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Value added products from glycerol

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Value added uses for crude glycerol from biodiesel plant

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Value added products from glycerol

  1. 1. Value-added uses for crude glycerol–a byproduct of biodiesel production Fangxia Yang, Milford A Hanna & Runcang Sun, Biotechnology for Biofuels 2012 Presented By: Bijaya K. Uprety PhD (Biotechnology) student
  2. 2. Background Fluctuating oil prices Depletion of fossil fuel Increasing energy demand Environmental issues Biodiesel? 1
  3. 3. What is biodiesel? • Alternative fuel to conventional or fossil diesel. • Can be produced from  oil from plants such as soybean & jatropha,  animal fats,  from microalgae or fungus. • Can be used in diesel engines with little or no modification. • Typically blended with petroleum diesel in the formulations referred to as B2, B5, B20 and B100 (pure biodiesel). 2
  4. 4. Biodiesel Compared to Petroleum Diesel Advantages Disadvantages Domestically produced from non-petroleum, renewable resources Use of blends above B5 not yet approved by many auto makers Can be used in most diesel engines, especially newer ones Lower fuel economy and power (10% lower for B100, 2% for B20) Less air pollutants (other than nitrogen oxides) Currently more expensive Less greenhouse gas emissions (e.g., B20 reduces CO2 by 15%) B100 generally not suitable for use in low temperatures (form gels) Biodegradable, non-toxic and safer to handle Biodiesel fuel distribution infrastructure needs improvement Biodiesel Diesel 3
  5. 5. Trans-esterification reaction for biodiesel production 4  Biodiesel is produced using Transesterification process  Reacting vegetable oils or animal fats catalytically with a short-chained aliphatic alcohol (typically methanol or ethanol).”  Glycerol is the byproduct.
  6. 6. Typical Production of Biodiesel from veg. oil 1.http://www.lct.ugent.be/sites/default/files/events/Lecture%202%20Studies%20on%20esterification%20of%20Free%20Fatty%20 Acids%20in%20biodiesel%20production.pdf. If feedstock contain <4% FFA: Trans-esterification reaction: Oil + Alcohol  Ester + Glycerol Catalyst: NaOH, KOH, & carbonates, H2SO4, HCl, lipases etc. (Acid catalyzed rxn is slow). If feedstock contains >4% FFA: i. Before trans-esterification, FFAs are converted into soaps and removed from the Oil (triglycerides). ii. Application of the Acid Catalysis method to trans-esterify the triglycerides & esterify the FFAs in parallel in the same reactor. 5
  7. 7. Glycerol as byproduct during biodiesel production • Glycerol (also known as glycerin) is a major byproduct in the biodiesel manufacturing process. • Biodiesel production will generate about 10% (w/w) glycerol as the main byproduct. • In general, for every 100 pounds of biodiesel produced, approximately 10 pounds of crude glycerol are created. • It is projected that the world biodiesel market would reach 37 billion gallons by 2016, which implied that approximately 4 billion gallons of crude glycerol would be produced. 6
  8. 8. Composition of crude glycerol However, almost every crude glycerol contains, Glycerol Light solvent (Methanol or ethanol, water) Soap Fatty acid methyl esters (FAME i.e. biodiesel) Glycerides (i.e. to mono, di & tri-glycerides), Free fatty acids (FFA) Ash Variations in biodiesel production methods variation in composition of crude glycerol 7 (Table adapted from: Xiao. et al., 2013)
  9. 9.  Catalyst type used- lipase, alkaline,acidic  Transesterification efficiency  Recovery efficiency of biodiesel  Impurities in feedstock  Recovery efficiency of methanol and catalyst Factors affecting the composition of crude glycerol 8
  10. 10. Present need for crude glycerol conversion • Increase production of crude glycerol world-widely • Decrease in price of pure glycerol/pound • To economize the biodiesel production process 0.9 MT (2009) 0.2 MT (2004)$0.7 (<2007) $0.3 (In 2007) 9
  11. 11. Value-added opportunities for crude glycerol Animal Feedstuff Feedstock for chemicals Other uses 10
  12. 12. Feedstuffs for animal • Glycerol as animal feed ingredient since 1970 • Crude glycerol (CG) as feed has been recently investigated. • Glycerol has high absorption & is good energy source. 85% of the CG samples from various biodiesel house showed (Dasari, 2007) Digestible energy (DE) values: 14.9-15.3 MJ/kg Metabolizable energy(ME)values: of 13.9-14.7 MJ/kg 11
  13. 13. Continue… • Research shows excellent source of calories for non- ruminants such as broilers, laying hens, and swine. • Has potential to replace corn in diets. • Weaned pigs upto 10% feed performance • Broiler  2.5-5% inclusion feed conversion ratio “But” Residual level of potassium in it wet litter or imbalances in dietary electrolyte balance in broilers 12
  14. 14. Continue.. • Daily gains by Pigs during growth period but not on the finishing period. Effective at certain stage of growth • Broiler  Improved feed conversion but no effect on growth performance and nutrient digestibility. • Dietary treatments had no significant effects on meat quality. “The influences of levels and quality of crude glycerol on pellet quality needs further study”. Dr. Liliana Revolledo stated in an article- The companies will need to guarantee more than 80 % of glycerol, a maximum of 12 % of moisture and maximum level of methanol of 150 ppm, apart from guarantee correct levels of sodium and chlorine. 1 http://www.veterinariadigital.com/uk/noticia.php?id=43 13
  15. 15. Crude glycerol in ruminant diets Ruminants Inclusion of crude glycerol Effects References Finishing lamb Up to 15% Improved weight, no change in carcass characteristics Gunn et al. (2010) Meat goats Up to 5% Improved weight Hampy et al. (2008) Cattle Up to 15% Improved weight and feed efficiency Parson et al. (2009) 14
  16. 16. Feedstocks for chemicals • Two approaches for conversion of crude glycerol into value- added chemicals. Biological conversion- use of mo’s Catalytic conversion • Various chemical produced via biological conversion includes,  1,3 Propandiol  Citric acid  Poly(hydroxyalkanoates)  Docosahexaenoic acid  Lipids 15
  17. 17. Continue… • Fermentation is the most common technique for the biological conversion of these products. 16
  18. 18. Feedstock for chemicals Products Organisms Method Notes References 1, 3 – propandiol Clostridium butyricum strains VP 13266, F2b, VPI1718 Klebsiella pneumonia (13.8 g/l) Anaerobic fermentation Chatzifragkou et al. showed  Methanol didn’t affect C. butyricum conversion and  NaCl had effect during continuous but not batch process Mu et.al (2006), BR et.al (2008) Citric acid Yarrowia lipolytica ACA-DC50109, Y. lipolytica N15 mutant Y. lipolytica wratislavia AWG7 strain Aerobic fermentation  Yarrowia lipolytica ACA-DC50109 produced citric acid was similar to the one obtained from conventional process using sugar. (SCO was also produced).  Y. lipolytica N15 produced high quantity i.e. 71 g/l using CG and 98 g/l using PG.  mutant Y. lipolytica produced 131.5 g/l using CG and 139 g/l using PG Papanikolaou et al (2003), Rywinska et al (2009), Kamzolova et al (2011) 17
  19. 19. Products Organisms Method Notes References Hydrogen Rhodopseudomonas palustris Photofermentation  Sabourin et al. (2009)- equal production from crude and pure glycerol.  Developing effective photo- bioreactor and enhancing light utilization efficiency is a problem for large scale production.  Crude glycerol used as co-substrate for enhanced hydrogen and methane production during anaerobic treatment of sewage sludge, solid waste etc. (Fountoulakis et al, Lopez et al) Sabourin et al (2009) Ethanol Enterobacter aerogenes HU 101 (facultative anaerobe) Fermentation  High yield of ethanol and hydrogen simultaneously (Nakashimadu et al, 2005).  K. pneumonia mutant strain and non-pathogenic kluyera cryocrescens S26 have been reported as promising strains. Nakashimadu et al, 2005). Choi etal (2011) 18
  20. 20. Products Organisms Notes Poly - hydroxyalkanoates (PHA) Paracoccus denitrificans Cupriavidus necator JMP 134 Zobellella denitrificans MW1 Pseudomonas oleovorans NRRL B- 14682 (promising strain)  Complex class of naturally occurring bacterial polyesters  Recognized as good substitute for non- biodegradable polymers.  10 million gallon/year biodiesel plant has potential to produce 20.9 ton PHB.  PHB is the most studied polyester belonging to group PHA  The polymers PHB produced by P. denitrificans and C. necator JMP 134 were similar to that obtained from glucose but the process was hindered by the presence of NaCl contamination.  Zobellella denitrificans MW1 can produce PHB even in presence of NaCl. 19
  21. 21. Products Organisms Notes Docosahexanoic acid (DHA) & EPA (Omega-3-fatty acid) Schizochytrium limacinum (algae)- Fermentation Pythium irregulare DHA:  Fermentation of alga S. limacinum using crude glycerol in the optimum range of 75-100 g/l  Highest DHA yield 4.91 g/l (Chi et al, 2007), temp 19.2 0C and ammonium acetate 1 g/l.  The resulting algae had similar content of DHA and comparable nutritional profile to commercial algal biomass. EPA:  Fortified foods through fungal fermentation with Pythium irregular  Less EPA content compared to microalgae for EPA.  Optimization of culture condition required. 20
  22. 22. Products Organisms Notes Lipids Schizochytrium limacinum SR21 (microalgae) Cryptococcus curvatus (fungus) Schizochytrium limacinum SR21  S. limacinum algal growth and lipid production were affected by the concentrations of glycerol.  Optimum crude glycerol concentration is 35 g/l  lipid content produced was 73.3%.  Methanol could harm the growth.  C. curvatus yeast growth wasn’t affected by the methanol presence  lipid content was 52%  Methanol didn’t show inhibitory action on growth.  Lipid had high concentration of monounsaturated fatty acid and was good biodiesel feedstock. 21
  23. 23. Products Organisms Notes Lipids Rhodotorula glutinis TISTR 5159 (yeast)  Cultured on crude glycerol produced lipids (10.05 yield, 60.7% lipid content) and carotenoids (6.10 g/l yield).  Ammonium sulfate and tween 20 addition enhanced the accumulation.  Additionally, Chatzifragkou et al. studied the potential of fifteen eukaryotic microorganisms to convert crude glycerol to metabolic products. Yeast accumulation (up to 22 wt.%, wt/wt < fungi accumulation (18.1 and 42.6%, wt/wt) 22
  24. 24. Continue… On-going research for various other chemicals Succinic acid - Basifia succiniciproducens DD1 Phytase - Pichia pastoris Butanol- Clostridium pasteurianum (0.30 g/g) > Clostridium acetobutylicum (0.15-0.20 g/g; glucose substrate) Fungal protein - Rhizopus microspores var. oligosporus Further understanding and optimization of the process still needed for upscaling 23
  25. 25. Chemicals produced through conventional catalytic conversion • (2,2-dimethyl-1,3-dioxolan-4-yl) methyl acetate (biodiesel additive)  Enhance the biodiesel viscosity, oxidation stability, and flash point. • Acrolein precursor for detergents, acrylic acid ester and super absorber polymers. • Syngas (H2 and CO )  Synthetic gas for the production of ammonia or methanol. CG gasified into these product Gasification (>700 0C, no combustion, controlled oxygen) with in situ CO2 removal was effective technique 24
  26. 26. • Production of monoglycerides via. glycerolysis of triglycerides with crude glycerol. • Its use as green solvent in organic reactions. • As fuel for generating electricity from microbial fuel cells. 25
  27. 27. Conclusion • Effective utilization of crude glycerol is very crucial for the further development of the biodiesel production. • Characterization of crude glycerol is important as impurities present in it play a major role in crude glycerol conversion. • Conventional catalysis and biotransformation are the two main routes for converting the crude glycerol into value added products. • Extensive studies on biological conversion has produced encouraging results in the recent past. However, all these conversion still have to overcome technological hurdles for its practical implementation on large scale. 26

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