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Summary of Lecture Nine

Advanced Bioproduct Systems: Ethanol Production

(Simultaneous Saccharification and Fermentation)
Degermed
Flour

25% solids

Mixing

Lecture Ten

Liquefaction

Water
Cooling and addition
of enzymes and yeast

Cellulosic Ethanol Production
DDGS

Ethanol

Drying at 60oC

Distillation

Simultaneous
Saccharification
and Fermentation
at 30oC

Biological and Ecological Engineering Department

Summary of Lecture Nine
Water and ethanol form a ‘positive azeotrope’ or minimal boiling mixture.

Summary of Lecture Nine
Distillation:

Pure ethanol (78.4°C) Pure water (100°C) Water-ethanol azeotrope (78.1°C)
Beer boiler

Rectifying
column

Ethanol (100%)

Beer tank
Ethanol (95%)
Ethanol (17%)

Centrifuge
Whole stillage

Stripper
column

Molecular
Sieves
Water (recycle)

Ref: Madson, P.W. Ethanol distillation fundamentals in Alcohol textbook

Advanced Bioproduct Systems: Ethanol Production

Advanced Bioproduct Systems: Ethanol Production

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2 DDGS 18 lb (8. CO2 18 lb (8.4 Kg) Ethanol 2.2 L) Evaporator DDGS Syrup Front end modifications Wet grains Whole stillage Centrifuge Rotary dryer Distillers dried grains with solubles (DDGS) Advanced Bioproduct Systems: Ethanol Production Summary of Lecture Nine Conventional Dry Grind Corn Corn Conventional Dry Grind Process Ethanol (2.2 Kg) Corn Thin stillage One bushel corn (56 lb /25.10 31. POSTED ON COURSE WEBSITE REQUIRED READING ! Advanced Bioproduct Systems: Ethanol Production 2 . al (2005).1 Oil 4.3 Starch 71.4 5.65 gal) Carbon Dioxide Corn DDGS Crude Protein 9.7 lb) Pericarp (4 lb) Germ (3.3 lb) Wet Fractionation Ref: Sanchez and Cardona (2008) Mosier et. Pretreatment processes are critically dependent on type of feedstock DDGS (15 lb) Corn Quick Germ Quick Fiber Process Ethanol (2.21 11.2 Kg) Coproduct modifications Advanced Bioproduct Systems: Ethanol Production Pretreatment Primary goal of any pretreatment process is to facilitate enzyme action by making the substrate available.7 gal (10.6 gal) Carbon Dioxide DDGS (7.9 Ash nd 5.8 Fiber nd 10.Summary of Lecture Nine Summary of Lecture Nine Centrifugation and Coproduct (DDGS) recovery Importance: Coproducts contribute ~15% of the plant revenues.

(2008) Advanced Bioproduct Systems: Ethanol Production Advanced Bioproduct Systems: Ethanol Production 3 . • CO2 Explosion • Does not depend on particle size • Minimizes energy and resource consumption • Ammonia Fiber Explosion (AFEX) Chemical Methods • Does not produce any waste streams • Acid Hydrolysis • Cheap • Alkali Hydrolysis • Safe • Ozonolysis • Organosolv Process • Oxidative Delignification Ref: Mosier et. (2008) Ref: Zhu et al. POSTED ON COURSE WEBSITE REQUIRED READING ! Ref: Sun and Cheng (2002) Advanced Bioproduct Systems: Ethanol Production Effect of Composition on Processing Biomass Advanced Bioproduct Systems: Feedstocks Effect of Physical Properties on Digestibility Pretreatment processes are critically dependent on type of feedstock. Ref: Zhu et al.Pretreatment Characteristics of an ideal pretreatment process are Pretreatment of Biomass Physio-Chemical Methods • Removes the barriers to effective hydrolysis of cellulose • Steam Explosion • Preserves sugars • Liquid Hot Water • Does not result in degradation of sugars or formation of inhibitors. al (2005).

bermuda grass Ref: Mosier et al. Efficiency of the subsequent hydrolysis process improves upon addition of sulfuric acid. low or no formation of inhibitors. aspen. hemiacetyl linkages. corn stover. variable solids loading 80-100% hemicellulose hydrolysis. destruction of a portion of xylans. reed canary grass Ref: Mosier et al. 88-98% xylose recovery. glucuranic acids) help in breakdown of ether linkages. (2005) Sanchez and Cardona (2008) Pretreatment of Biomass Liquid Hot water: Pressurized hot water and temperature (170-230°C) for up to 46 min. Solids content <20% Mode of action: water acts as an acid at high temperatures.Pretreatment of Biomass Steam explosion: Saturated steam at 160-290°C up to 1 min followed by decompression 80-100% hemicellulose hydrolysis. Lignin not solubilized but redistributed Feedstocks: Bagasse. Douglas fir (softwood) Bagasse. (2005) Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks 4 . formation of inhibitors Mode of action: Removal of hemicellulose from the lignocellulose matrix. alfaalfa fiber Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks Pretreatment of Biomass Pretreatment of Biomass Configurations of liquid hot water preprocessing Dilute acid hydrolysis: 0. rice and barley straw. wheat. corn Stover.75-5% mineral acids. acids released (acetic. temperature (160-200°C). 75-90% xylose recovery. dissolves lignin. sulfur dioxide or carbon dioxide. alfa alfa. wheat. barley and rye straw. eucalyptus.olive pulp. 45-65% xylose recovery. timothy grass. Lignin is not solubilized. corn stover. 80-100% hemicellulose hydrolysis. switch grass. Further cellulose conversion >90% Feedstocks pretreated: Bagasse. Energy efficient size reduction compared to grinding or comminuation Feedstocks: Poplar.

Lignin removal (up to 55%). cellulose swells increasing surface area and pore volume. Cellulose I Cellulose II. ~10-20% lignin solubilization for high lignin biomass Mode of action: reduces lignin. bermuda grass. Ca(OH)2. switch grass. low inhibitor formation. cane leaves Wheat straw: Before pretreatment Wheat straw: After pretreatment with 1% H2SO4 Ref: Gonzalez et al (1985) Ref: Sun and Cheng (2002) Advanced Bioproduct Systems: Feedstocks Pretreatment of Biomass Advanced Bioproduct Systems: Feedstocks Effect of Pretreatment Conditions on Cellulose Ammonia Fiber Explosion (AFEX): 1-2 kg ammonia/kg dry biomass temperature 90°C. cleave acetyl linkages in hemicellulose. barley and rice straw. Feedstocks: Hardwood. corn stover. 4 hr at 120°C >50% hemicellulose hydrolysis. Regeneration Cellulose I NH3 (l) . no formation of inhibitors. Subsequent cellulose hydrolysis >90%. cellulose depolymerization to some degree. 60-75% xylose recovery. hemicellulose is solubilized.NH3(g) Cellulose IIIII Heat Heat Feedstocks: Aspen wood chips.Pretreatment of Biomass Pretreatment of Biomass Dilute alkali hydrolysis: Dilute NaOH at 60°C for 2 hr. bagasse. corn stover. bagasse. newsprint Mercerization Cellulose IVII Ref: O’Sullivan (1997) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks 5 . decrystallizes cellulose. cellulose swelling Mode of action: Dissolve lignin.NH3(g) Cellulose IIII Cellulose IV1 Ref: Sun and Cheng (2002) Cellulose II NH3 (l) . alfaalfa. wheat. up to 30 min 0-60% hemicellulose hydrolysis depending on moisture.

glucuronic and galacturonic acids) Ref: Sun and Cheng (2002) Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks Pretreated Biomass Conditioning Effect of Biomass on Pretreatment Removal of inhibitors and toxic compounds is an important downstream step in cellulosic biomass processing. ethylene glycol. Some of the methods are: • Evaporation • Extraction with organic solvents • Adsorption on activated charcoal. almost total lignin solubilization. 30-60 min. 185198°C. molecular sieves • Neutralization • Alkaline Detoxification (Over liming) • Combined alkaline detoxification • Ionic exchange • Enzymatic detoxification • Microbial detoxification Ref: Dien et al (2005) Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks 6 . solvent recovery required Feedstocks: Poplar and mixed soft wood Pretreated Biomass Conditioning Removal of inhibitors and toxic compounds is an important downstream step in cellulosic biomass processing. formic.4 Almost total hemicellulose hydrolysis.0-3. triethylene glycol) or their mixture with 1% H2SO4 or HCl. Inhibitors produced during pretreatment: • Hexose (Glucose): Hydroxy Methyl Furfural (HMF) • Pentose (Xylose): Furfural • Lignin: Cinnamaldehyde. pH 2. acetone. high xylose recovery.Pretreatment of Biomass Organosolv process: Organic solvents (methanol. ethanol. p-hydroxybenzaldehyde and syringaldehyde • Hemicellulose degradation products: acetate.

microorganisms • Possible non optimal conditions for enzymatic hydrolysis and fermentation Ref: Sanchez and Cardona (2008) Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks 7 . • Exoglucanases: Degrade the glucans into cellobiose units. Three main categories of cellulases: • Endoglucanases: Produce glucans by attacking regions of low crystallinity. lignin content) • Substrate to enzyme ratio • Enzyme activity • Product inhibition SSF of Pretreated Biomass Advantages of SSF over separate hydrolysis and fermentation (SHF) of pretreated biomass: • Lower sugar concentration • Increased rate of hydrolysis • Lower enzyme requirement • Inhibition of competing microorganisms • Lower capital costs However: • Ethanol inhibition of enzymes. mesophilic/ thermophilic. Cellulases are produced by many types of microorganisms: bacteria/fungi. • Beta-Glucanases: Break down cellobiose into glucose. Ref: Mosier et al (2005) Ref: Sanchez and Cardona (2008) Advanced Bioproduct Systems: Feedstocks Advanced Bioproduct Systems: Feedstocks Enzymatic Hydrolysis of Pretreated Biomass Factors influencing enzymatic hydrolysis of cellulose • Physical characteristics (surface area. crystallinity) • Chemical characteristics ( Degree of polymerization.0 )with resulting n cost savings.Effect of Pretreatments on Biomass Enzymatic Hydrolysis of Pretreated Biomass Enzymatic hydrolysis of cellulose is preferred over other methods as it can be accomplished under milder conditions ( <50°C. pH <5. porosity. aerobic and anaerobic. Both final titer and rate of production are important for production of cellulases commercially.

Advanced Bioproduct Systems: Ethanol Production Thank you Biological and Ecological Engineering Department 8 .