Cellulose (2009) 16:547–565
DOI 10.1007/s10570-009-9317-x
An economic and environmental comparison
of a biochemical and a thermochemical lignocellulosic
ethanol conversion processes
Thomas D. Foust Æ Andy Aden Æ Abhijit Dutta Æ
Steven Phillips
Received: 20 October 2008 / Accepted: 24 May 2009 / Published online: 10 June 2009
Ó Springer Science+Business Media B.V. 2009
Abstract With the world’s focus on rapidly deploy-
ing second generation biofuels technologies, there
exists today a good deal of interest in how yields,
economics, and environmental impacts of the various
conversion processes of lignocellulosic biomass to
transportation fuels compare. Although there is a
good deal of information regarding these conversion
processes, this information is typically very difficult
to use on a comparison basis because different
underlying assumptions, such as feedstock costs,
plant size, co-product credits or assumed state of
technology, have been utilized. In this study, a
rigorous comparison of different biomass to trans-
portation fuels conversion processes was performed
with standard underlying economic and environmen-
tal assumptions so that exact comparisons can be
made. This study looked at promising second-gener-
ation conversion processes utilizing biochemical and
thermochemical gasification technologies on both a
current and an achievable state of technology in 2012.
The fundamental finding of this study is that although
the biochemical and thermochemical processes to
ethanol analyzed have their individual strengths and
weaknesses, the two processes have very comparable
yields, economics, and environmental impacts.
Hence, this study concludes that based on this
T. D. Foust (&)
A. Aden
A. Dutta
S. Phillips
National Bioenergy Center, National Renewable Energy
Laboratory, Golden, CO 80401, USA
e-mail: thomas_foust@nrel.gov
analysis there is not a distinct economic or environ-
mental impact difference between biochemical and
thermochemical gasification processes for second
generation ethanol production.
Keywords Biofuel
Biochemical

Thermochemical
Biomass
Feedstock
Ethanol

Corn stover
Gasification
Catalyst
Fuel synthesis

Pretreatment
Enzymatic hydrolysis
Fermentation

Energy efficiency
Emission
Inhibitor
Recycle

Mixed alcohol
Introduction
Transportation fuels are almost exclusively made
from crude oil, in fact over 97% of transportation fuel
needs are made from crude oil (Sandalow 2008). To
reduce the dependence on crude oil to meet trans-
portation needs, while simultaneously reducing the
environmental impacts of crude oil usage such as
greenhouse gas emissions, a number of countries and
regions are rapidly developing and deploying biofuels
and have set some very aggressive goals for near-and
long-term deployment. For example, the EU has
mandated that biofuels account for 10% of transpor-
tation fuel use by 2020 (Trostle 2008). Furthermore,
the United States has set both a near term goal of a 20
percent reduction in 2007 gasoline usage by 2017 to
be met predominantly with increased biofuels
123
548
production (US DOE Biomass Multi-Year Program
Plan 2008); as well as a long term ‘‘30 9 30’’ goal to
displace 30% of the 2006 gasoline demand with
biofuels by 2030 (Foust et al. 2007).
Although many countries are rapidly deploying
biofuels worldwide, this is almost exclusively first
generation biofuels technology. Brazil and the United
States are rapidly moving forward with developing
and deploying ethanol technology, with Brazil using
sugarcane as the feedstock and the United States
using corn. Brazilian sugar cane ethanol is generally
regarded as having little to no impact on primary food
supplies and prices, since Brazil has increased its
production of sugar cane to more than offset the
amount of sugar diverted to ethanol production.
However, food supply and price concerns have been
raised about corn ethanol production in the United
States (Mitchell 2008) because corn grain is an
important food and animal feed commodity. The EU,
the largest biodiesel producer, uses rapeseed oil as its
main feedstock and again concerns about fats and oils
supplies and prices have been raised over the
diversion of rapeseed oil to biodiesel production.
Because of these concerns and the overall limita-
tions of first generation biofuels technology primarily
due to competition with feed and food production,
advanced or second generation biofuels technologies
will be required to meet aggressive volume goals for
biofuels deployment (Farrell et al. 2006). A number
of different conversion technologies exist (Farrell
et al. 2006; Rammamorth et al. 2000; Huber et al.
2006) for the conversion of cellulosic biomass to
biofuels. The predominant differentiation between
the conversion options is the primary catalysis system
(Foust et al. 2008). Biochemical conversion routes
rely on biocatalysts, such as enzymes and microbial
cells, in addition to heat and chemicals to convert
biomass first to an intermediate mixed sugar stream
and then to ethanol or other fermentation produced
biofuel. Conversely, thermochemical conversion
technologies rely on heat and/or physical catalysts
to convert biomass to an intermediate gas or liquid,
followed by a conversion step to convert that
intermediate to a biofuel. Thermochemical conver-
sion technologies tend to be grouped in two distinct
categories for fuel production: gasification and pyro-
lysis (Energy production from biomass 2002). Gas-
ification is a complete depolymerization of biomass
with limited oxygen at high temperatures, typically
123
Cellulose (2009) 16:547–565
[850 °C, to a gaseous intermediate (syngas), which
consists of H2 and CO. A good review of the different
types of gasification techniques that exist and their
relative advantages and disadvantages is provided by
Spath and Dayton (2003). Pyrolysis on the other
hand, is the milder depolymerization of biomass
producing a liquid intermediate (pyrolysis oil or ‘‘bio-
oil’’) in the absence of oxygen at lower temperatures,
typically in the range of 400–650 °C. Good reviews
of pyrolysis techniques and the current technical
status of these techniques are provided by Bridgwater
and Peacocke (2000) and Czernik and Bridgwater
(2004).
Each primary technology conversion approach,
biochemical and thermochemical, has its particular
advantages; for example, high selectivity and con-
version efficiencies are advantages commonly cited
for biochemical conversion (Himmel et al. 2007;
Houghton et al. 2005), whereas technology robust-
ness and ability to accept a wide range of feedstocks
are advantages commonly put forward for thermo-
chemical conversion (Milne et al. 1998; Hallen et al.
1998). Although both conversion approaches have
their unique advantages, two main questions are
commonly raised. (1) How do these processes
compare both from a cost of conversion basis and
an efficiency basis both in the near and long term? (2)
How do these processes compare from an environ-
mental impact perspective.
Some work has been done to date to address these
important questions. Wright and Brown (2007)
compared the economics of dry mill ethanol produc-
tion to cellulosic ethanol from a biochemical conver-
sion route (Wooley et al. 1999), as well as biomass
thermochemically converted to methanol (Hamelinck
and Faaij 2002), hydrogen (Williams et al. 1995) and
Fischer-Tropsch diesel (Timensen et al. 2002). They
concluded that based on the current state of techno-
logy, neither the biochemical or thermochemical
approaches had clear cost advantages. Additionally,
they concluded that both approaches for advanced
biofuels production have opportunities to compete
against grain ethanol as corn prices continue to rise.
Zeman (2007) also looked at the merits of biochem-
ical versus thermochemical routes for advanced
biofuel production and although no comparative
economics were presented in this report, Zeman
concluded that marketplace economics should decide
which conversion approaches are utilized. Hamelinck
Cellulose (2009) 16:547–565
and Faaij (2005) looked at which of the biofuel
options have the best potential for the short-term and
best long-term (2030) prospects and what develop-
ments are necessary to improve the performance of
advanced biofuels production and use. There study
summarized and normalized results for methanol,
ethanol, hydrogen and synthetic diesel. They con-
cluded that methanol and FT diesel provide the best
near term potential, with lignocellulosic ethanol
emerging in the near term with hydrogen ultimately
providing the best long-term prospect but requiring
breakthroughs in hydrogen storage technology.
Although these studies address some important
areas in providing economic assessments of advanced
biofuels, significantly more work needs to be done in
this regard since it is critical to the successful
development of advanced biofuels. Investors in
advanced biofuels need credible information to use
as a basis for making investments both in the near-
and long-term and they want assurances that invest-
ments made in biorefineries will remain economically
viable over the long-term. Beyond the straightfor-
ward economics of the conversion comparison issue,
other questions need to be asked. These are: is either
approach better suited for particular feedstocks
(Perlack et al. 2005); is the higher temperature/higher
pressure thermochemical process more capital inten-
sive; and what are the major inhibitors/poisons for
each process? The objectives of this study are to
perform a rigorous economic comparison of a
biochemical and thermochemical lignocellulosic eth-
anol conversion approach on both an operating cost
and capital cost basis. Additionally, this study
investigated yields, thermal efficiencies, and impor-
tant sustainability metrics, such as water usage.
Methods
Biochemical and thermochemical technologies are
clearly not a ‘‘one size fits all’’; many possible
configurations exist for each conversion approach. In
biochemical conversion there are a multitude of
pretreatment approaches (Mosier et al. 2005), as well
as fermentation approaches. In thermochemical con-
version there are a multitude of gasification, as well
as fuel synthesis options (Wender 1996), in addition
to multiple pyrolysis to fuels options. However, in
order to make more direct comparisons between
549
biochemical and thermochemical biofuels, specific
conversion processes need to be chosen for analysis.
For purposes of this study, two peer-reviewed ethanol
models were utilized with the same level of detail and
same basis for design. The biochemical process
design was originally published in 2002 by Aden
et al. (2002) and the thermochemical design was
published in 2007 by Phillips et al. (2007) and
Phillips (2007). These designs were based on targets
deemed to be achievable in the 2012 timeframe. Both
of these designs utilized detailed Aspen Plus simu-
lations to provide the material and energy balance
data using 2000 dry metric tonnes per day of biomass.
Spreadsheet-based discounted cash flow calculations
were also performed for both processes to generate
capital and operating costs. In addition, the lowest
ethanol price required to generate a 10% internal rate
of return (IRR) was calculated. This is also known as
the Minimum Ethanol Selling Price (MESP, $/gallon
ethanol). Detailed descriptions of these two processes
can be found in Aden and coworkers and Phillips and
coworkers reports referenced above. A general over-
view of the respective processes is described next.
Biochemical process
The biochemical design is illustrated in Fig. 1 and
uses a corn stover feedstock. Baled corn stover is
delivered to the plant and the bales are washed and
milled. From there, the stover is loaded to
pretreatment at 30% total solids concentration.
Dilute sulfuric acid is used to solubilize much of
the hemicellulose to soluble sugars during this step.
Pretreatment also serves to disrupt the matrix of
biomass polymeric compounds in order to facilitate
enzymatic cellulose hydrolysis further downstream.
Once pretreated, the hydrolysate is conditioned
using a process known as overliming. The liquor
and solid fractions of the hydrolysate are separated,
and the liquor fraction is conditioned by adding
sufficient lime to raise the pH to 10.0. This serves
to neutralize the acid present and provide further
detoxification. The reaction of lime and sulfuric
acid results in a gypsum precipitate that is sepa-
rated from the process and hauled off as waste. The
conditioned liquor is then reacidified to the proper
pH (determined by the enzyme system) and mixed
with the pretreated solids prior to entering enzy-
matic saccharification.
123
550
Fig. 1 Biochemical
conversion process
In this design, a hybrid hydrolysis and fermenta-
tion (HHF) is utilized. Purchased cellulase enzymes
are added to the saccharification fermentors and the
biomass is loaded at 20% total solids. The mixture is
held at 65 °C for approximately 36 h. At this point,
saccharification is largely but not entirely complete.
The mixture is then cooled to 41 °C and sent to
fermentation, where the rest of the cellulose is
saccharified and Zymomonas mobilis bacteria (Gao
et al. 2002) ferment the sugars to ethanol. The total
saccharification and fermentation residence time is
assumed to be 3 days. CO2 produced from fermen-
tation is scrubbed of organics and vented to the
atmosphere.
The fermented broth is then distilled in a two-
column system to produce azeotropic ethanol. The
azeotrope is then broken using conventional molec-
ular sieve dehydration technology. The stillage from
distillation enters a series of dewatering steps. First,
solid/liquid separation is used to recover the insol-
uble lignin-rich residue. This is sent to a biomass
combustion system onsite where steam and electric-
ity are generated to power the biorefinery. The
overall biorefinery as designed is steam-limited,
therefore excess electricity remains after meeting the
electric needs of the refinery. This is sold to the
power grid for a slight coproduct credit equal to
$0.04/kWh. Once the insoluble residue is separated
and combusted, the remaining liquor is sent through
123
Cellulose (2009) 16:547–565
a triple-effect evaporator system to reduce the
hydraulic load that would otherwise be sent to
wastewater treatment. Much of the evaporated
condensate is recycled back to the front end of the
process while the evaporator syrup is sent to the
combustor. The remaining stillage is then sent to
anaerobic and aerobic wastewater treatment. Treated
water is also recycled within the process.
Thermochemical process
The thermochemical design is illustrated in Fig. 2
and uses a different feedstock than the biochemical
design. Wood chips instead of corn stover are
converted to ethanol and other higher alcohols though
a series of solid-phase and gas-phase reactions. Wood
chips are brought to the plant and then screened,
milled, and dried. The wood is then gasified using a
circulating fluidized bed indirect gasification system.
Biomass char and a small slipstream of unreformed
synthesis gas are combusted and this heat is trans-
ferred to the gasifier through the circulation of hot
sand (olivine) between the two process vessels. The
crude synthesis gas (syngas) is primarily composed of
CO, H2, CO2, CH4, tars, and water.
The tars (including benzene) are then reformed
into useful syngas using a fluidizeable tar reforming
catalyst. De-activated reforming catalyst is separated
from the effluent syngas and regenerated on-line
Cellulose (2009) 16:547–565 551

Fig. 2 Thermochemical
conversion process

similarly to fluidized catalytic cracking (FCC) tech- Table 1 summarizes many of the major discounted
nology used in petroleum refining. The hot syngas is cash flow parameter assumptions used for this
cooled through a series of heat exchange and water analysis. For site-specific projects, these parameters
scrubbing steps. The scrubber removes impurities will often vary depending on a company’s location,
such as particulates and residual tars. This scrubber business practices, desired profit margin, etc. The
water undergoes primary treatment onsite to recover assumptions in Table 1 represent a generalized list of
a portion of the quench water, while the rest is sent values, not tied to any specific site or company.
offsite for further wastewater treatment. The cooled Whereas this design assumes 100% of the financing
syngas is compressed to 435 psi before it enters an to come from equity sources (as opposed to loans), a
amine unit to remove a majority of the acid gases more typical business approach is to fund such a
(CO2, H2S) present. The CO2 is vented to the project with a mixture of debt and equity financing.
atmosphere and the sulfur is captured in its elemental Straight-line depreciation is not used in this analysis.
form using a Klaus-like unit called, LO-CAT. Instead, the IRS Modified Accelerated Cost Recovery
The cleaned and conditioned syngas is further
compressed to the required synthesis pressure and Table 1 Major economic parameters used in the cash flow
sent through a fixed-bed molybdenum-sulfide-based analysis
catalyst to synthesize a variety of mixed alcohols.
Plant life 20 years
After synthesis, the alcohols are cooled and con-
Discount rate 10%
densed away from the unconverted syngas. The
General plat depreciation Modified Accelerated Cost
unconverted syngas is recycled to the tar reformer Recovery System (MACRS)
while the condensed alcohols undergo distillation and General plant recovery period 7 years
purification to recover pure ethanol. Methanol is Steam plant depreciation 150% declining balance
recovered and recycled to the synthesis reactor in Steam plant recovery period 20 years
order to boost ethanol and higher alcohol yields. The Federal tax rate 39%
C3? alcohols are then sold as a co-product based on
Financing 100% equity
an assumed fuel value ($1.15/gallon). In this design,
Construction period 2.5 years
the steam cycle is integrated throughout the process
Working capital 5% of total capital investment
while driving compressors and generating electricity
Start-up time 6 months
as well.

123
552
System (MACRS) was used because it offered the
shortest recovery period and largest tax deductions.
Discussion
Costs—operating and capital
The biochemical and thermochemical ethanol design
reports were completed 5 years apart. As a result,
costs for much of the equipment and raw material
inputs (chemicals, etc.) were developed using differ-
ent year’s dollars. Because of inflation and other
factors, the time value of money for each year
changes. Therefore, it was necessary to put all costs
in the same year’s dollars in order to make them all
more directly comparable. This was done using a
factored indexing approach for capital costs, chem-
ical costs, and labor costs as described by Aden and
coworkers and Phillips and coworkers using well
known cost indices. The cost indices for non-labor
costs have risen significantly since 2003 due to a
variety of international demands for materials and
increased energy costs. For this comparison, all costs
are shown using year $2007.
A direct comparison of the costs is shown in
Table 2 for biochemical and thermochemical ethanol
processes. Process alcohol yields are also shown.
Note that while the feedstocks are different for each
process, identical delivery costs ($46/dry ton) are
assumed. The identical feedstock price assumption
Table 2 Cost comparison between biochemical and thermochemical ethanol production from biomass
Biochemical
Year dollars ($) $2007
Feedstock Corn stover
Minimum ethanol selling price, MESP ($/gallon) $1.33
Total installed cost ($MM) $127
Total project investment ($MM) $220
Delivered feedstock cost ($/dry ton) $46
CoProduct credit Electricity ($0.04/kWh)
CoProduct credit/gallon EtOH $0.09
Ethanol production (MM Gal/yr) 69.3
Total alcohol production (MM Gal/yr) 69.3
Ethanol yield (gal/dry ton feed) 89.7
Total alcohol yield (gal/dry ton feed) 89.7
123
Cellulose (2009) 16:547–565
was made for purposes of this study to keep the two
processes on the same cost basis, in reality markets
will determine actual feedstock costs and they may in
fact be different. The minimum ethanol-selling price
(MESP, $/gallon) is slightly lower for the thermo-
chemical process despite having lower ethanol yields
than the biochemical process. One primary reason for
this is the fact that the total alcohol yield from
thermochemical production is slightly higher than for
biochemical production, and the higher alcohols co-
product returns a larger co-product credit than the
power credit the biochemical process receives. Sub-
tracting the co-product credits from the respective
MESP values results in ethanol costs that are almost
identical, especially within the margin of uncertainty
for these models.
As shown the Total Product Investment of each
process is also substantially similar (within 5%).
Investigating these capital costs in more detail has
revealed that the installation factors used in each
study differ. The biochemical study used individual
installation factors for each separate piece of equip-
ment, whereas the thermochemical study used a
single average factor for the entire process. Also, the
biochemical overall average installation factor was
1.6, whereas the thermochemical average was 2.5.
The installation factors and added capital costs used
in these reports were obtained from multiple sources,
including standard engineering texts and engineering
experience for design and construction of similar
industrial processes (starch-based ethanol and pulp
Thermochemical
$2007
Wood chips
$1.22
$151
$210
$46
Higher Alcohols (C3?) ($1.15/gallon)
$0.21
61.8
72.6
80.1
94.1
Cellulose (2009) 16:547–565 553

Fig. 3 Biochemical costs Capital Recovery Charge Raw Materials & Waste Process Electricity
distributed by process area Grid Electricity Total Plant Electricity Fixed Costs

Biomass 51.1¢

Feed Handling (Included in Price of Purchased Feedstock)

Pretreatment /
Conditioning 24.7¢

Hybrid Hydrolysis
10.4¢
& Fermentation

Cellulase Enzyme 9.9¢

Distillation and Solids

14.9¢
Recovery

Wastewater Treatment 2.4¢

13.0¢ (Net)
Boiler/Turbogenerator
Utilities 5.1¢

Storage 1.3¢ $1.33 MESP

-$0.20 -$0.10 $0.00 $0.10 $0.20 $0.30 $0.40 $0.50 $0.60

Fig. 4 Thermochemical Capital Recovery Charge Catalysts, Raw Materials, & Waste Process Electricity
costs distributed by process Electricity Generated Co-Product Credits Fixed Costs
area
Feedstock 57.3¢

Feed Handling & Drying 14.4¢

Gasification 11.1¢

Tar Reforming; Acid

34.2¢
Gas & Sulfur Removal

Alcohol Synthesis -
Compression 9.7¢

Alcohol Synthesis -
Other -17.8¢ (Net)

Alcohol Separation 4.5¢

Steam System &

Power Generation 5.4¢ (Net)

Cooling Water & Other

Utilities 3.4¢ $1.22 MESP

-$0.30 -$0.20 -$0.10 $0.00 $0.10 $0.20 $0.30 $0.40 $0.50 $0.60 $0.70

and paper). These installation and other economic
factors are being further investigated to determine
what realistic difference might be expected between
the two processes.
The costs are further broken down into respective
process areas as shown in Figs. 3 and 4. For both
cases, the single largest cost component is the
biomass feedstock, though the absolute contribution
in $/gallon differs because of the different ethanol
process yields. In the biochemical process, the lignin
residue boiler and turbogenerator section represents a
huge portion of the overall capital costs; however,
much of this is offset by the heat and power generated
for the process. Therefore, the net cost of this process
area is diminished. The next largest net cost area of
the biochemical process is pretreatment and condi-
tioning, accounting for $0.25/gallon (or 19%) of the
overall cost. Much of this is due to the high capital
cost of the pretreatment reactors needed for dilute
sulfuric acid. For the thermochemical process, the

123
554 Cellulose (2009) 16:547–565

largest cost area is the tar reforming and syngas
conditioning section, which accounts for $0.34/gallon
(or 28%) of the overall cost. Reductions in costs for
pretreatment and syngas cleanup and conditioning
will lead to significant reductions in the overall cost
of ethanol for each process. This also helps to explain
why each of these respective areas is a key focus of
process R&D.
It is important to remember that each of these
respective designs do not represent current techno-
logy, but rather future states of technology that need
to be achieved for the conversion processes to be cost
competitive. For example, the cellulase enzyme cost
in Fig. 1 equates to roughly $0.10/gallon ethanol.
However current estimates (Aden 2008) put today’s
cellulase enzyme systems at least three times this
amount or higher. This context must be kept in mind
when comparing biochemical and thermochemical
processes.
Energy efficiencies
The overall energy efficiencies of each process were
also compared, though direct comparison is somewhat
difficult. Each process was analyzed to compare the
energy available in its products to the maximum energy
available from the biomass feed. However, the bio-
chemical energy analysis was completed using a higher
heating value (HHV) basis and the thermochemical
analysis was completed using a lower heating value
basis (LHV). An HHV basis is convenient for a
biochemical process since there is a lot of liquid water
flowing through the process, and for an HHV basis, the
liquid process water has virtually zero contribution to
the energy potential of any stream, with the exception
of minor sensible heat differences between stream
temperatures and the reference temperature (25 °C).
For the base case thermochemical process the calcu-
lated LHV and HHV basis efficiencies for the overall
process (45.9 and 47.4% respectively) were close and
within 2%. Note that the differences in LHV and HHV
based efficiencies reflect the relative closeness of the
ratios of LHV and HHV of the input biomass and the
product alcohols and not that the LHV and HHV of the
products are very close (they differ by about 10% for
the product alcohols).
Table 3 presents a summary of the energy analysis
for both biochemical and thermochemical processes.
The overall energy efficiency of the thermochemical
process as designed is 47.4% on an HHV basis,
whereas the overall energy efficiency of the bio-
chemical process on an HHV basis is 53.2%.
However, this result is well within the margin of
error for this type of analysis, so essentially both
processes can be considered 50% efficient (±5%)
based on the ratio of the energy content of ethanol
and co-products to the energy content of the
feedstock. For the biochemical process, the energy

Table 3 Overall energy analysis for biochemical and thermochemical ethanol production
Biochemical (HHV-basis) Thermochemical (LHV-basis)
Energy flow Ratio to Energy flow Ratio to
(MMBTU/h) feedstock energy (MMBTU/h) feedstock energy

Energy inlets
Feedstock 1420.7 1.000 1269.7 (wet) 1.000
Air 7.9 0.006 2.3 0.002
Water -7.9 -0.006 -133.4 -0.105
Energy outlets
Ethanol 690.5 0.486 619.1 0.488
Coproduct 63.5 0.045 122.1 (C3? Alcohols) 0.096
Cooling tower 313.5 0.221 17.0 0.013
Flue gas 214.3 0.151 46.2 0.037
Compressor heat – – 178.3 0.140
Heat from air-cooled exchangers – – 222.0 0.175
Other 138.9 0.098 -66.1 -0.052

123
Cellulose (2009) 16:547–565 555

losses from the system are primarily from the cooling
tower and from the flue gas. Ambient losses amount
to 6%. For the thermochemical process, energy losses
from the system come substantially through air-
cooled heat exchangers and from compressor heat
losses. The cooling tower evaporation losses are
much lower than for the biochemical process because
less cooling was required from the cooling water.
This was done in order to minimize overall process
water demand. Flue gas losses were also small
compared to those seen in the biochemical process.
The negative flows seen in the analysis represent
water streams where the temperature is lower than the
reference temperature.
Environmental assessment
The emissions profile for both processes is surpris-
ingly similar. This data is shown in Table 4 for all
solid, liquid, and gaseous emissions from these
processes as designed. Each process has two primary
vapor emissions point sources: a flue gas stream and a

Table 4 Emissions from biochemical and thermochemical ethanol processes

Description Solids Liquid (N/A) Vapor
Gypsum waste Boiler ash Scrubbed fermentation offgas Flue gas

Biochemical
Total flowrate (kg/h) 7,347 4,492 24,013 352,975
Component flowrates (kg/h)
Water 1,261 0 432 68,775
N2 0 0 0 206,380
O2 0 0 196 10,278
CO2 0 0 23,381 65,695
CO 0 0 0 61
CH4 0 0 0 3
NOx 0 0 0 61
SOx 0 0 0 100
Other 452 177 4 1,622
Ash 0 4,287 0 0
Gypsum 5,634 28 0 0
Description Solids Liquid Vapor
Sand and ash Sulfur Wastewater Flue gas CO2 vent

Thermochemical
Total flowrate (kg/h) 1,101 49 528 452,822 23,878
Component flowrates (kg/h)
Water 110 0 528 102,108 0
N2 0 0 0 240,887 0
O2 0 0 0 10,978 0
CO2 0 0 0 80,955 23,878
CO 0 0 0 0 0
CH4 0 0 0 0 0
NOx 0 0 0 122 0
SOx 0 0 0 51 0
Other \1 49 \1 17,721 \1
Sand and ash 991 0 0 0 0

123
556
carbon dioxide vent stream. When totaled, slightly
more CO2 is emitted from the thermochemical process
than the biochemical process. The thermochemical
process also has one liquid stream that is sent to
wastewater for treatment whereas the biochemical
process has wastewater treatment designed onsite.
Both processes also have two solids waste streams.
Each process has an ash stream from combustion. The
higher ash in the biochemical process is reflective of
the fact that corn stover has a higher ash content than
the wood chips used in the thermochemical process.
The thermochemical process has an additional ele-
mental sulfur stream that can be sold as a refined
product, whereas the biochemical process has a
gypsum waste stream that is very impure and must
be disposed of as waste. NREL is examining the use of
ammonium hydroxide instead of lime in the condi-
tioning area (Jennings and Schell 2006), and this
design change would eliminate the gypsum waste.
In addition to the emissions shown in Table 4,
evaporation losses from cooling utilities are about
70,000 kg/h for the thermochemical and 168,000 kg/h
for the biochemical processes, with further scope for
reductions in the biochemical process.
Catalyst inhibitors and poisons
Catalysts for the biochemical process, with the
exception of the dilute sulfuric acid used during
pretreatment, are by definition biological, whereas
the catalysts for the thermochemical process are
synthetic manufactured catalysts. Therefore, the par-
ticular inhibitors and poisons for each system are
significantly different.
Biological catalysts include both the enzymes as
well as the fermenting organisms, which can be yeast
or bacteria. One of the most important inhibitors to the
organisms is acetic acid. This is largely derived from
the raw feedstock itself, particularly the acetyl groups
within the hemicellulosic matrix. There are effective
conditioning methods (ion exchange) and agents (lime,
ammonium hydroxide) for reducing the toxicity of
pretreated biomass hydrolysate; however, these steps
add cost to the process and also have the potential to
reduce sugar yields. Ongoing research is currently
focused on developing a more fundamental under-
standing of what compounds are inhibiting the fer-
mentation organisms for the biochemical process, and
this research is also investigating the origin of these
123
Cellulose (2009) 16:547–565
inhibitors (feedstock or byproduct of processing) and
the mechanisms of inhibition. More specifically,
researchers have begun to explore this issue in detail
by: (1) developing high throughput methods to analyze
hydrolysates for the presence of toxic compounds, (2)
identifying novel interactions between individual
components, (3) determining the mode of action of
toxic compounds individually and in combination, (4)
determining the method by which fermentation micro-
organisms respond to these compounds, and (5) using
this information to craft hypotheses for improved
conditioning methods for hydrolysate and for genetic
manipulation of the fermentation organism to enhance
resistance to the toxic compounds.
Understanding the source and mode of action of
hydrolysate toxic compounds and the means by
which some organisms develop a resistance to these
compounds (Pienkos and Zhang 2008) is important so
that effective conditioning approaches can be devel-
oped to reduce this toxicity. Synergies have been
detected in simple combinations of known inhibitors,
and the ability to test for toxic effects in a high
throughput manner will allow the identification of
more complex combinations of individual com-
pounds or fractions. Systematic studies (Zhang and
Nagle 2008) have also been conducted to analyze the
chemical composition of the hydrolysates and to
correlate them against organism growth kinetics. The
chemical analysis of hydrolysates, including both
organic and inorganic compounds, has revealed
compositional differences between the ammonia
hydroxide conditioned and overlimed hydrolysates,
indicating that the mechanism of inhibitor removal is
different for these two conditioning methods. Inor-
ganic salts/ions primarily due to their high concen-
tration after conditioning, along with the sugar
degradation products and acetic acid, have been
shown to be important contributors to the toxicity of
hydrolysate on microbial growth. Data suggests that
either inorganic or organic compounds can be the
dominant contributor to this toxicity, depending on
their relative concentrations.
In the thermochemical process, the tar reforming
catalyst is utilized to reform the tars to additional
syngas. The assumed catalyst is nickel-based, and
therefore is extremely susceptible to sulfur com-
pounds, such as H2S. Chlorine ions can also be
inhibitory or toxic to these catalysts as well. These
inhibitors are also largely derived from the feedstocks
Cellulose (2009) 16:547–565 557

being used. Ongoing research activities are geared Table 5 Typical dry basis percent compositions of corn stover
towards minimizing the effects of sulfur and other and hardwood
compounds that may deactivate the catalysts. One Component Corn Yellow poplar
approach that is being explored is the use of sulfur stover (hardwood)
sorbents for in-line use to reduce the concentration of
Glucan 37.4 42.67
sulfur that the catalyst sees (Torres et al. 2007).
Xylan 21.1 19.05
Another synergistic approach that is being investi-
Lignin 18.0 27.68
gated (Albertazzi et al. 2007) is to determine the
Ash 5.2 1.0
exact mechanism of deactivation and given this
Acetate 2.9 4.64
information make the determination if it is reversible
Protein 3.1
or irreversible deactivation. In other words, research-
Extractives 4.7
ers are determining the regeneration capacity of these
Arabinan 2.9 0.79
catalysts in the presence of sulfur and other
inhibitors. Galactan 2.0 0.24
In prior research, catalytic deactivation models Mannan 1.6 3.93
with residual activity were developed and evaluated Unknown soluble solids* 1.1
based on experimentally measured changes in con- Moisture 15.0% 47.98%
version efficiencies as a function of time on stream * Indicates that the compound ‘‘unknown soluble solids’’ is
for the catalytic reforming of tars, benzene, methane, something not measured experimentally, but is used within the
and ethane (Bain et al. 2005). Both first- and second- model to close material balance of the dry wt biomass to 100%
order models were evaluated for the reforming Italicized values helps to separate the assumed moisture
content of the feedstock from the rest of the dry weight
reaction and for catalyst deactivation. Comparison composition
of experimental and modeling results showed that the
reforming reactions were adequately modeled by compositions of corn stover compared to yellow
either first-order or second-order global kinetic poplar. There are other more potent inhibitors present
expressions. in smaller quantities, such as aromatic aldehydes and
The mixed alcohols synthesis catalyst; however, is C6 to C9 organic acids (McMillan 1994). High
not poisoned by sulfur. In fact, the molybdenum concentrations of salts and metal ions in the feedstock
sulfide (MoS2)-based catalyst that was assumed for also inhibit fermentation. Other fermentation inhibi-
this study must actually be sulfided in order to tors, such as hydroxy-methyl-furfural (HMF) and
maintain activity. Less is known about what specific furfural are formed by the degradation of sugars
compounds are inhibitory to these catalysts. What is during the pretreatment process are a function of the
known is that compounds such as CO2 and CH4, can conversion process and can be reduced by process
act either as diluents or can reduce the alcohol yields modifications and are hence not directly related to
if present in sufficient quantities or partial pressures. feedstock composition. Besides inhibitors, other com-
positional aspects can also influence the processing,
Feedstock considerations e.g., softwoods (pine) contain considerably higher
amounts of mannan than hardwoods (hybrid poplar)
It is important to choose the correct process techno- (Wyman 1996). The mannan needs to be converted to
logy to make the best of the variations in feed ethanol in order to increase process yields. This is
compositions. Depending on the conversion process, usually not a problem, considering that even common
physical and chemical characteristics of the feedstock Baker’s yeast can ferment mannose to ethanol.
can lead to the formation of compounds that are Biomass composition also affects thermochemical
detrimental or inhibitory to the conversion process. processing, albeit in a different manner. Gasification
For example, acetic acid derived from acetylated converts the organic portion of biomass into syngas,
pentosans (e.g., xylan) in hemicellulose is usually the hydrocarbons and some tars. The inorganics, predom-
most abundant inhibitor for biochemical processing. inantly salts and alkaline earth metals, are carried
Acetyl groups are more abundant in hardwoods through as ash. The presence of ash will increase
compared to corn stover. Table 5 shows the conversion costs even after the cost of the feedstock is

123
558
adjusted for the weight of the ash (Aden et al. 2002).
Ash content in corn stover is significantly higher than
in wood; wood is the preferred feedstock for thermo-
chemical conversion in this respect. The ability of
thermochemical processes to convert the lignin
portion of the biomass to liquid fuels, also points to
advantages of converting wood, which has higher
lignin content. Sulfur content in feedstock is detri-
mental to catalysts for tar reforming and alcohol
synthesis. Although a considerable amount of work is
focused on making tar-reforming catalysts more
sulfur tolerant (Sato and FujiMoto 2007; Nishikawa
et al. 2008) the task becomes more difficult with
increased amounts of sulfur in the feed. Results from
ultimate analysis have shown that sulfur contents are
2–8 times higher in corn stover compared to wood (Yu
et al. 2007). The higher sulfur content in corn stover
makes it more difficult to process thermochemically.
Process designs should factor the anticipated
variations in feedstock. More specifically, if a
thermochemical plant will handle only woody feed-
stocks it can get away with catalysts with lower sulfur
tolerance and minimal sulfur removal mechanisms.
There usually are inherent advantages of using either
the biochemical or thermochemical process for a
chosen feedstock. This should be recognized before
picking a process. The details of the processing steps
will also be determined by the specifics of the range
of expected feedstock variability.
Integration and recycle
There are two key design elements that have been
applied to both the biochemical and thermochemical
processes utilized for this study: (1) energy self-
sufficiency and integration, and (2) significant pro-
cess recycle. These are very important aspects that
improve energy efficiency, reduce process costs, and
enable both processes to be more sustainable.
In the biochemical process, energy self-sufficiency
comes from combusting lignin-rich residue to gener-
ate steam and electricity for the biorefinery. Sufficient
residue exists to fully meet the heating and electric
demands of the plant. In the thermochemical process,
a slipstream of unreformed syngas is combusted
(along with the char from the gasifier) to provide the
entire energy needs of the biorefinery. While this
slightly lowers the overall ethanol yields, it does
eliminate the need to purchase fossil-derived energy
123
Cellulose (2009) 16:547–565
sources. Pinch analysis was used to develop an
integrated system of heat exchangers that generate
process steam and increase the overall energy
efficiency of the process.
Process recycle is employed in the biochemical
process mostly in the form of water recycle. In fact,
process water recycle is crucial for both processes in
order to minimize the overall water demand of the
biorefinery. In the biochemical process, a number of
unit operations are used to dewater and purify process
streams, including pressure belt filters, triple-effect
evaporators, and onsite water treatment (anaerobic
and aerobic). This water is then recycled back to
various locations within the process, including pre-
treatment and enzymatic hydrolysis. Similar water
recycle techniques are also used in conventional
biofuels processes that utilize corn grain to provide
what are known as ‘‘net zero discharge’’ designs.
Because of this significant process water recycle, most
of the water demand for biochemical processes is
actually makeup to compensate for losses from
utilities instead (Aden 2007). The biochemical pro-
cess as currently designed uses 6 gallons of water per
gallon of ethanol produced, which is approximately
twice as high as commercial corn ethanol. However,
water optimization has not been employed for this
process and several opportunities for water reduction
have been identified. For the thermochemical process,
water reduction strategies have been implemented,
which have successfully brought water use below
2 gallons per gallon of ethanol. Water reduction and
optimization will be key aspects of the updated
biochemical design report to be completed for the
DOE Office of the Biomass Program by mid-2009.
Recycled materials in the thermochemical process
are primarily unconverted syngas and methanol. The
unconverted syngas leaving the mixed alcohol syn-
thesis reactor can be used in a variety of ways. It can
be combusted to generate process heat, recycled to the
throat of the fuel synthesis reactor, or recycled to the
gasifier or tar reformer. Recycling the unconverted
syngas back across the tar reformer has several
advantages including avoiding the buildup of methane
in the process and producing higher overall yields.
Biofuels other than ethanol
Whereas many feedstocks are appropriate for both
conversion processes, there are also many different
Cellulose (2009) 16:547–565
biofuels that can be produced from both processes as
well. Alcohols (methanol, ethanol, butanol, mixed
alcohols) can be made from either process. Hydro-
carbon fuels can also be manufactured both biochem-
ically and thermochemically. Companies such as LS9
and Amyris Biotechnologies have recently developed
processes for biological production of these hydro-
carbons, while thermochemical production of hydro-
carbons, through Fischer-Tropsch and other
chemistries, have been known and researched for
decades. The analysis presented in this paper is
specific to ethanol and since conversion processes are
somewhat unique to the biofuel produced, it is not
reasonable to draw general conclusions about the
overall economics of biochemical and thermochem-
ical conversion processes for biofuels production
from the results of this study.
Technical barriers towards achieving analyzed states
of technology
As stated earlier, the comparison cases for both the
biochemical and thermochemical do not represent the
current state of technology, but instead a near-term
state of technology that could be achieved with an
aggressive applied R&D program. When any target is
Fig. 5 Cost sensitivity
analyses for biochemical
conversion
559
not met, the cost of the overall conversion process is
affected to various degrees. Sensitivity analyses have
been performed (Foust et al. 2007) on the cost
impacts on the individual targets and are shown in
Figs. 5 and 6 for the biochemical and thermochem-
ical process respectively. Market and financial cost
sensitivities are also included for completeness. For
both the biochemical and thermochemical cases these
cost sensitivity analyses show that for the technical
targets, it is not a single area that dominates but rather
a number of areas that combine to have a significant
impact on the overall cost effectiveness of the
processes. This is in contrast to the market and
financial sensitivities where clearly plant size and
required Return on Investment (ROI) have the
overwhelming effect on the overall process cost.
Foust et al. (2007) outlined a research plan aligned by
key barriers to achieve and demonstrate at the pilot
plant scale the states of technology outlined in Aden
and coworkers and Phillips and coworkers for
biochemical and thermochemical conversion, respec-
tively. Conversion costs can be reduced by increasing
efficiencies or reducing capital costs recognizing that
these two factors are highly interrelated.
Based on this cost sensitivity analyses, R&D
programs need to address all of these areas in an
123
560 Cellulose (2009) 16:547–565

Fig. 6 Cost sensitivity Recycling Unconverted Syngas to Synthesis Reactor (25%:0%:0%)

Catalyst cost ($2.50:$5.25:$2,250 per lb)
analyses for Catalyst Poison Allowability (100:50:10 ppm)
Catalyst Lifetime (10 yrs:5yrs: 1 yr)
thermochemical conversion Total Alcohol Catalyst Productivity (1,000:600:200 g/kg-cat/hr)
Operating Pressure (800:1000:2,000 psia)
Research
CO Selectivity to Alcohols (95%:90%:70%)
Single Pass CO conversion (80%:60%:30%)

Level of CO2 removal (10:5:0.1 mol%)

Acid Gas Removal Costs (-10%:baseline:+100%)
Tar Reformer Equipment Costs (-10%:baseline:+100%)
Combined Tar Reformer Conversions
Tar Reformer Tar Conversion (99.9%:99.9%:95%)
Tar Reformer Benzene Conversion (99.9%:99%:90%)
Tar Reformer Methane Conversion (95%:80%:50%)

Olivine cost (1/10:baseline:10X)

Reduced CH4 to CO (baseline:baseline:25%)

Feed Moisture Content (15%:50%:70%)

Sulfur Content (Baseline to 4X)
Feedstock Quality - Ash (1%:1%:12%)
Feedstocks (Lignin:wood:Corn Stover)
Feedstock Cost ($10:$35:$53 per dry ton)

Loan vs. Equity Financing (100% debt @ 7.5%:100% Equity:100% Equity)

Financial / Market
Return on Investment (0%:10%:30%)
Contingency (0%:3%:15% of TIC)
Average Installation Factors (-10%:baseline:+30%)
Total Project Investment (-10%:baseline:+30%)

Plant Size (10,000:2000:600 dry tonnes/day).

Co-Product Values (69% Chemical Market:baseline:Fuel Oil Value)
($0.50) ($0.25) $0.00 $0.25 $0.50 $0.75 $1.00 $1.25 $1.50

Fig. 7 Process schematic

for biochemical conversion

integrated manner to ensure the highest probability of
success in achieving the required state of technology
for cost competitiveness. Following is a brief
description of the major areas that need to be
addressed.
Biochemical conversion
Achieving the assumed level of technology perfor-
mance will require additional technology advance-
ment in the key areas of pretreatment, enzymatic
hydrolysis, and fermentation processes. Figure 7
depicts the overall biochemical conversion process
and the technical barrier areas that will need to be
addressed for each particular unit operation to
achieve the target state of technology used in this
study. The following sections highlight the research
and development needed to address the technical
barriers for the individual unit operations as well as
the integration challenges for the overall conversion
process.
Pretreatment and hydrolysate conditioning
The main functions of pretreatment are to hydrolyze
the hemicellulose structural polysaccharides to oligo-
meric and monomeric sugars, and to condition the
cellulose to make it more susceptible to cellulase
enzymatic digestion. Ideally, pretreatment processes
accomplish these objectives at the highest solids
loadings possible to maximize capital utilization and
at the mildest possible process conditions to mini-
mize sugar degradation and the need for conditioning.
Aden et al. identified overliming as the most

123
Cellulose (2009) 16:547–565
promising conditioning process for the hydrolyzate
for dilute acid pretreatment. Although effective,
overliming is problematic because it requires an
associated solid–liquid separation step that increases
both capital and operating costs; it also leads to
significant sugar losses. There are other hydrolysate
conditioning processes under development, i.e.,
ammonia conditioning (Phillips 2007) that signifi-
cantly reduce sugar losses when compared to over-
liming and show promise for not requiring an
associated solid–liquid separation step. Ideally, the
need for conditioning could be eliminated altogether
by reducing the severity of pretreatment and/or
increasing the robustness of fermentation organisms.
There are some pretreatments under development
(Lau et al. 2008) that show considerable promise for
eliminating or greatly reducing the need for extensive
conditioning that would be very beneficial both from
a capital and operating cost, as well as an overall
process simplicity perspective. These reduced sever-
ity pretreatments tend to produce more of the
hemicellulose sugars as oligomers versus monomers
for the higher severity pretreatments, thus developing
low-cost hemicellulase enzymes, such as exo-xylan-
ases to hydrolyze these oligomers to monomers will
be required (Selig et al. 2008).
Enzymatic production and hydrolysis
Although considerable progress has been made to
date on reducing the cost of cellulase enzymes (Terter
et al. 2006; Genecor and release 2004) much more
needs to be done in this regard to achieve the target
state of technology used in this study. There are two
research paths that need to be pursued to reduce
enzyme costs: increase enzyme-specific activity and
decrease the enzyme production costs. Although both
research paths are necessary to accomplish the
enzyme cost reduction goals, the development of
enzymes with increased specific activities provides
the added benefit of reducing saccharification time,
which increases capital utilization.
Fermentation
Developing a robust, commercially available micro-
organism (yeast or bacteria) capable of fermenting
both the 5- and 6- carbon biomass sugars to ethanol is
a major barrier that needs to be overcome. Significant
561
progress has been made in this regard and there are a
number of microorganisms under development for
fermenting biomass mixed sugars to ethanol. The
target state of technology in Aden et al. (2002) has a
fermentation organism that converts 95% of glucose
and 85% of all hemicellulose sugars to a minimum
six percent ethanol titer in 3 days in a combined
hybrid saccharification and fermentation.
Integration/process engineering R&D
It is important that all the unit operations integrate into
an efficient overall conversion process. Whereas
performance targets for individual unit operations
are defined as levels of conversion at specific condi-
tions, overall integration targets are defined as overall
cost, both capital and operating, efficiency and
availability. Ideally, the overall conversion process
is as simple as possible and robust providing maxi-
mum availability.
Thermochemical conversion
The thermochemical conversion case assumed in the
Phillips et al. (2007) study utilizes indirect gasifica-
tion as the gasification approach. Although very
attractive from a cost and efficiency perspective,
indirect gasification faces some significant challenges
for syngas quality. Achieving the target state of
technology used in this study requires additional
technology advancement in key areas of gas cleanup,
conditioning and fuels synthesis. Figure 8 depicts the
overall thermochemical conversion process and the
technical barrier areas that will need to be addressed
for each particular unit operation to achieve the target
state of technology used in this study. The following
sections describe the R&D needed to overcome these
barriers for the individual unit operations as well as
the overall integrated conversion process.
Gasification
Mixed alcohol synthesis, like most gas to liquid
processes, is very sensitive to gas quality and
composition. Although indirect gasification in gen-
eral looks very good for economically producing
syngas at large scales, it has the problem of producing
relatively high amounts of tars in the gas stream
(Zwart and Boerrigter 2005). Although there have
123
562
Fig. 8 Thermochemical
conversion process and
technical barrier areas
been a number of studies on the amounts and types of
tars formed during biomass indirect gasification
(Carpenter et al. 2007; Nunes et al. 2008), surpris-
ingly little has been done to understand the processes
that lead to tar formation. Fundamental heat and mass
transfer as well as tar kinetic mechanistic studies are
required for developing a better understanding of how
tars are formed; this can lead to the ultimate goal of
designing indirect gasifiers that produce lesser
amounts of tars.
Gas cleanup and conditioning
Although water quench is an effective approach for
removing tars and other particulates from the syngas,
it is highly problematic from both efficiency and
waste disposal perspectives. Additionally, steam
methane reforming of methane and other light
hydrocarbons adds an additional step that is undesir-
able from both a cost and operational simplicity
perspective. Therefore, consolidated tar and light
hydrocarbon catalytic reforming into additional syn-
gas in a single step is highly desirable from a number
of perspectives. Although a number of catalysts exist
that show these types of activities they tend to
deactivate fairly quickly in the sulfur environments
that are typically seen for biomass gasification
(Magrini-Bair et al. 2007). The challenge is to
develop catalysts and/or regeneration protocols that
maintain high tar and light hydrocarbon reforming
activities over extended operating periods.
123
Cellulose (2009) 16:547–565
Mixed-alcohol synthesis
The commercial success of mixed-alcohol synthesis
has been limited by poor selectivity and low product
yields. Single-pass yields are on the order of 10%
syngas conversion (38.5% carbon monoxide conver-
sion) to alcohol, with methanol typically being the
most abundant alcohol produced (Wender 1996;
Herman 2000). Improvements in mixed-alcohol syn-
thesis catalysts that increase alcohol yields and the
selectivity of ethanol are needed. These catalyst
improvements would have the added benefit of
improving the overall economics of the process by
requiring fewer syngas recycling loops and thus
facilitate better efficiencies of the overall process.
Integration and demonstration
For any sophisticated conversion process, combining
individual unit operations into a complete, integrated,
efficient process is a significant challenge. As is the
case for the biochemical conversion process, the
integration challenge is to design and validate a
conversion process that affords maximum efficiencies
and operational robustness.
Conclusion
This study performed a rigorous comparison of a
biochemical and thermochemical biomass to biofuels
Cellulose (2009) 16:547–565
process. In order that this could be an ‘‘apples to
apples’’ comparison, ethanol was the chosen biofuel
in both cases. Additionally every attempt was made
to make this as identical comparison as possible
including identical plant sizes, and financial assump-
tions were utilized. It is shown that the overall
economics of the two processes are very similar. The
biochemical case has a slightly higher Total Product
Investment and MESP, but lower co-product credit
dependence. On a macro sense there is essentially no
discernable difference between the two cases on an
overall cost basis. However, the individual cost
components are quite different in the two cases. On
an energy efficiency basis, these processes are
essentially the same when the energy credits for the
co-products are factored in. This is also true from an
environmental perspective with very similar emission
profiles for both conversion processes. Therefore,
from an overall cost, efficiency, and environmental
perspective, these two biomass conversion processes
analyzed here are essentially similar within the
margin of error.
However, when feedstock choices and fuel
choices are included in the analysis, there are
considerable differences in the two processes. Her-
baceous feedstocks seem particularly well suited for
biochemical conversion and present some significant
challenges for the thermochemical conversion case,
primarily due to the high sulfur content. Conversely,
whereas softwood feedstocks are well suited for
thermochemical conversion, they present some chal-
lenges for biochemical conversion. Additionally,
some major differences in the two processes arise
when fuel choice is factored into the analysis. For
butanol production, biochemical conversion routes
appear to be well suited but hydrocarbon fuel
production tends to favor the thermochemical con-
version routes.
Ultimately, processors should consider feedstock
availability and market choices when making the
decision whether to pursue a biochemical or a
thermochemical conversion route and, indeed, there
should be a role for both in advanced biofuel
deployment.
Acknowledgments The work was supported by the US DOE
Office of the Biomass Program.
563
References
Aden A (2007) Water use in current and future biofuels pro-
cesses. Southwest Hydrology Magazine, vol 6/No 5,
September/October 2007. University of Arizona
Aden A (2008) Biochemical production of ethanol from corn
stover: 2007 state of technology model, NREL/TP-510-
43205, Golden. http://www.nrel.gov/docs/fy08osti/43205.pdf
Aden A, Ruth M, Ibsen K, Jechura J, Neeves K, Sheehan J,
Wallace B, Montague L, Slayton A, Lukas J (2002) Ligno-
cellulosic biomass to ethanol process design and economics
utilizing co-current dilute acid prehydrolysis and enzymatic
hydrolysis for corn stover. NREL/TP-510-32438, Golden.
http://www.nrel.gov/docs/fy02osti/32438.pdf
Albertazzi S, Basile F, Brandin J, Einvall J, Fornasari G,
Hulteberg C, Sanati M, Trifiro F, Vaccari A (2007) Effect
of fly ash and H2S on a Ni-based catalyst for the
upgrading of a biomass-generated gas. Biomass Bioener-
gy 32(4):345–353. doi:10.1016/j.biombioe.2007.10.002
Bain R, Dayton DC, Carpenter DL, Czernik SR, Feik CJ,
French RJ, Magrini-Bair KA, Phillips SD (2005) Evalu-
ation of catalyst deactivation during catalytic steam
reforming of biomass-derived syngas. Ind Eng Chem Res
44(21):7945–7956. doi:10.1021/ie050098w
Bridgwater AV, Peacocke GVC (2000) Fast pyrolysis pro-
cesses for biomass. Renew Sustain Energy Rev 4(1):1–73
Carpenter DL, Deutsch SP, French RJ (2007) Quantitative
measurement of biomass gasifier tars using a molecular-
beam mass spectrometer: comparison with traditional
impinger sampling. Energy Fuels 21(5):3036–3043. doi:
10.1021/ef070193c
Czernik S, Bridgwater AV (2004) Overview of applications of
biomass fast pyrolysis oil. Energy Fuels 18(2):590–598
Energy production from biomass (2002) Part 2: conversion
technologies. Bioresour Technol 83(1):47–54
Farrell AE, Plevin RJ, Turner BT, Jones AD, O’Hare M,
Kanman DM (2006) Ethanol can contribute to energy and
environmental goals. Science 311:506–509. doi:
10.1126/science.1121416
Foust TD, Wallace R, Wooley R, Sheehan J, Ibsen K, Dayton
D, Himmel M, Ashworth J, McCormick R, Hess JR,
Wright C, Radtke C, Perlack R, Mielenz J, Wang M,
Synder S, Werpy T (2007) A national laboratory market
and technology assessment of the 30 9 30 scenario.
Technical Report, NREL/TP-510-40942
Foust TD, Ibsen KI, Dayton DC, Hess JR, Kenney KE (2008)
The biorefinery. In: Himmel ED (ed) Biomass recalci-
trance, deconstructing the plant cell wall for bioenergy,
Chap. 2. Blackwell Publishing
Gao Q, Zhang M, McMillan JD, Kompala DS (2002) Char-
acterization of heterologous and native enzyme activity
profiles in metabolically engineered Zymomonas mobilis
strains during batch fermentation of glucose and xylose
mixtures. Appl Biochem Biotechnol 98–100:341–355.
doi:10.1385/ABAB:98-100:1-9:341
Genecor, NREL press release (2004) Available from: http://
www.genecor.com/cms/connect/genecor/media_relations/
news/archive/2004/gen_211004_en.html
123
564
Hallen RT, Sealock LT, Cuello R, Bridgwater AV (1998) In:
Kuester JL (ed) Research in thermochemical biomass
conversion. Elsevier, London
Hamelinck CN, Faaij A (2002) Future prospects for production
of methanol and hydrogen from biomass. J Power Sources
111:1. doi:10.1016/S0378-7753(02)00220-3
Hamelinck CN, Faaij APC (2005) Outlook for advanced bio-
fuels. Energy Policy 34(17):3268–3283. doi:
10.1016/j.enpol.2005.06.012
Herman RG (2000) Advances in catalytic synthesis and utili-
zation of higher alcohols. Catal Today 55(3):233–245.
doi:10.1016/S0920-5861(99)00246-1
Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR,
Brady JW, Foust TD (2007) Biomass recalcitrance:
engineering plants and enzymes for biofuels productions.
Science 315:804–807
Houghton J, Weatherwax S, Ferrell J (2005) Breaking the
biological barriers to cellulosic ethanol: a joint research
agenda, biomass to biofuels, Rockville, 7–9 Dec 2005 (to
order the report http://genomicsgtl.energy.gov/biofuels/
b2workshop.shtml#orderform)
Huber GW, Iborra S, Corma A (2006) Synthesis of transpor-
tation fuels from biomass: chemistry, catalysts, and
engineering. Chem Rev 106:4044–4098. doi:10.1021/
cr068360d
Jennings E, Schell D (2006) Evaluate alternative conditioning
technology with the potential to eliminate sugar losses,
NREL Internal Report (submitted)
Lau MW, Dale BE, Balan V (2008) Ethanolic fermentation of
hydrolysates from ammonia fiber expansion (AFEX)
treated corn stover and distillers grain without detoxifi-
cation and external nutrient supplementation. Biotechnol
Bioeng 99(3):529–539. doi:10.1002/bit.21609
Magrini-Bair KA, Czernik S, French R, Parent YO, Chornet E,
Dayton DC, Feik C, Bain R (2007) Fluidizable reforming
catalyst development for conditioning biomass-derived
syngas. Appl Catal Gen 318:199–208. doi:10.1016/
j.apcata.2006.11.005
McMillan JD (1994) Conversion of hemicellulose hydrolyzates
to ethanol. In: Himmel ME, Baker JO, Overend RA (eds)
Enzymatic conversion of biomass for fuels production,
ACS Symposium Series 556, American Chemical Society,
Washington, DC, pp. 411–437
Milne TA, Evans RJ, Abatzoglou N (1998) Biomass gasifier
tars: their nature, formation and conversion; Report No.
NREL/TP-570-25357, National Renewable Energy Lab-
oratory: Golden. http://www.osti.gov/bridge
Mitchell D (2008) A note on rising food prices. Policy
Research Working Paper 4682, The World Bank Devel-
opment Prospects Group
Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple
M, Ladisch M (2005) Features of promising technologies
for pretreatment of lignocellulosic biomass. Bioresour
Technol 96:673–686. doi:10.1016/j.biortech.2004.06.025
Nishikawa J, Nakamura K, Asadullah M, Miyazawa T, Kuni-
mori K, Tomishige K (2008) Catalytic performance of Ni/
CeO2/Al2O3 modified with noble metals in steam gasi-
fication of biomass. Catal Today 131(1–4):146–155. doi:
10.1016/j.cattod.2007.10.066
Nunes SM, Paterson N, Herod AA, Dugwell DR, Kandiyoti R
(2008) Tar formation and destruction in a fixed bed
123
Cellulose (2009) 16:547–565
reactor simulating downdraft gasification: optimization of
conditions. Energy Fuels 22(3):1955–1964. doi:10.1021/
ef700662g
Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes
BJ, Erbach DC (2005) Biomass as a feedstock for a bio-
energy and bioproducts industry: the technical feasibility
of a billion-ton annual supply, DOE/GO-102005-2135.
Oak Ridge National Laboratory, Oak Ridge
Phillips SD (2007) Technoeconomic analysis of a lignocellu-
losic biomass indirect gasification process to make ethanol
via mixed alcohols synthesis. Ind Eng Chem Res
46(26):8887–8897. doi:10.1021/ie071224u
Phillips S, Aden A, Jechura J, Dayton D, Eggeman T (2007)
Thermochemical ethanol via indirect gasification and
mixed alcohol synthesis of lignocellulosic biomass.
NREL/TP-510-41168, Golden. http://www.nrel.gov/docs/
fy07osti/41168.pdf
Pienkos PT, Zhang M (2008) Assemble comprehensive liter-
ature review on hydrolysate toxicity issue. NREL Internal
Report (submitted)
Rammamorth R, Kastury S, Smith WH (2000) Bioenergy:
vision for the new millennium. Science Publishers,
Enfield
Sandalow D (2008) Freedom from oil: how the next president
can end the United States’ oil addiction, McGraw Hill,
ISBN-13: 978-0-07-148906-5
Sato K, FujiMoto K (2007) Development of new nickel based
catalyst for tar reforming with superior resistance to sulfur
poisoning and coking in biomass gasification. Catal
Commun 8(11):1697–1701. doi:10.1016/j.catcom.2007.
01.028
Selig MJ, Knoshaug EP, Decker SR, Baker JO, Himmel ME,
Adney WS (2008) Heterologous expression of Aspergillus
niger B-D-Xylosidase (XlnD): characterization on ligno-
cellulosic substrates. Appl Biochem Biotechnol 146:57–
68. doi:10.1007/s12010-007-8069-z
Spath PL, Dayton DC (2003) Preliminary screening—technical
and economic assessment of synthesis gas to fuels and
chemicals with emphasis on the potential for biomass-
derived syngas. NREL/TP-510-34929. National Renew-
able Energy Laboratory, Golden
Terter SA, Xu F, Nedwin GE, Cherry JR (2006) Enzymes for
biorefineries, Chap. 16. In: Kamm B, Gruber PR, Kamm
M (eds) Biorefineries-industrial processes and products
status quo and future directions, vol 1, Verlag Gmbh and
Co., Wiley-VCH, Weinheim, Gemany
Timensen JAM, Faaij APC, Hemelinck CN (2002) Exploration
of the possibilities for production of Fischer-Tropsch
liquids and power via biomass gasification. Biomass
Bioenergy 23:129. doi:10.1016/S0961-9534(02)00037-5
Torres W, Pansare SS, Goodwin JG (2007) Hot gas removal of
tars, ammonia and hydrogen sulfide from biomass gasifi-
cation gas. Catal Rev Sci Eng 49(4):407–456
Trostle R (2008) Global agricultural supply and demand: fac-
tors contributing to the recent increase in food commodity
prices, USDA—a report form the Economic Research
Service, WRS-0801
US DOE Biomass Multi-Year Program Plan (2008) Office of the
biomass program, energy efficiency and renewable energy,
U.S. DOE. http://www1.eere.energy.gov/biomass/pdfs/
biomass_program_mypp.pdf
Cellulose (2009) 16:547–565
Wender I (1996) Reactions of synthesis gas. Fuel Process
Technol 48(3):1041–1048. doi:10.1016/S0378-3820(96)
01048-X
Williams RH, Larson ED, Katofsky RE, Chen J (1995)
Methanol and hydrogen from biomass for transportation,
with comparisons to methanol and hydrogen from natural
gas and coal. PU/CEES Report 292, Center for Energy
and Environmental Studies, Princeton University,
Princeton
Wooley R, Ruth M, Glassner D, Sheehan J (1999) Process
design and costing of bioethanol technology: a tool for
determining the status and direction of research and
development. Biotechnol Prog 15:794. doi:10.1021/
bp990107u
Wright MM, Brown RC (2007) Comparative economics of
biorefineries based on the biochemical and thermochem-
ical platforms. Published online in Wiley InterScience
(www.interscience.wiley.com). Biofuels, Bioproducts Bio-
refining 1:49–56. doi 10.1002/bbb.8
565
Wyman CE (1996) Handbook on bioethanol: production and
utilization. Applied Energy Science Technology Series.
Taylor and Francis
Yu F, Deng SB, Chen P, Liu YH, Wan YQ, Olson A, Kittelson
D, Ruan R (2007) Physical and chemical properties of
bio-oils from microwave pyrolysis of corn stover. Appl
Biochem Biotechnol 137:957–970. doi:10.1007/s120
10-007-9111-x
Zeman Z (2007) Thermochemical versus biochemical. Bio-
mass Magazine, June 2007
Zhang M, Nagle N (2008) Define the relationships between
corn stover hydrolysate conditioning and fermentation
performance in lab equipment. NREL Internal Report
(submitted)
Zwart RWR, Boerrigter H (2005) High efficiency co-produc-
tion of synthetic natural gas (SNG) and Fischer-Tropsch
(FT) transportation fuels from biomss. Energy Fuels
19(2):591–597. doi:10.1021/ef049837w
123