The Role of Thermochemical Processing in Future Biorefineries

Final Report
Iowa Energy Center


Iowa Energy Center Grant No.: 0606

Report Period: July 1, 2006 June 30, 2008

Principal Investigator: Robert C. Brown
Organization: Iowa State University






















Signature of PI






The Role of Thermochemical Processing in Future Biorefineries
Principal Investigator: Robert C. Brown

Executive Summary


The overall goal of this project was to evaluate the role of thermochemical processing in the
emergence of advanced biorefineries. This goal has been accomplished through the preparation
of three papers on the technical and economic aspects of advanced biorefineries. An extensive
review of biorefinery technologies has been completed and is included in this report. Two
journal articles, Comparative Economics of Biorefineries Based on the Biochemical and
Thermochemical Platforms and Establishing the optimal sizes of different kinds of
biorefineries, have been published in Biofuels, Bioproducts, and Biorefining, These studies
show that thermochemical conversion, as well as hybrid biological/thermochemical platforms,
holds great potential in expanding biomass conversion pathways.

The review paper Routes to Biofuels describes the variety of pathways for conversion of
biomass to transportation fuels. Biological, thermochemical, and hybrid biological/thermo-
chemical platforms are all included in this report which takes into consideration potential biofuel
applications and limitations. This report also draws from previous analyses to determine the
economics of these technologies. This project reviewed the current biorefinery concepts and
identified potential roles for thermochemical processing; evaluated the current status of biomass-
derived transportation fuels, and assessed the technical feasibility of various methods proposed
for the conversion of biomass to fuels.

Comparative Economics of Biorefineries Based on the Biochemical and Thermochemical
Platforms describes a technoeconomic study that compares biochemical and thermochemical
processing. This comparison took into consideration technology maturity, plant capacity, energy
content of the fuel, feedstock costs, method of calculating capital charges, and year in which the
original analysis was assumed. Results from this analysis showed that capital costs for advanced
biochemical and thermochemical biorefineries will require capital investments of four to five the
capital of comparably sized grain ethanol plants. Nevertheless, fuel costs from advanced
biorefineries will be similar to grain ethanol at feedstock prices of $3.00 per bushel of grain.

A second technoeconomic study, Establishing the optimal sizes of different kinds of
biorefineries explored the factors that influence the optimal plant size and resulting fuel cost of
advanced biorefineries. Common economies-of-scale calculations predict lower unit production
prices for large facilities. Biomass facilities producing hundreds of millions of gallons of fuel
will require transportation of tens of thousands of tons of feedstock daily generating a significant
delivery expense. The combination of these factors establishes an optimal plant size at which
fuel production costs per gallon of gasoline equivalent reaches a minimum value. This study
concluded that advanced biorefineries converting lignocellulosic biomass would be optimally
sized at 240 to 486 million gallons of gasoline equivalent compared to 79 million for grain
ethanol plants.


Routes to Biofuels
Robert C. Brown and Mark Wright
1 Introduction
The current generation of biofuels is based on grain ethanol and biodiesel from soybeans or other
high-oil content plants. However, it is unlikely that corn and oil crops can provide more than a
small fraction of world-wide demand for transportation fuels, displacing no more than about 12
billion gallons of gasoline in the United States, for example, whereas the national target is 60
billion gallons of ethanol by 2030
1
. Cellulosic (fibrous) biomass will likely be required to make
up the difference.
Much of the discussion about advanced biofuels centers around cellulosic ethanol, assumed to be
produced by enzymatically hydrolyzing hemicellulose and cellulose into five-carbon and six
carbon sugars that can be fermented into ethanol.
2
In fact, a number of advanced biofuels are
possible including hydrogen, butanol, methanol, mixed alcohols, esters, ethers, Fischer-Tropsch
liquids, and so-called green diesel produced by hydrocracking vegetable oils, bio-oil, and
biocrude. Accordingly, it may be too early to select the advantaged molecule(s) for use as
advanced biofuels or the processes by which to produce these future fuels.
This paper reviews the various fuels under consideration for production from biomass and the
biochemical, thermochemical, and hybrid processes that could produce them. In instances where
relatively complete techno-economic data is available the various processes are compared in
terms of optimal size, capital costs, and operating costs.
2 Potential Biofuels
Biobased transportation fuels, also known as biofuels, are currently dominated by ethanol and
mono alkyl esters (biodiesel). However, there are other candidate liquid biofuels including
methanol, butanol, mixed alcohols, Fisher-Tropsch liquids, methylated furans, and so-called
green diesel, as well as gaseous biofuels including hydrogen, methane, ammonia, and dimethyl
ether. Ethanol is currently produced by fermentation of glucose derived from starch crops or
sugar crops. Fermentation can also produce hydrogen, methane, butanol, and even mono alkyl
esters, although none are widely produced biologically for use as transportation fuels at present.
Alternatively, thermochemical processes can be used to produce biofuels. The major
thermochemical pathways include gasification, fast pyrolysis, hydrothermal processing, and
catalytic dehydration of carbohydrates. The first of these produces a gaseous product, fast
pyrolysis yields mostly a liquid product, hydrothermal processing can produce either gaseous or
liquid products depending upon the processing conditions, and catalytic dehydration produces
liquids. Both gaseous and liquid products typically require upgrading before they are suitable as
transportation fuel. Upgrading processes include syngas catalysis, syngas fermentation,
1
2
hydrocracking of vegetable oils and thermally-derived liquids, and catalytic dehydration of
carbohydrates to furans.
Biomass gasification is the process in which plant materials are thermally decomposed into a
gaseous mixture consisting primarily of carbon monoxide (CO) and hydrogen (H
2
) known as
producer gas if it contains substantial quantities of nitrogen or syngas if it contains little
nitrogen.
3
Nitrogen content depends upon whether the solid fuel feedstock is processed in air,
oxygen, or in the complete absence of oxygen. Producer gas or syngas can be reacted with steam
to produce hydrogen fuel or passed over metal catalysts to synthesize ethanol, mixtures of
alcohols, Fisher-Tropsch (F-T) liquids, or dimethyl ether. This gas can also be fermented by
certain bacteria into hydrogen, ethanol, and esters.
4
Gasification at high pressures and low
temperatures can also be used to generate methane (CH
4
). Usually heat and pressure are the
driving forces of gasification but sometimes catalysts are employed to allow processing at lower
temperatures and to improve product selectivity.
5
Fast pyrolysis is the rapid heating of biomass in the absence of oxygen to generate a liquid
product known as bio-oil along with smaller amounts of gas and char. The bio-oil consists of a
carbohydrate-derived phase and a lignin-rich phase.
6
Bio-oil can be used directly as boiler fuel
or burned in appropriately modified stationary diesel engines or gas turbines, but for
transportation applications, it must be upgraded to a higher quality liquid fuel. This can be
accomplished by gasifying the bio-oil to syngas followed by catalytic transformation to Fisher-
Tropsch diesel. Alternatively, upgrading can be achieved by hydrocracking the bio-oil to
hydrocarbons
7
that are sometimes known as green diesel to reflect its origin.
Hydrothermal processing employs a high pressure, aqueous-phase environment to convert
biomass into gaseous or liquid products.
8
The nature of the products depends upon the reaction
conditions. The mildest processing conditions (200-250 C and 50-100 bar) yields carbohydrate
that can be hydrolyzed to fermentable sugars.
9, 10
More severe processing conditions
(300-350 C and 120-180 bar) yields so-called biocrude, which contains a variety of organic
compounds suitable for upgrading to gasoline or diesel fuel.
11
The highest temperatures and
pressures (600 C and 230 bar) yield a gaseous mixture of hydrogen, carbon monoxide, and
methane.
12
Table 1 summarizes the properties of various biofuel options and compares them to fossil-fuel
derived gasoline and diesel. The properties include specify gravity, kinematic viscosity, boiling
point range, flash point, autoignition temperature, octane number, cetane number, heat of
vaporization, and lower heating value. In the case of fuels that are gaseous at ambient
conditions, specific gravity is reported for saturated liquids at their boiling point.
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3
2.1 Biodiesel
Vegetable oils, which are triglycerides of fatty acids, have long been recognized as potential
fuels in diesel engines. Compared to petroleum-based diesel fuels, vegetable oils have higher
viscosity and lower volatility, which results in fouling of engine valves and less favorable
combustion performance, especially in direct-injection engines.
14
The solution to this problem is
to convert the triglycerides into methyl esters or ethyl esters of the fatty acids, known as
biodiesel, and the byproduct 1,2,3-propanetriol (glycerol).
Table 1 illustrates that fuel properties of biodiesel are similar to petroleum-based diesel although
biodiesel has a lower cloud point, which can cause fuel filters to plug under cold weather
conditions. In general, oil crops from traditional agriculture are lower yielding than starch crops
and biodiesel is more expensive than ethanol on an energy basis. For these reasons, vegetable
oils are unlikely to make significant contributions to world-wide demand for transportation fuels
unless dramatical improvements in crop productivity and process costs are achieved.
Oil palm grown in the tropics can yield over ten times as much vegetable oil as soybeans grown
in temperate climates although there are concerns that rain forests are being cleared to expand oil
palm plantations.
15
Algal biomass is gaining increasing attention as a source of triglycerides
because theoretical productivity in desert (high insolation) regions of the world is one hundred to
two hundred times higher than for soybeans.
16
2.2 Green Diesel
Diesel derived from renewable biomass is commonly known as green diesel. These are typically
produced via gasification to syngas and catalytic upgrading to liquid fuels. Fischer-Tropsch
synthesis is one of the most promising pathways for large scale production of green diesel, which
comprises up to 40% of Fischer-Tropsch liquid products. Fischer-Tropsch diesel properties
contribute to a clean combustion performance. Nevertheless, low density and low aromatic
content result in lower energy content than petroleum diesel and unattractive blending properties.
Some of the concerns with green diesel vehicle use include complications with fuel injection
systems, power output, and lubrication properties. Biomass diesel is capable of penetrating
elastomers present in fuel injection systems due to the polarity of the diesel and base polymeric
units of the elastomer
17
. Fischer-Tropsch diesel naphtenes and paraffins have a lower density and
volumetric heating value than aromatics
18
, and this can reduce diesel engine power output
19
.
Hydroprocessed diesel, both renewable and fossil-based, have poor lubrication properties caused
by the reduction of surface-active polar compounds
20
, but this can be improved with additives.
A proposed solution to improve green diesel properties for use as a conventional diesel
alternative is to blend biomass based diesel with coal based diesel.
21
Although green diesel has
high compatibility value with existing infrastructure and transportation system, it currently
cannot compete economically with low sulfur diesel and may require large cost reductions.
22
4
2.3 Ethanol
The biological production of ethanol and its distillation has been practiced for thousands of
years. This fact combined with the wide availability of suitable fermentation feedstocks (grains
and sugar cane) explains the early entry of ethanol into the biofuels market. In fact, Henry Ford
had intended to fuel the Model T with ethanol, but inexpensive gasoline soon replaced it.
Ethanol has some shortcomings compared to gasoline. On a volumetric basis, it only has 66% of
the heating value of gasoline. However, fuel economy depends on many complex interactions
between a fuel and the combustion environment within an engine, which some argue improves
the relative performance of ethanol
23
. For example, the higher octane number for ethanol
compared to gasoline (109 vs. 91- 101) allows engines to be designed to run at higher
compression ratios, which improves both power and fuel economy. Estimates for efficiency
improvements in engines optimized for ethanol instead of gasoline range are 15% to 20%,
resulting in a driving range approaching 80% of that of gasoline.
24
A significant problem with ethanol-gasoline blends is water-induced phase separation. Water
contaminating a storage tank or pipeline is readily absorbed by ethanol, resulting in a lower
water-rich layer and an upper hydrocarbon-rich layer, which interferes with proper engine
operation. Water contamination is a problem that has not been fully addressed by the refining,
blending, and distribution industries; thus transportation of ethanol-gasoline blends in pipelines
is not permitted in the United States and long-term storage is to be avoided.
25
2.4 Methanol
Methanol is one of the ten most produced chemicals in the world. Methanol is a clear, odorless,
flammable liquidthat can be generated from any hydrocarbon. Methanol production is a mature
process with process efficiencies of 99% or higher. According to Davenport
26
, almost all
methanol synthesis derives from natural gas because of cost considerations. It is an intermediate
chemical in the production of formaldehyde, dimethyl ether, acetic acid, and others. Methanol
can also be blended with gasoline for use as a clean transportation fuel.
As a transportation fuel, it has many of the same advantages and disadvantages as ethanol.
27
The
fuel properties of methanol are similar to those of ethanol: narrow boiling point range, high heat
of vaporization, and high octane number. It has only 49% of the volumetric heating value of
gasoline. However, methanol is considerably more toxic than ethanol. Recent rulings by the U.S.
Environmental Protection Agency (EPA) are likely to ban the closely related and similarly toxic
MTBE as a fuel additive because of concerns about ground water contamination.
A promising application for methanol is in fuel cell technology. Methanol is a leading candidate
to provide the hydrogen necessary to power fuel cell vehicles, the next generation of automotive
technology.
28
5
2.5 Biobutanol
Before the rise of the petrochemical industry, butanol was traditionally produced by the acetone-
butanol-ethanol (ABE) fermentation using Clostridium acetobutylicum. In a relatively
complicated and difficult to control process, the ABE fermentation begins by producing butyric,
propionic, lactic, and acetic acids, followed by a shift to butanol, acetone, isopropanol, and
ethanol. The butanol yield from glucose is low, in the range of 15-25%. Butanol concentrations
are typically lower than 13 g/L due to product inhibition. Because of these low yields and
process challenges, butanol has remained an expensive fuel product.
Butanol has physical properties that make it more attractive than other alcohols for use as a
motor fuel.
29
Its volumetric heating value is 89% of gasoline, improving its fuel economy
compared to ethanol and methanol. Its relatively low vapor pressure compared to other alcohols
reduces problems with vapor lock and the emission of volatile organic compounds (VOCs) from
fuel tanks. Although its octane rating is lower than ethanol and methanol, it is higher than
gasoline. Butanol-gasoline blends are less susceptible to phase separation in the presence of
water contamination, which should improve engine performance compared to ethanol and allow
butanol to be transported through existing gasoline pipelines.
In an attempt to revive the production of butanol from biomass, cell recycle, cell immobilization
and extractive fermentation have been explored. Advanced fermentation technologies
30
produce
only hydrogen, butyric acid, and butanol, and have the potential to produce almost as many
gallons of fuel from corn as ethanol fermentation
31,32
2.6 Mixed Alcohols
Efforts in Germany during World War II to develop alternative motor fuels discovered that iron-
based catalysts could yield appreciable quantities of water-soluble alcohols from syngas
33
.
These early efforts yielded liquids containing as much as 45-60% alcohols of which 60-70% was
ethanol with lesser amounts of methanol, butanol, and other alcohols.
Some researchers have advocated the use of mixed alcohols as transportation fuels because the
product typically contains a mixture methanol, ethanol, 1-propanol, and 2-propanol. One
advantage is the ability to use lower H
2
:CO ratios than is required for methanol or Fischer-
Tropsch synthesis.
34
An extensive review of mixed alcohol synthesis technology is found in
Reference 35.
2.7 Fischer-Tropsch Liquids
The technology was extensively developed and commercialized in Germany during World War
II when it was denied access to petroleum-rich regions of the world. Likewise South Africa,
faced with an world oil embargo during their era of apartheid, employed F-T technology to
sustain its national economy. A comprehensive bibliography of F-T literature can be found on
the Web.
36
6
Fischer-Tropsch liquids composition depends on the process selectivity. To obtain high amounts
of heavy hydrocarbons, a high liquid selectivity is required. Process selectivity is affected by
various factors including catalyst and feed gas properties. The Anderson-Schulz-Flory (ASF)
distribution describes the probability of hydrocarbon chain growth where the molar yield for a
carbon chain can be calculated using the following equation:
37
C
n
=
n-1
(1-) (1)
where is the chain growth probability of a hydrocarbon of length n. Light hydrocarbons
(mostly methane) can be fed into a gas turbine to provide power. Fischer-Tropsch liquids can be
separated into various products in a process similar to petroleum distillation. Hydrogen can also
be used in hydrotreating, hydrocracking, and hydroisomerization processes to upgrade fractions
of the Fischer-Tropsch liquids into common transportation fuels although there is a limit.
Senden et. al. calculated a theoretical limit for gasoline yield selectivity to be 48%
38
. Fischer-
Tropsch diesels selectivity limit is estimated to be even lower at 40%. Remaining fractions can
be used as a substitute to petroleum-based chemicals. Low selectivity towards gasoline and
diesel makes it critical for Fischer-Tropsch derived chemicals to compete economically in the
market.
2.8 Hydrogen
Hydrogen is often touted as an ideal fuel because it is clean burning and the combustion products
include no greenhouse gases. It may be one of the most cost-effective ways to produce
transportation fuels from biomass because a relatively small number of unit operations are
involved in its production. Commercial production of hydrogen is dominated by steam
reforming of natural gas although it can be produced from any carbonaceous fuel including coal
and biomass:
C
x
H
y
O
z
+ (2x-z)H
2
O xCO
2
+ (2x + y/2 z)H
2
(2)
This endothermic reaction either needs an external source of heat to drive the reaction, or oxygen
needs to be added in sufficient quantities to support the exothermic reaction:
C + 1/2O
2
CO (3)
in a process known as autothermal reforming.
Although this might be one of the most cost-effective ways to produce clean-burning biofuel, the
physical characteristics of hydrogen present challenges in its use as transportation fuel. In
particular, its low density even under cryogenic or high pressure conditions limits on-board
storage of this fuel. Its wide flammability range also presents unique safety problems in its use
in transportation systems
39
.
7
2.9 Methane
Methane (CH
4
) is a clean burning gas that is the main component of natural gas, widely used for
residential and industrial heating applications and in electric power generation. Compressed
natural gas is used in some urban mass transit applications
40
and efforts are underway in Europe
to use biomass-derived CH
4
as renewable transportation fuel
41
. Liquefied natural gas (LNG) is
sometimes produced to ease shipping of stranded natural gas to distant markets. However, most
automotive applications contemplate its use as compressed gas.
Renewable methane from biomass can be produce by either biochemical or thermochemical
processes. Biochemical production of methane (anaerobic digestion) is most suitable for high
moisture, low value feedstocks such as manure, food processing byproducts, or waste water.
Thermochemical production of CH
4
(gasification) requires relatively low moisture feedstocks to
avoid high thermal energy penalties.
Anaerobic digestion is the decomposition of organic wastes, including polysaccharides, proteins,
and lipids, to gaseous fuel by bacteria in an oxygen-free environment
42
. The process occurs in
stages, each involving specific types of bacteria, to successively break down the organic matter
into simpler organic compounds. The desired product, known as biogas, is a mixture of about
60 vol-% CH
4
and 40 vol-% CO
2
. It also contains traces of other gases, most importantly
hydrogen sulfide (H
2
S), which must be scrubbed from the gas before it is used as fuel to prevent
emissions of sulfur dioxide into the atmosphere.
Gasification can also yield methane by a process known as hydrogasification:
43
C + 2H
2
CH
4
(4)
CO + 3H
2
CH
4
+ H
2
O (5)
These exothermic reactions require low temperatures, high pressures, and large quantities of
hydrogen. Separate generation of hydrogen and catalysts to achieve reasonable reaction rates are
usually required to achieve high methane yields. It has been demonstrated at the commercial
scale using coal as the carbonaceous fuel.
2.10 Dimethyl ether
Dimethyl ether, like liquefied petroleum gas (LPG), is a non-toxic, flammable gas at ambient
conditions that is easily stored as liquid under modest pressures
44
. It is currently used as an
aerosol propellant in the cosmetic industry, but has excellent potential as a fuel for heating,
cooking, and power. It is particularly attractive as a substitute for petroleum-based diesel fuel
since it has comparable cetane number but yields essentially zero particulate emissions and low
NO
x
emissions. It is produced either catalytically from syngas
3H
2
+ CO CH
3
OCH
3
+ CO
2
(6)
8
or through the dehydration of methanol by reactions at high pressure over catalysts.
45,46
2CH
3
OH CH
3
OCH
3
+ H
2
O (7)
The direct reaction from syngas is thermodynamically more efficient. Either of these routes
ultimately involves the production of syngas from carbonaceous feedstocks, including fossil
fuels, and much of the current interest in this alternative fuel arises from the possibility of
manufacturing it from inexpensive stranded natural gas.
2.11 Methylated furans
Furans are heterocyclic aromatic ethers consisting of a ring of four carbon atoms and one oxygen
atom. Furans are colorless, water-insoluble, flammable liquids with volatility comparable to
hydrocarbons of similar molecular weight. They were originally derived from the destructive
distillation of wood although a number of synthesis routes are possible.
47
Methylated furans
have heating values and octane numbers comparable to gasoline making them attractive as
transportation fuel.
48
2,5 dimethyl furan in particular has received recent interest because new
catalytic synthesis routes from sugars have been developed.
49, 50
However, neither the fuel
properties nor toxicity of this compound have been much studied raising questions as to the
ultimate practicality as transportation fuel.
3 Biochemical Processing
3.1 Starch-to-ethanol
Starch is a polymer that accumulates as granules in many kinds of plant cells where they serve as
a storage carbohydrate. Mechanical grinding readily liberates starch granules. The hydrogen
bonds between the basic units of maltose in this polymer are easily penetrated by water, making
depolymerization and solubilization relatively easy. Cereal grains also contain other components,
such as protein, oil and fiber, which may be of sufficient value to recover along with the starch.
Hydrolysis, the process by which water splits a larger reactant molecule into two smaller product
molecules, is readily accomplished for starch. Acid catalyzed hydrolysis in starch cookers at
temperatures of 150 200 C proceeds to completion in seconds to minutes. In recent years
enzymatic hydrolysis has supplanted acid hydrolysis due to higher selectivity.
The capital investment for dry milling is less than that for a comparably sized wet-milling plant.
However, the higher value of its by-products, greater product flexibility, and simpler ethanol
production can make a wet-milling plant a more profitable investment.
A typical dry milling plant will produce about 9.5-9.8 L (2.5-2.6 gal) of ethanol per bushel of
corn processed. Yields of coproducts per bushel of corn are 7.7-8.2 kg (17-18 lb) of DDGS and
7.3-7.7 kg (16-17 lb) of carbon dioxide evolved from fermentation, the latter of which can be
sold to the carbonated beverage industry. As a rule of thumb, the three products are produced in
9
approximately equal weight per bushel, with each accounting for approximately one-third of the
initial weight of the corn.
3.2 Cellulose to Ethanol
Much of the carbohydrate in plant materials is structural polysaccharides, providing shape and
strength to the plant. This structural material, known as lignocellulose, is a composite of
cellulose fibers embedded in a cross-linked lignin-hemicellulose matrix
51
. Depolymerization to
basic plant components is difficult because lignocellulose is resistant to both chemical and
biological attack
52
.
Cellulose to ethanol consists of five steps: pretreatment, enzymatic hydrolysis, fermentation, and
distillation.
53
Of these, pretreatment is the most costly step, accounting for about 33% of the
total processing costs
54
. An important goal of all pretreatments is to increase the surface area of
lignocellulosic material, making the polysaccharides more susceptible to hydrolysis. Thus,
comminution, or size reduction, is an integral part of all pretreatments. Some pretreatments are
thought to reduce crystallinity of cellulose, which improves reactivity, but this does not appear to
be the key for many successfully pretreatments.
Three basic methods for hydrolyzing structural polysaccharides in plant cell walls to fermentable
sugars are available: concentrated acid hydrolysis, dilute acid hydrolysis, and enzymatic
hydrolysis
52, 55
. The two acid processes hydrolyze both hemicellulose and cellulose with very
little pretreatment beyond comminution of the lignocellulosic material to particles of about 1 mm
size. The enzymatic process must be preceded by extensive pretreatment to separate the
cellulose, hemicellulose, and lignin fractions.
Enzymatic hydrolysis was developed to better utilize both cellulose and hemicellulose from
lignocellulosic materials. Pretreatment solubilizes hemicellulose under milder conditions than
those required for acid hydrolysis of cellulose. Subsequent enzymatic hydrolysis of the cellulose
does not degrade pentoses released during prehydrolysis. Cellulose is a homopolysaccharide of
glucose linked by -1,4-glycosidic bonds. Thus, enzymatic hydrolysis of cellulose proceeds in
several steps to break glycosidic bonds by the action of a system of enzymes known as cellulase.
The system of enzymes also usually contains hemicellulase to hydrolyze any hemicellulose not
solubilized by prehydrolysis.
Simultaneous saccharification and fermentation (SSF) has been developed for fermenting sugars
released from lignocellulose
52, 55
. The SSF process combines hydrolysis (saccharification) and
fermentation to overcome end product inhibition that occurs during hydrolysis of cellobiose. By
combining hydrolysis and fermentation in the same reactor, glucose is rapidly removed before it
can inhibit further hydrolysis. The SSF process is illustrated in Figure 1. The biomass feedstock
is milled and then prehydrolyzed to yield a mixture of pentoses, primarily xylose and arabinose,
and fiber. The pentose is separated from the undigested fibers and fermented with appropriate
yeast or bacterial to yield ethanol. The pretreated fibers are mixed with cellulases, which are
either purchased commercially or produced on site, along with yeast and nutrients. The cellulose
is solubilized to hexose (glucose), which is simultaneously fermented to ethanol. The rate-
10
limiting s
used as b
sugar or
step is the hy
boiler fuel. T
starch ferme
ydrolysis of
The beer is d
entations.
cellulose to
distilled to et
glucose. Li
thanol in a p
ignin is sepa
process ident
arated from t
tical to that e
the mixture a
employed aft
and
fter
4 The
4.1 Ga
Thermoly
gasificati
Gasificat
monoxid
gas, can b
The syng
methanol
produce h
are gaseo
transport
usually p
various a
sulfur, ch
produce t
The ratio
synthesis
Biomass
process.
syngas an
Figure
ermoche
asificatio
ytic processi
ion (to produ
tion involves
de gaseous m
be further pr
gas gas can b
l, ethanol, m
hydrogen (H
ous compoun
tation fuels.
preferred for
amounts of li
hlorine, and
the desired p
o of H
2
to CO
s favors a 2.1
gasification
Hydrogen e
nd steam ove
CO + H
2
O
1 Cellulose-
emical P
on
ing of carbon
uce a gaseou
s the partial
mixture called
rocessed to n
be catalytical
mixed alcoho
H
2
), methane
nds at ambie
A relatively
synthesizing
ight hydroca
ammonia, so
proportions o
O in the synt
15 to 1 ratio
n does not ne
enrichment, w
er a catalytic
O CO
2
+ H
-to-ethanol
Process
n based mat
us product) o
combustion
d synthetic g
numerous pr
lly processed
ls, and Fishe
e (CH
4
), dim
ent condition
y pure mixtu
g these comp
arbons, tar, p
ome downstr
of H
2
and CO
thetic gas is
while metha
ecessarily yie
which increa
c bed, which
H
2
processing
sing
erials can be
or fast pyroly
of carbon-ri
gas (syngas).
roducts.
d to a variety
er-Tropsch (
ethyl ether (
ns but can be
ure of carbon
pounds. Sinc
particulate m
ream treatm
O.
significant f
anol can be p
eld the H
2
to
ases the H
2
t
h promotes th
(via enzyma
e generally c
ysis (to prod
ich materials
. Synthetic g
y of liquid tr
(F-T) liquids
(CH
3
OCH
3
),
e compressed
n monoxide (
ce raw produ
matter, and tr
ent of the ga
for catalytic
processed w
o CO ratio re
to CO ratio,
he water-gas
atic hydroly
categorized a
duce primaril
s to a hydrog
gas, also kno
ransportation
s. It can also
and ammon
d or liquefied
(CO) and hy
ucer gas can
ace contami
as stream ma
synthesis. Fi
with 3:1 H
2
to
equired for th
can be achie
s shift reactio
ysis)
as either
ly liquid pro
gen and carb
own as produ
n fuels inclu
o be used to
nia (NH
3
), w
d for use as
ydrogen is
n also contain
nants such a
ay be require
ischer-Trops
o CO ratio
35
.
he subsequen
eved by pass
on:
11
oduct).
bon
ucer
uding
which
n
as
ed to
sch
.
nt
sing
(8)
Low temperatures thermodynamically favor this slightly exothermic reaction. To obtain
satisfactory reaction rates, catalysts are employed in one or more fixed bed reactors operated in
the temperature range of 250-400 C. It is possible to catalyze this reaction with a chromium
promoted iron formulation
56
.
An alternative approach to obtaining neat ethanol from syngas is to first synthesize methanol and
subsequently reacting this product with additional syngas:
57
CH
3
OH + 2CO + H
2
CH
3
CH
2
OH + CO
2
(9)
Direct carbonylation of methanol has the advantage of yielding ethanol without coproduct water,
which would eliminate energy-intensive distillations. The cost-effectiveness of this approach to
ethanol synthesis has not been proven.
Particles, contaminants, and catalyst poisons are among a number of undesired components
present in the syngas. Gas cleaning is a required process to remove these undesired contaminants
that can cause catalyst deactivation. As shown in Figure 12, gas cleaning typically precedes
catalytic synthesis. Large particles (about 5 m) are generally removed with cyclone separators.
Smaller particle removal can be accomplished with venturi scrubbers, electrostatic precipitators,
and fabric filters. The presence of certain impurities in extremely small concentrations can cause
poisoning, reducing the effectiveness of the catalyst. Various processes have been proposed that
target specific gas phase contaminants. Sulfur is particularly targeted due to its significant
catalyst poisoning activity. A listing of poisons related to methanol synthesis is found in Table 2.
Catalysts are most commonly used in thermochemical processes to convert the synthetic gas into
liquid transportation fuels. Commercial considerations require the use of catalysts to alter the
reaction kinetics in such a way that the desired yield rate is viable. There is considerable amount
of active research focused on increasing catalyst activity and reliability. The choice of catalyst
depends on the desired product, operating conditions (temperature and pressure particularly), and
economic considerations among others.
Table 2. Methanol Catalyst Poisons and Tolerance Levels
Poison Tolerance Level Reference
Sulfur 0.5 ppmv [58]
Halides 0.001 ppmv [59]
Iron and Nickel 0.005 ppmv [58]
4.2 Hydrogen Production
The production of hydrogen is generally done through catalytic steam reforming. Biomass
conversion to hydrogen has been demonstrated to be economical by Spath et. al.
60
. Nevertheless,
conversion of hydrocarbons from solid feedstock involves higher processing difficulty and
12
capital costs than light hydrocarbons. The representative reaction involves a methane and steam
conversion to hydrogen and carbon monoxide.
CH
4
+ H
2
O CO + 3H
2
(10)
Steam reforming requires heat addition and can be catalyzed over a nickel catalyst.
Gasification to produce hydrogen is usually carried under high pressure and temperature
conditions. The high pressure is especially necessary when the produced hydrogen serves as
feedstock for a subsequent process. Biomass feeding to high pressure systems is an expensive
requirement which if resolved could lower plant costs considerably.
Once hydrogen has been generated, it is separated from the synthesis gas. Pressure swing
adsorption is a recent technology which involves selective gas to solid adsorption. With this
technology, CO
2
and H
2
O are adsorbed by a bed of activated carbon. A second bed with a zeolite
molecular sieve further purifies the gas stream. High hydrogen purities of up to 99.99% can be
achieved through recycling of the product stream. Ceramic membranes are another advanced
technology capable of both gas separation and shift that show great promise.
4.3 Methanol from Syngas
Methanol synthesis development correlates closely with Fischer-Tropsch research. Methanol is
currently a commercial product produced mostly from natural gas
61
. Methanol is formed by the
exothermic reaction of one mole of carbon monoxide with two moles of hydrogen:
62
CO + 2H
2
CH
3
OH (11)
Low temperatures and high pressures thermodynamically favor the production of methanol.
Current commercial operations use a fixed catalytic bed operated at 250 C and 60 - 100
atmospheres with gas recycle to remove the large amount of heat released by this exothermic
reaction. More recently, liquid-phase slurry reactors have been introduced to improve contact
between syngas and catalyst as well as enhance the removal of heat from the reactor
63
.
Gas-phase methanol leaving the reactor is mixed with water and higher alcohols. To separate the
methanol, a distillation plant is employed where water and volatiles are collected. The remaining
syngas is recycled to the reactor increasing the conversion efficiency significantly. Liquid-phase
methanol synthesis could reduce investment costs of methanol plants
64
.
4.4 Mixed Alcohols from Syngas
Efforts in Germany during World War II to develop alternative motor fuels discovered that iron-
based catalysts could yield appreciable quantities of water-soluble alcohols from syngas,
especially ethanol:
65
CO + 3H
2
CH
3
CH
2
OH (12)
13
These early efforts yielded liquids containing as much as 45-60% alcohols of which 60-70% was
ethanol. Working at pressures of around 50 bar and temperatures in the range of 220-370 C,
researchers have developed catalysts with selectivity to alcohols of over 95%, but production of
pure ethanol has been elusive.
Some researchers have advocated the use of mixed alcohols as transportation fuels because the
product typically contains a mixture methanol, ethanol, 1-propanol, and 2-propanol. One
advantage is the ability to use lower H
2
:CO ratios than is required for methanol or Fischer-
Tropsch synthesis:
66
nCO + 2nH
2
C
n
H
2n+1
OH + (n-1)H
2
O (13)
with n typically ranging from 1 to 8. The process was commercialized in Germany between
1935 and 1945 but eventually abandoned because of the increased availability of inexpensive
petroleum. Working at pressures of around 50 bar and temperatures in the range of 220-370 C,
researchers have developed catalysts with selectivity to alcohols of over 95%, but production of
pure ethanol has been elusive.
An alternative approach to obtaining neat ethanol from syngas is to first synthesize methanol and
subsequently reacting this product with additional syngas:
67
CH
3
OH + 2CO + H
2
CH
3
CH
2
OH + CO
2
(14)
Direct carbonylation of methanol has the advantage of yielding ethanol without coproduct water,
which would eliminate energy-intensive distillations. The cost-effectiveness of this approach to
ethanol synthesis has not been proven.
4.5 Fischer-Tropsch Synthesis
The biomass to Fischer-Tropsch fuel is a catalyst-based process with precedents in the coal-to-
liquids industry. FT catalysts produce hydrocarbons of various lengths of which a significant
fraction can be processed into high quality diesel products. Tijmensen et al.
68
modeled various
configurations for the conversion of biomass to FT liquids. Fischer-Tropsch synthesis produces a
large variety of hydrocarbons including light hydrocarbon gases, paraffinic waxes, and alcohols
according to the generalized reaction:
68
CO + 2H
2
CH
2
+ H
2
O (15)
Product distribution is a function of temperature, pressure, feed gas composition (H2/CO),
catalyst type and composition. Depending on the types and quantities of F-T products desired,
either low (200240 C) or high temperature (300350 C) synthesis at pressures ranging
between 10 to 40 bar are used. For example, high gasoline yield can be achieved using high
process temperatures and an iron catalyst. F-T synthesis requires careful control of the H
2
/CO
ratio to satisfy the stoichiometry of the synthesis reactions as well as avoid deposition of carbon
14
on the catalysts (coking). An optimal H
2
/CO ratio of 2:1 is maintained through the water-gas
shift reaction.
Cobalt and iron are the main active catalyst ingredients used for Fischer-Tropsch synthesis.
Cobalt catalysts last longer than iron catalysts and have improved carbon conversion to products
due to reduced CO
2
generation. Iron, on the other hand, suffers from increased carbon deposition.
Since cobalt catalysts can operate at lower pressures, they are commonly used as an alternative to
iron catalysts. The costs for cobalt catalysts are about 230 times more expensive than iron, but
this cost is offset by lower operating costs.
35
Ruthenium is the most active Fischer-Tropsch
catalyst but has a prohibitive cost. Much research has been done on improving catalyst activity,
lifetime, and selectivity. Adding promoters, improving catalyst preparation, and using zeolites
among other methods, can achieve this.
Fischer-Tropsch catalyst can have limited lifetime due to loss of catalyst activity. Poisoning is a
controllable problem that can cause significant catalyst deactivation. Table 3 describes the
recommended tolerance levels for various poisons. Sulfur is the main Fischer-Tropsch catalyst
poison agent, and it is present in both natural gas and coal. Recommendations for sulfur levels
are as low as 60 ppb.
71
Other poisons include nitrogen compounds and halides. Moisture in the
synthetic gas can also have an inhibiting effect due to its water gas shift activity. The efficiency
of poison removal will generally be driven by economical considerations since it is nearly
impossible to completely remove all synthetic fuel impurities.
Table 3. Fischer-Tropsch Catalyst Poisons and Tolerance Levels
Poison Tolerance Levels Reference
Sulfur 0.2 ppm,
1 ppmv,
60 ppb
[69]
[70]
[71]
Halides 10 ppb [70]
Nitrogen 10 ppmv NH3,
0.2 ppmv NOx,
10 ppb HCN
[71]
4.6 Fast Pyrolysis
The first fast pyrolysis experiments date from the 1970s and have developed into multiple reactor
designs and process configurations. Fast pyrolysis liquids have attracted attention as an
intermediate product for the conversion of biomass to liquid fuels and chemicals
72
.
Fast pyrolysis is the rapid thermal decomposition of organic compounds in the absence of
oxygen to produce liquids, gases, and char
73
. Liquid yields range between 60 to 75%. Typical
process conditions consist of moderate temperatures (425-500 C), short vapor residence times
(less than 2 seconds), and rapid quenching of pyrolysis vapors and aerosols
74
.
15
Depolymerization
Levoglucosan
Fast
Char + water
Alkali-catalyzed
dehydration
Slow
Cellulose
Hydroxyacetaldehyde
Figure 2 Reaction pathways in fast pyrolysis
Pyrolysis liquid from flash pyrolysis is a low viscosity, dark-brown fluid with up to 15 to 20%
water, which contrasts with the black, tarry liquid resulting from slow pyrolysis or gasification.
Typical product yields for two kinds of stored biomass feedstock are given in Table 4. These
include acids, aldehydes, sugars, and furans, derived from the carbohydrate fraction, and
phenolic compounds, aromatic acids, and aldehydes, derived from the lignin fraction.
Table 4 Material Balance for Fluidized Bed Pyrolysis of Stored Biomass
Material Balance Switchgrass Corn Stover
Gas (%) 11.0 15.4
Char/ash (%) 20.3 15.9
Water + organics (%) 61.5 52.7
Total 92.8 90.9
Gases
CO 3.4 3.7
CO
2
7.1 9.9
CH
4
0.2 0.4
C
2
H
4
na 1.2
C
4
H
6
0.3 na
The liquid, despite its high water content, shows no appreciable phase separation. However, if
an equal volume of water is added to the liquid, the high molecular weight, largely aromatic
compounds are precipitated. Since most of the aromatic compounds can be traced to the lignin
content of the biomass, this precipitate is widely known as pyrolytic lignin. The low pH of
pyrolysis liquids, which arises from organic acids derived primarily from the hemicellulosic
content of the feedstock, makes the liquid highly corrosive. The liquid also contains fine
16
particulate char. The higher heating values of pyrolysis liquids range between 17 and 20 MJ/kg
with liquid densities of about 1280 kg/m
3
. Assuming conversion of 72% of the biomass
feedstock to liquid on a weight basis, yield of pyrolysis oil is about 560 L/ton.
Recovery of high-value chemicals is another possibility, suggesting an integrated approach to
production of both chemicals and fuel. For example, levoglucosan is obtained at high yields
upon fast pyrolysis of pure cellulose or starch. Even woody or herbaceous biomass can yield
significant levoglucosan if metal ions, particularly potassium, are washed from the material
before it is pyrolyzed. Levoglucosan is considered a potential building block for synthesis of
dextrin-like polymers, pharmaceuticals, pesticides, and surfactants. Microorganisms have been
identified that can ferment levoglucosan to citric acid and itaconic acid, which may be an
attractive source of these chemicals if the levoglucosan is obtained from inexpensive
lignocellulosic materials.
4.7 Bio-oil Gasification
Bio-oil gasification of fast pyrolysis slurries is one possible application for fast pyrolysis liquids
with various notable advantages. Gasification of pyrolysis slurries allows for further conversion
of pyrolysis products to value-added products such as chemicals and synthetic fuels.
The liquid, char, and tar products from fast pyrolysis can be mixed into a viscous slurry.
Pyrolysis slurries can contain up to 85% of the input feedstocks mass, and an even higher
portion of the feeds energy. Pyrolysis char can be highly reactive and requires careful handling.
Mixing the char with pyrolysis oil to form a slurry allows for much easier handling and
transportation. This slurry appears almost as a solid. Even at low char concentrations, the
mixture loses much of its liquid characteristics because the char absorbs some of the tar and
pyrolysis liquids. At 20% straw char and 80% pyrolysis liquids, the mixture can be described as
crumbly, thick, and wet bulk material. Various pretreatment measures are necessary prior to
feeding the slurry into the gasifier. Atomization of the particles is important for complete carbon
conversion with low residence times. Char also has a tendency to agglomerate, and further
mechanical means such as using a colloid mixer may be required to break apart the char.
Figure 3 consists of a schematic for a biomass to liquid concept via fast pyrolysis and
gasification to Fischer-Tropsch synthesis. As shown, a pyrolyzer unit converts fibrous biomass to
gas with some entrained char. Separators, such as cyclones and electro-static precipitators,
retrieve the char from the gas. The pyrolysis gas is condensed, optionally at different
temperatures, to produce various bio oil fractions in similar manner to petroleum distillation. The
char and oil can then be combined as mentioned earlier into a slurry which can be pumped to the
gasifier. Once gasified, the synthetic gas generated can be catalytically converted to green diesel
fuel.
Bio-oil gasification experiments have been carried out in Germany by Forschungszentrum
Karlsruhe
75
in collaboration with Future Energy
76
. Their entrained-flow gasification plant has
350 to 500 kg/h capacity and is configured at 26 bars of pressure. These experiments used straw
as feedstock. Slurries with different compositions were used consisting of various pyrolysis
17
liquids and char particle sizes. Char particle sizes ranged from 6 to 50 m, and did not seem to
affect the process. Carbon conversion rates of more than 99.5% at 1400 C were estimated.
Viscosities of 2 Pas and up to 39% solid content were sampled. Problems associated with
plugging of nozzles or pipe sedimentation were not reported.
Conversion efficiencies for the pilot plant ranged between 50 and 71%, which are much lower
than the theoretical value, but may be due to heat losses associated with the gasifier size. Inert
gas flows were also higher (9 to 17% N
2
) than would be expected for a large scale gasifier. It is
estimated that a ton of synthetic fuel can be produced for every 7.5 tons of biomass. Electricity
can be generated from the gasification heat to provide energy required for the biomass
pretreatment as well as generation and compression of oxygen in the plant.
Figure 3 Bio-oil Gasification
P
y
r
o
l
y
z
e
r
Bio-Oil
Recovery
Slurry
Preparation
Pump
E
n
t
r
a
i
n
e
d

F
l
o
w

G
a
s
i
f
i
e
r
Fibrous
biomass
Bio-oil vapor
Slag
Cyclone
Bio-Oil
Char
F
i
s
c
h
e
r

T
r
o
p
s
c
h

R
e
a
c
t
o
r
Green
Diesel
P
y
r
o
l
y
z
e
r
Bio-Oil
Recovery
Slurry
Preparation
Pump
E
n
t
r
a
i
n
e
d

F
l
o
w

G
a
s
i
f
i
e
r
Fibrous
biomass
Bio-oil vapor
Slag
Cyclone
Bio-Oil
Char
F
i
s
c
h
e
r

T
r
o
p
s
c
h

R
e
a
c
t
o
r
F
i
s
c
h
e
r

T
r
o
p
s
c
h

R
e
a
c
t
o
r
Green
Diesel
4.8 Bio-Oil Hydrocracking
Bio-oil from fast pyrolysis has superficial resemblance to crude petroleum but its chemical
composition is dominated by oxygenated organic compounds rather than hydrocarbons. Thus,
efforts to upgrade bio-oil into motor fuel must recognize the considerable mass and energy losses
associated with removing oxygen. Early efforts focused on upgrading hydrotreated whole bio-
oil at high pressures (2000-2500 psi) and low velocities (0.1 0.2 LHSV) to yield an
intermediate product that was cracked in an FCC or hydrocracker to produce gasoline.
77
Under
these circumstances hydrodeoxygenation predominated, requiring large quantities of hydrogen to
remove oxygen and generating large amounts of water.
A more attractive approach to upgrading bio-oil is illustrated in Figure 4.78 Whole bio-oil
consists of a carbohydrate-derived aqueous phase and a lignin phase. The lignin phase has lower
oxygen content than the carbohydrate-derived phase, making it more attractive for hydrotreating.
The carbohydrate-derived phase can be steam reformed to provide the hydrogen required for
hydrotreating and hydrocracking. Hydrogen consumption could further be reduced by
18
hydrotreating at lower pressures, which favors decarboxylation as the mechanism for oxygen
removal.
Hydrotreating tests conducted by UOP LLC and Pacific Northwest National Laboratories
78
on
pyrolytic lignin are summarized in Table 5. Acid number of the hydrotreated samples dropped to
15 30 compared to 30-150 for the raw pyrolytic lignin. Oxygen content dropped from 30% to
6-20%. Further tests were conducted on steam reforming the aqueous phase of bio-oil into oil.
Only a small portion of hydrogen was needed to hydrotreat the lignin fraction of the bio-oil; the
rest could be used to provide the hydrogen demand for a petroleum hydrocracking at a refinery
that was processing both bio-oil and petroleum. The economics of using this biomass-derived
hydrogen become attractive when carbon dioxide credits reach $30/ton and bio-oil sells for
$10/bbl.
P
y
r
o
l
y
z
e
rCarbohydrate derived
aqueous phase
Bio-Oil
Recovery
Phase
Separation
Steam
Reformer
H
y
d
r
o
c
r
a
c
k
e
r
Fibrous
biomass
Bio-oil vapor
Hydrogen
Diesel
fuel
Cyclone
Lignin
Char
P
y
r
o
l
y
z
e
rCarbohydrate derived
aqueous phase
Bio-Oil
Recovery
Phase
Separation
Steam
Reformer
H
y
d
r
o
c
r
a
c
k
e
r
Fibrous
biomass
Bio-oil vapor
Hydrogen
Diesel
fuel
Cyclone
Lignin
Char
Figure 4 Bio-oil Hydrocracking
Table 5 Results of hydrocracking pyrolytic lignin
78
PNNL UOP
WHSV * 0.52 1.0
LHSV ** 0.22 0.68
Catalyst Pd/C NiMo
Pressure 1900 2000 1500
Liquid yield % 55.6 40.8
% Oxygen removal 69 93
% Oxygen in product 19.5 5.9
Acid number of product 34 15
% Naphtha in liquid 30 60
*Weight hourly space velocity
**Liquid hourly space velocity
19
4.9 Hydrothermal Processing
Hydrothermal processing (HTP) describes the thermal treatment of wet biomass to produce
carbohydrate, liquid hydrocarbons, or gaseous products depending upon the reaction
conditions.
79,80
As the desired reaction temperature increases, higher pressures are required to
prevent boiling of the water in the wet biomass. Thus, processing conditions range from hot,
compressed water at 200 C to supercritical water above 374 C.
At 200 C and 20 bar pressure, fibrous biomass undergoes a fractionation process to yield
cellulose, lignin, and pentose (from hemicellulose). This low temperature HTP has potential
application as a pretreatment for enzymatic hydrolysis of cellulose.
At 300 350 C and 120 180 bar pressure and reaction times of 5-20 minutes, biomass
undergoes more extensive chemical reaction. Reaction products include a hydrocarbon-rich
fraction known as biocrude representing as much as 45 wt-% of the product. Products also
include 25 wt-% non-condensable gas, which is mostly CO
2
, and 30% aqueous phase which is
about 30 wt-% dissolved organic compounds such as acetic acid and ethanol. The biocrude is
attractive for its low oxygen content (10-18 wt-% compared to 45 wt-% for the original biomass)
and high lower heating value (30 35 MJ/kg). A number of companies have attempted to
commercially develop the technology including Biofuel B. V., Changing World Technologies,
EnerTech Environmental, Inc., Shell, and TNO.
At 600- 650 C and 300 bar pressures, supercritical conditions prevail. For reaction times of 0.5-
2.0 minutes, gas is the primary reaction product and the process is referred to as supercritical
gasification. Typical volume fractions of gas constituents are: H
2
56 vol-%; CH4 47 vol-%;
CO
2
33 vol-%; and CO 4 vol-%. The combination of relatively low temperature and high
pressure makes high methane yields, which is problematic for Fischer-Tropsch synthesis and
steam reforming of the gas seems inevitable.
4.10 Catalytic Processing to Methylated Furans
Methylated furans have properties that are potentially attractive as transportation fuels. A
schematic of various methylated furans relevant to transportation fuels is shown in Figure 5.
They can be produced from both the hexose and pentose content of lignocellulosic biomass and
other carbohydrate-rich plant materials. Treatment with acid and/or heat can drive dehydration
reactions that ultimately yield furans. Catalysts can improve yields by making furan-producing
pathways more selective among the large number of competing reactions that can occur during
pyrolysis of biomass.
Sugars consisting of five-member rings like xylose (a pentose) or fructose (a ketohexose) are
readily dehydrated to the five-member rings of furan compounds.
81
Dehydration of xylose yields
furfural (an aldehyde) while fructose yields 5-hydroxymethylfurfural (a dimethylated furan). All
described methods of the synthesis of 5-hydroxymethylfurfural require thermal dehydration in
acidic medium, which presents some challenges in isolation of this unstable compound. A
diagram of proposed reaction pathways to hydroxymethylfurfural is shown in Figure 6.
20
Aldohexo
considera
while fru
oses like glu
able more di
uctose is obta
ucose can als
ifficulty. Xy
ained from s
so be dehydr
ylose is obta
sucrose or th
rated to 5-hy
ined from th
he isomerizat
ydroxymethy
he hemi-cellu
tion of gluco
ylfurfural bu
ulose conten
ose.
ut with
nt of biomasss
Figur
Neither f
upgraded
methyl fu
Figure
(HMF):
Dumesic
an acid c
to a low-
conversio
have imp
The HMF
two oxyg
re 5 Furans
furfural nor 5
d. Furfural c
uran, dimeth
6 Proposed
: fructopyra
and cowork
catalyst are d
boiling-poin
on is 77% w
proved upon
F is next con
gen atoms lo
relevant to
5-hydroxym
can be methy
hyl furan, trim
d reaction pa
anose (1), fr
kers use a bip
dissolved in t
nt solvent (m
with half the H
previous HM
nverted to D
owering the b
the produc
proces
methylfurfura
ylated by rea
methyl furan
athway for
ructofurano
4) an
phasic reacto
the water ph
methyl isobut
HMF ending
MF synthesi
MF using a
boiling point
tion of tran
ssing of suga
al is suitable
action with m
n, and tetram
conversion
ose (2), two i
nd HMF (5)
4
or to convert
hase of the re
tyl ketone).
g up in the o
is by increas
copper-base
t to a range t
nsportation f
ars
as motor fue
methanol ove
methyl furan.
of fructose
intermediat
49
t fructose to
eactor. HMF
In an optim
rganic phase
ing yields an
ed catalyst. T
that makes it
fuels by the
el and must b
er zeolite cat
.
82, 83
to hydroxym
te stages of d
HMF.
49
Th
F is extracted
mized system,
e. Dumesic a
nd improvin
This convers
t suitable as
ermochemiccal
be further
talyst to yielld
methylfurfu
dehydration
ural
n (3,
he fructose a
d as it is form
, fructose
and coworke
g extraction
sion remove
motor fuel.
nd
med
ers
.
s
21
Zhao and coworkers have developed an alternative approach for converting sugars into HMF.
Instead of an aqueous solution and acid catalyst, they use ionic liquids as solvent and metal
chlorides as catalysts. The absence of an aqueous phase prevents secondary reactions that
introduce contaminants to the desired product. The process also works well on both fructose
(90% yield) and glucose (70% yield).
50
5 Hybrid Processing
Hybrid thermochemical/biological processing thermolytically decomposes fibrous plant
materials into a uniform intermediate product that can be biologically converted into a biobased
product. There are two distinct approaches to hybrid processing: (1) gasification followed by
fermentation of the resulting gaseous mixture of carbon monoxide (CO), hydrogen (H
2
) and
carbon dioxide (CO
2
), and (2) fast pyrolysis followed by hydrolysis and/or fermentation of the
anhydrosugars found in the resulting bio-oil.
5.1 Syngas Fermentation
A number of microorganisms are able to utilize the gaseous constituents of syngas (or producer
gas) as substrates for growth and production. These include autotrophs, which use C
1
compounds as their sole source of carbon and hydrogen as their energy source, and
unicarbonotrophs, which use C
1
compounds as their sole source of both carbon and energy.
Clean syngas from a gasifier can therefore be fed into a stirred fermentor to produce various
biobased fuels as shown in Figure 7. Among the fermentation products are carboxylic acids,
alcohols, esters, and hydrogen.
In a comprehensive review on the prospects for ethanol from cellulosic biomass, Lynd noted that
syngas fermentation represents an end run with respect to acid or enzymatic hydrolysis of
biomass since it avoids the costly and complicated steps of extracting monosaccharide from
lignocellulose.
84
It also has the potential for being more energy efficient since it effectively
utilizes all the constituents of the feedstock, whether cellulose, hemicellulose, lignin, starch, oil,
or protein.
Syngas fermentation also has advantages compared to the use of inorganic catalyst in the
production of synthetic fuels.
85
Most catalysts used in the petrochemical industry are readily
poisoned by sulphur-bearing gases whereas syngas-consuming anaerobes are sulphur tolerant. In
conventional catalytic processing, the CO/H
2
ratio of the syngas is critical to commercial
operations whereas biological catalysts are not sensitive to this ratio; indeed, the water-gas shift
reaction is implicit in the metabolism of autotrophic and unicarbonotrophic anaerobes. Gas-
phase catalysts typically employ temperatures of several hundreds of degree Centigrade and at
least 10 atmospheres of pressure whereas syngas fermentation proceeds at near ambient
conditions. Finally, biological catalysts tend to be more product specific than inorganic catalysts.
22
Gasifier
Syngas
Gas Cleaning
Oxygen
Fiber
Fermenter
Biobased
fuels
CO
2
Gasifier
Syngas
Gas Cleaning
Oxygen
Fiber
Fermenter
Biobased
fuels
CO
2
Figure 7 Gasification to biofuels via syngas fermentation
Nevertheless, as described by Grethlein and Jain, syngas fermentation has several barriers to
overcome before it can be commercialized.
85
Among these are relatively low rates of growth and
production by anaerobes, difficulties in maintaining anaerobic fermentations, product inhibition
by acids and alcohols, and difficulties in transferring relatively insoluble CO and H
2
from the gas
phase to the liquid phase, where the anaerobes can utilize the gas. Of these, mass-transfer
limitations probably represent the main bottleneck to commercializing this technology. However,
studies by Worden and coworkers give encouragement that the use of non-toxic surfactants and
novel dispersion devices can enhance mass transfer through the generation of microbubbles to
carry syngas into bioreactors.
86
5.2 Bio-Oil Fermentation
Bio-oil fermentation is based on the observation that under rapid pyrolytic conditions, pure
cellulose yields levoglucosan, an anhydrosugar with the same empirical formula as the
monomeric building block of cellulose: C
6
H
10
O
5
.
87
Anhydrosugar is a sugar from which one or
more molecules of water have been removed, resulting in the formation of an internal acetal
structure as shown in Figure 8.
On the other hand, addition of a small amount of alkali inhibits the formation of levoglucosan
and promotes the formation of hydroxyacetaldehyde; for slower heating rates and lower
temperatures char rather than liquids is preferentially formed. These multiple reaction pathways
for pyrolysis of cellulose are illustrated in Figure 2.
88
Scott and coworkers at the University of Waterloo in Ontario, Canada recognized that alkali in
biomass catalyzed the char-forming pathway.
89
If these cations are removed by soaking the
feedstock in dilute acid before pyrolysis, the lignocellulose is depolymerized to anhydrosugars,
primarily levoglucosan, at very high yields. Levoglucosan is readily hydrolyzed to glucose.
23
Brown and his collaborators evaluated the effect of alkali removal on the pyrolytic products of
cornstover.
90
Three pretreatments were evaluated: acid hydrolysis, washing in dilute nitric acid,
and washing in dilute nitric acid with the addition of (NH
4
)
2
SO
4
as a pyrolytic catalyst. All three
acid treatments were able to substantially increase the yield of anhydrosugars from less than 3
wt-% to as high as 28 wt-%. Acid hydrolysis of this anhydrosugar yielded 5% solutions of
glucose and other simple sugars.
The resulting glucose solutions can be fermented, as demonstrated by Prosen et al.
91
However,
the resulting substrate derived from the bio-oil contains fermentation inhibitors that must be
removed or neutralized by chemical or biological methods. Chemical methods that have been
evaluated on bio-oil derived substrate include solvent extraction, hydrophilic extraction, and
adsorption extraction
92
. Khiyami explored the use of ligninolytic enzymes to remove toxins
from bio-oil
93
.
One manifestation of a biorefinery based on fermentation of bio-oil is illustrated in
Figure 9. Fibrous biomass is pretreated with dilute acid to simultaneously remove alkali and
hydrolyzes the hemicellulose fraction to pentose. The remaining fraction, containing cellulose
and lignin, is pyrolyzed at 500 C to yield char, gas, and bio-oil. The bio-oil is separated into
pyrolytic lignin and levoglucosan-rich aqueous phase. The char, gas, and lignin are burned to
generate steam for distillation and other process heat requirements of the plant while the
levoglucosan is hydrolyzed to hexose. The pentose and hexose are fermented to ethanol.
Figure 8 Chemical structure for levoglucosan (1,6-anhydro-beta-D-glucose)
24
Figure 9 Bio-oil Fermentation
6 Economics of Biorefineries
6.1 Biochemical Refineries
Representative of biochemical refineries is the corn grain to ethanol process. Fuel ethanol is
commercially available as a transportation fuel or additive. Most fuel ethanol production is
derived of fermentation of corn glucose or sucrose in the US
94
and sugarcane in Brazil
95
respectively. Dry milling and wet milling are general classifications for the processing of corn-
based ethanol. Due to lower requirements for capital and labor, dry milling has dominated the
recent grain ethanol industry. Advanced biochemical refineries convert cellulose from plant
fibers to ethanol. Ethanol from lignocellulosic biomass employs hydrolysis, or other pre-
treatments, to break down the cellulosic material prior to fermentation. Enzymatic processes are
expected to have much lower costs in the future than current starch based processes
96
.
Fermenter
Fiber
P
y
r
o
l
y
z
e
r
Anhydrosugar & other
carbohydrate
Bio-Oil
Recovery
Phase
Separation
Detoxification
Lignin
Hot water
extraction
Pentose
Fiber
byproduct
Bio-oil vapor
Fermenter
Distillation
Water
Ethanol
Cyclone
Char
D
r
i
e
r
Fermenter
Fiber
P
y
r
o
l
y
z
e
r
Anhydrosugar & other
carbohydrate
Bio-Oil
Recovery
Phase
Separation
Detoxification
Lignin
Hot water
extraction
Pentose
Fiber
byproduct
Bio-oil vapor
Fermenter
Distillation
Water
Ethanol
Cyclone
D
r
i
e
r
Char
25
6.1.1 Grain Ethanol
Starch-based ethanol fermentation plants are relatively inexpensive to build and operate. The
general operation of the plant follows the schematic outlined in Figure 10. Capital costs for 25
million gallons of ethanol capacity can be as low as $27.9 million
97
. Production cost estimates in
the USA and Europe range between $0.96
98
and $1.37
99
per gallon depending on assumptions,
especially feedstock costs. McAloon et. al. estimated the operating costs of a 25 million gallon
per year capacity plant to total $1.00 (2005 dollars) per gallon of ethanol. Table 6 consists of the
operating cost components of this plant.

consists of the
operating cost components of this plant.




The purchase of corn grain is the greatest expense for fermentation plants. Corn grain prices have
historically been about $2 per bushel, but current trends find the price upwards of $3 per bushel.
Distillation is an energy intensive process that adds considerable cost. The fermentation process
yields a mixture of mostly water and 4-5% by weight ethanol. Distillation followed by filtration
through vapor-phase molecular sieves is required to achieve 99.5% ethanol purity. This process
also produces various by-products such as distillers dried grain (DDGS). Revenue from DDGS
can offset operation and management costs.
The purchase of corn grain is the greatest expense for fermentation plants. Corn grain prices have
historically been about $2 per bushel, but current trends find the price upwards of $3 per bushel.
Distillation is an energy intensive process that adds considerable cost. The fermentation process
yields a mixture of mostly water and 4-5% by weight ethanol. Distillation followed by filtration
through vapor-phase molecular sieves is required to achieve 99.5% ethanol purity. This process
also produces various by-products such as distillers dried grain (DDGS). Revenue from DDGS
can offset operation and management costs.


Table 6 Corn Grain Production Costs (McAloon et. al. 1999) Table 6 Corn Grain Production Costs (McAloon et. al. 1999)

Annual Annual Per Gallon Per Gallon
Shelled Corn $17,000,000 $0.68
Other Raw Materials $1,600,000 $0.06
Denaturant $600,000 $0.03
Utilities $4,000,000 $0.16
Labor, Supplies, and Overhead Expenses $3,100,000 $0.13
Depreciation of Capital $2,800,000 $0.11
DDG Credit -$7,100,000 -$0.29
Total Production Cost $22,000,000 $0.88
CO
2
Starch
Enzymes
Fermenter
Grain
Cooking
Stillage
Drying
Distillation
Grinding
Ethanol
Distillers
Dried
Grains
Figure 10 Grain-to-ethanol processing
26
6.1.2 CCellulosic Ethanol
Advance
the corn
estimates
capital co
with adva
The bioc
ethanol p
enzymes
to produc
technolog
annual ca
upon the
be emplo
Projected
be $3.33
$0.89 per
Processin
requires m
carbohyd
residence
recycled
by-produ
F
d biochemic
stalk that is
s at $50 per M
osts remain h
anced techno
hemical plat
platform in th
; enzymatic
ce ethanol; a
gy, capital c
apacity. Ope
assumption
oyed. A repr
d capital cost
- $4.44 per
r gallon of e
ng of cellulo
more intensi
drates require
e time. The m
and used for
ucts, such as
Figure 11 C
cal refineries
typically not
Mg. While f
higher due to
ology as hig
tform based
he unit opera
hydrolysis o
and distillatio
osts are estim
erating costs
s made abou
resentative s
t for future p
gallon ethan
thanol.
103
osic biomass
ive pretreatm
es additiona
main by-prod
r process he
organics.
Cellulosic Et
s use cellulos
t harvested,
feedstock co
o added proc
gher process
on enzymat
ations involv
of cellulose t
on to produc
mated to be
are estimate
ut feedstock
schematic of
plants emplo
nol annual ca
differs from
ment depend
l energy, and
duct from ce
at. Addition
thanol Oper
sic biomass
has a much
sts are lower
cess complex
efficiencies
ic hydrolysi
ved: pretreat
to sugars; fe
ce neat ethan
between $4.
ed to be betw
costs, enzym
f operating co
oying more a
apacity with
m corn grain
ding on how
d the fermen
ellulosic biom
al revenue m
rating Costs
as feedstock
lower cost th
r for the adv
xity. Operat
of up to 48%
s of cellulos
tment to mak
rmentation o
nol. Based o
.03 and $5.6
ween $1.34
1
me costs, and
osts compon
advanced tec
operating co
in some key
it is delivere
ntation proce
mass conver
may be deriv
s (50 Million
k. Corn stove
han corn gra
vanced bioch
ing costs can
% are achiev
er, a portion
ain with curr
hemical proc
n be reduced
ved
100
.
of
rent
cess,
d
e is very sim
ke the cellulo
of sugars by
on the curren
60 per gallon
101
and $1.69
d the kind of
nents is show
chnologies ar
osts droppin
milar to the g
ose accessib
yeast or bac
nt state of
n of ethanol
9
102
depend
f pretreatmen
wn in Figure
re estimated
ng to $0.40 an
grain
ble to
cteria
ing
nt to
11.
d to
nd
y areas. Cellu
ed. Reducing
ess necessita
rsion is ligni
ved from othe
ulosic bioma
g the comple
ates a longer
in, which can
er small volu
ass
ex
n be
ume
n Gallons peer Year)
27
6.2 Thermochemical Refineries
Unlike the biochemical platform, for which the fuel product is defined (ethanol) and there is
reasonable consensus as to the unit operations to be employed, there is a greater diversity of
opinion on how the thermochemical platform should be configured. Thermolytic processing of
biomass can generally be categorized as either gasification (to produce a gaseous product) or fast
pyrolysis (to produce primarily liquid product). A variety of catalytic
104
or even biocatalytic
schemes
4
have been proposed to upgrade the thermolytic products into alcohols, ethers, esters, or
hydrocarbons. A typical catalytic synthesis plant based on biomass gasification can be described
by the diagram shown in Figure 12. Thermochemical plants are better suited for large-scale, 100
million to 500 million or more gallons per year, deployment due to high capital costs. Economies
of scale allow for lower costs per unit volume, but transportation costs need to be taken into
consideration as well as feedstock availability. Based on capital, operating, and transportation
costs, an optimum plant size can be determined at which fuel production costs are minimized.
6.2.1 Hydrogen
Thermochemical treatment of biomass to produce hydrogen, or methanol, has a high efficiency
of 50%, and 45% respectively. The implication of this is that for the same energy input hydrogen
plants can yield a greater amount of fuel energy than corn grain ethanol for example. This is
reflected in a lower feedstock cost due to a lower feed input requirement. Operation and
management costs are small, and in some cases, completely accounted for through by-product
revenues. Hydrogen plants can be configured to produce heat or electricity from excess methanol
production.
The literature includes several studies on the cost of hydrogen from biomass. Capital costs range
from $0.65 to $1.33 per gallon of hydrogen capacity
105, 106
, depending upon the type and size of
gasifier plant. Operating costs range from $0.31 to $0.44 per gallon of hydrogen produced
107
depending upon the cost of biomass and the kinds of processes employed
108
. Hamelinck and
Faaij
109
represent one of the most recent studies (2002) on biomass to hydrogen. For a
gasification plant producing 182 million gallons hydrogen fuel per year, the estimated capital
Catalytic Synthesis
Gasifier
Syngas
Gas Cleaning
Biobased
fuels
CO
2
Oxygen
ber Fi
Figure 12 Gasification to fuels via catalytic synthesis
28
cost is $2
includes
206 MUS wi
the major op
ith operating
perating cost
g costs of $0
t component
.24 per gallo
ts for a hydro
on hydrogen
ogen plant.
n produced. FFigure 13
Figur re 13 Annuaal operatingg costs for 4400 MW hyddrogen plannt
6.2.2 MMethanol S Synthesiss
Productio
Previous
from $0.6
and Faaij
gasificati
investme
Operatin
on costs for
techno-econ
62 to $1.11 p
j analyzes bo
ion plant pro
ent of $276 M
g cost comp
methanol ar
nomic studie
per gallon of
oth hydrogen
oducing 87 m
MUS. The pr
onents are sh
re identical w
es of methan
f methanol
11
n and metha
million gallo
roduction co
hown in Fig
within a 30%
nol plants ind
10, 111
. The t
nol plants. B
ns of methan
ost of methan
gure 14.
% uncertainty
dicate that m
techno-econo
Based on ave
nol per year
nol was $0.6
y to those of
methanol cost
omic analysi
erages from
would requi
62 per gallon
f a hydrogen
ts would ran
is of Hameli
their analysi
ire a capital
n of methano
plant.
nge
inck
is, a
ol.
Hamelinc
productio
processin
specific i
pressure
refining a
importan
than hydr
hydrogen
ck and Faaij
on of methan
ng sections a
investments
swing adsor
and make up
nt considerati
rogen at 16 M
n is required
modeled th
nol and hydr
are interchan
costs related
rption units a
p compresso
ion is the en
MJ/L (comp
to provide t
e costs of va
rogen. While
ngeable for e
d to the gene
at a cost of a
r add up to $
nergy content
pared to 8 M
the same am
arious therm
e the gasifica
either hydrog
eration of eac
about $30 mi
$30 million f
t of the fuel.
J/L hydroge
mount of ener
mochemical c
ation, gas cle
gen or metha
ch fuel. Hyd
illion for a 4
for an equiv
. Methanol h
en), therefore
rgy.
configuration
eaning, and
anol product
drogen produ
400 MW plan
alent plant. A
has twice the
e a larger vo
ns for the
syngas
tion, there ar
uction requir
nt. Methano
Another
e energy den
lume of
re
res
l
nsity
29
6.2.3 M
In April o
with hyd
natural g
mixed alc
Some eco
13% for M
technolog
cost of m
et. al. sug
ethanol b
Feed
P
Retu
Figu
Mixed Alco
of 2005, ther
drocarbon ch
as due to eco
cohols.
onomic stud
MTBE from
gy develope
mixed alcoho
ggest that eth
by 2012
116
.
T
Product(s)
d Rate (Pet C
Feed Cost
Plant Cost
Product Valu
urn on Invest
re 14 Annu
ohols
re were no c
ains of six c
onomical rea
dy results are
m C
1
to C
4
alc
rs include D
ols from othe
hanol and m
Table 7 Mix
Coke)
ue
tment
al operating
commercial p
arbons or le
asons. Synga
e included in
cohols, and
Dow
113
, Snam
er references
mixed alcohol
xed Alcohol
B
MTBE fro
1
$35
$0.85
g costs for 4
plants dedica
ss
112
. Mixed
as from biom
n Table 7. Th
15% for etha
mprogetti (SE
s is shown in
l synthesis c
Economics
Bechtel
117
om C1/C4 al
800 TPD
$0/ton
50-400MM
5 cents/gal M
~13%
400 MW me
ated to the p
d alcohols ar
mass can be
he expected r
anol, propan
EHT)
114
, an
n Table 8. C
could be cost
s Study Com
cohols E
MTBE
ethanol plan
production of
re generally p
used to cata
return on inv
nol, and pow
d IFP (Subst
onclusions m
t competitive
mparison
Fluor/E
Ethanol, Prop
475
$0
estimated at
$1.15
alcohols
~
nt
f mixed alco
produced fro
lytically pro
ohols
om
oduce
vestment is a
wer. Other
tifuel)
115
. Th
made by Phi
e with corn
about
he
llips
Ecalene
118
panol, and Po
58 TPD
0/ton
t >$1 billion
cents/gal fo
, 4.4 cents/k
power
~15%
ower
n63
or
kWh
30
Table 8 Mixed Alcoohol Producction Costs ((adapted from Spath 22003)
Prod
(ton
55
38
60
73
635,000
~1,7
6.2.4 F
Biomass
Tropsch
natural g
Capital c
slurry ph
Previous
would ra
complete
al.
68
The
about 35
about $2
F
duction
nne/yr)
0,000
6,000
0,000
0,000
0-730,000
700,000
Fischer-Tr
to Fischer-T
commercial
as or coal ad
cost estimate
hase reactors
studies of b
ange from $1
e techno-eco
ey estimate t
million gall
.37 per gallo
Figure 15 An
ropsch Sy
Tropsch fuel
plants empl
dds additiona
es by Sasol fo
equal about
biomass gasif
.1 to $4.1 pe
nomic analy
the capital co
lons of F-T d
on of F-T die
nnual opera
Metha
50
63
(60-70)
70
70/30
70
ynthesis
studies are
loying other
al cost and s
for a two trai
t $25,000 pe
fication plan
er gallon of F
yses of a Fisc
ost for an ox
diesel per ye
esel. A summ
ating cost fo
nol/C
5
+
0/50
/35
)/(30-40)
0/30
, 50/50
0/30
generally ba
fossil fuels.
some comple
n Gas-To-Li
er BPD capac
nts producing
F-T diesel
35,
cher-Tropsch
xygen-blown
ear to be abou
mary of the o
or 367 MW
Cost ($/
$167
$255 -
$31
$395 -
$282 -
$318 -
/tonne)
7.7
$198
3.9
$110
$205
$279
ased on the a
The use of b
exity due to p
iquids plant
city
125
.
g Fischer-Tr
, 105
. Among
h diesel plan
n, pressurized
ut $341 MU
operating co
biomass Fis
already estab
biomass as a
pretreatment
with 30,000
ropsch diese
the most rec
nt is that by T
d gasifier pla
US with oper
st is shown i
scher-Trops
Cost Year
1986
1989
1983
1982
1986
na
r Refer
[11
[12
[12
[12
[12
[12
ence
9]
0]
1]
2]
3]
4]
blished Fisch
a substitute t
t considerati
0 barrels per
her-
to
ions.
day
l suggest cos
cent and
Tijmensen e
ant producin
ating costs o
in Figure 15
sts
et
ng
of
5.
sch plant
31
Fischer-Tropsch synthesis yields a wide variety of hydrocarbon chains. Small hydrocarbons (C
1
C
4
) can be recycled and used as process heat. Long hydrocarbons can be broken into smaller
chains if necessary. The Anderson-Schulz-Flory (ASF) distribution describes the relation
between hydrocarbon yield and chain growth
126
. Commercializing the by-products is important
for Fischer-Tropsch biomass diesel to be become economically viable.
6.2.5 Bio-oil Fermentation
So and Brown
127
have performed one of the only techno-economic analyses of bio-oil
fermentation. As summarized in Table 9, total capital investment for an ethanol plant based on
fermentation of bio-oil producing 95 million L of ethanol was estimated to be $69 million, while
the annual operating cost was about $39.2 million, resulting in an ethanol production cost of
$ 0.42/L.
Table 9 Production cost of ethanol from cellulosic biomass
Annual ethanol output 95 million L
Annual biomass input 240 x 10
6
kg
Total capital $69 million
Raw materials ($46/ton) $11.1 million
Labor, utilities, maintenance $6.18 million
Indirect costs $8.07 million
Annual capital charges $13.8 million
Annual operating costs $39.2 million
Production cost of ethanol $0.42/L
1
1997 US $
6.2.6 Syngas Fermentation
Although syngas fermentation to ethanol is undergoing commercial development, there are no
publications on ethanol production from syngas fermentation to date. We have performed a
preliminary economic assessment on syngas fermentation to hydrogen and polyhydroxyalkonate
(PHA), a biodegradable polymer of commercial interest.
128
A diagram of the process is included
in Figure 16.
This analysis assumes 20 tpd of PHA and 55 tpd of hydrogen. The capital costs, detailed
in Table 10, are estimated to be $103 million. The operating costs for this plant, shown in Table
11, yields a production cost of $2.80/kg of PHA assuming a credit for co-product hydrogen equal
to $1.90/kg, which is based on a U.S. Department of Energy long-term target price for this fuel.
This PHA production cost compares favorably with the production cost of PHA from glucose,
which may be as much as $5-7/kg.
32
Tar Cracker
Methane Reformer
Syngas Bioreactor Separations
Gasifier
Figure 16 Conceptual schematic of biorefinery to produce hydrogen and PHA
coproducts from fibrous biomass
Table 10 Estimated capital costs for biorefinery to produce hydrogen and PHA coproducts
from fibrous biomass
Gasifier $18.6 million
Estimated from: Larson and
Svenningsson (1990)
Fermenter $59.1 million
Estimated as 25% of total cost of
an ethanol plant
Separation equipment $25.3 million
Estimated as 30% of total costs of
a fermentation plant
Grassroots Capital $103 million
33
34
Table 11 Estimated operating costs for biorefinery to produce hydrogen and PHA
coproducts from fibrous biomass
Annual H2 output
18.1 x 10
6
kg
Based on 20% CO to cell mass;
35% cell mass to PHA
Annual PHA output
6.5 x 10
6
kg
Annual input
210 x 10
6
kg
90% capacity factor
Total Capital $119 million
Raw materials $12.6 million Purchased at $0.06/kg
Credit for H2 ($34.3 million) Assumed to sell for $1.90/kg
Labor, utilities, maintenance $15.6 million
Indirect costs $10.4 million
Annual capital charges $13.9 million 10% interest, 20 yrs
Annual operating costs $18.2 million
PHA Production costs $2.80 / kg
7 Conclusions
Current generation biofuels will continue to be heavily employed due to the infrastructure and
policies already in place. Advanced fuels from biorenewable sources, particularly cellulosic
biomass, will be necessary to displace larger amounts of fossil fuel resources. Various
technologies stand to profit from the renewed interest in alternative sources of energy.
As shown in this paper, each of the potential biofuels considered has its advantages and
disadvantages in terms of market applications, environmental benefits, and process economics.
This results in a situation where no single biofuel may ultimately dominate in similar fashion to
gasoline. Niche markets and regional considerations will heavily influence the best choice of fuel
for specific applications. Finally, increased research efforts could yield raise new possibilities
that change the outlook of any, and all, bio-based fuels.
Although biochemical processing is the dominant form of biomass based fuel in the current
generation, thermochemical and hybrid processing stand to increase their contributions. A major
motivation for the interest in these advanced pathways is the increased in biochemical feed costs
due to the high demand and competition with food demand. Cellulosic based technologies enjoy
a larger pool of feed sources, including waste materials, and are more flexible in terms of the
biomass inputs. Hybrid processing allows for the combination of the thermochemical flexibility
with the biochemical established technology.
It is almost certain that the predominant biofuel choice will be based on a combination of market
forces, environmental concerns, and public policy drivers. At this point, there may not be enough
information to determine a winner among the various choices. Nevertheless, increased efforts
in this research area should help narrow down the available choices to biorenewable resources
that can serve as a foundation for our energy future.
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109 C. N. Hamelinck, and A. Faaij. Future prospects for production of methanol and hydrogen
from biomass. Journal of Power Sources 111 1 (2002).
110 R. E. Katofsky, The Production of Fluid Fuels from Biomass, Center for Energy and
Environmental Studies, Princeton University, Princeton (1993).
111 R. H. Williams, E.D. Larson, R.E. Katofsky, J. Chen, Methanol and hydrogen from biomass
for transportation, with comparisons to methanol and hydrogen from natural gas and coal,
41
PU/CEES Report 292, Center for Energy and Environmental Studies, Princeton University,
Princeton, NJ (1995) p. 47.
112 Mixed Alcohols from Syngas: State of Technology Nexant, NREL Contract ACO-5-
44027, May 2005.
113 Nirula, S. C. (1994). "Dow/Union Carbide Process for Mixed Alcohols from Syngas."
PEP Review no. 85-1-4, SRI International, Meno Park, CA.
114 Olayan, H. B. M. (1987). "Selection of technology for synthesis gas based products in
Saudi Arabia." Energy Progress, 7(1), 9-17.
115 Courty, P., Chaumette, P., Raimbault, C., and Travers, P. (1990). "Production of
methanol-higher alcohol mixtures from natural gas via syngas chemistry." Revue de
l'Institut Francais du Petrole, 45(4), 561-78.
116 S. Phillips, A. Aden, J. Jechura, D. Dayton, and T. Eggeman. Thermochemical Ethanol via
Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass. NREL/TP-
510-41168 April 2007.
117 Economics of MTBE via Mixed Alcohol SynthesisAlternative Fuels and Chemicals from
Synthesis Gas, cooperative agreement DE-FC22-95PC93052. 1996.
118 Fluor 2003 Gasification Technologies Conference paper, ibid.
119 Optimization of Electricity-Methanol Coproduction. Configurations of Integrated-
Gasification-Combined-Cycle/Once-Through. ChemSystems. EPRI/GS-6869, 1990.
120 Salmon, R. "Economics of Methanol Production from Coal and Natural Gas."
ORNL-6091, Oak Ridge National Laboratory. 1986.
121 Courty, P., Arlie, J. P., Convers, A., Mikitenko, P., and Sugier, A. "C1-C6
Alcohols from Syngas." Hydrocarbon Processing, 63(11), 105-108. 1984.
122 Ricci, R., Paggini, A., Fattore, V., Ancillotti, F., and Sposini, M. "Production of
methanol and higher alcohols from synthesis gas." Chemia Stosowana, 28(1), 155-68. 1984.
123 El Sawy, A. H. "Evaluation of Mixed Alcohol Production Processes and Catalysts." NTIS.
DE90010325. SAND89-7151, Mitre Corporation. 1990.
124 Bechtel Corporation. "Task 4.2 Commercial Applications - Economics of MTBE via Mixed
Alcohol." Subcontract No. PT5781-B, Prepared for Air Products and Chemicals. 1998.
125 Lutz, B. (2001). "New age gas-to-liquids processing." Hydrocarbon Engineering 6(11):
23-26, 28.
126 Schulz H. Short history and present trends of FT synthesis. Applied Catalysis A: General
1999;186:116.
127 So, K.S., Brown, R. C. (1999) Economic analysis of selected lignocellulose to ethanol
conversion technologies, Applied Biochemistry and Biotechnology 77-79, 633-640.
128 Brown, R. C. (2007) Hybrid thermochemical/biological processing of biomass, Applied
Biochemistry and Biotechnology 137-140, 947 956.
49
Review
Comparative economics
of bioreneries based on the
biochemical and
thermochemical platforms
Mark M. Wright and Robert C. Brown, Center for Sustainable Environmental Technologies, Iowa State University
Received 17 May 2007; revised version received 11 June 2007; accepted 11 June 2007
Published online in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.8;
Biofuels, Bioprod. Bioref. 1:4956 (2007)
Abstract: A variety of biochemical and thermochemical technologies have been proposed for the production of
biofuels. Meaningful economic comparisons require that they be evaluated on the same bases in terms of technol-
ogy maturity, plant capacity, the energy content of the fuel, feedstock costs, method of calculating capital charges,
and year in which the analysis is assumed. Such an analysis for rst-generation biomass-to-biofuels plants reveals
that capital costs will be comparable for advanced biochemical and thermochemical bioreneries, costing four to
ve times as much as comparably sized grain ethanol plants. The cost of advanced biofuels, however, will be similar
to that of grain ethanol as corn prices exceed $3.00 per bushel. 2007 Society of Chemical Industry and John
Wiley & Sons, Ltd
Keywords: biochemical platform; thermochemical platform; biofuel; economics
Introduction
T
he commercial success of the grain ethanol industry
has increased interest in processes that convert fbrous
biomass (lignocellulose) into biofuels. Much of this
attention has been directed towards enzymatic hydrolysis of
cellulose to simple sugars and its subsequent fermentation
to ethanol, the so-called biochemical platform. However,
the recent announcement by the Department of Energy
that three of the six biorefnery projects selected for federal
funding include gasifcation technologies has increased
interest in the thermochemical platform.
1
Tis approach
thermolytically transforms biomass into gaseous or liquid
intermediate chemicals that can be upgraded to transporta-
tion fuels or commodity chemicals. Te thermochemical
platform is related to the commercially successful proc-
esses used by the petroleum and petrochemical industries
to transform fossil fuels into fuels and chemicals, although
biomass and coal have very diferent physical and chemical
properties and their processing will difer in some respects.
Correspondence to: Robert C. Brown, Center for Sustainable Environmental Technologies, 286 Metals Development,
Iowa State University, Ames, IA-50010, USA. E-mail: rcbrown@iastate.edu
2007 Society of Chemical Industry and John Wiley & Sons, Ltd
50
MM Wright, RC Brown Review: Comparative economics of biorefineries
Opinions vary widely on which of these platforms is most
likely to prevail in the emergence of cellulosic biofuels.
Although a number of techno-economic studies of various
manifestations of these two platforms have appeared in the
literature, direct comparisons of them on the same bases are
dif cult to fnd.
Tis paper compares the capital costs and operating costs
of the current generation of starch-based ethanol plants with
those of frst-generation lignocellulose-to-biofuels plants.
Tese lignocellulosic biofuels platforms include enzymatic
hydrolysis of cellulose to ethanol (the biochemical platform)
and three manifestations of the thermochemical platform in
which biomass is gasifed and upgraded to hydrogen, meth-
anol, or FischerTropsch (F-T) liquids.
Background
Current ethanol production is based on either sugar or
starch crops, with the former dominating in Brazil and
the latter in the USA, the two largest commercial ethanol
producers in the world. Te present study focuses on dry
milling of corn (a starch crop) because of its relevance to
US markets. Although wet milling has some ef ciency and
production cost advantages, dry milling has dominated the
recent grain ethanol industry because of its lower require-
ments for capital and labor.
Dry milling consists of four major operations: grinding
to make the starch accessible to enzymes; cooking with
enzymes to hydrolyze the starch to sugars; fermentation
of sugars by yeast to produce ethanol, and distillation to
produce neat ethanol. Te byproduct of this process is
distillers dried grains, a fber and protein-rich material that
is used as livestock feed.
Techno-economic analyses of dry grind ethanol in the USA
and Europe estimate production costs to be between $0.80
and $1.36 per gallon of ethanol depending upon assumptions,
especially feedstock costs.
24
Te present study employs, for
the grain ethanol base case, the ofen cited 2000 report by
McAloon and colleagues at the National Renewable Energy
Laboratory.
5
Tis report estimates that a dry grind corn
processing plant producing 25 million gallons of ethanol per
year would cost $27.9 million (1999, USA). Te operating cost
of this plant was estimated to be $0.88 per gallon of ethanol
based on feedstock cost of $1.94 per bushel of corn grain.
Te advanced biochemical platform employs cellulose
(and hemicellulose) from plant fbers instead of starch in the
production of ethanol. Te process of biologically converting
structural carbohydrate into ethanol consists of four major
operations: pretreatment of plant fbers to make cellulose
accessible to enzymes (which ofen chemically hydrolyzes
hemicellulose to simple sugars); treatment with enzymes to
hydrolyze cellulose to glucose; fermentation of the simple
sugars to produce ethanol; and distillation to produce neat
ethanol. Lignin is a byproduct of this process, which can be
used as boiler fuel.
Based on the current state of technology, capital costs
for biochemical ethanol from cellulose are estimated to
be between $4.03 and $5.60 per gallon of ethanol annual
capacity.
69
Operating costs are estimated to be between
$1.34 and $1.69 depending upon the assumptions made
about feedstock costs, enzyme costs, and the kind of
pretreatment to be employed.
69
Tese cost estimates refect
early implementations of cellulose-based technologies.
Projected capital cost for future plants employing antici-
pated improvements in conversion technologies are esti-
mated to be $3.334.44 per gallon ethanol annual capacity
with operating costs dropping to $0.40 and $0.89 per gallon
of ethanol.
10
Te present study uses the recent analysis of
Hamelinck et al.,
10
which builds upon earlier studies and
employs more recent information on the unit operations
employed for frst-generation technology. Te process is
based on dilute acid pretreatment and enzymatic hydrolysis.
Te total capital investment was calculated to be $294
million, while the operating costs were an estimated
$1.51 per gallon of ethanol.
Unlike the biochemical platform, for which the fuel product
is defned (ethanol) and there is reasonable consensus as to
the unit operations to be employed, there is greater diver-
sity of opinion on how the thermochemical platform should
be confgured. Termolytic processing of biomass can
generally be categorized as either gasifcation (to produce
a gaseous product) or fast pyrolysis (to produce primarily
liquid product). A variety of catalytic
11
or even biocatalytic
12

schemes have been proposed to upgrade the thermolytic
products into alcohols, ethers, esters, or hydrocarbons. Te
present analysis focuses on gasifcation followed by catalytic
synthesis to three fuels: hydrogen, methanol, and F-T liquids.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb 51
Review: Comparative economics of biorefineries MM Wright, RC Brown
Hydrogen can be manufactured from syngas via the
watergas shif reaction:
CO + H
2
O CO
2
+ H
2
Tis reaction requires the mixing of steam with syngas
since biomass gasifcation rarely releases suf cient water
vapor for this purpose. Although hydrogen might be one of
the most cost-efective clean-burning biofuels to produce,
the physical characteristics of hydrogen present challenges in
its use as transportation fuel.
13

Methanol is commercially manufactured from syngas
using a copper-based catalyst via the reaction:
14
CO + 2H
2
CH
3
OH
As a transportation fuel, it has many of the same advan-
tages and disadvantages as ethanol.
15
However, methanol is
considerably more toxic than ethanol. Recent rulings by the
US Environmental Protection Agency (EPA) are likely to ban
the closely related and similarly toxic methyl tertiary butyl
ether (MTBE) as a fuel additive because of concerns about
groundwater contamination.
16
FischerTropsch liquids are synthetic hydrocarbon fuels
produced from syngas by the action of metal catalysts at
elevated pressures. Te primary products of F-T synthesis
are a mixture of light hydrocarbon gases, paraf n waxes,
and alcohols according to the generalized reaction:
17
CO + 2H
2
CH
2
+ H
2
O
Te optimal H
2
:CO ratio of 2:1 is achieved through the
watergas shif reaction ahead of the synthesis reactor.
Depending on the types and quantities of F-T products
desired, either low (200240C) or high (300350C)
temperature synthesis is used with either an iron (Fe) or
cobalt catalyst (Co). Additional processing of the F-T prod-
ucts yields diesel fuel or gasoline.
Te fve major unit operations of the thermochemical
platform based on gasifcation include fuel preparation,
gasifcation, gas clean-up, catalytic processing to the desired
fuels, and separations. Fuel preparation is typically size
reduction and drying to levels consistent with the gasif-
cation technology employed. Although a large variety of
biomass gasifcation technologies can be envisioned,
18
the
thermochemical base cases included in this analysis assume
oxygen-blown, high-temperature gasifcation with the F-T
process also employing pressurized gasifcation. Gas clean-
up includes removal of particulate matter and trace contam-
inants including sulfur, chlorine, and ammonia. Separations
are designed to yield pure fuel. Catalytic processing may
require multiple catalysts operating at diferent conditions
of temperature and pressure. Te watergas shif reaction
is common to the production of most synfuels, including
hydrogen, methanol, and F-T liquids. Methanol synthesis is
optimal at a syngas H
2
:CO ratio of 3:1 while F-T synthesis
favors a H
2
:CO ratio of 2.15.
19
Of course, hydrogen produc-
tion involves the complete reaction of CO and steam to
form hydrogen fuel. Separations are an integral part of
thermochemical processing but, unlike the aqueous phase
processes of the biochemical platform, thermochemical
processes employ vapor-phase reactions that do not require
energy-intensive distillations to remove water from the
fuel product. Although some would argue that the ther-
mochemical platform is technically mature because of its
commercial implementation using coal as feedstock as early
as the 1930s, this presumes a close similarity between coal
and biomass feedstocks. In fact, they difer considerably in
volatile content, char reactivity, and mineral content. Tus,
like the biochemical platform, technical improvements are
anticipated through research and development, although
no attempt is made to anticipate these improvements in the
present analyses.
Te literature includes several studies on the cost of
hydrogen from biomass based on the present state of the
art in gasifcation and synfuels catalysts. Capital costs
range from $0.65 to $1.33 per gallon of liquid hydrogen
capacity
20, 21
depending upon the type and size of gasifer
plant. Operating costs range from $0.31 to $0.44 per gallon
of liquid hydrogen produced
22
depending upon the cost of
biomass and the kinds of processes employed.
23
Te study
by Hamelinck and Faaij
24
is one of the most recent studies
(2002) on biomass-to-hydrogen and includes data in suf -
cient detail to serve as the base case for the present study.
For a gasifcation plant producing 220 million gallons of
liquid hydrogen fuel per year, the estimated capital cost is
$206 million with operating costs of $0.24 per gallon of
liquid hydrogen produced.
52 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb
MM Wright, RC Brown Review: Comparative economics of biorefineries
Early techno-economic studies of methanol plants report
that production costs range from $0.91 to $1.11 per gallon of
methanol.
22, 25
Te techno-economic analysis of Hamelinck
and Faaij was chosen for this study because it analyzes both
hydrogen and methanol plants. Based on averages from their
analysis, a gasifcation plant producing 87 million gallons
of methanol per year would require a capital investment of
$276 million. Te production cost of methanol was $0.62 per
gallon of methanol.
Previous studies of gasifcation plants producing F-T diesel
suggest that costs range from $1.1 to $4.1 per gallon of F-T
diesel.
26, 27
Among the most recent and complete techno-
economic analyses of a F-T diesel plant is that by Tijmensen
et al.
28
Tis analysis employs the oxygen-blown, pressurized
gasifer of the Institute of Gas Technology confgured to
achieve the preferred H
2
to CO ratio. A reformer and water
shif reactor are not necessary for this confguration. Te
product selectivity for hydrocarbon chains of fve carbons
or longer is 73.7 to 91.9%. Capital cost for a plant producing
about 35 million gallons of F-T diesel per year is estimated
to be about $341 million with operating costs of about $2.37
per gallon of F-T diesel.
Table 1 summarizes the data on plant capacity, capital
cost, fuel ef ciency, and heating value of the fuel produced
for each of the fve biofuel plants analyzed in this study.
Fuel ef ciency is defned as the fraction of total energy
inputs that appear as chemical energy of the product fuel,
which in this analysis is neat ethanol, hydrogen, meth-
anol, or F-T liquids. Te energy inputs can come from
either fossil energy or renewable energy. For example, the
production of grain ethanol has both biomass energy inputs
(grain) and fossil energy inputs (natural gas or coal) while
all four cellulosic biofuels processes obtain their energy
requirements exclusively from biomass. Energy outputs
other than biofuels, such as process heat, electricity, and
distillers dried grains, do not fgure in fuel ef ciency calcu-
lations but count towards credits in calculating net
operating costs.
Table 2 breaks down the operating costs for each plant.
Clearly, direct comparisons among these fve plants are
Table 1. Capital costs of reference plants.
Plant type
Plant capacity
(MMGPY)*
Capital cost
($ million)
Fuel efciency
(%)** Basis year
Fuel heating
value (MJ/L)
Source
reference
Grain ethanol 25 27.9 35 1999 21
Cellulosic ethanol 50 294 35 2005 21 10
Methanol 87 254 45 2002 16 24
Hydrogen 182 244 50 2002 8 4
FischerTropsch 35 341 46 2002 36 28
* Millions of gallons per year; all fuels assumed to be liqueed.
** Dened as the fraction of energy inputs into the plant that appears as chemical energy of the product fuel.
Table 2. Operating cost components of reference plants.
Plant Type
Biomass
feedstock
($ million)
Operation and
management
($ million)
Credits
($ million)
Capital charges
($ million)
Total
($ million)
Grain Ethanol 17.0 10.5 $7.1 2.8 22.0
Cellulosic Ethanol 35.4 11.1 * 29.4 76.0
Methanol 24.8 10.2 $8.68 30.2 56.5
Hydrogen 24.7 9.76 $9.88 29.0 53.6
Fischer-Tropsch 29.2 14.6 * 43.8 87.5
* Byproducts or waste energy are used for process heat within the plant.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb 53
Review: Comparative economics of biorefineries MM Wright, RC Brown
dif cult without placing them on a common basis, as
described in the methodology section.
Methodology
Te approach to this study was to place existing techno-
economic analyses in the published literature on the same
bases. Te frst step was to identify studies that assumed the
deployment of frst-generation technology for the produc-
tion of biofuels from lignocellulosic biomass. Although some
studies anticipate technology improvements and estimate
the costs for mature biofuels plants, the present study is
limited to state-of-the-art technology for which more reli-
able data is available. Te data for these baseline cases were
adjusted to account for diferences in plant capacity, the
gasoline equivalency of the fuel, feedstock costs, method of
calculating capital charges, and the year for which costs were
estimated. Readers desiring further details on the techno-
economic analyses employed in this study should refer to the
original publications.
Since economies of scale strongly infuence the cost
of production, capital costs in the original studies were
adjusted to a common plant size of 150 million gallons per
year gasoline equivalent. Tis size was selected as represent-
ative of expected early generation cellulosic biofuel plants,
but no attempt was made to optimize plant size (which will
be diferent for each of the technologies employed). Capital
costs were scaled to plant size using a simple power law
commonly employed to account for economies of scale.
29

A scaling exponent of 0.63 was assumed
5
for the grain
ethanol and cellulosic ethanol (biochemical) platforms while
a scaling exponent of 0.7 was assumed
6
for the thermo-
chemical platforms. Tese exponents were selected based on
recommendations from the referenced studies and refect
the current understanding of the scaling behavior of these
respective technologies. Following usage in the petroleum
industry, capital costs are expressed as dollars per barrel per
day (pbpd) of production capacity. Te capacity factor of the
plant is assumed to be 0.9.
Plant capacity is customarily reported as the volume of fuel
produced although the volumetric energy density (MJ/L)
can vary considerably among diferent kinds of fuels. For
example, ethanol, the most prominent biofuel manufac-
tured today, has only 2/3 the enthalpy of an equal volume of
gasoline. Tus, production capacity and production cost are
reported in this paper on the basis of the gasoline equiva-
lence of the fuel produced.
Operating costs are broken down into categories of
biomass feedstock, operation and management, byproduct
credits, and capital charges. Biomass costs are propor-
tional to plant capacity and process ef ciency in converting
biomass into fuels. Cellulosic feedstock costs are assumed
to be $50 Mg
1
. Corn is priced at $2.12 per bushel, the price
prevailing in the basis year (2005). Operation and manage-
ment costs include plant and management labor, materials
and supplies to operate the plant, and utilities. Credits are
given in some instances for byproducts. For example, grain
ethanol produces distillers dried grains, which can be sold
as cattle feed. Gasifcation generates high temperature heat
that can be used for electric power generation. A realistic
analysis of operating costs must include the cost of capital
although this calculation can be complicated by the fact that
actual projects are usually fnanced by a combination of debt
and investor capital. To simplify the evaluation, this study
assumes 100% debt fnancing over 20 years at an annual
interest rate of 8%. Infation can make it dif cult to compare
studies performed in diferent years. Accordingly, all costs
were adjusted to 2005 dollars.
Results
Te capital costs and operating costs for the various
biochemical and thermochemical biofuels plants on a
common basis are compared in Table 3. It is clear that
advanced biofuels will come at very high capital costmore
than fve times that of comparably sized starch ethanol
plantsbased on the current state of technology. In terms
of least capital cost, the order of preference for cellulosic
biofuels is thermochemical hydrogen, methanol, lignocel-
lulosic ethanol, and F-T diesel. Te diference in capital
costs among the cellulosic biofuel options is signifcant:
F-T diesel requires almost 50% greater investment than
thermochemical hydrogen. Tis diference refects the addi-
tional unit operations required to convert syngas into F-T
diesel. Te two most fungible fuels among the advanced
biofuels, lignocellulosic ethanol and F-T diesel, are the most
capital-intensive processes. At $76,000 pbpd and $86,000
pbpd, respectively, their capital costs are essentially the
54 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb
MM Wright, RC Brown Review: Comparative economics of biorefineries
same within the uncertainty of the analysis (+/ 30%). In
comparison, the capital cost for a grain to ethanol plant is
only $13,000 pbpd.
Te rank ordering in terms of operating costs is the same
as for capital costs, with thermochemical hydrogen being
the least expensive followed by methanol, lignocellulosic
ethanol, and F-T diesel. Operating costs range from a low of
$1.05 per gallon of gasoline equivalent for hydrogen to $1.80
per gallon of gasoline equivalent for F-T diesel. In compar-
ison, grain ethanol for this size of plant could be produced
for $1.22 per gallon of gasoline equivalent. Tis is cheaper
than all the cellulosic biofuels except hydrogen.
Figure 1 helps one to understand the diferences in oper-
ating costs for the various biofuels plants. Much of the
advantage of thermochemical hydrogen comes from its
relatively low biomass costs, which arises from its high fuel
ef ciency. As shown in Table 1, thermochemical hydrogen
has a fuel ef ciency of 50% compared to about 45% for the
other two thermochemical technologies. Whereas hydrogen
production from syngas requires only watergas shif reac-
tion and gas separation, methanol production requires an
additional catalytic step, and F-T diesel requires at least two
additional catalytic steps, each with attendant loses in ef -
ciency. At 35%, lignocellulosic ethanol is even less ef cient,
Table 3. Capital cost and operating costs for 150 MMGPY gasoline equivalent plants (2005 dollars).
Fuel
Total capital cost
($ millions)
Capital cost per unit
production (pbpd)*
Operating cost
($ per gallon)**
Grain ethanol 111 13,000 1.22
Cellulosic ethanol 756 76,000 1.76
Methanol 606 66,000 1.28
Hydrogen 543 59,000 1.05
Fischer-Tropsch 854 86,000 1.80
* Per barrel per day gasoline equivalent.
** Gallons gasoline equivalent.
Figure 1. Operating costs for 150 MMGPY of gasoline equivalent.
-$1.00
-$0.50
$0.00
$0.50
$1.00
$1.50
$2.00
Grain
Ethanol
Cellulosic
Ethanol
Methanol Hydrogen Fischer-
Tropsch
O
p
e
r
a
t
i
n
g

C
o
s
t

(
$
/
g
a
l
l
o
n

o
f

g
a
s
o
l
i
n
e

e
q
u
i
v
a
l
e
n
t
)
Credits
Operation and
Management
Biomass Costs
Capital Costs
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb 55
Review: Comparative economics of biorefineries MM Wright, RC Brown
which arises from the inability to convert the non-carbohy-
drate fraction of lignocellulose into biofuel.
Grain ethanol has the highest biomass costs among the
fve technologies evaluated. Tis refects a combination of
relatively low fuel ef ciency (about one-third of the corn
grain ends up as the byproduct distillers dried grains) and
high fuel cost (corn grain at $2.12 per bushel is almost 75%
more than lignocellulosic biomass on a dry weight basis).
However, as Fig. 1 illustrates, the byproduct from a dry mill
corn ethanol plant (distillers dried grains) yields a produc-
tion credit almost three times greater than that achieved by
any of the other processes. If the expanding grain ethanol
industry produces an oversupply of distillers dried grains
(assumed to be worth $99 Mg
1
in the present study), the
attractive production cost for corn ethanol could
evaporate.
Another scenario that could diminish the attractive
production cost of grain ethanol is already developing. Te
present analysis was based on the 2005 price for corn grain,
which was only $2.12 per bushel. Substituting $3.00 per
bushel, which is more typical of the selling price in late 2006,
increases production cost of grain ethanol to $1.74 per gallon
of gasoline equivalent, which is comparable to the price for
cellulosic ethanol and F-T diesel.
Conclusions
Te rapidly expanding renewable fuels industry will soon
have to turn to technologies that convert lignocellulosic
biomass into biofuels. Although much of the attention on
advanced biofuels has focused on lignocellulosic ethanol,
thermolytic processes have also been proposed for produc-
tion of renewable fuels. Meaningful comparison of advanced
fuels technologies with the current grain ethanol process
requires that techno-economic analysis be on the same basis.
Such an adjustment to techno-economic analyses has
been done for 150 million gallon (gasoline equivalent), frst-
generation lignocellulosic biofuels plants based on biochem-
ical production of ethanol and thermochemical production
of hydrogen, methanol, and F-T diesel. Tis analysis reveals
that advanced biofuels will come at very high capital cost
more than fve times that of comparably sized starch ethanol
plants. Tus, raising the $0.5 billion to almost $1 billion in
capital for a cellulosic biofuels plant will be much more
dif cult than has proved to be the case for grain ethanol
plants. Te smaller number of unit operations associated
with thermochemical hydrogen makes it the least capital
intensive of the four advanced biofuels options evaluated,
including lignocellulosic ethanol. However, the larger prob-
lems of hydrogen storage and distribution infrastructure
compared to other fuels makes it less likely to be adopted
within the 10-year time frame envisioned for signifcant
expansion of biofuels in the USA. Te capital costs for ligno-
cellulosic ethanol and F-T diesel, probably the most fungible
fuels among the four advanced biofuels options considered,
are essentially the same within the uncertainty of the anal-
ysis, costing about $80,000 pbpd.
Termochemical hydrogen also has the lowest production
cost, at about $1.05 per gallon of gasoline equivalent, of the
four advanced biofuels options for a plant of 150 million
gallons gasoline equivalent annual capacity. It even bests
grain ethanol, which would cost $1.27 per gallon of gaso-
line equivalent. Lignocellulosic ethanol and F-T diesel have
almost the same production costs, at about $1.78 per gallon
of gasoline equivalent. If corn prices increase from $2.12 per
bushel that prevailed in the basis year of this analysis (2005)
to $3.00 per bushel found in late 2006 and expected in future
years because of increased corn demand, then biofuels
from lignocellulosic biomass will have comparable costs of
production. Future improvements in the biochemical and
thermochemical platforms for processing lignocellulose have
the potential to further reduce the costs of biofuels.
From these comparisons it is concluded that, for the
current state of the technology, neither the biochemical nor
thermochemical platforms have clear advantages in capital
costs or operating costs for production of advanced biofuels.
Both technologies have opportunities to compete against
grain ethanol as corn prices continue to rise, especially if
the high capital costs of advanced biofuels plants can be
dramatically reduced.
Acknowledgements
Tis study was supported by the Iowa Energy Center under
Contract No. 0606 and the USDA under Contract No.
5819356654. We would like to acknowledge the encourage-
ment and support of Norm Olson of the Iowa Energy Center
and Akwasi Boateng of the Eastern Regional Research
Center, ARS, USDA.
56 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:4956 (2007); DOI: 10.1002/bbb
MM Wright, RC Brown Review: Comparative economics of biorefineries
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191
Review
Establishing the optimal
sizes of different kinds
of bioreneries
Mark Wright and Robert C. Brown, Iowa State University, Ames, USA
Received August 3, 2007; revised version received August 19, 2007; accepted August 20, 2007
Published online October 9, 2007 in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.25;
Biofuels, Bioprod. Bioref. 1:191200 (2007)
Abstract: This paper explores the factors that inuence the optimal size of bioreneries and the resulting unit cost
of biofuels produced by them. Technologies examined include dry grind corn to ethanol, lignocellulosic ethanol via
enzymatic hydrolysis, gasication and upgrading to hydrogen, methanol, and Fischer Tropsch liquids, gasication
of lignocellulosic biomass to mixed alcohols, and fast pyrolysis of lignocellulosic biomass to bio-oil. On the basis of
gallons of gasoline equivalent (gge) capacity, optimally sized gasication-to-biofuels plants were found to be
50100% larger than biochemical cellulosic ethanol plants. Bioreneries converting lignocellulosic biomass into
transportation fuels were found to be optimally sized in the range of 240486 million gge per year compared to
79 million gge per year for a grain ethanol plant. Among the biofuel options, ethanol, whether produced biochemi-
cally or thermochemically, is the most expensive to produce. Lignocellulosic bioreneries will require 4.77.8 million
tons of biomass annually compared to 1.2 million tons of corn grain for a grain ethanol plant. Factors that could
reduce the optimal size of lignocellulosic bioreneries are discussed. 2007 Society of Chemical Industry and John
Wiley & Sons, Ltd
Keywords: biorenery; optimal size; unit cost; gallons of gasoline equivalent
Introduction
T
he petroleum-based motor fuels industry is charac-
terized by giant refneries, processing petroleum at
rates equivalent to ten gigawatts of power or more
(140 000 barrels of petroleum per day). Tis situation exists
because operating costs are driven by economies of scale,
which causes operating costs to increase more slowly as plant
size gets larger. Tus, unit costs for transportation fuels and
commodity chemicals derived from fossil fuels are expected
to decrease monotonically with increasing plant size.
Te situation is dramatically diferent for biorefneries
where biomass feedstocks are obtained from a multiplicity
of farm gates as opposed to a single mine mouth or well
head of a refnery based on fossil fuels. Tese farm gates
are widely distributed geographically, resulting in transpor-
tation costs to the plant that strongly depend upon the size
of the processing plant. Furthermore, transport of solid,
*Correspondence to: Robert C. Brown, Iowa State University, Center for Sustainable Environmental Technologies,
285 Metals Development Bldg, Ames, IA 50011-3020, USA. E-mail: rcbrown@iastate.edu
2007 Society of Chemical Industry and John Wiley & Sons, Ltd
192 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb
M Wright, RC Brown Review: Optimal sizes of different kinds of biorefineries
low density biomass is more labor intensive and expensive
than the movement of gaseous and liquid fuels, like natural
gas or petroleum. As a result, it has been argued that
biomass processing will occur at relatively small scales,
drawing biomass from a distance as little as 15 miles
around the plant. Te corresponding rate of processing
of biomass is equivalent to several hundred megawatts of
power at least an order of magnitude smaller than petro-
leum refneries.
In fact, there is an optimal size for biorefneries since unit
costs for processing go down while feedstock transportation
costs go up as the plant size increases.
13
Te optimal size for
diferent kinds of biomass processing plants are not estab-
lished but they are expected to depend upon the nature of
biomass processed and the kind of processes employed.
Tis paper expands upon a previous study by the authors
which compared the economics of advanced biorefneries
based on the biochemical and thermochemical platforms.
4

While the previous paper compared capital and operating
costs of comparably sized plants, the present paper explores
the factors that infuence the optimal size of biorefneries
and calculates the optimal size of several kinds of biofuels
plants and the resulting unit costs for biofuels produced
in them. Technologies examined include dry grind corn to
ethanol,
5
lignocellusic ethanol via enzymatic hydrolysis,
6

gasifcation and upgrading to hydrogen, methanol, and
Fischer Tropsch liquids,
7,8
conversion of lignocellulosic
biomass to mixed alcohols,
9
and fast pyrolysis of lignocellu-
losic biomass to bio-oil.
10

Background
Biochemical conversion of sugar cane or grain crops (partic-
ularly corn) to ethanol is commercially available and widely
practiced in Brazil and the USA, respectively. Grain ethanol
plants are generally classifed as wet or dry milling based on
the grain pretreatment. Wet milling plants have the advan-
tage of lower production costs and higher ef ciencies, but
the grain ethanol industry is currently dominated by dry
milling plants due to the lower capital and labor costs of the
latter
11
and is thus the focus of this study.
Figure 1 illustrates the fve major steps of dry milling of
corn to ethanol: grinding to expose the starch to enzymes;
liquefaction by the action of heat and enzymes; saccharifca-
tion by enzymatic activity; fermentation of sugars by yeast
to produce ethanol; and distillation to neat ethanol. A by-
product of this process is distillers dried grains (DDGS), a
fber and protein-rich material that is used for livestock feed.
Technical and economic data for the dry grind ethanol
process are taken from McAloon et al.
5
Tey determined
that a plant capacity of 25 million gallons of ethanol per year
had a production cost of $0.88 per gallon of ethanol (2000
basis year).
As shown in Fig. 2, biochemical conversion of cellulosic
biomass into ethanol consists of four major steps: chemical
and mechanical pre-treatments to release sugars from
hemicellulose and to make cellulose accessible to enzymes;
acid or enzymatic hydrolysis of cellulose into glucose;
fermentation of the resulting hexose and pentose to ethanol,
and distillation to yield neat ethanol. A by-product of this
process is lignin, which can be employed as boiler fuel.
Technical and economic data for biochemical conversion
of biomass to ethanol are from the analysis by Hamelinck
et al.
5
which assumes dilute acid pretreatment and enzy-
matic hydrolysis. Te analysis found that a plant of
50 million gallons per year capacity would produce ethanol
at a cost of $1.51 per gallon of ethanol (2005 basis year).
Figure 1. Process ow diagram for dry grind of corn to ethanol.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb 193
Review: Optimal sizes of different kinds of biorefineries M Wright, RC Brown
Termochemical conversion of biomass ofers a diversity
of pathways to a number of biofuels. In general, these path-
ways are based on either gasifcation of biomass to gaseous
products or fast pyrolysis to liquid products. In both cases
these products represent intermediates in the manufacture
of transportation fuels.
Gasifcation of lignocellulosic biomass yields syngas, which
consists mostly of hydrogen (H
2
) and carbon monoxide
(CO).
12
A variety of catalytic and even biocatalytic schemes
have been developed to upgrade syngas into alcohols, ethers,
esters, and hydrocarbons. In this study, four fuels from
syngas are considered: hydrogen, methanol, mixed alcohols
(with the purpose of maximizing ethanol synthesis), and
Fischer Tropsch liquids. Te optimal H
2
:CO molar ratio
difers for each synthesis route. Methanol synthesis favors
a hydrogen-to-carbon monoxide molar ratio of 3:1 while
Fischer Tropsch diesel is optimized at a ratio of 2.15:1.
13

Mixed alcohols optimized for ethanol production employs a
syngas ratio of 0.6:1.
9

As illustrated in Fig. 3, gasifcation routes to biofuels have
four major operations in common: comminution of the
feedstock; gasifcation; gas cleaning to remove tar, particu-
late matter, and inorganic contaminants; and watergas
shif reaction to enrich hydrogen with respect to carbon
monoxide.
14
If pure hydrogen is the desired product, at
least two stages of watergas shif are employed followed by
gas purifcation to remove carbon dioxide. Conversion of
biomass to methanol, mixed alcohols, or Fischer Tropsch
liquids adds catalytic synthesis steps afer the watergas shif
unit operation. Production of mixed alcohols further adds
a distillation step to separate fuel ethanol from the other
alcohols. In all cases, unit operations are highly integrated
to achieve heat recovery and utilize waste heat in electricity
production.
Technical and economic data for hydrogen and methanol
production are from Hamelinck and Faaij,
7
who assumed
biomass throughput equivalent to 400 MW thermal and
pressurized, oxygen-blown gasifcation. Tis represents a
hydrogen plant yielding 182 million gallons per year at a
cost of $0.24 per gallon of hydrogen or a methanol plant
yielding 87 million gallons per year at a cost of $0.62 per
gallon (2002 basis year). Technical and economic data for
production of Fischer Tropsch liquids are from a study by
Tijmensen et al.
8
which assumes pressurized, oxygen-blown
Figure 2. Process ow diagram for biochemical conversion of lignocellulosic biomass to ethanol.
Figure 3. Process ow diagram for gasication to hydrogen, methanol, mixed alcohols, or Fischer
Tropsch liquids.
194 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb
M Wright, RC Brown Review: Optimal sizes of different kinds of biorefineries
gasifcation. Tis analysis found that a plant of 35 million
gallons per year capacity would produce Fischer Tropsch
liquids at a cost of $2.37 per gallon (2002 basis year). Tech-
nical and economic data for production of mixed alcohols
are taken from a study by Phillips et al.
9
which assumed
atmospheric, indirectly heated gasifcation. Tis analysis
found that a plant capacity of 61.8 million gallons of ethanol
per year would have a production cost of $1.01 per gallon
(2005 basis year).
Fast pyrolysis is another thermochemical route to liquid
fuels. Rapid heating of biomass at moderate temperatures
(450500C) in the absence of oxygen directly yields a liquid
product. As illustrated in Fig. 4, bio-oil production involves
four major operations: comminution of the feedstock; fast
pyrolysis; gas cleaning to remove particulate matter; and
recovery of bio-oil. Although bio-oil can be directly used as
boiler fuel or even fred in certain kinds of engines, it is not
suitable as a transportation fuel without further upgrading.
However, the optimal size of a plant to produce bio-oil is
included in this study because it illustrates the opportunities
to explore distributed processing of biomass. Technical and
economic data are taken from Ringer et al.
10
Teir analysis
found that a plant of 28 million gallons per year capacity
(assumed 90% capacity factor) would have a production cost
of $0.34 per gallon of bio-oil (2003 basis year).
One option for upgrading bio-oil is hydrocracking it to
diesel fuel and gasoline.
15
Another option for upgrading
bio-oil is gasifcation followed by catalytic synthesis to
Fischer Tropsch liquids. However, insuf cient technical and
economic data is currently available to include these biofuel
options in the present study.
Methodology
Te petroleum-based motor fuels industry is characterized
by giant refneries, processing petroleum at a rate equivalent
to gigawatts of power. Tis situation exists because plant
operating costs are driven by economies of scale, which
causes plant operating costs to increase more slowly as a
plant gets bigger. Specifcally, the operating cost (excluding
fuel costs) of a plant, C
P
, scales with plant capacity, M,
according to the power law:
C
P
C
Po
(M/M
o
)
n
(1)
where C
Po
is the plant operating cost for a plant of capacity M
o

and n is a power law exponent less than unity, ofen assumed
to be 0.6 (the sixth-tenth rule). Ngyuen and Prince
2
suggest
that n is likely to be in the range 0.6 to 0.8 while Jenkins,
3
in
analyzing the optimal size of electric power plants, argues
that this range is only appropriate for biomass power plants
of size less than 50 MW electrical. He cites a study by Fisher
et al.
16
that supports values of n as large as 0.930.94 for coal-
power plants in the size range 1001400 MW.
Te total cost, C
T
, for producing a quantity M of motor fuel
from fossil fuel is the sum of the cost of plant operations, C
P
,
the cost of feedstock at the mine mouth, C
F
, and the cost of
feedstock delivery (transportation), C
D
:
C
T
C
P
C
D
C
F
(2)
C
Po
(M/M
o
)
n
C
Fo
(M/M
o
) C
Do
(M/M
o
) (3)
where C
Fo
is the feedstock cost and C
Do
is the feedstock
delivery cost for a plant of capacity M
o
. Te unit cost for the
resulting motor fuel ($ per gallon) is determined by dividing
through by the plant capacity M:
(C
T
/M) (C
Po
/M
o
n
) M
n1
(C
Fo
/M
o
) (C
Do
/M
o
) (4)
Tus, for n less than unity, it is evident that the unit cost
of the motor fuel from fossil fuel feedstocks decreases as the
plant gets bigger, without limit.
Te case is more complicated for biomass fuel since it does
not come from a single mine mouth located a fxed distance
from the plant but is dispersed over a large area surrounding
the plant. Tus, delivery cost for a unit of biomass fuel
increases as the capacity of the plant increases because
Figure 4. Process ow diagram for production of bio-oil from fast pyrolysis.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb 195
Review: Optimal sizes of different kinds of biorefineries M Wright, RC Brown
the biomass must be delivered from increasingly greater
distances. Such an analysis has been explored by several
researchers.
13
Te cost of biomass delivery is proportional to both trans-
port distance and the quantity of biomass transported.
Since the amount of biomass around a plant increases as the
square of distance, D, from the plant, the cost of delivery is:
C
D
C
Do
(D/D
o
)(M/M
o
) C
Do
(M/M
o
)
0.5
(M/M
o
)
C
Do
(M/M
o
)
1.5
C
Do
(M/M
o
)
m
(5)
where D
o
is the delivery distance for a plant of capacity M
o

and m has been substituted for 1.5 to allow for some varia-
tion in this power law. Nguyen and Prince
2
argue that the
power law exponent m might be as large as 2 if available land
for biomass becomes increasingly sparse with distance from
a plant, although in most cases 1.5 is probably a realistic
value for m.
Te total cost for producing a quantity of biomass-derived
motor fuel is the cost of plant operations, C
P
, the cost of
biomass fuel delivery, C
D
, and the cost of biomass fuel at the
farm gate, C
F
:
C
T
C
P
C
D
C
F
(6)
C
Po
(M/M
o
)
n
C
Do
(M/M
o
)
m
C
Fo
(M/M
o
) (7)
Tis expression is divided by M
o
to obtain the unit cost for
motor fuel produced from biomass:
(C
T
/M) (C
Po
/M
o
n
) M
n 1
(C
Do
/M
o
m
) M
m 1
(C
Fo
/M
o
)
(8)
Since n 1 is less than zero and m 1 is greater than zero,
the frst term on the right-hand side of Eqn (8) decreases with
plant capacity, while the second term increases with plant
capacity. Tus, there is an optimum plant size to achieve
minimum unit cost of motor fuel derived from biomass,
which is obtained by diferentiating Eqn (8), setting it equal
to zero, and solving for M
opt
/M
o
. Te result obtained is:
(M
opt
/M
o
) {[(1 n)/(m 1)](C
Po
/C
Do
)}
1/(m n)
(9)
It is evident from this expression that if operating costs
C
Po
for a baseline plant of size M
o
are much greater than the
transportation cost C
Do
of biomass, then the optimum plant
size M
opt
will be much greater than the size of the baseline
plant.
Further insight into plant size optimization can be found
by rearranging Eqn (9) as follows:
C
Do
(M
opt
/M
o
)
m
/ C
Po
(M
opt
/M
o
)
n
(1 n)/(m 1) (10)
Te quantity on the lef-hand side of Eqn (10) is recognized
as the ratio of cost of delivery of biomass to the cost of plant
operations, R, under the conditions of optimization; thus:
R
opt
(C
D
/C
P
)
opt
(1 n)/(m 1) (11)
Tis indicates that, for a plant sized to give the minimum
unit cost of motor fuel, the ratio of delivery cost to operating
cost depends only on the power law exponents m and n.
For example, assuming n is 0.6 (the sixth-tenth rule of
economies of scale) and m is 1.5, delivery costs will equal
80% of plant operating costs in an optimally sized plant for
minimum unit cost of motor fuel.
Once values of n and m are selected, the unit cost of
biofuel as a function of plant of size M can be calculated
from Eqn (8) and from knowledge of the cost of plant
operations, the cost of feedstock, and the cost of feedstock
delivery for a plant of arbitrary baseline size M
o
. Te cost of
plant operations, C
Po
, for baseline cases of the various kinds
of biofuel plants was obtained from the literature cited in
the background section of this paper. All plant operating
costs were infation adjusted to place them in the common
basis year of 2005. Te farm gate cost of feedstock was
assumed to be $75.71 ton
1
($2.12 bushel
1
) for corn (the
price in the basis year 2005) and $40 ton
1
of lignocellulosic
biomass.
Te cost of delivering feedstock from the farm gate to the
plant gate is calculated from:
C
Do
= C
DU
.
__
D .F (12)
where C
DU
is the unit cost for feedstock delivery (dollars per
ton per mile),
__
D is the average delivery distance of feedstock,
and F is the tons of feedstock delivered annually to the
plant. Te unit cost of feedstock delivery for corn grain
17
is
$0.018 bushel
1
mile
1
and for lignocellulosic biomass
18

is $0.71 ton
1
mile
1
.
196 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb
M Wright, RC Brown Review: Optimal sizes of different kinds of biorefineries
For biomass uniformly distributed around a processing
plant, the maximum radius r
max
around the plant from
which feedstock must be delivered is given by:
r
max

___

F

___

fY
(13)
where f is the fraction of the acreage around a plant devoted
to feedstock production (assumed to be 60% in this study)
and Y is the annual yield of feedstock (assumed to 140 bushel
acre
1
or 3.92 ton acre
1
for corn grain and 5 ton acre
1
for
lignocellulosic biomass).
Te average (land area-weighted) radius from which feed-
stock is obtained around the plant is two-thirds of r
max
. Te
actual distance traveled by a truck delivering biomass is
greater than the radial (straight-line) distance to the plant
depending upon the nature of the road network. To account
for this additional distance, a tortuosity factor is defned
as the ratio of actual distance traveled to the straight-line
distance from the plant. Tortuosity factors can be about 1.2
for developed agriculture regions where roads are laid out in
rectangular grids or as great as 3.0 for less developed regions.
Te present analysis assumes the tortuosity factor is 1.5.
Based on these adjustments, the average delivery distance is:
D

2
_
3

___

F

___

fY
(14)
Table 1 details the average delivery distances and annual
cost of delivering biomass to the baseline plants calcu-
lated according to Eqns (14) and (12), respectively. Average
delivery distance ranges between 5.5 miles and 11.8 miles for
these seven base cases. Te table also includes the volumetric
(lower) heating values of the biofuels produced for each
process because comparisons among the diferent fuels are
done on the basis of gallons gasoline equivalency (gge).
Table 2 is a compilation of plant size, capital cost (infation
adjusted to 2005), plant operating costs (infation adjusted
to 2005), unit cost of biofuels production, and R value of the
various baseline biofuel plants to support the subsequent
analysis of this study. Te fact that none of the R values
approaches the optimal value of 0.8 suggests that these base-
line plants are far from the size that yields the minimum
unit cost of biofuels production.
Results
Table 3 summarizes the results of the plant size optimiza-
tion for processing cost power law exponent, n, and delivery
cost power law exponent, m, equal to 0.6 and 1.5 respectively
(corresponding to R equal to 0.8). Te biofuels plants are
listed in order of increasing optimal plant capacity in
terms of gallons of gasoline equivalent (gge): corn grain
ethanol, fast pyrolysis to bio-oil, biochemical production of
Table 1. Average delivery distances and delivery costs for baseline cellulosic biomass plants.
Plant
Biofuel heating
value (MJ L
1
)
Plant size
(million gge
a
)
Biomass input
(million tons)
Average delivery
distance
b
(miles) C
Do
c
(million $)
Grain ethanol 21 16.7 0.25 6.44 1.16
Biochemical cellulosic
ethanol
21 33.5 0.66 11.8 5.51
Gasication to hydrogen
(liquid)
6 47.9 0.67 10.5 4.99
Gasication to methanol 16 43.4 0.67 10.5 4.95
Gasication to mixed
alcohols
21 41.2 0.77 11.3 6.15
Gasication to Fischer
Tropsch diesel
36 40.4 0.64 10.3 4.66
Fast pyrolysis to bio-oil 19.6 17.3 0.18 5.46 0.70
a
Gallons gasoline equivalency.
b
Assumes feedstock yield of 3.92 ton acre
1
for corn grain and 5 ton acre
1
for lignocellulosic biomass; land utilization factor of 60%; and
tortuosity factor of 1.5.
c
Assumes feedstock delivery cost of $0.018 bushel
1
mile
1
for corn grain and $0.71 ton
1
mile
1
for lignocellulosic biomass.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb 197
Review: Optimal sizes of different kinds of biorefineries M Wright, RC Brown
Table 3. Optimum plant annual capacity and operating costs (R 0.8).
Process
M
(million
gge
a
)
Biomass
input
(million
tons)
Capital
cost
b
(million $)
Operating costs (million $)
C
T
/M ($
per gge
a
)
Volumetric
annual plant
capacity
(million
gallons)
C
T
/M
($ per
gallon) C
P
b
C
D
C
F
C
T
Grain ethanol 79 1.18 70.9 14.9 12 90 117 1.48 119 0.98
Fast pyrolysis
to bio-oil 104 1.08 88.4 12.7 10.2 43.1 66.0 0.63 168 0.39
Biochemical
cellulosic
ethanol 240 4.72 957 132 105 189 426 1.78 359 1.19
Gasication
to methanol 346 5.34 884 140 112 214 466 1.35 694 0.67
Gasication
to hydrogen 365 5.11 826 131 105 204 440 1.21 1387 0.32
Gasication
to mixed
alcohols 418 7.81 551 249 199 312 760 1.82 627 1.21
Gasication
to Fischer
Tropsch
diesel 486 7.69 1516 243 194 308 745 1.53 422 1.77
a
Gallons gasoline equivalency.
b
Adjusted to 2005 basis year.
Table 2. Base case sizes and annual costs.
Process
M
0
(million
gge
a
)
Biomass
input
(million
tons)
Capital
costs
b
(million $)
Operating costs (million $) C
T
/M
o
($ per
gge
a
) R
c
C
Po
b
C
Do
C
Fo
C
To
Grain ethanol 16.7 0.25 27.9 5.86 1.16 18.9 25.9 1.55 0.20
Biochemical
cellulosic ethanol 33.5 0.66 294 40.5 5.51 26.4 72.4 2.16 0.14
Gasication to hydrogen (liquid) 47.9 0.67 244 38.8 4.99 26.8 70.6 1.47 0.13
Gasication to methanol 43.4 0.67 254 40.4 4.95 26.8 72.2 1.66 0.12
Gasication to mixed alcohols 41.2 0.77 137 61.9 6.15 30.8 98.9 2.40 0.10
Gasication to Fischer Tropsch
diesel 40.4 0.64 341 54.6 4.66 25.6 84.8 2.10 0.09
Fast pyrolysis to bio-oil 17.3 0.18 30 4.35 0.695 7.20 12.2 0.71 0.16
a
Gallons gasoline equivalency.
b
Adjusted to 2005 basis year.
c
R is the ratio of cost of delivery of biomass to the cost of plant operations.
cellulosic ethanol, and gasifcation of lignocellulosic biomass
to methanol, hydrogen, mixed alcohols, and Fischer Tropsch
diesel. Te relatively low unit cost of plant operations rela-
tive to feedstock delivery for corn grain ethanol allows it to
be built at an optimal scale of 79 million gge. In compar-
ison, biochemical cellulosic ethanol requires a plant of 240
million gge capacity and the gasifcation-based biofuel
plants range in size from 346 million gge to 486 million gge
198 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb
M Wright, RC Brown Review: Optimal sizes of different kinds of biorefineries
to produce biofuel at minimum unit cost. On the basis of
gallons of gasoline equivalency, optimally sized plants based
on gasifcation are 50100% larger than biochemical cellu-
losic ethanol plants. With the exception of the pyrolysis to
bio-oil plant, all optimally-sized biofuel plants using ligno-
cellulosic biomass as feedstock consume 4.77.8 million tons
of biomass annually compared to 1.2 million tons of corn
for the optimally sized grain ethanol plant.
Capital costs range from a low of $71 million for the
79 million gge grain ethanol plant to $1.52 billion for the 486
million gge Fischer-Tropsch diesel plant. All of the cellulose-
to-biofuels plants exceed one-half billion dollars to build at
their optimal size (which are larger than 240 million gge of
biofuels). Te unit cost of bio-oil is only $0.63 per gge for
the optimally scaled plant although bio-oil is not suitable
as motor fuel without additional upgrading. It is followed
by hydrogen at $1.21, methanol at $1.35, grain ethanol at
$1.48, Fischer Tropsch diesel at $1.53, biochemical cellu-
losic ethanol at $1.78, and ethanol from the mixed alcohols
process at $1.82. Among the cellulosic biofuel options,
ethanol, whether produced biochemically or thermochemi-
cally, is the most expensive to produce.
Te total production costs for each of the plants (with
the exception of the fast pyrolysis process) are plotted as
functions of plant size in Fig. 5. As expected, total costs
at frst decline rapidly as plant capacity increases. Even-
tually total costs reach a minimum value. Tese minima
are remarkably shallow. With the exception of the grain
ethanol plant, capacity can be varied by 100 million gge or
more around the optimal capacity without substantially
afecting unit cost of biofuel production. Below about
50 million gge, or 75 million gallons ethanol, the grain
ethanol process yields the lowest unit cost of biofuel. At
larger plant capacities, grain ethanol becomes more
expensive than hydrogen (at 50 million gge), methanol
(at 100 million gge), and Fischer Tropsch diesel (at 325
million gge). Ethanol produced from lignocellulosic
biomass, either biochemically or thermochemically is
more expensive than ethanol from $2.12 bushel
1
corn
grain even at plant capacities of one billion gge.
Relatively optimistic assumptions were made about
lignocellulosic biomass yield (5 ton acre
1
) and the
percentage of land around the plant that would be devoted
to growing this biomass (60%). Reductions in either yield
or the percentage of land use could signifcantly reduce the
optimal size of biomass processing plants as calculated in
this study. For example, substituting an agriculture residue
such as corn stover for a dedicated energy crop might reduce
Figure 5. Unit cost of biofuels production versus plant size.
2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb 199
Review: Optimal sizes of different kinds of biorefineries M Wright, RC Brown
the yield of lignocellulosic biomass to 2.5 ton acre
1
. Alter-
natively, the number of producers surrounding the plant
willing to produce a dedicated energy crop like switchgrass
might control only 30% of the land surrounding a processing
plant. In either case, the optimal size of plants processing
lignocellulosic biomass would be reduced by about 30%.
Another scenario that would result in smaller optimally
sized processing plants is illustrated in Fig. 6, which is a
plot of optimum plant size as a function of the power law
exponent n that describes the scaling of feedstock processing
costs with plant size. For low values of n, the optimal plant
capacity increases with increasing n. Afer a maximum
optimum plant size is reached, optimal plant sizes decrease
rapidly with increasing n indicating that small biofuels
plants could be economically built if linear scaling (n
approaching unity) prevailed. In principle, linear scaling
could be approached by mass production of small-scale
biofuels plants whereas today plants are custom designed
and constructed. However, the authors are not aware of
any such instances of mass production that demonstrate
the practicality of this principle. Of course, any technology
advances that reduce the capital cost and hence capital
charges in the plant operating costs would also tend to
reduce the optimal size of plants.
On the other hand, it is also easy to envision changes
to the grain ethanol plant that would increase its optimal
size and reduce the cost of grain ethanol production. For
example, many ethanol producers are considering the addi-
tion of front-end separation of corn oil to their dry-grind
ethanol plants, which would increase plant processing costs.
Transportation costs for these plants could be signifcantly
reduced if grain was shipped by rail or barge instead of by
truck. According to Eq. 9, these factors will increase the
optimal size of a grain ethanol plant to larger than the 79
million gge calculated in this study and lower the cost of
grain ethanol.
Conclusions
Unlike fossil fuel processing plants, for which unit cost
of fuel product decreases as the plant gets larger, optimal
biomass processing plant capacities that achieve the lowest
unit cost of biofuel production are expected. Te optimal
capacity depends upon the value of power law exponents
used in scaling relationships that describe the costs of feed-
stock processing and delivery, respectively, and upon the
relative cost of feedstock processing compared to feedstock
delivery.
Figure 6. Effect of processing cost scale factor n on the optimal size of biofuels plants.
200 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 1:191200 (2007); DOI: 10.1002/bbb
M Wright, RC Brown Review: Optimal sizes of different kinds of biorefineries
Data from the published literature were used to evaluate
the optimal size of several biorefnery concepts. In the order
of their increasing optimal plant size these are: corn grain
ethanol, fast pyrolysis to bio-oil, biochemical production
of cellulosic ethanol, gasifcation to methanol, gasifcation
to hydrogen, gasifcation to mixed alcohols, and gasifca-
tion to Fischer Tropsch diesel. Optimally sized plants based
on gasifcation are 50100% larger (gge basis) than the
biochemical cellulosic ethanol plant. Biorefneries converting
lignocellulosic biomass into transportation fuels are opti-
mally sized in the range 240 to 486 million gge per year and
require 4.77.8 million tons of biomass annually compared
to 1.2 million tons of corn grain for an optimally sized grain
ethanol plant. Capital costs for advanced biofuel plants
are similarly much greater than for a grain ethanol plant,
ranging from $551 million for a mixed alcohols plant to $1.52
billion for a Fischer Tropsch diesel plant compared to $70.9
million for the grain ethanol plant. Among the cellulosic
biofuel options, ethanol, whether produced biochemically or
thermochemically, is the most expensive to produce.
Te minima in the unit cost of cellulosic biofuel versus
plant capacity are so shallow that, with the exception of
the fast pyrolysis plant, plant size can be varied by as much
as 100 million gge around the optimal capacity without
substantially afecting unit cost of biofuels production.
Although optimally sized biorefneries based on lignocel-
lulosic biomass are predicted in this study to process four
to seven times as much feedstock as grain ethanol plants,
three factors could reduce the optimal size of these advanced
biorefneries. First, reductions in either biomass yield or the
percentage of land surrounding a plant dedicated to biomass
crops would signifcantly increase the distance required to
collect biomass, making it too expensive to build as large a
plant as projected in this study. Second, making the power
law for biomass processing nearly linear through mass
production of small-scale biofuels plants might reduce the
optimal size of these plants. Finally, technology advances
that reduce capital costs of the plant would reduce the size of
plant that produces biofuel at the lowest unit cost.
Acknowledgments
Tis study was supported by the Iowa Energy Center under
Contract No. 0606 and the USDA under Contract No.
5819356654.
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