Membrane Osmotic Distillation

63 downloads 0 Views 2MB Size Report
properties after co-polymerization. • biocompatibility to human tissue in surgical ... W.R. Grace and Company. PHB and PHBV. Cupriavidus necator NCIB. 11599.
Production of Biodegradable Plastics (Polyhydroxyalkanoate - PHA) through Biological Processes: Challenges and Opportunities Tjandra Setiadi, Rety Setiawaty and Martha Aznury

Presented at International Postgraduate Conference on Biotechnology, August 25, 2016, ITS, Surabaya

Department of Chemical Engineering ITB [email protected] 1

Outline Introduction Polyhidroxyalkanoate (PHA) Biosynthesis of PHA PHA Production by Mixed Culture PHA Production by Pure Culture Challenges and Opportunities

2

Introduction

degradable plastic, n—a plastic designed to undergo a significant change in its chemical structure under specific environmental conditions resulting in a loss of some properties that may vary as measured by standard test methods appropriate to the plastic and the application in a period of time that determines its classification.

biodegradable plastic, n—a degradable plastic in which the degradation results from the action of naturally-occurring micro-organisms such as bacteria, fungi and algae. Definition according ASTM and ISO

3

World’s Biodegradable Plastic Demand 2010

2011

2016

(Million Pound)

(Million Pound)

(Million Pound)

PLA1

470

578

1.655

23.4

Starch-based

251

289

582

15.0

PHA & other polyesters2

50

65

279

33.8

Total

771

932

2516

22.0

Biodegradable Polymer/ Plastic

Average annual increase (%)

Source : Plastics Europe Market Research Group (PEMRG), BCC-Research

4

Biodegradable plastics

Partially biodegradable

Completely biodegradable

PCL

Starch/PE

Natural

Fermentation

PHA

Modification of cellulose products

Cellulose

Starch/ PVA

Fermentation/synthesis

Polilactide

Starch/ PCL

Chemical synthesis

Aliphatic polyester PET-PCL

Chitosan/ cellulose

Biodegradable plastics (Chang, 1994) PE – polyethylene; PCL – polycaprolactone; PHA – polyhydroxyalkanoate; PET - Polyethylene5 terephthalate; PVA - polyvinyl alcohol

Polyester Polymers

Polyesters

Aromatic (Ring Polymers)

PBS (butyl succinate)

PCL (polycaprolactone)

PBSA (Polybutylene succinate adipate)

PHA (polyhydroxyalkanoates)

PHB (polyhydroxybutyrate)

PHB/PHV

Aliphatic (linear Polymers)

PHB/PHH

PLA (polylactic acid)

PHV (polyhydroxyvalerate)

PHH (polyhydroxyhexanote)

PHB/PHV

PHB/PHH

Modified PET

AAC (aromatic copolyesters)

PBAT (polybutylene adipate terphthalate)

PTMAT (polymethylene adipate terephthalate

Synthetic / Renewable Synthetic / Nonrenewable Natural / Renewable

6

Polihydroxyalkanoate (PHA)

Poly Hydroxy Alkanoate

Polyhydroxyalkanoates (PHAs) are polyesters of various (R)-hydroxy carboxylic acids, which are accumulated as carbon/energy storage or reducing power materials in numerous microorganisms usually under the unfavourable growth condition in the presence of excess carbon source 7

Polyhydroxyalkanoate (PHA)

Ojumu et al., 2004 8

PHA advantages • complete biodegradability • wide ranging physical and mechanical properties after co-polymerization • biocompatibility to human tissue in surgical applications

PHA Biosynthesis

Source: Magdouli et al., 2015

10

PHA Biosynthesis • PHA is biodegradable and can be produced biologically using various substrates including organic wastewater (Du et al., 2001). This makes PHA an alternative to petroleum-based plastics used today. • Currently, the commercial PHA branded with different trade names, such as Biopol, Metabolix, Nodax, etc. produced from glucose using different species (Magdouli et al., 2015) 11

Commercialized PHAs with their trade names

Polymer

Strain

P(3HB) PHB and PHBV

Manufacturers

Rhizobium

W.R. Grace and Company

Cupriavidus necator NCIB 11599

ICI Ltd (Imperial Chemical Industries Ltd) (BiopolTM)

Recombinant E. coli K12

Metabolix, Inc.

Recombinant E. coli

(NodaxTM)

Table 1 Commercialized PHAs with their trade names and manufacturing companies. -

PHB and mclPHA P(3HB-co3HHx)

12

PHA Biosynthesis • It was commercially produced as early as 1976 by ICI, however the production was terminated in 1998 for a number of reasons (Koller et al., 2016). • Recently, on July 6, 2016, Newlight Technology (USA) and Paques Holding bv (the Netherlands) have come to an agreement that will allow Paques to manufacture, process and sell bioplastics (PHA) based on Newlight’s biocatalyst process to convert greenhouse gases (methane) to PHA (named AirCarbon) at a rate of up to 1.3 million metric tons/year 13

PHA Production • However, the drawback is that the PHA production cost is still much higher than that of petroleum plastics, due to the cost of the substrate (Bengtsson et al., 2008). • On the other hand to use the pure culture also involves the high operational costs due to media sterilization and reactor maintenance (Reddy and Mohan, 2012a). • The potential reduction in cost is using organic material from agriculture and food industry wastewater as much as possible and mixed cultures system as the microbial agent (Din et al., 2012; Reddy and Mohan, 2012b).

14

PHA Production with Mixed Cultures Setyawati, R., Setiadi, T., Katayama-Hirayama, K., Kaneko, H. and Hirayama, K. (2012). Polyhydroxyalkanoate (PHA) production from tapioca industrial wastewater treatment: Influence of operating conditions on PHA content, Sustain. Environ. Res., 22 (2), 123-127

15

Activated Sludge and Wastewater

16

Sequencing batch reactor (SBR) • fill and draw processes : fill, react, settle/sedimentation, draw/decant, and idle • aeration and settling in the same tank • can manipulate the environmental change for microorganisms activities

Sequencing batch reactor (SBR)

18

Conclusions • Although results showed large variations, the following conclusions can be drawn: • (1) Tapioca industrial wastewater treatment using a SBR with activated sludge as the source of microorganisms can produce PHA with average PHA content 0.03-0.10 g PHA/g MLSS. • (2) COD was not effectively removed. Average COD removal efficiencies were 20-40%. And • (3) Combination of aerobic and anaerobic periods did not have a significant effect on PHA content and COD removal.

19

PHA Production with a pure culture Setiadi, T., Aznury, M., Trianto, A. and Pancoro, A. (2015). Production of polyhdroxyalkanoate (PHA) by Ralstonia eutropha JMP 134 with VFAs from palm oil mill effluent as precursors. Water Science & Technology, 72(11), 1889-1895.

20

Materials and Method (1) Acidogenic fermentation

Distillation POME

Anaerobic fermentation

Fermented POME

Mineral medium

Figure 1. Two-step PHA production process from POME by Ralstonia eutropha JMP 134

Ralstonia eutropha Glucose

VFAs

Aerobic fed-batch fermentation

PHA

(2) PHA production

21

The Schematic diagram of PHA production Cell Cell production

Substrate

PHA production

VFA from POME

Separation

Supernatant (effluent)

Cell destruction

PHAs Purification

Addition of VFA either in Batch or Fed-Batch Mode

22

Identification of PHA with different analysis methods FTIR Analysis Precursor

Cultivated Mode

VFAs from Distillated Fermented POME (DFP)

Batch

VFAs from Distillated Fermented POME (DFP)

Fed-Batch

Melting Point (oC)

Wave length (cm-1)

Possible structure ofPHA

GC Analysis Monomer compostion (%mol)

169.5

1.728 1.282

3-HB

100(3-HB)

139

2.927 1.737 1.303 1.229 1.196 797

3-HB and 3-HV

88(3-HB), 12(3-HV)

1

H NMR analysis

References Zakaria, et al. 2010:Chakrabor ty et al. 2009 (GC) Choi dan Lee, 1999 (GC) Shamalaet al. 2014 (FTIR and 1 H NMR)

It could be determined that the PHA from batch mode was fully mono polymer of 3-hydroxybutyrate (100 % 3HB) and from fed-batch mode was a copolymer with 3-hydroxyvalerate content of 12 % mol (% 3-HV). 23

Comparison of the batch and fed-batch mode operation in PHA production Batch Substrate/ microorganism

VFAs

Fed batch

Productivity (g/L/h)

PHA (g/gDCW)

3HV (% mol)

0.014

39

0

Glucose/ Ralstonia eutropha JMP 134

VFAs from Distillated Fermented POME (DFP)

Mineral salts medium (MSM)/ Comamonas sp. EB172

VFAs (fermented POME)

Glucose/ Ralstonia eutropha JMP 134

VFAs from Distillated Fermented POME (DFP

Mineral salts medium (MSM)/ Comamonas sp. EB172

acetic, propionic acids

-

20

9

Condensed corn solubles/ Ralstonia eutropha

acetic acid

0.024

29.3

-

Substrate/ microorganism

VFAs

References

Productivity (g/L/h)

PHA (g/gDCW)

3HV (% mol)

0.048

51

12

This study

-

49

12

Zakaria et al..(2010)

Chakraborty et al.(2009)

Glucose/ Ralstonia eutropha

VFAs (fermented POME)

0.01

51

-

Hassan et al.(2002)

The PHA productivity in the fed-batch mode was 0.048 g/L/h, it is much higher than those of other studies (Table 3) and it was not much different to the productivity obtained by Campanari et al. (2014), i.e. 0.06 g/L/h, using VFAs from fermented Olive Oil Mill wastewater in a mixed culture. However it is in the lower range of values obtained by pure cultures reported, namely 0.04 to 0.9 g/L/h (Kim, 2000) 24

Conclusions • The highest VFAs production from POME was obtained at an anaerobic fermentation time of 1 day and pH of 4.43 with the distillated fermented-POME (DFP) consisted of acetic, propionic and butyric acid having a concentration of 2.79 g/L, 1.18 g/L, and 3.04 g/L, respectively. • PHA productivity in the fed batch mode gave a value of 0.048 g/L/h being an increase of 342 % compared to the batch mode. The addition of DFP in a fed batch mode could also increase the 3HV became 12 % mol. 3HV, whereas in the batch mode was only 0% mol. 3HV. • The PHA product structure could be well identified by different analysis methods, such as melting point, GC, FTIR, and NMR. These methods supported each other resulting the products were composed of 3-HB and 3-HV functional group. 25

Examples of PHA Products

Challenges and Opportunities • Although there is an increase research on this topic in the last twenty years, however the industrialization of this product is still a challenge. • The sustainability of PHA production in the near future will be depend on several factors, such as strain selection, feedstock selection, bioreactor cultivation mode, downstream processing and product processing development.

31

Challenges and Opportunities

32

Koller, M. Marsalek, L. de Sousa Dias, M.M., Braunegg, G. (2016)

Production Strain Selection • Wild-type vs genetically engineered strains • Mesophile vs extremophile organisms • Pure culture vs mixed microbial culture

33

Feedstock Selection • Ethically clear (no interference with food- and feedprocesses • Seasonal availability of feedstocks (“Off-season” availability) • Addressing variability and stability of feedstock composition • Impact of applied feedstock on polymer composition (homo- vs co-polyester); quality (molar masses, coloration, etc.) and sensory quality (coloration, odor) • Upgrading of waste streams to feedstocks • Integration into existing production lines, etc. 34

Bioreactor Cultivation Mode (“Process Design”) • Discontinuous vs single- or multistage continuous mode • Solid state fermentation • Recycling of Spent fermentation broth • Self-sufficiency of energy supply, etc.

35

Downstream Processing • Solvent selection (non-toxic solvents, recyclability) • Solvent-free methods • Recycling and reuse of cell debris and other side streams of recovery process, etc.

36

Processing • Production of compatible Composites and Blends by utilization of ecologically benign materials (preferably inexpensive and renewable), etc.

37

West Hall INSTITUT TEKNOLOGI BANDUNG

38