanol
Source
SCTO
SCTO
SCTO
SCTO SCTO SCTO NCTO (H)
Type
Closed reaction flask Closed reaction flask Condenser (with molecular sieve) Condenser (with molecular sieve) Condenser Condenser Condenser
Amount of sulfuric acid (ml)
Amount of methanol (ml)
Reaction time (hours)
Temp. ( C)
Yield of biodiesel (wt%)
3
350
1
55
52.9
3
350
6
55
60.5
3
350
1
65
55.4
3
350
6
65
55.8
3 3 3
350 350 350
6 20 20
65 65 65
57.4 56.7 46.1
Production of biodiesel from crude tall oil
Biodiesels produced from SCTO, NCTO and VO using the acetyl chloride and sulfuric acid method
Characterization of biodiesel
Characterization of biodiesel Introduction To evaluate product quality To compare with other diesel and biodiesel products
Properties
Density Viscosity Heating Value Composition
Density Introduction Mass per unit volume Low density desired for biodiesel
Measurement procedure Weighing 1 ml of biodiesel ρ = m/v ρ = density of biodiesel, g/cm3 m = mass of biodiesel, g v = volume of biodiesel, cm3
Density Results and discussion Type of Biodiesel
Temp. ( C)
Yield of biodiesel (wt %)
Density of biodiesel (g/cm3)
NCTO (Na),1:3, 24 h NCTO (Na),1:3,1 h NCTO (Na),1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:0.3, 1 h SCTO,1:0.3, 6 h SCTO, Sulfuric acid,1 h SCTO, Sulfuric acid, 6 h VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)
25 55 55 25 25 55 55 55 55 65 65 55 65 65 65 65 65
29.9 25.2 36.9 52.7 52.7 65.9 66.0 60.6 55.7 52.9 60.5 88.5 97.7 81.7 81.7 84.5 86.3
0.921 0.920 0.924 0.844 0.840 0.914 0.949 0.928 0.934 0.879 0.946 0.926 0.905 0.887 0.904 0.935 0.929
Note: 1:3 or 1:0.3 are molar ratios of tall oil to acetyl chloride and 1 h, 6 h and 24 h are hours of reaction
Viscosity Introduction An internal property of a fluid that is a measure of resistance to the flow of the fluid Dynamic viscosity [ ] poise
Kinematic viscosity [ ] measure of resistive flow of a fluid under the influence of gravity stokes
Viscosity Measurement procedure Viscometer
U-shaped tube with capillary and glass bulb Principle Usage of std. fluid (Biodiesel)
(Standard)
T (Biodiesel) T (Standard)
(Biodiesel) (Standard)
T (Biodiesel) T (Standard)
= kinematic viscosity of biodiesel, cm2/s = kinematic viscosity of standard fluid, cm2/s = time taken by biodiesel to flow through capillary, s = time taken by standard fluid to flow through capillary, s
Viscosity Results and discussion
Description of type of Biodiesel
NCTO (Na),1:3, 24 h NCTO (Na),1:3,1 h NCTO (Na),1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:3, 1 h SCTO,1:3, 6 h SCTO,1:0.3, 1 h SCTO,1:0.3, 6 h SCTO, Sulfuric acid,1 h SCTO, Sulfuric acid, 6 h VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)
Temp. ( C)
Yield of biodiesel (wt %)
Density of biodiesel (g/cm3)
Viscosity of biodiesel (cm2/s)
25 55 55 25 25 55 55 55 55 65 65 55 65 65 65 65 65
29.9 25.2 36.9 52.7 52.7 65.9 66.0 60.6 55.7 52.9 60.5 88.5 97.7 81.7 81.7 84.5 86.3
0.921 0.920 0.924 0.844 0.840 0.914 0.949 0.928 0.934 0.879 0.946 0.926 0.905 0.887 0.904 0.935 0.929
8.70 7.61 8.46 9.90 10.91 13.98 12.75 10.62 9.51 10.14 11.93 10.28 6.87 7.06 9.05 9.85 8.95
Note: 1:3 or 1:0.3 are molar ratio of tall oil to acetyl chloride and 1 h, 6 h and 24 h are hours of reaction
.
Heating Value Introduction Heat of combustion Energy released (combustion with oxygen) Measured by ASTM procedures
Measurement procedure Empirical/approximate method Based on comparison Amount of fuel consumed to raise temp of water from 30 C to 80 C
Heating Value Results and discussion
Fuel
Fuel consumed in process of heating from 30 C to 80 C, g
Commercial Diesel Biodiesel from SCTO
0.357 0.357 0.414 0.412
Average Heat of heat of combustion combustion (HHV), BTU/lb BTU/lb 19673* 19673* 19673* 16960 16993 17025
* Source: - Petroleum-based fuels property database, National Renewable Energy Laboratory (NREL)
Composition Introduction To quantify product To find out reasons for differences between different biodiesels and raw materials
Measurement procedure
Using Gas Chromatography (GC) Using internal standard and standard methyl esters Factor calculation Comparing sample peaks with respective standard peaks
Composition
Figure 6.1: Standard peaks using standard methyl esters
Figure 6.6: Biodiesel from vegetable oil (transesterification method)
Figure 6.4: Biodiesel from SCTO (acetyl chloride and methanol method)
Figure 6.3: Biodiesel from NCTO (soap skimmed form)
Composition of biodiesel Description of type of Biodiesel
Methyl palmitate (wt%)
Methyl linoleate (wt%)
Methyl oleate (wt%)
Methyl stearate (wt%)
Total (wt%)
NCTO (Na),1:3, 24 h, 25 C NCTO (Na),1:3,1 h, 55 C NCTO (Na),1:3, 6 h, 55 C SCTO,1:3, 1 h, 25 C SCTO,1:3, 6 h, 55 C SCTO,1:3, 1 h, 55 C SCTO,1:3, 6 h, 55 C SCTO,1:0.3, 1 h, 55 C SCTO,1:0.3, 6 h, 55 C SCTO, Sulfuric acid,1 h, 65 C SCTO, Sulfuric acid, 6 h, 65 C VO (Acetyl Chloride) VO (Transesterification) WVO(Transesterification) Chicken Fat(Transesterification) Bacon Fat(Transesterification) Beef Fat(Transesterification)
8.3 7.8 7.5 6.3 6 4.9 4.8 4.5 5.6 6.2 5.7 9.1 8.6 5.7 21.8 30.4 25.3
49.4 46.1 45.1 33.5 30.8 27.2 24.7 22.6 27.8 31.5 30.9 53.8 54.1 35.8 14.4 6.5 0
6.6 6.3 6.2 33.9 31 26.7 24.2 22.7 27.4 31.3 31.7 20.4 19.9 52.8 33.5 46.5 27
2.2 2 2 2 1.6 1.3 1.1 1.2 1.6 1.7 1.8 3.2 2.9 5.5 4.9 16 15.4
66.5 62.2 60.8 75.7 69.4 60.1 54.8 51.0 62.4 70.7 70.1 86.5 85.5 99.8 74.6 99.4 67.7
Note: 1:3 or 1:0.3 are molar ratios of tall oil to acetyl chloride and 1 h, 6 h, and 24 h are hours of reaction.
Conclusions Biodiesel can be produced from CTO SCTO gives higher yield than NCTO Acidified as well as soap skimmed form can be used for NCTO Can be produced at temperatures: 25 C,35 C,45 C,55 C Closed reaction produces better results Strong acidic condition is critical Acetyl chloride or sulfuric acid can be used Speculation: Any other strong acid can be used Biodiesel from VO can be produced by acetyl chloride-methanol method can Produced biodiesel has similar properties Density, viscosity, heating value, etc.
Conclusions We postulate following reaction RCOOH + CH3OH + Acid
Methanol
CH3COCl Acetyl chloride
RCOOCH3 + CH3COOH + HCl Ester
Acetic acid
MO,MP,ML, and MS major compound of any biodiesel Comprise more than 50% of the total biodiesel
Hydrochloric acid
Future work Kinetics and mechanism of biodiesel production from SCTO and/or NCTO using acetyl chloride and methanol Kinetics and mechanism of biodiesel production from SCTO and/or NCTO using sulfuric acid and methanol Exploration of various pathways to utilize resin acids of tall oil to produce any valuable material such as fuel, wax, varnishes etc Conversion of batch process into a continuous one Pilot scale study of production of biodiesel from tall oil using acetyl chloride/sulfuric acid and methanol Characterization of the biodiesels produced by measuring some more properties and their comparison with those of commercial diesel
Acknowledgements SUNY-ESF Financial support
Thank you.
Questions
?
