Overview of technical barriers and implementation of cellulosic

ethanol in the U.S.

Tae Hoon Kim
a
, Tae Hyun Kim
b,
*
a
Department of Applied Chemical Engineering, Dankook University, Cheonan, Chungnam 330-714, Republic of Korea
b
Department of Environmental Engineering, Kongju National University, 1223-24 Cheonandae-Ro, Budae-dong, Cheonan, Chungnam 330-717,
Republic of Korea
a r t i c l e i n f o
Article history:
Received 26 January 2013
Received in revised form
12 July 2013
Accepted 6 August 2013
Available online 10 October 2013
Keywords:
Ethanol industry
Biofuels
Biorenery
Cellulosic ethanol
Commercialization
Pretreatment
a b s t r a c t
There is mounting concern about the buildup of carbon dioxide (CO
2
) and other so-called greenhouse
gases in the atmosphere. In general, bioethanol production requires minimal fossil fuel input in the
conversion step, and ethanol is considered a promising alternative fuel to petroleum-derived products. It
is anticipated that ethanol production with second-generation biomass, i.e. lignocellulosic materials, will
be possible on a large scale in the near future. Latest efforts have been focused on overcoming technical
challenges in bioconversion, particularly pretreatment, and nding the solutions required to implement
biorenery on a large scale. This paper introduces and reviews the current status of research, and of the
ethanol industry in the U.S. In addition, other important concepts in biofuels, cellulosic ethanol, and
biorenery in general are reviewed, and the key technical issues in bioconversion of cellulosic ethanol,
such as pretreatment and factors affecting bioconversion of biomass are also discussed.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
The economy of the United States is the worlds largest national
economy. Its nominal GDP was estimated to be over $15.7 trillion in
2012 [1]. The U.S.s present economy is mostly dependent on fossil
energy sources including oil, coal, natural gas, and so on. The United
States was ranked second in the world after China in terms of CO
2
emitted as of 2011; China and the U.S. emitted 23.3% and 18.2% of the
global total, respectively [2]. The amount of CO
2
released has resulted
in growing pressure by the international community for the U.S. to
join the mandatory reduction programs. Under the Kyoto Protocol of
1997, which is a working agreement of the UNFCCC (United Nations
Framework Convention on Climate Change), Annex I countries must
reduce their aggregate emissions of greenhouse gases by at least ve
percent from 1990 levels during the 2008e2012 period.
It is also anticipated that the future energy system in the US will
be more dependent on the various alternative energy technologies
including solar, wind, tidal, geothermal, fuel cells, and biofuels from
biomass. In particular, according to the U.S. EISA (Energy Inde-
pendence and Security Act), the consumption of biofuels, such as
biomass-based diesel and advanced biofuels, will increase one
hundred-fold during the next 10 years [3].
A biorenery is a new concept in which fuels, power, and
chemicals can be produced from biomass in the same way that
todays petroleum reneries produce multiple fuels and products
from petroleum. Biorenery technologies have been generally
identied as the most promising route to the creation of a new
domestic bio-based industry, to the development of a sustainable
industrial society, to energy independence, and to the effective
management of greenhouse gas emissions [4e7].
There is no doubt that renewable energy will be the most
important product of the future bio-based economy. Among
various alternative or renewable energies, ethanol production from
renewable resources is now being accepted across the world as a
visible substitute for traditional petroleum based fuels. In partic-
ular, cellulosic ethanol, in other words bioethanol, can be produced
from inexpensive and abundant lignocellulosic biomass. This
lignocellulosic biomass is the most available potential feedstock for
the production of bioethanol, which is currently the most widely
used liquid biofuel alternative to fossil fuels [8].
Use of bioethanol has many advantages in terms of the environ-
ment, national energy security, and rural economic improvement.
Currently, a lot of research and work towards commercialization are
being done to meet rapidly growing energy demands. Ethanol is
* Corresponding author. Tel.: 82 41 521 9426; fax: 82 41 552 0380.
E-mail addresses: hitaehyun@gmail.com, thkim@kongju.ac.kr (T.H. Kim).
Contents lists available at ScienceDirect
Energy
j ournal homepage: www. el sevi er. com/ l ocat e/ energy
0360-5442/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2013.08.008
Energy 66 (2014) 13e19
presently being promoted as a promising alternative fuel for trans-
portation; the use of fossil fuels has contributed to the buildup of
carbondioxideintheatmosphere, however ethanol is a clean-burning
fuel that makes a signicantly lower contribution to global warming
thananyother fossil fuels because the carbondioxide producedby the
combustionof ethanol isconsumedbyplant growth, thus maintaining
the natural carbon cycle balance.
This paper introduces and reviews the current status of
research, of technical barriers in bioconversion, and of the ethanol
industry in the U.S., which is one of the leading countries in bio-
renery, specically ethanol research and industry, and has vast
cropland available for the planting of biomass, as well as abundant
biomass resources.
2. Feedstock and present ethanol industry
In general, biomass can be divided into rst generation crops
such as sugars fromsugar cane or sugar beets, and starch fromcorn,
rice, wheat, and so on, and second generation energy sources such
as various lignocelluloses and algae including macro- and micro-
algae (Fig. 1). Corn grain is the primary feedstock used for the
production of fuel ethanol in the United States, producing about
13.3 billion gallons of corn ethanol in 2012 [9]. Therefore, ethanol
production is concentrated in the Midwest corn-belt states.
Meanwhile, the RFA (Renewable Fuel Association) reported that
there were only 50 ethanol plants in 2000, a number which had
increased to 198 by 2011 (Fig. 2). Fig. 2 also indicates that 76 plants
were under construction in 2005, while this number dropped
sharply to seven in 2011. It collectively suggests that the ethanol
demand in the US appears to be the saturation point and govern-
ment corn-starch ethanol mandates are only three years or 12%
away from reaching their maximum [10].
Various cellulosic biomass resources are widely distributed
across the United States. The NREL (National Renewable Energy
Laboratory) provided information on the biomass resources avail-
able in the United States, which include agricultural residues, wood
residues, and dedicated energy crops. According to the biomass
resource distribution map, less biomass resources are available in
the West, while greater inventories are available in the Mid-west,
East, and South [11].
According to other reports, there are about 120 million dry tons
of cellulosic biomass, mainly corn stover, corn ber, wheat, rye, and
barley straw, that can be sustainably harvested today, and which is
enough to produce about ve billion gallons of ethanol, roughly
equal to half what the U.S. is making today fromcorn starch. On the
other hand, more than one billion tons of biomass could potentially
be harvested if dedicated energy crops could be developed, grown,
and harvested sustainably. If this, along with sustainable harvesting
of forestry and paper mill wastes were achieved, the U.S. could
supply about 60 billion gallons of fuel ethanol; 30% of U.S. liquid
transportation fuel needs [12e15].
Achieving the cellulosic biofuel targets set forth in the Energy
Independence and Security Act (EISA) of 2007 will require a very
large increase in harvested cellulosic biomass feedstocks from
agricultural, forest, and other resources. It is estimated that by
2022, nearly 180 million dry tons of biomass will be needed
annually to produce the 16 billion gallons of cellulosic biofuels
called for by EISA [16].
3. Advanced biofuels
Biofuels including bioethanol were typically categorized into
rst, second, and third generation biofuels. First generation biofuel
is made from oil, sugars and starch, which can easily be converted
to diesel, ethanol, and butanol using conventional technology.
Fig. 1. Various biomass and classication.
Fig. 2. Corn ethanol industry overview in the U.S. Source: Renewable Fuel Association
http://www.ethanolrfa.org/ [9].
T.H. Kim, T.H. Kim / Energy 66 (2014) 13e19 14
Second generation biofuels, mainly cellulosic ethanol, are made
from lignocellulosic biomass such as forestry residues, agricultural
residues, and dedicated energy crops, and they are much more
difcult to convert than oil, sugars, and starch.
Third generation biofuels are much more similar in composition
and fuel value to petroleum. In general, these so called drop-in
fuels are replacements for gasoline, diesel, and jet fuel produced
from various sustainable sources such as cellulose, municipal
waste, or algae; for example, Mascoma Corporation (Waltham, MA,
USA) suggested consolidated bioprocessing which utilizes devel-
opment of organisms that break down biomass and produce bio-
fuels with no added enzymes or pretreatment, and LS9 Inc. (South
San Francisco, CA, USA), Amyris Inc. (Emeryville, CA, USA) and Gevo
Inc. (Englewood, CO, USA) used synthetic biology by development
of new organisms with new pathway to produce renewable pe-
troleums, in other word third generation biofuels, directly from
multiple feedstocks.
Meanwhile, characterizing biofuels by genealogy is confusing and
not always meaningful. RFS2 (Renewable Fuel Standard 2) from the
EPA (Environmental Protection Agency) and the Energy Indepen-
dence and Security Act of 2007, suggested that advanced biofuels is
more appropriate to describe second and third generation biofuels
[17]. In this paper, conventional and advanced biofuels (bioethanol)
are used to describe biofuels in terms of their performance.
RFS2 lays the foundation for achieving signicant reductions of
greenhouse gas emissions from the use of renewable fuels, for
reducing imported petroleum, and for encouraging the develop-
ment and expansion of USs renewable fuels sector. EISA of 2007
established specic lifecycle GHG (greenhouse gas) emission
thresholds for each renewable fuel, requiring a percentage
improvement compared to lifecycle GHG emission for gasoline or
diesele(1) any renewable fuel: 20% reduction; (2) advanced biofuel
(or biomass-based diesel): 50% reduction; (3) cellulosic biofuel:
60% reduction.
In 2005, Congress enacted the Renewable Fuel Standard as part
of the Energy Policy Act and amended it in the 2007 EISA. The aim
of the RFS is to encourage development of biofuels, lower depen-
dence on foreign oil, and reduce greenhouse gas emissions [18]. The
RFS called for 36 billion gallons of renewable fuel to be blended
with traditional fuels by 2022, and the vast bulk of this will come
from corn ethanol. It also called for the volume requirement of
cellulosic biofuels for the year 2012 to be 0.5 billion gallons, and for
an increase in advanced biofuels to 16 billion gallons by the year
2022 [19] (Fig. 3). Specically, the law mandates that the United
States must produce 16 billion gallons of cellulosic biofuels by 2022,
along with 15 billion gallons of conventional corn-based ethanol, 1
billion gallons of biodiesel, and 4 billion gallons of advanced
biofuels.
In 2007, the U.S. Department of Energy selected six cellulosic
ethanol projects to receive up to $385 million in grants. This project
was established to satisfy two major goals of the US government:
(1) to make ethanol out of nonfood biomass, including billions of
pounds of agricultural waste, at a cost competitive with gasoline by
2012, and (2) to increase the use of renewable and alternative fuels.
For this project, more than $1.2 billion was to be invested to build
six biorenery facilities across the U.S. However, only one is under
construction as of 2011.
The lesson learned was that in order for commercialization of
biofuel production to be successful, many hurdles, including securing
feedstock and nancing construction, will need to be overcome [20].
In the US, the supply of advanced biofuels (2nd generation) was
determined to be behind schedule, and this is due to limited feed-
stock supply and to the economic cost of conversion technologies.
Overall, the main reason is that the initial costs for most advanced
biofuels will be very high; (1) plant capital costs are 5e10 times as
much as corn ethanol plants, (2) production costs are 2e5 times
more expensive than corn ethanol, and (3) not enough low-cost
feedstock is available.
4. Biorenery and sustainability
The term sustainability is rooted in the term sustainable
development [21,22]. The concept suggests that it is possible to
achieve economic growth and industrialization without environ-
mental damage. The core of mainstream sustainability thinking has
become the idea of three dimensions, environmental, social and
economic sustainability [23]. In addition, the NREL (National
Renewable Energy Laboratory in Golden City, CO, USA) dened the
biorenery as a facility that integrates biomass conversion pro-
cesses and equipment to produce fuels, power, and chemicals from
biomass. The biorenery concept is analogous to todays petro-
leum reneries, which produce multiple fuels and products from
petroleum [11].
Biorenery technologies will include several different conver-
sion processes and different sized installations, due to a variety of
feedstocks, and different local circumstances. Optimization and
high efciency are the keys to making bioreneries sustainable and
economically viable [24,25]. Although biorenery has great po-
tential for replacement of petroleum-derived products, the in-
dustry is still in a nascent state. To date, most of the industrial
bioreneries have been focused on the production of bio-based
products from corn grain, ethanol, animal feeds, corn syrup, and
other chemical building blocks. On the other hand, numerous
research efforts have been focused on the use of second-generation
biomass such as lignocellulosic biomass, and the consensus among
researchers is that these will probably be ready for large-scale
commercial production within ten years.
In order to facilitate the commercialization of lignocellulosic
integrated bioreneries, industry must employ the best technolo-
gies for harvest, storage, transportation, pretreatment, sacchari-
cation, and fermentation. The development of technology in the
aforementioned sectors will push the industrialization of bio-
reneries and in particular the mass production of cellulosic
ethanol on a commercial scale.
5. Key technical issues in commercialization of advanced
bioethanol
The biological conversion of ethanol from lignocellulosic biomass
can be achieved by three major stepsepretreatment, enzymatic hy-
drolysis and sugar fermentation. The OBPs (Ofce of the Biomass
Fig. 3. The 2007 Energy Independence and Security Act required aggressive increase in
advanced biofuels. Source: 2007 Energy Independence and Security Act [19].
T.H. Kim, T.H. Kim / Energy 66 (2014) 13e19 15
Program) roadmap from the Biomass to Biofuels Workshop in 2006,
identied barriers to realizing the potential of cellulosic biofuels, and
also highlighted related high-level topical areas [26] (Table 1). In this
report, key scientic milestones to achieving progress toward OBP
goals were identied by workshop participants, and included four
topical areas; (1) feedstocks for biofuels, (2) biomass (feedstocks)
deconstruction to sugars, (3) sugar fermentation to ethanol, and (4)
consolidated processing.
The commercialization of cellulosic ethanol production depends
signicantly on the improvement of technologies in biomass
deconstruction to sugar. This is because cellulosic ethanol prices
will depend heavily on the cost of the cellulase and hemicellulose
enzymes used to break down the cellulosic biomass into ferment-
able sugars. Reducing enzyme costs increases the market potential
of biofuels [27]. However, all four topical areas are to be considered
equally important. In 2010, a report indicated that enzyme costs
were estimated at about $0.50 per gallon, and signicant work was
underway to reduce this to about $0.10 per gallon [28].
The goal, either reduction of total enzyme cost used or reduction
of total enzymes used in the process, can possibly be achieved by
means of improving pretreatment technology and improving
enzyme efciency. A general approach for the conversion of
biomass into ethanol is to break down the cellulose and hemicel-
lulose chains, comprising two-thirds to three-quarters of the
lignocellulosic biomass, by chemical pretreatment and enzyme
saccharication, into their component sugars, and then ferment
those sugars into ethanol.
5.1. Pretreatment
Lignocellulosic biomass consists primarily of three different
types of polymersecellulose, hemicellulose and lignin, which are
tightly associated with each other [29,30]. The lignin-hemicellulose
association shields the cell wall polysaccharides from enzyme hy-
drolysis, and thus a pretreatment process is required to permit
saccharication. Cellulose and hemicellulose portions in lignocel-
lulosic biomass are carbohydrates, which can be converted into
fuels and chemical by fermentation. In order to produce fuels and
chemicals from lignocellulosic biomass, cellulose and hemicellu-
lose in this feedstock should be hydrolyzed to produce various
monomeric sugars either by acid or enzymes.
Acid hydrolysis of lignocellulosic biomass can depolymerize
cellulose and hemicellulose into monomers without pretreatment,
but the acid must be recovered for environmental and economic
reasons. It has been challenging to develop a low-cost acid recovery
process to meet these needs [31,32]. Only biological conversion
using enzymes and microbes is widely accepted as a mean of
cellulosic ethanol and biochemical production.
Lignocellulosic biomass has a recalcitrant nature, which makes
it resistant to enzymatic hydrolysis. In the bioconversion processes
of lignocellulosic biomass, pretreatment is the most essential step
to improve the microbial conversion yield of fermentation from a
lignocellulosic biomass. Although the corn ethanol industry is
currently producing ethanol at a cheap price, production of ethanol
from lignocellulosic biomass is a very different system than that
used for corn grain because carbohydrates in lignocellulosic
biomass are much more difcult to solubilize than the starch in
grain [33]. Moreover, lignocellulosic material is very resistant to
enzymatic break down, requiring pretreatment in order to open up
the rigid structure and to enhance the susceptibility of the biomass
to the enzyme [34].
The common effects of pretreatment include the following: (1)
Decrease of lignin, hemicellulose, and extraneous components, (2)
Increase of surface area, porosity, and pore size, (3) Reduction of the
crystallinity of cellulose, and (4) Enhancement of the accessibility of
enzymes to the cellulosic substrate.
5.2. Factors affecting biological conversion
There are many factors affecting biological conversion of
lignocellulosic biomass. Lignocellulosic material is not a naturally
digestible material, since it is provided with many chemical/phys-
ical barriers that inhibit the enzyme hydrolysis of lignocellulose
[35]. As described earlier, the biological conversion of lignocellu-
losic biomass to fuels and chemicals can be achieved by pretreat-
ment, enzymatic hydrolysis and fermentation. Pretreatment is one
of the key elements in the bioconversion of this non-digestible
biomass. It is required for efcient enzymatic hydrolysis of
biomass because of the physical and chemical barriers that inhibit
the accessibility of enzymes to the cellulose substrate [36].
A number of factors have been suggested to affect enzymatic
hydrolysis. Among the known chemical barriers are lignin [37e39],
Table 1
DOE-OBP Research milestones.
Topic Technology goals
Feedstocks
Develop sustainable technologies
to supply biomass to bioreneries
Better composition
and structures for
sugars production
Domestication
Better agronomics
Sustainability
Biomass (feedstock) deconstruction to sugars
Develop biochemical conversion
technologies to produce low-cost
sugars from lignocellulosic biomass
Pretreatment Reduced severity
Reduced waste
Higher sugar yields
Reduced inhibitors
Reduction in non-fermentable sugars
Enzyme hydrolysis
to sugars
Higher specic activity & thermal tolerance
Reduced product inhibition
Broader substrate range
Cellulases and cellulosomes
Sugar fermentation to ethanol
Develop technologies to produce
fuels, chemicals, and power from
biobased sugars and chemical
building blocks.
Cofermentation of
sugars
C-5 and C-6 sugar microbes
Robust process tolerance
Resistance to inhibitors
Marketable by-products
Consolidated processing
Reduce process steps and
complexity by integrating
multiple processes in single
reactor
Enzyme production,
hydrolysis, and
cofermentation
combined in one
reactor
Production of hydrolytic enzymes,
fermentation of needed products
Process tolerance & stable integrated
traits; All processes combined in a
single microbe or stable culture
T.H. Kim, T.H. Kim / Energy 66 (2014) 13e19 16
hemicellulose [40], and the acetyl group [37,41]. The physical factors
of biomass, suchas crystallinity[38,40], surface area [42,43], particle
size [44], pore size [45], and degree of polymerization[46], have also
been known to inuence enzymatic hydrolysis. Among the many
factors, lignin has been considered the major impediment.
5.3. Various pretreatment technologies
Enzymatic hydrolysis can produce high yields of relatively pure
glucose syrups without generating glucose degradation products,
and utility costs are low since the hydrolysis occurs under mild
reaction conditions [47]. The methodology used to achieve this goal
varies widely depending on the specic application: treatments
with various types of acids, alkaline treatments, steam treatment,
and simple thermal-mechanical treatments. The net effect of the
pretreatment also varies widely in terms of its physical and
chemical characteristics.
As summarized in the Table 2, there have been numerous at-
tempts to enhance the enzymatic reactionegrinding/milling
[46,48], steam/steam explosion [40,49], hot water/autohydrolysis
[50,51], acid treatment [42,45,52], alkali treatment [53,54], and
other methods [55,56].
The various pretreatments are usually designed to make
biomass more susceptible to enzyme hydrolysis by removing lignin
and/or hemicellulose, reducing the cellulose crystalline structure,
and increasing the pore size and surface area. Many kinds of
chemical and physical pretreatment methods have been used to
enhance the enzymatic reaction. Considerable attention has been
devoted to agents that will cause swelling of the cellulose and
disrupt the crystalline structure by cleavage of hydrogen bonds in
cellulose. In chemical pretreatments, there are two ways in which
this may occur; (1) intercrystalline swelling caused by uptake of
water and chemicals between the crystal units, which causes a
reversible volume change of up to about 30 percent, and (2)
intracrystalline swelling, which involves the penetration of the
crystalline structure and can lead to unlimited swelling or complete
solution of the cellulose.
Sodium hydroxide, amines, and anhydrous ammonia have been
used for intercrystalline swelling. In Europe, during World War II,
high concentrations (70e75 percent) of sulfuric acid or fuming
hydrochloric acid and metal chelating solvents were used for
intracrystalline swelling.
Most of the chemical pretreatment methods for improving enzy-
matic digestibility generate hydrolysates containing a mixture of
hexose and pentose sugars and lignin. Usually the hydrolysate from
the pretreatment/fractionation process requires detoxication,
because the microorganisms used in the subsequent fermen-
tation step [57] poorly withstand the inhibitory environment of
lignocellulose-hydrolysates [58e64]. Detoxication of the hydroly-
sates will increase the cost of pentose (xylose) fermentation. This is
a disadvantage that most of chemical treatment methods must
overcome.
5.4. An example of recent progress; low moisture anhydrous
ammonia pretreatment
To date, various pretreatment methods have been suggested to
enhance the enzymatic digestibility and fermentability of lignocel-
lulosic biomass. Although a few of them may be effective, several
cost barriers which prohibit scale-up still exist, including (1) high
chemical input and (2) excessive water use [65]. In order to solve
these problems, a simpler pretreatment method using anhydrous
ammonia has been developed [66]. In order to eliminate the addi-
tional water washing step and to improve the cost-effectiveness of
ammonia pretreatment processes, the LMAA (low moisture anhy-
drous ammonia) pretreatment method was recently suggested [66].
As shown in Fig. 5, this method comprises four steps for ethanol
production; ammoniation, pretreatment, evaporation for excessive
ammonia recovery, and SSF (simultaneous saccharication and
Fig. 4. Factors to be considered in designing of pretreatment method.
Table 2
Various pretreatment technologies and representative reaction conditions (source [52,68e70]).
Methods Reaction condition Features
Dilute acid
(co-current)
130e200

C, high pressure (3e15 atm),
0.1e3.0% sulfuric acid, 2e30 min,
solid loading 10e40%
Most of hemicellulose is solubilized. 20e40% delignication.
Steam explosion Acid impregnation with H
2
SO
4
, SO
2
,
(160e270

C), 1e30 min
70e90% hemicellulose dissolution. 20e40% delignication.
Hot water
(pH controlled)
160e190

C, 20e60 min, high pressure
(6e14 atm), solid loading 5e30%
Most of hemicellulose is solubilized. 30e40% delignication.
Ammonia recycle
percolation (ARP)
150e170

C, 10e20 min, 10e15% ammonia,
high pressure (9e17 atm), solid loading 15e30%
50% hemicellulose dissolution. 70e95% delignication.
Soaking in aqueous
ammonia (SAA)
30e90

C, 4-72 h, 5e30% ammonia,
solid loading 15e30%
10e20% hemicellulose dissolution. 60e70% delignication.
Very mild reaction cond. Simple process scheme.
Low moisture
anhydrous
ammonia
(LMAA)
Ambiente80

C, w72 h, ammonia gas,
no washing, moisture w50%
No washing is required; low liquid loading
(only w50% moisture is enough).
Mild reaction condition.
AFEX 70e90

C, w5 min, high pressure (15e20 atm),
anhydrous ammonia, (solid loading 60e90%)
Hemicellulose remains in solid form. No lignin removal.
Popcorn effect.
Lime (with or
without air)
Lime 25e130

C, 1 he2 months, 0.05e0.15 g
Ca(OH)
2
water)/g of biomass (solid loading 5e20%)
20e40% hemicellulose dissolution, form. 60e80%
delignication, de-acetylation.
Low energy intensity.
T.H. Kim, T.H. Kim / Energy 66 (2014) 13e19 17
fermentation). In the rst step, ammoniation, biomass with 30e
70% moisture was put into contact with anhydrous ammonia in a
simple reactor under mild conditions (near ambient conditions).
After the ammoniation step, biomass was subjected to a simple
pretreatment step at moderate temperatures (40e120

C) for 48e
144 h, which can be carried out in a simple closed plastic bag or
container. In the subsequent SSF step, treated biomass is saccha-
ried and converted into ethanol without a post-washing step.
Although this method enhanced bioconversion yield of the agri-
cultural residues, this alkaline method has not been proven to be
effective for woody biomass such as hardwood or softwood.
The main features of this method include the fact that LMAAwas
designed to reduce energy input and ammonia consumption
signicantly. Pretreatment of biomass with low moisture using
gaseous ammonia leads to short exposure time and can be carried
out under ambient conditions, allowing low capital costs to be
projected. In addition, it has been speculated that ammoniation can
also supply assimilable nitrogen (up to 1.2 weight percent (wt.%) of
dry biomass) for microbial growth in the fermentor using the
treated biomass as substrate [67]. Furthermore, corn stover can
typically be harvested once a year in the fall, but not all of the
harvested corn stover can be converted into the desired products in
the biorenery within a few weeks of harvesting. Long-term stor-
age of the feedstock with minimal destruction of the available
carbohydrates, for example by microbial biodegradation, is highly
desirable. Ammonia has been known to be effective against bac-
teria. It was reported that the antimicrobial effect of ammoniating
allowed long-term storage of biomass with minimal biodegrada-
tion of carbohydrates [68]. Thus, it is suspected that the LMAA
pretreatment method can also be integrated with long-term stor-
age of the biomass feedstock while awaiting processing.
6. Integration of pretreatment into the biomass conversion
process
It is important to look for adequate and abundant sources of
local lignocellulosic biomass from which ethanol can be produced
at a reasonable cost with available resources. If the feedstock is
selected, the pretreatment method should be selected by consid-
ering the biomass characteristics and the overall bioconversion
scheme. In order to design the pretreatment method as a critical
part of the integrated bioconversion process, many factors should
be considered, as shown in Fig. 4.
Some of pretreatment methods such as acid, hot-water, and
steam explosion, designed to improve enzymatic digestibility,
generate hydrolysates containing a mixture of sugars and lignin,
while alkaline pretreatment methods such as ARP (ammonia
recycle percolation), SAA (soaking in aqueous ammonia), AFEX
(ammonia ber explosion) and lime pretreatment solubilize most
lignin and/or part of hemicellulose [69e71]. Soluble lignin present
in the pretreatment liquid is known to inhibit the enzymatic hy-
drolysis and bioconversion processes [37e40,43].
Hydrolysates of common pretreatment processes, especially
pretreatments using various acids and high temperature, also contain
various other toxic compounds that create aninhibitory environment
in which microorganisms cannot sustain the viability required for
efcient bioconversion [58e64]. In addition to toxic compounds,
various chemical reagents used for pretreatment should be removed
or recovered. In order to utilize these soluble sugars, the contami-
nated hydrolysates must be cleaned and detoxied before they are
subjected to microbial fermentation. Pretreatment is a component of
the integrated biomass conversionprocess that has not been tested at
the commercial scale and still requires further development. It is one
of the most important aspects of the overall process, not only tech-
nologically but also economically [69].
7. Conclusion
For several decades, ethanol has been promoted as a promising
alternative fuel for transportation. At present, corn grain and sugar
cane are the primary feedstocks for conventional fuel ethanol
production. However, shifting from edible food crop to non-food
materials will offer great opportunities for the future biorenery
industry because the conventional fuel ethanol market is almost
saturated. It is anticipated that ethanol production with second-
generation biomass on a large scale will be possible in the near
future. A strong focus on the implementation of cellulosic ethanol
production and biorenery will lie on effective deconstruction and
economic conversion process of lignocellulosic biomass.
Acknowledgments
This research was supported by Basic Science Research Pro-
gram through the National Research Foundation of Korea (NRF)
funded by the Ministry of Education (No. 2013R1A1A2010001) and
Human Resources Development program (No. 20134030200230)
of the Korea Institute of Energy Technology Evaluation and Plan-
ning (KETEP) grant funded by the Korea government Ministry of
Trade, Industry and Energy.
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