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The US Corn Ethanoil Industry
The US Corn Ethanoil Industry
The U.S. corn ethanol industry: An butyl ether (ETBE). Several Midwest
States mandate the use of ethanol. The
overview of current technology and Federal government has also encour-
aged the use of ethanol by exempting
future prospects it from the federal gasoline excise tax.
This tax exemption was set to expire in
by Bruce S. Dien, Rodney J. Bothast, Nancy N. Nichols, 2000, but has since been renewed
until 2006. Several Midwestern States
and Michael A. Cotta also introduced further financial
incentives for ethanol. These incen-
USDA-ARS, National Center for Agricultural Utilization Research, tives are designed to favor smaller
1815 N. University Street, Peoria, IL, USA. ethanol plants, such as those built by
farmer cooperatives. Typical is
Minnesota's Tax incentive, which gives
20 cents per gal per year for 10 years
Abstract should continue to increase as indi- for a maximum of 50 million gals per
vidual States phase out the use of year. Many ethanol plants designed
Last year, 1.77 billion gallons of fuel methyl tertiary butyl ether (MTBE) as around this incentive have since
ethanol were produced in the U.S., a fuel oxygenate. The California expanded capacity.
over 90% of which was produced Energy Commission has estimated Ethanol demand is expected to
from corn. Ethanol demand is expect- that production capacity is expected increase dramatically over the next
ed to more than double in the next to grow to more than 4 billion gals/yr several years because of environmen-
several years as it is used to replace by 2006 (MacDonald et al., 2001). tal concerns associated with the use of
the fuel oxygenate, methyl tertiary- The growth in the use of fuel MTBE. MTBE, which has leaked from
butyl ether (MTBE). Corn is prepared ethanol can be traced to environmen- gasoline storage tanks, has been dis-
for ethanol fermentation by either tal legislation and Federal and State covered to be a major ground water
wet milling or dry grinding. Most economic incentives. In 1990, the contaminant and more resilient to
newly constructed ethanol plants use Clean Air Act amendment was passed microbial degradation than other
dry grinding because of its lower cap- which required the use of oxygenated common organic water pollutants
ital costs. However, corn wet millers fuel and reformulated gasoline to (Anonymous, 1999). As a result of
have also expanded production by reduce carbon monoxide emissions. these findings, California and States
adding on to existing plants. Current The list of available fuel oxygenates located in Eastern United States have
technology allows for 2.5 (wet milled)
to 2.7 (dry grind) gal of ethanol per
bushel of corn. An opportunity exists CO 2000
for increasing this yield by also con- 0
verting the fibrous components of the X $ Ethanol
corn kernel (i.e. pericarp and germ)
to ethanol. Fermenting these non-
1500
starch fractions could increase the
I-
yield from a bushel of corn by a max- 0
imum of 10%. In this brief review, the 0
economic and technical aspects of 0
ethanol production will be explored 1000
Co
as well as future prospects for 0
iF
increasing ethanol yield from corn by
fermenting the non-starch fractions.
Introduction
0)
II
iTFITFFiFFFFRi
0
50:
The United States produced 1.77 bil-
lion gal of fuel ethanol (2001) and
over 90% of it was produced from
w II
9801981198219831984198519861987198819891990199119921993199419951996997199819992000200
corn. U.S. ethanol production has
expanded dramatically since 1980 Year
(Fig. 1) and today utilizes over 5% of
Figure 1. Growth in U.S. ethanol production
the corn crop. Ethanol production
Midwest) blend with gasoline. ElO dextrins. The mash is heated to above
and E85 lower petroleum use by 6% 110°C using ajet cooker. The jet cook-
Corn Grind and 74% per gallon, respectively er is a special tube reactor/pump that
(Wang et al., 1999). ElO also reduces uses direct steam heating to heat and
greenhouse gas emissions by 1% and shear the starch granules. The corn
E85 by 34% (ibid). Finally, ethanol is mash is kept at the elevated tempera-
Saccharification good for rural development by supply- ture for several minutes by pumping it
through a holding tube equipped with
ing an important market for corn and
providing jobs at rurally located a backpressure valve. The mash flows
ethanol plants. In 1997, it was esti- from the holding tube into a flash tank
mated that fuel ethanol increased and the temperature is allowed to fall
FLiquefaction farm income by 4.5 billion dollars and to 80-90°C. The rest of the alpha amy-
led to the creation of 195,200 jobs lase is added and the mash is liquefied
(Evans et al., 1997). for at least 30 minutes. Liquefaction
greatly reduces the size of the starch
polymer.
Fermentation Current ethanol production processes
/
The liquefied mash is placed in the
Corn is processed to ethanol by either bioreactor and cooled to 32°C. The pH
dry grinding or wet milling. Last year, is lowered to 4.5-5.0 using backset
for the first time, dry grinding produc- (recycled from the distillation col-
Ethanol DDGS tion (55%) exceeded that of wet umn) and phosphoric acid. The fer-
milling in the U.S. Growth of dry mentation stage is started by adding
Figure 2. Corn dry grind process grind mill capacity has exceeded that the glucoamylase and the yeast inocu-
for producing ethanol. of wet mills because dry grind mills lum. Glucoamylase converts liquefied
have lower capital costs. Capital costs starch into glucose by breaking down
indicated interest in phasing out for dry grind mills have been estimat- alpha-1,4 glucosidic linkages. Enough
MTBE. In June 2001, the Bush ed at $1.25-1.50 per gal. In recent glucoamylase is added such that the
Administration refused California's times, no new wet mills have been saccharification of the starch to glu-
request for a waiver of the oxygenate built; instead producers have relied on cose, which occurs continually
fuel requirement, thereby, forcing the expanding existing facilities. through the fermentation, does not
use of ethanol if production of MTBE Descriptions of the dry grinding and limit the rate of ethanol production.
is stopped. The annual California wet milling processes follow. In addition, either (NH 4)2 5O4 or urea
ethanol market is expected to grow by is added as a nitrogen source for the
500 - 800 million gals (McDonald et Dry grind process growth of the yeast. Recently, ethanol
al., 2001). A possible comprise has dry grind mills have also begun to add
recently been worked out in the U.S. Sometimes the ethanol dry grind proteases that break down the corn
Senate. In the proposed National process is referred to as dry milling. protein to a free amino acid, which
Energy Bill (currently in the U.S. Dry grind process, however, is the pre- serve as an additional source of nitro-
Senate) the oxygenate requirement ferred term as it avoids confusion with gen for the yeast. The fermentation
would be abolished and, instead, a dry milling corn for production of lasts 48-72 hours and has a final
renewable fuels standard established corn grits and flour. A schematic of a ethanol concentration of 10-12% v/v.
for promotion of ethanol (Brown, dry grinding process is shown in The pH of the beer declines during the
2002). The bill specifies a target Figure 2 (for detailed reviews: Jacques fermentation to below 4 because of
ethanol production goal of 5 billion et al., 1999; Elander and Putsche, carbon dioxide formed during the
gals/yr by 2012 (ibid). 1996). Corn is hammer milled to pass ethanol fermentation. The decrease in
Beyond its use as an oxygenate, through a 1/8-3/16 inch screen. If the pH is important for increasing the
proponents of the use of fuel ethanol grits exit the mill too coarse, not all of activity of glucoamylase and inhibit-
cite the following benefits: reduces the starch becomes available for fer- ing the growth of contaminating bac-
reliance on imported oil, lowers mentation and if it is too fine, the teria.
greenhouse gas emissions, and pro- residual biomass is difficult to sepa- Dry grind plants can reduce the
motes rural development. A study to rate following fermentation. amount of glucoamylase added by sac-
be published this spring (2002) by the Once ground, the corn is mixed charifying the liquefied starch at 65°C
USDA has estimated that ethanol has with water to form a mash. The pH of prior to fermentation. However,
a 34% net energy balance (Shapouri the mash is adjusted to 6.0 with plants have gone to SSF (simultane-
personal communication, for an older ammonia followed by addition of 1/3 ous saccharifi cation and fermenta-
report see Shapouri et al., 1995). of the alpha-amylase. Alpha amylase tion) because it lowers the opportuni-
Ethanol is available as a 10% v/v (El 0) is added to begin to break down the ty for microbial contamination. SSF
and 85% v/v (E85; only in the starch polymer and produce soluble also lowers the initial osmotic stress
L05^
INT. SUGAR JNL., 2002, VOL. 104, NO. 1241
The U.S. corn ethanol industry: An overview of current technology and future prospects
INT. SUGAR JNL., 2002, VOL. 104, NO. 1241
[2O7
The U.S. corn ethanol industry: An overview of current technology and future prospects
making the cellulose fraction suscep- However, these harsh conditions lead
[Size Red tible to enzymatic hydrolysis by cellu- to the formation of inhibitors and, so,
lase. Inhibitors are formed by subse- (in the literature) enzymatic digestion
quent degradation of sugars freed has been favored. Often, the cellulase
Pretreatment during hydrolysis, releasing organic enzymes are added to the fermenta-
acid side-groups (e.g., acetate) from tion broth and carried out as a simul-
F catalyzed hydrolysis)
cid
the xylan component, and also from taneous saccharification and fermen-
lignin break down products. tation. Carrying out hydrolysis during
Neutralization & Conditions that optimize cellulose the fermentation lowers the amount of
Inhibitor Abatement recovery tend to also favor degrada- enzyme required and circumvents the
tion of the xylan sugars and, there- sensitivity of the cellulase enzymes to
fore, optimal pretreatment conditions end product inhibition. Even when
Enzymatic Hydrolysis of require a compromise. A wide variety the best treatment for pre-treating cel-
Cellulose to Glucose of pretreatments have been investi- lulose is used, cellulase loading is
gated for biomass, and the best pre- much higher than that needed for
Fermentation treatment, as expected, depends upon amylases. Thus, the cost of cellulases
the source of biomass. is considered a major technical con-
/ Most pretreatments are either straint to implementing biomass fer-
Ethanol Fermentation chemical or a combination of chemi- mentations.
Residuals cal and physical (for review: Hsu T.A., Corn fiber, corn bran, and corn
1996). Pretreatments described in the germ meal are readily hydrolyzed
Figure 4. Lignocellulose literature include: dilute acid, strong with dilute acid (Asghari et al., 1996,
conversion to ethanol. acid, alkaline hydrogen peroxide, Dien et al., 1999, Grohmann and
ammonium fiber explosion (AFEX), Bothast, 1997, Saha and Bothast,
challenge. However, fermenting steam explosion with S02 , and hot 1999). Dilute sulfuric acid hydrolysis
available corn stover could conceiv- water. Pretreating with acid is capable of corn fiber at 140-160°C and pH 1.5
ably boost ethanol production 10 of completely hydrolyzing the xylan - 2.0 for 10-30 min followed by enzy-
fold. There is a commercial corn fraction. Alkali and hot water methods matic saccharification of dextrans
stover collection facility in Harlan, IA will only dissolve and partially gave a yield of 81-87% of total carbo-
(Glassner et al., 1998). hydrolyze xylan. This means hydroly- hydrates as free sugars (Grohmann
A considerable amount of research sis will need to be completed using and Bothast, 1997). Only 7 interna-
has gone into developing processes either enzymes or acid. Steam explo- tional filter paper units of cellulase
for conversion of fibrous biomass into sion tends to be more destructive to per g corn fiber cellulose were
ethanol. A simplified schematic of pentose sugars than some of the other required, which is 2-7 times less
what such a process would look like is methods. Acid pretreatments are the activity than usually added to dilute
shown as Figure 4. The first step is to only ones that have been used com- acid pretreated cellulose (ibid). Other
prepare the biomass for fermentation mercially. For efficient recovery of the pretreatments used with corn fiber
by pre-treating. While size reduction xylan sugars, the cellulose fraction (AFEX, alkaline peroxide, and hot
will not be required for treatment of needs to be hydrolyzed in a separate water), while effectively preparing
corn fiber, some type of milling will step. cellulose for enzymatic treatment, do
be needed for corn stover. A success- Hydrolysis of the cellulose fraction, not completely hydrolyze the xylan
ful pretreatment step should accom- to release glucose, can be accom- (Well et al., 1998, Moniruzzaman et
plish multiple goals: (1) converting plished enzymatically or chemically. al., 1997, Leathers and Gupta, 1996).
the xylan fractions to monosaccha- Acid hydrolysis, under sufficiently Hydrolysis of AFEX treated corn
rides in high yields, (2) forming a harsh conditions, can completely fiber xylan with commercial xylanas-
minimum of inhibitors, and (3) hydrolyze cellulose to glucose. es only converted 25% to monosac-
charides (Hespell et al., 1997). Corn
Table 3. Comparison of recombinant microorganisms for production of ethanol germ xylan was more readily digest-
ed (ibid). The relative digestibility of
Pretreatment Strain Max ethanol Yield' Max. productivity hot water treated corn fiber xylan has
(gilitre) (gig) (g/litre/hr) not yet been reported. The AFEX and
hot water treatments are still of inter-
Dilute acid E. co//K011 34.7 0.41 1.16
Dilute acid E. co/A SL40 31.7 0.42 1.12
est because they do not generate gyp-
Dilute acid E. co/i FBR3 28.0 0.46 0.97 sum waste, which is associated with
Dilute acid Zymomonas CP4 (pZB5) 22.6 0.47 1.05 neutralization of the dilute-acid
AFEX Saccharomyces 1400 (pLNH32) 21.0 0.50 1.60 treated biomass, and have lower
concentrations of microbial
grams ethanol per grams sugar consumed; maximum possible is 0.51 g/g.
inhibitors.
Fermentation of the sugars recov- fiber was held in the tank for 15 min- Bothast, R.J., Nichols, N.N., and
ered from the xylan fraction is prob- utes at 145°C. The liquid portion was B.S. Dien. 1999. Fermentations with
lematic because the traditional yeast, recovered for fermentation. The new recombinant organisms.
S. cerevisiae, does not ferment pen- hydrolysate syrup contained a total of Biotechnology Progress. 15:867-875.
toses. Naturally occurring yeast that 76 g/litre of sugars, which is 95% of Brown R. 2002. National Energy
do ferment xylose require aeration for theoretical, excluding cellulose. The Bill could Trigger a Boom for Ethanol.
growth, have low productivity, are corn fiber hydrolysate was next over- Chemical Market Reporter. 261(10):1.
acutely sensitive to inhibitors - espe- limed to remove inhibitors. This Dien, B.S., Iten, L.B., and R.J.
cially acetate, and have fairly low process consists of adjusting the pH to Bothast. 1997. Conversion of corn
ethanol tolerances. There are no com- 10 with Ca(OH) 2 and treating the fiber to ethanol by recombinant
mercially suitable naturally occurring hydrolysate to 90°C for 30 minutes. Escherichia co/i strain FBR3. Journal
bacteria or yeast for fermenting The hydrolysate was neutralized with of Industrial Microbiology and
xylose to ethanol (Bothast et al., sulfuric acid to pH 7 and the resulting Biotechnology. 22:575-581.
1999). Therefore, research has gypsum formed removed by centrifu- Dien, B.S., Nichols, N.N., O'Bryan,
focused upon developing recombinant gation. Yeast extract and tryptone P.J., and R.J. Bothast. 2001.
organisms to ferment pentoses to were added as nitrogen sources. The Development of new ethanologenic
ethanol. Two strategies have been hydrolysates were fermented using an Escherichia co/i strains for fermenta-
used to develop the needed biocata- ethanologenic E. co/i strain. The fer- tion of lignocellulosic biomass.
lyst: (1) expressing genes needed for mentation was completed within Applied Biochemistry and
xylose utilization in efficient ethanol approximately 65 hours and the Biotechnology. 84-86:181-196.
producing microorganims or (2) ethanol yield was 92% of theoretical. Eckhoff, S.R., Rausch, K.D., Fox,
expressing genes needed for ethanol Residual xylose was 3.5 g/litre. E.J., Tso, C.C., Wu X., Pan, Z., and P.
production in bacteria capable of Even if ethanol production is Buriak. 1993. A laboratory wet
using xylose and arabinose. As exam- increased to 5 billion gallons per year milling procedure to increase repro-
ples of the first approach, by 2012, as being considered by the ducibility and accuracy of product
Saccharorn yces sp. (Hahn-Hagerdal et U.S. Congress, fuel ethanol would yields. Cereal Chemistry 70(6):723-
al., 2001; Ho et al., 1998) and multiple only displace 3.05% of the U.S. pro- 727.
Zymomonas mobi/is strains (Zhang et jected automotive fuel demand. Elander, R.T. and V.L. Putsche.
al., 1995) have been constructed that Increasing ethanol supplies to greater 1996. Ethanol from corn: technology
ferment xylose. Examples of the sec- production levels will eventually and economics. In: Handbook on
ond approach are ethanologenic E. require fermenting lignocellulosic bio- Bioethanol. Ed. C.E. Wyman.
co/i strains (Dien et al., 1999, Ingram mass (e.g. corn stover). Likewise, even Publisher: Taylor and Francis,
et al., 1998, Ohta et al., 1991). Several though corn hulls and germ contain Washington D.C. 329-350.
of these recombinant organisms have lignocellulose, they are also in limited Evans, M.K. February 1997. The
been used to ferment corn fiber supply as an ethanol feedstock. economic impact of the demand of
hydrolysate (Table 3; Bothast et al., However, fermentation of these ethanol. Prepared for: Midwestern
1999). Of those listed in Table 3, only fibrous material can act as a stepping Governors' Conference. Lombard,
the K. oxytoca and F. co/i are capable stone towards development of other, Illinois.
of fermenting arabinose. Arabinan more challenging source so biomass, Glassner, D.A., Hettenhaus, J.R.,
represents 3-5% of the total carbohy- such as corn stover. and T.M. Schechinger. 1998. Corn
drates of corn stover (Wiselogel et al., Stover Collection Project. In:
1996) and 16% of that for corn fiber References BioEnergy '98-Expanding Bioenergy
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was fermented, which left the cellu- 99-021. phuric acid and enzymes. Process
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