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


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

Summary of Lecture Nine

Summary of Lecture Nine

Centrifugation and Coproduct (DDGS) recovery


Importance: Coproducts contribute ~15% of the plant revenues.

CO2 18 lb
(8.2 Kg)
Corn

Thin stillage

One bushel corn


(56 lb /25.4 Kg)

Ethanol 2.7 gal


(10.2 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 (2.65 gal)


Carbon Dioxide

Corn

DDGS

Crude Protein

9.10

31.3

Starch

71.4

5.1

Oil

4.21

11.9

Ash

nd

5.8

Fiber

nd

10.2

DDGS 18 lb
(8.2 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. Pretreatment processes are critically
dependent on type of feedstock

DDGS (15 lb)

Corn

Quick Germ
Quick Fiber
Process

Ethanol (2.6 gal)


Carbon Dioxide
DDGS (7.7 lb)

Pericarp (4 lb)

Germ (3.3 lb)

Wet Fractionation
Ref: Sanchez and Cardona (2008) Mosier et. al (2005). POSTED ON COURSE WEBSITE REQUIRED READING !

Advanced Bioproduct Systems: Ethanol Production

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.

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. al (2005). 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. (2008)

Ref: Zhu et al. (2008)

Advanced Bioproduct Systems: Ethanol Production

Advanced Bioproduct Systems: Ethanol Production

Pretreatment of Biomass
Steam explosion: Saturated steam at 160-290C up to 1 min followed by
decompression
80-100% hemicellulose hydrolysis; destruction of a portion of xylans, 45-65%
xylose recovery, formation of inhibitors
Mode of action: Removal of hemicellulose from the lignocellulose matrix.
Efficiency of the subsequent hydrolysis process improves upon addition of
sulfuric acid, sulfur dioxide or carbon dioxide. Energy efficient size reduction
compared to grinding or comminuation
Feedstocks: Poplar, aspen, eucalyptus, Douglas fir (softwood)
Bagasse, corn Stover, wheat, rice and barley straw, timothy
grass, alfa alfa, reed canary grass

Ref: Mosier et al. (2005) Sanchez and Cardona (2008)

Pretreatment of Biomass
Liquid Hot water:
Pressurized hot water and temperature (170-230C) for up to 46 min; Solids
content <20%
Mode of action: water acts as an acid at high temperatures, hemiacetyl
linkages, acids released (acetic, glucuranic acids) help in breakdown of ether
linkages, dissolves lignin,
Lignin is not solubilized; 80-100% hemicellulose hydrolysis; 88-98% xylose
recovery, low or no formation of inhibitors. Further cellulose conversion
>90%
Feedstocks pretreated: Bagasse, corn stover,olive pulp, 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: 0.75-5% mineral acids, temperature (160-200C),


variable solids loading
80-100% hemicellulose hydrolysis; 75-90% xylose recovery, Lignin not
solubilized but redistributed
Feedstocks: Bagasse, corn stover, wheat, barley and rye straw, switch grass,
bermuda grass

Ref: Mosier et al. (2005)

Ref: Sanchez and Cardona (2008)

Advanced Bioproduct Systems: Feedstocks

Advanced Bioproduct Systems: Feedstocks

Pretreatment of Biomass

Pretreatment of Biomass
Dilute alkali hydrolysis: Dilute NaOH at 60C for 2 hr; Ca(OH)2, 4 hr at
120C
>50% hemicellulose hydrolysis; 60-75% xylose recovery, Lignin removal
(up to 55%), low inhibitor formation; cellulose swelling
Mode of action: Dissolve lignin, cleave acetyl linkages in hemicellulose,
cellulose swells increasing surface area and pore volume.
Feedstocks: Hardwood, bagasse, corn stover, 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 90C, up to 30 min
0-60% hemicellulose hydrolysis depending on moisture; no formation of
inhibitors; cellulose depolymerization to some degree. Subsequent cellulose
hydrolysis >90%; ~10-20% lignin solubilization for high lignin biomass
Mode of action: reduces lignin, hemicellulose is solubilized, decrystallizes
cellulose, Cellulose I Cellulose II.

Regeneration

Cellulose I
NH3 (l)
- NH3(g)

Cellulose IIII

Cellulose IV1

Ref: Sun and Cheng (2002)

Cellulose II
NH3 (l)
- NH3(g)

Cellulose IIIII
Heat

Heat

Feedstocks: Aspen wood chips, bagasse, wheat, barley and rice straw, corn
stover, switch grass, bermuda grass, alfaalfa, newsprint

Mercerization

Cellulose IVII

Ref: OSullivan (1997)

Advanced Bioproduct Systems: Feedstocks

Advanced Bioproduct Systems: Feedstocks

Pretreatment of Biomass
Organosolv process: Organic solvents (methanol, ethanol, acetone, ethylene
glycol, triethylene glycol) or their mixture with 1% H2SO4 or HCl; 185198C, 30-60 min, pH 2.0-3.4
Almost total hemicellulose hydrolysis; high xylose recovery, almost total
lignin solubilization, 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.
Inhibitors produced during pretreatment:
Hexose (Glucose): Hydroxy Methyl Furfural (HMF)
Pentose (Xylose): Furfural
Lignin: Cinnamaldehyde, p-hydroxybenzaldehyde and syringaldehyde
Hemicellulose degradation products: acetate, formic, 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. Some of the methods are:
Evaporation
Extraction with organic solvents
Adsorption on activated charcoal, 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

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 ( <50C, pH <5.0 )with resulting n cost
savings.
Three main categories of cellulases:
Endoglucanases: Produce glucans by attacking regions of low
crystallinity.
Exoglucanases: Degrade the glucans into cellobiose units.
Beta-Glucanases: Break down cellobiose into glucose.
Cellulases are produced by many types of microorganisms: bacteria/fungi,
aerobic and anaerobic, mesophilic/ thermophilic. Both final titer and rate of
production are important for production of cellulases commercially.

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, porosity, crystallinity)
Chemical characteristics ( Degree of polymerization, 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, 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

Advanced Bioproduct Systems: Ethanol Production

Thank you

Biological and Ecological Engineering Department