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AD Biorefinery Concept

AD Biorefinery Concept. Shihwu Sung. Department of Civil, Construction & Environmental Engineering Iowa State University. Anaerobic Treatment Short Course Part 7. Biorefinery Concepts. Trees Grassess Agricultural Crops Agricultural Residues Animal Wastes Municipal Waste Sludge. USES

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AD Biorefinery Concept

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  1. AD Biorefinery Concept Shihwu Sung Department of Civil, Construction & Environmental Engineering Iowa State University Anaerobic Treatment Short Course Part 7

  2. Biorefinery Concepts • Trees • Grassess • Agricultural Crops • Agricultural Residues • Animal Wastes • Municipal Waste Sludge USES Fuels -Ethanol -Renewable Diesel Power -Electricity -Power Chemicals -Plastics -Solvents -Chemical Intermediates -Phenolic -Adhesives -Furfural -Fatty Acids -Acetic Acid -Carbon Black -Paints -Dyes, Pigments and Ink -Detergents -Etc. Food and Feed Biomass Feedstock Conversion Process • Enzymatic Fermentation • Gas/Liquid Fermentation • Acid Hydrolysis • Gasification • Combustion • Co-firing www.bioproducts-bioenergy.gov

  3. Biorefinery Research ISU Environmental Engineering Program

  4. Anaerobic Digestion (1) Complex Organics Carbohydrates Proteins Lipids 1. Hydrolysis Simple Organics (2) Volatile Organic Acids Propionate, Butyrate, etc. 2. Acidogenesis Acetate H2 + CO2 (3) 3. Methanogenesis CH4 + CO2

  5. Animal Waste-to-Biodiesel Plant Smithfield Foods, Inc.

  6. Anaerobic Sequencing Batch reactor (earthen dikes with membrane cover) Settling Tanks (solid/liquid separation)

  7. Methane-to-Methanol Production Smithfield Foods, Inc.

  8. Methanol-to-Biodiesel Production Smithfield Bioenergy, Inc.

  9. O O || || CH - O - C - R CH - O - C - R 2 1 3 1 | | O O CH - OH 2 | || || | CH - O - C - R + 3 CH OH  CH - O - C - R + CH - OH 2 3 3 2 | (KOH) | | O O CH - OH 2 | || || CH - O - C - R CH - O - C - R 2 3 3 3 Triglyceride (oil & fat) methanol mixture of fatty esters glycerin Transesterification Biodiesel

  10. Tallow, edible, Corn, 2,453 , 10% 2,075 , 8% Cottonseed, 725 , 3% Sunflower, 320 , 1% Lard, 1,075 , 4% Canola, 541 , 2% Safflower, 89 , 0% Soybean, 18,435 , 72% Feedstock Availability in US Unit: cents/pound Unit: million lb • Fats and oils was 26 billion lb in 2002 (~3.5 billion gallons of biodiesel) • Soybean oil is dominant and relatively cheap material

  11. Smithfield Bioenergy Utah Plant • Swine Waste • Average 50,000 lb/d Pig Manure (~144,000 pigs) • Supplemented with 6,000 lb/d Glycerin • Biogas Production • 400,000- 500,000 cuft/d from Pig Manure • 1,000,000 cuft/d with Glycerin • Products • Every 1,000cuft biogas could produce one gallon of methanol • 500,000 cuft Biogas => 5,000 gallon Methanol 1,000,000 cuft => 10,000 gallon Methanol per day

  12. Biodiesel Yield at Smithfield Energy 100 lb oil + 21.71 lb methanol → 100.45 lb biodiesel + 10.40 lb glycerol + 10.86 lb XS methanol 100 gal of oil + 24.65 gal methanol → 103.3 gal biodiesel + 7.42 gal glycerol + 12.33 gal XS methanol Typical proportions for the chemicals used: Reactants • Fat or oil (e.g. 100 lb soybean oil) • Primary alcohols (e.g. 10 lb methanol) Catalyst • Mineral base (e.g. 0.3 lb sodium hydroxide)

  13. Biohydrogen Production from Renewable Organic Wastes

  14. H2 and acid production Glucose Solvent production EMP Pathway H2 Pyruvate Acetate Acetyl CoA Ethanol Acetoacetyl CoA Propanol Butyrate Butyryl CoA Butanol Dark Fermentation • Dark fermentation carried out by genus Clostridium

  15. Metabolic Pathway of Biological Hydrogen Production • Biological hydrogen production accompanied with organic acid production C6H12O6+2H2O 2CH3COOH + 2CO2 + 4H2 C6H12O6CH3CH2CH2COOH + 2CO2 + 2H2 4C6H12O6+2H2O  2CH3COOH +3CH3CH2CH2COOH + 8CO2 + 10H2

  16. Kinetic parameters of Michaelis-Menten equation NFDM: Non-fat dry milk • NFDM: 57% carbohydrate; • Food waste: 43% carbohydrate • Hydrogen production rate: lactose > sucrose (Woodward et al., 2000 )

  17. Batch Study Conclusion • The higher carbohydrate content, the higher substrate affinity • High Ks value: high substrate concentration requirement • Not appropriate to use particulate organic waste for hydrogen fermentation

  18. ASBR Study Conclusion • Effect of HRT • Optimum HRT: 16 h • At short HRT, ORP increased to hostile the survive of anaerobic microbes. • Effect of pH • The best performance: pH 4.9 Effect of substrate (sucrose) concentration • Effect of substrate concentration • The best performance: 25 g COD/L

  19. Organic Acids Adsorption – Recovery - Purification • Adsorption:Mesoporous silica media incorporated with a layer of amines to adsorb organic acids • Recovery:Akali wash off the organic acids and regenerate the media • Purification:Harvest organic acids through purification e.g. distillation

  20. Pore Diameter = 10 to 200 Å Channel Depth = 0.1 to 1 micron Surface Area = ~ 900 m2g-1 Mesoporous MCM-41 Silica Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S. Nature, 1992, 359, 710.

  21. Chitin, the wonder substance • Cosmetics and toiletry • Water Treatment • Medical • Pulp and paper • Biotechnology • Food • Membranes http://www.meronbiopolymers.com/html/mbio2apln.htm

  22. Chitin Prediction • "Chitosan and chitosan oligosaccharide are ideal biomaterials which hold much promise for the future," (Prodex's Joseph Nichols). • "There has been increased interest by scientists worldwide and industry is beginning to recognize their possibilities. They could very well be important biomaterials in the next decade. The day has come for these natural polymers to come into their own."

  23. Chitin Sources Crawfish/Crabs Shrimp Fungi Chitin 25-30% 30-40 15-40%  Protein 15% 35% 5-10%  CaCO3 55% 30% Glycans  Lipids 2-5% 5-10% 5-10% Chitin is a valuable neutraceutical

  24. Isolation of Chitin/Chitosan from Fungi 10% NaOH, 24 hr, RT Proteins, Lipids, Pigments, Hemicelluloses Chitin/glucan 50:50 Acetic acid Insolubles Solubles Mixture of glucanases pH = 5.5, 4 days, 37 C 50% NaOH to gel Chitosan Chitin pH = 5.5, chitin deacetylase, 37 C, 5 days

  25. Growing fungus Rhizopus oligoporus on thin stillage Day 0 Day 4 Day 5 Day 8 Fungal biomass

  26. Fungal biomass with solids attached Effluent collected

  27. Nisin production from Soy Whey Nisin is an antimicrobial peptide usually produced by the certain species of Lactococcus. Nisin exhibits the broad antimicrobial activity against Gram-positive bacteria including food borne pathogens. In this study, nisin fermentation was conducted in soy whey as growth media by using the strains of Lactococcus lactis.

  28. Agar Well Diffusion Assay for nisin quantification Growth of Micrococcus luteus Zone of inhibition

  29. Results:Maximum nisin activity was observed at 36 h of growth period

  30. Question?

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