Biorefineries: Current Status, Challenges, and Future Direction

Sandun Fernando,* Sushil Adhikari, Chauda Chandrapal, and Naveen Murali

Department of Agricultural and Biological Engineering, Mississippi State UniVersity,
Mississippi State, Mississippi 39762
ReceiVed March 2, 2006. ReVised Manuscript ReceiVed May 16, 2006
Conventional resources mainly fossil fuels are becoming limited because of the rapid increase in energy
demand. This imbalance in energy demand and supply has placed immense pressure not only on consumer
prices but also on the environment, prompting mankind to look for sustainable energy resources. Biomass is
one such environmentally friendly renewable resource from which various useful chemicals and fuels can be
produced. A system similar to a petroleum refinery is required to produce fuels and useful chemicals from
biomass and is known as a biorefinery. Biorefineries have been categorized in three phases based on the
flexibility of input, processing capabilities, and product generation. Phase I has less or no flexibility in any of
the three aforementioned categories. Phase II, while having fixed input and processing capabilities, allows
flexibility in product generation. Phase III allows flexibility in all the three processes and is based on the
concept of high-value low-volume (HVLV) and low-value high-volume (LVHV) outputs. This paper reviews
the concept of biorefinery, its types, future directions, and associated technical challenges. An approach of
streamlining biorefineries with conventional refineries in producing conventional fuels is also presented.
Furthermore, twelve platform chemicals that could be major outputs from an integrated biorefinery are also
discussed.
1. Introduction
Currently, the energy requirements of the world are largely
met by fossil fuels. The limited deposits of these fossil fuels
coupled with environmental problems, such as greenhouse gases,
have prompted mankind to look for sustainable resources as
alternatives to meet the increasing energy demand. Biomass is
one of the few resources that has the potential to meet the
challenges of sustainable and green energy systems. Biomass
is a plant matter of recent (nongeologic) origin or material
derived there from and could be used to produce various useful
chemicals and fuels.
1
A system similar to a petroleum refinery
called a biorefinery has been proposed to produce useful
chemicals and fuels from biomass. According to National
Renewable Energy Laboratory (NREL), a biorefinery is a
facility that integrates conversion processes and equipments to
produce fuels, power, and chemicals from biomass.
2
To achieve
the goals of sustainable development, biorefineries have to play
a dominant role in the coming millennia. An effort has been
made in this paper to review the biorefinerys development to
date and its future directions.
2. The Biorefinery Concept
The concept of producing products from agricultural com-
modities (i.e., biomass) is not new. However, using biomass as
an input to produce multiple products using complex processing
methods, an approach similar to a petroleum refinery where
fossil fuels are used as input, is relatively new. Biomass consists
of carbohydrates, lignin, proteins, fats, and to a lesser extent,
various other chemicals, such as vitamins, dyes, and flavors.
3
The goal of a biorefinery is to transform such plentiful biological
materials into useful products using a combination of technolo-
gies and processes. Figure 1 describes the elements of a
biorefinery in which biomass feedstocks are used to produce
various useful products such as fuel, power, and chemicals using
biological and chemical conversion processes.
The main goal of a biorefinery is to produce high-value low-
volume (HVLV) and low-value high-volume (LVHV) products
using a series of unit operations. The operations are designed
to maximize the valued extractibles while minimizing the waste
streams by converting LVHV intermediates into energy. The
high-value products enhance the profitability, while the high-
volume fuels help to meet the global energy demand. The power
produced from a biorefinery also helps to reduce the overall
* To whom correspondence should be addressed. Phone: +1 662 325
3282. Fax: +1 662 325 3853. E-mail: sf99@abe.msstate.edu.
(1) Lynd, L. R.; Jin, H.; Michels, J. G.; Wyman, C. E.; Dale, B.
Bioenergy: background, potential, and policy. Available from http://
rmtools.org/ref/Lynd_et_al_2002.pdf (June 24, 2005).
(2) National Renewable Energy Laboratory. Conceptual biorefinery.
Available from http://www.nrel.gov/biomass/biorefinery.html (August 1,
2005).
(3) Askew, M. The biorefinery concept. Available from http://europa.e-
u.int/comm/research/energy/pdf/renews3.pdf (August 1, 2005).
Figure 1. Simple three-step biomass-process-products procedure.
4
1727 Energy & Fuels 2006, 20, 1727-1737
10.1021/ef060097w CCC: $33.50 2006 American Chemical Society
Published on Web 06/27/2006
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cost.
2
In contrast to a petroleum refinery, a biorefinery uses
renewable resources and produces fuels and chemicals that
contribute less to environmental pollution. Table 1 depicts the
increase in biobased products sales worldwide from 1983 to
1994. This clearly shows there is a growing interest in biobased
products. Similarly, Table 2 depicts the United States targets
for biobased products in the selected years.
3. Types of Biorefineries
Three types of biorefineries known as phase I, II, and III have
been described by Kamm et al.
6
and Van Dyne et al.
7
A phase
I biorefinery plant has fixed processing capabilities and uses
grain as a feedstock. A dry mill ethanol plant, illustrated in
Figure 2, is an example of a phase I biorefinery which produces
a fixed amount of ethanol, other feed products, and carbon
dioxide and has almost no processing flexibility.
6,7
A process involving current wet milling technology could
be considered a phase II biorefinery which uses grain feedstock
as input similar to dry milling. However, it has the capability
(4) Sokhansanj, S.; Cushman, J.; Wright, L. Collection and delivery of
biomass for fuel and power production. Available from http://www.ten-
nesseebiomass.com/storage.php (June 27, 2005).
(5) Biobased Industrial Products: Research and Commercialization
Priorities; The National Academies Press: Washington, DC, 2000.
(6) Kamm, B.; Kamm, M. Principles of biorefinery. Appl. Microbiol.
Biotechnol. 2004, 64, 137-145.
(7) Dyne, D. L. V.; Blase, M. G.; Clements, L. D. A strategy for returning
agriculture and rural America to long-term full employment using biomass
refineries. In PerspectiVes on New Crops and New Uses; Janick, J., Ed.;
ASHS Press: Alexandria, VA, 1999.
Figure 2. Dry mill ethanol process plant.
8
Figure 3. Representation of whole-crop biorefinery process and products.
6
1728 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.
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to produce various end products and far more processing
flexibility
6,7
depending upon a product demand, prices, and
contract obligations. The typical products are starch, high-
fructose corn syrup, ethanol, and corn oil. A phase III, the most
developed biorefinery, uses a mix of biomass feedstocks and
yields an array of products by employing combination of
technologies.
6
It allows a mix of agricultural feedstocks, has
the ability to use various types of processing methods, and has
the capability to produce a mix of higher-value chemicals while
coproducing ethanol.
9
It is based on both the HVLV and LVHV
principles. The Phase III biorefineries, namely, whole-crop,
green, and lignocellulose feedstock (LCF) biorefineries, are still
in research and development.
6
3.1. Whole-Crop Biorefinery. A whole-crop biorefinery
processes and consumes the entire crop to obtain useful products.
Raw materials such as wheat, rye, triticale, and maize can be
used as input in the feedstock in the unit operations of a whole-
crop biorefinery as depicted in Figure 3. The process of
converting biomass into energy is initiated by mechanical
separation of biomass into different components that are then
treated separately. Biomass is the starting material for the
production of syngas where syngas can be used as the basic
material for the synthesis of fuels and methanol using the Fischer
Tropsh process.
6
Corn either can be used directly after grinding
to meal or can be converted to starch. Further processing can
be carried out as follows: (i) breaking up, (ii) plasticization,
(iii) chemical modification, and (iv) biotechnological conversion
via glucose.
3.2. Green Biorefinery. A green biorefinery is a multiproduct
system which handles its refinery cuts, product, and fractions
(8) Lasure, L. L.; Zhang M. Bioconversion and biorefineries of the future.
Available from http://www.pnl.gov/biobased/docs/biorefineries.pdf (August
1, 2005).
(9) Tyson, K. S.; Bozell, J.; Wallace, R.; Petersen, E.; Moens, L. Biomass
oil analysis: research needs and recommendations. NREL Technical Report.
Available from http://www.eere.energy.gov/biomass/pdfs/34796.pdf (August
1, 2005).
Figure 4. Representation of green biorefinery process and products.
6
Table 1. Worldwide Sales of Biotechnology Products, 1983 and
1994
a
1983 ($ millions) 1994 ($ millions)
fuel and industrial ethanol 800 1500
high-fructose syrups 1600 3100
citric acid 500 900
monosodium glutamate 600 800
lysine 200 700
enzymes 400 1,000
specialty chemicals 1300 3000
total 5400 11 000
a
Table excludes pharmaceutical products.
5
Table 2. United States Biobased Industry Targets
5
biobased production levels
biobased
product current level
future target
intermediate (2020)
future target
ultimate (2090)
liquid fuels
a
1-2% 10% up to 50%
organic
chemicals
b
10% 25% >90%
materials
c
90% 95% 99%
a
Large-scale production of biobased ethanol is a long-term possibility
and the projection assumes advanced technologies are in place for processing
lignocellulosic materials.
b
Include oxygenated chemicals such as butanol
or butyl butyrate that can be processed into other intermediate and specialty
chemicals traditionally dependent on fossil fuel feedstocks.
c
Include
traditional forest products such as lumber, as well as novel biopolymers,
such as bioplastics. Many new products in this market will be high-value
materials that cannot be produced from petroleum feedstocks.
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1729
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in accordance with the physiology of the corresponding plant
material as described by Kamm et al.
6
and illustrated in Figure
4. A green biorefinery uses natural wet feedstocks derived from
untreated products, such as grass, green plants, or green crops
as inputs, which are produced in large quantities in green plants.
The first step of the refinery is to treat the green biomass
Figure 5. Representation of LCF biorefinery process and products.
6
Figure 6. Sugar-lignin platform biorefinery.
12
1730 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.
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substances in their natural form using wet-fractionation to
produce a fiber-rich press cake and a nutrient-rich green juice.
The press cake contains cellulose, starch, valuable dyes and
pigments, crude drugs, and other organics, whereas the green
juice includes proteins, free amino acids, organic acids, dyes,
enzymes, hormones, other organic substances, and minerals. The
pressed cake can be also used for the production of green feed
pellets, as a raw material for the production of chemicals, such
as levulinic acid, and for conversions to syngas and synthetic
fuels.
6
3.3. Lignocellulose Feedstock (LCF) Biorefinery. LCF
consists of three basic chemical fractions: (i) hemicellulose,
five carbon sugar polymers, (ii) cellulose, six carbon glucose
polymers, and (iii) lignin, phenol polymers.
9
A LCF biorefinery
as depicted in Figure 5 uses hard fibrous plant materials
generated by lumber or municipal wastes. Initially, plant material
is cleaned and broken down into the three fractions (hemicel-
lulose, cellulose, and lignin) via chemical digestion or enzymatic
hydrolysis. Hemicellulose and cellulose can be produced by
alkaline (caustic soda) and sulfite (acidic, bisulfite, alkaline, etc.).
Lignin in plant materials is broken down with enzymes such as
ligninases, lignin peroxidases, laccases, and xylanolytic en-
zymes. The sugar polymers (hemicellulose and cellulose) are
converted to their component sugars (Figure 5) through hy-
drolysis. In the case of hemicellulose, it consists of short, highly
branched chains of sugars. In contrast to cellulose, which is a
polymer of only glucose, a hemicellulose is a polymer of five
different sugars. It contains five-carbon sugars (usually D-xylose
and L-arabinose), six-carbon sugars (D-galactose, D-glucose, and
D-mannose), and uronic acid. The hydrolysis process of hemi-
cellulose results in aforementioned sugars. The following
chemical reactions provide a general overview of the conver-
sions that take place in a LCF biorefinery.
The xylose fraction from hemicellulose is important because
it can be converted to furfural which is one of the starting
materials for nylon 6.
6
Furthermore, furfural has many uses: it
can be used in the refining of motor oils, as a precursor of certain
plastics, and as cleaning agents in liquid fuels.
The hydrolysis of cellulose to glucose can be carried out either
by enzymatic processing or chemical processing
7
which pro-
duces useful products, such as ethanol, acetic acid, acetone,
butanol, succinic acid, and other fermentation products. Al-
though the hemicellulose and cellulose fractions have numerous
uses, it is not yet the case for lignin. Currently, lignin has limited
uses such as an adhesive or binder and as a fuel for direct
combustion. However, the lignin scaffold has tremendous
potential to produce various forms of monoaromatic hydrocar-
bons, which, if isolated in an economically efficient way, could
add significant value to the primary LCF process. It should be
noticed that there are no obvious, natural enzymes to split the
naturally occurring lignin into its basic monomers as easily as
is possible for naturally formed polymeric carbohydrates or
proteins.
6
The LCF plant in Missouri produces around 180
10
6
tons of ethanol and 323 10
3
tons of furfural annually
from daily feedstock consumption of 4000 tons.
7
If substantial
Table 3. Composition of Bio-oil Compounds, Part I
type compound wt % type compound wt %
acids formic (methanoic) 0.3-9.1 nitrogen compounds ammonia
acetic (ethanoic) 0.5-12 methylamine
0.1-1.8 pyridine
hydroxyacetic 0.1-0.9 methyl pyridine
2-butenic (crotonic) alcohols methanol 0.4-2.4
butanoic 0.1-0.5 ethanol 0.6-1.4
pentanoic (valeric) 0.1-0.8 2-propene-1-ol
2-Me butenoic isobutanol
4-oxypentanoic 0.1-0.4 3-methyl-1-butanol
hexanoic (caproic) 0.1-0.3 furans furan 0.1-0.3
benzoic 0.2-0.3 2-methyl furan 0.1-0.2
heptanoic 0.3 furfural 0.1-1.1
esters methyl formate 0.1-0.9 3-methyl-2(3h)furanone 0.1
methyl acetate furfural alcohol 0.1-5.2
methyl propionate furoic acid 0.4
butyrolactone 0.1-0.9 methyl furoate
methyl crotonate 5-methylfurfural 0.1-0.6
methyl n-butyrate 5-OH-methyl-2-furfural 0.3-2.2
valerolactone 0.2 dimethyl furan
angelicalactone 0.1-1.2 guaiacols 2-methoxy phenol 0.1-1.1
aromatics methyl valerate 4-methyl guaiacol 0.1-1.9
benzene ethyl guaiacol 0.1-0.6
toluene eugenol 0.1-2.3
xylenes isoeugenol 0.1-7.2
naphthalene 4-propylguaiacol 0.1-0.4
phenanthrene acetoguiacone 0.8
fluoranthene
chrysene
Figure 7. Conceptual map of SPB and syngas platform-based
biorefinery.
2
lignocellulose + H
2
O ) lignin + cellulose + hemicellulose
hemicellulose + H
2
O ) xylose
xylose (C
5
H
10
O
5
) + acid catalyst )
furfural (C
5
H
4
O
2
) + 3H
2
O
cellulose (C
6
H
10
O
6
) + H
2
O ) glucose (C
6
H
12
O
6
)
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1731
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microbial conversion of glucose can be carried out, it can be
used as an alternative route
6,10,11
for the petrochemically
produced substances, such as hydrogen, methane, propanol, and
acetone.
In a more modern approach, the U.S. Department of Energy/
NREL have described conversion technologies for expanded
biomass based on the platforms because the basic technology
would generate base or platform chemicals from which industry
could make a wide range of fuels, chemicals, materials, and
power. Five platforms have been suggested: sugar platform
biorefineries (SPBs), thermochemical or syngas platform, biogas
platform, carbon-rich chains platform, and plant products
platform. The sugar platform focuses on the fermentation of
sugars extracted from biomass feedstocks. The objective is to
biologically process the sugars to produce fuel, such as ethanol,
or other building block chemicals. SPBs are closely related to
LCF biorefineries in the conventional nomenclature. The unit
operation of a SPB is provided in Figure 6.
The thermochemical or syngas platform focuses on the
gasification of the biomass feedstocks. This approach converts
the solid biomass into gaseous and liquid fuels by mixing it
with limited oxygen prior to combustion. Various components
produced through this process can be separated into fuels or
(10) Zeikus, J. G.; Jain, M. K.; Elankovan, P. Biotechnology of succinic
acid production and markets for derived industrial products. Appl. Microbiol.
Biotechnol. 1999, 51, 545-552.
(11) Willke, T.; Vorlop, K. D. Industrial bioconversion of renewable
resources as an alternative to conventional chemistry. Appl. Microbiol.
Biotechnol. 2004, 66, 131-142.
Figure 8. Schematic of an integrated biorefinery.
13
Table 4. Composition of Bio-oil Compounds, Part II
type compound wt % type compound wt % type compound wt %
ketones acetone 2.8 aldehydes formaldehyde 0.1-3.3 sugars levoglucosan 0.4-1.4
2-butenone acetaldehyde 0.1-8.5 glucose 0.4-1.3
2-butanone (MEK) 0.3-0.9 2-propenal (acrolein) 0.6-0.9 fructose 0.7-2.9
2,3-butandione 2-butenal trace D-xylose 0.1-1.4
cyclopentanone 2-methyl-2-butenal 0.1-0.5 D-arainose 0.1
2-pentanone pentanal 0.5 cellobiosan 0.6-3.2
3-pentanone phenols phenol 0.1-3.8 1,6-anhydroglucofuranose 3.1
2-cyclopentenone 2-methyl phenol 0.1-0.6 4-methoxy catechol 0.6
2,3-pentenedione 0.2-0.4 3-methyl phenol 0.1-0.4 miscellaneous
oxygenates
hydroxyacetaldehyde 0.9-13
3-Me-2-cyclo-penten2ollone 0.1-0.6 4-methyl phenol 0.1-0.5 acetol (hydroxyacetone) 0.7-7.4
Me-cyclopentanone 2,3-dimethyl phenol 0.1-0.5 methylal
2-hexonone 2,4-dimethyl phenol 0.1-0.3 dimethyl acetal
methylcyclohexanone 2,6-dimethyl phenol 0.1-0.4 acetyloxy-2-propanone 0.8
2-Et-cyclopentanone 0.2-0.3 3,5-dimethyl phenol 2-OH-3-Me-2-cyclopentene-1-one 0.1-0.5
dimethlycyclopentenone 0.3 2-ethyl phenol 0.1-1.3 methyl cyclopentenolone 0.1-1.9
trimethylcyclopentenone 0.1-0.5 2,4,6-TriMe phenol 0.3 1-acetyloxy-2-propanone 0.1
trimethylcyclopentenone 0.2-0.4 1,2-DiOH benzene 0.1-0.7 2-methyl-3-hydroxy-2-pryrone 0.2-0.4
syringols 2,6-DiOMe phenol 0.7-4.8 1,3-DiOH benzene 0.1-0.3 2-Methoxy-4-methylanisole 0.1-0.4
methyl syringol 0.1-0.3 1,4-DiOH benzene 0.1-1.0 4-OH-3-methoxybenzaldehyde 0.1-1.1
4-ethyl syringol 0.2 alkenes 2-methyl propene maltol
propyl syringol 0.1-1.5 dimethyl
cyclopentene
0.7
syringal dehyde 0.1-1.5 R-pinene
4-propenyl syringol 0.1-0.3 dipentene
1732 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.
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valuable chemicals. NRELs main focuses are on the SPB and
syngas platforms. The concept of these two biorefinery
platforms is described in Figure 7.
The biogas platform is a widely used technology particularly
in developing countries for producing cooking gas. This platform
decomposes biomass with natural microorganisms in closed
tanks known as anaerobic digesters. The process produces
methane and carbon dioxide. The carbon-rich chains platform
uses plant oils, such as soybean, corn, palm, and canola oils,
which are presently used for food and chemical production.
Transesterification of the vegetable oil or animal fat produces
fatty acid methyl esters, commonly known as biodiesel. Biodie-
sel is already in use as an important commercial air-emission
reducing additive or substitute for petroleum diesel. Selective
breeding and genetic engineering can be used to develop plant
strains that produce greater amounts of desirable feedstocks,
chemicals, or even compounds that the plant does not naturally
produce. The intention is to perform the biorefining in the
biological plant itself rather than in an industrial plant. This
approach is known as the plant products platform.
3.4. Integrated Biorefinery. The biorefinery types that we
discussed previously are based on one conversion technology
to produce various chemicals. A biorefinery is a capital-intensive
project, and when it is based on just one conversion technology,
as is the case for the previously described biorefineries, it
increases the cost of outputs (or products) generated from such
biorefineries. Hence, several conversion technologies (thermo-
chemical, biochemical, etc.) are combined together to reduce
the overall cost, as well as to have more flexibility in product
generation and to provide its own power. Figure 8 provides a
schematic of an integrated biorefinery. Three different platforms,
namely: thermochemical, sugar, and nonplatform or existing
technologies are integrated. An integrated biorefinery produces
various products, which include electricity produced from
thermochemical and bioproducts from the combination of sugar
and other existing conversion technology platforms.
An emerging concept in the biorefinery arena is conversion
of bio-oil, the product from biomass pyrolysis, which could be
routed via a conventional petrochemical refinery (Figure 8) to
generate various chemicals. The advantage of this route is that
all necessary infrastructures for the separation and purification
of products generated are already in place. This concept makes
perfect sense since most petroleum refineries are well equipped
to handle variable feedstock with the assumption that no two
batches of crude oil are the same.
Tables 3 and 4 give the composition of bio-oil compounds.
Bio-oil chemical properties vary with the feedstock but woody
biomass typically produces a mixture of 30% water, 30%
phenolics, 20% aldehydes and ketones, 15% alcohols, and 10%
miscellaneous compounds.
14
A process known as hydrodeoxy-
genation (HDO) could be applied to replacing oxygen by
hydrogenation of the raw bio-oils. After several HDO treatment
steps the bio-oil could be transformed into a liquid hydrocarbon
with properties similar to those of petroleum crude oil.
15
The
deoxygenated bio-oils can potentially be refined in existing
petroleum refineries, with only minor adjustments to the current
petroleum industry refinery infrastructure that is set up for
hydrodesulfurization (HDS) process.
16
HDO treatment of bio-
oils with metallic catalysts, such as sulfated Co, Mo, W, or Ni,
have been adopted from the petroleum industry.
16-25
It has been
shown that a two-stage process is required.
17,26
The first stage
applies a mild hydrogenation at relatively low temperatures
below about 270 C. Full HDO of bio-oils requires temperatures
above 300 C which results in polymerization of the highly
oxygenated compounds in raw bio-oils.
27
It is also important to standardize the quality requirements
of biorefinery products at the onset of this technology to
minimize variability. Such standardization will help focus future
research to attain products with specific quality. As an example,
it will be helpful for bio-oil researchers to know the minimum
qualities to target if bio-oil is to be routed through a petroleum
refinery. Identifying these minimum qualities is a challenge,
especially, because of the multidisciplinary nature of the subject
and should be done in close collaboration with petroleum
engineers, bioenergy engineers, chemists, and biologists.
As with petrochemical refineries, the main objective of the
bio-oil-based biorefinery is to produce multiple products,
including higher-value chemicals, as well as fuels and power.
Hence, it is important to look at the value-added chemicals
produced from the integrated biorefinery, which economically
and technically support the production of fuel and power
produced from these refineries. NREL and PNNL (Pacific
Northwest National Laboratory) researchers carried out an
exhaustive study to identify valuable sugar-derived chemicals
and materials that could serve as an economic driver to the
integrated biorefinery.
28
Increased productivity, lower production
cost, and efficiency could be achieved by employing operations
(12) National Renewable Energy Laboratory. Available from http://
www.eere.energy.gov/biomass/pdfs/sugar_enzyme.pdf (August 1, 2005).
(13) Energy Efficiency and Renewable Energy, Office of the Biomass
Program. Multiyear Analysis Plan (FY04-FY08). (August 15, 2005).
(14) Bridgewater, A.; Czernik, C.; Diebold, J.; Mekr, D.; Radlein, P.
Fast Pyrolysis of Biomass: A Handbook; CPL Scientific Publishing
Services, Ltd: Newbury, U.K., 1999; p 188.
(15) Scholze, B. Long-term stability, catalytic upgrading, and application
of pyrolysis oilssimproving the properties of a potential substitute for fossil
fuels. Dissertation, Department of Physical Chemistry, University of
Hamburg, Hamburg, Germany, 2002.
(16) Bridgewater, A. v.; Cottam, M. L. Opportunities for biomass
pyrolysis liquids production and upgrading. Energy Fuels 1992, 6, 113-
120.
(17) Baker, E. G.; Elliott, D. C. Catalytic hydrotreating of biomass-
derived oils. In Pyrolysis Oils from Biomass; Soltes, E. J., Milne., T. A.,
Eds.; American Chemical Society Symposium Series 376; American
Chemical Society: Washington, DC, 1988; p 353.
(18) Centeno, A.; David, O.; Vanbellinghen, C.; Maggi, R.; Delmon, B.
Behaviour of catalysts supported on carbon in hydrodeoxygenation reactions.
In DeVelopments in Thermochemical Biomass ConVersion; Bridgewater,
A. V., Boocock, D. G. B., Eds.; Blackie Academic and Professional:
London, 1997; Vol. 1, p 1648.
(19) Conti, L.; Scano, G.; Boufala, J.; Mascia, S. Bio-crude oil hy-
drotreating in a continuous bench-scale plant. In DeVelopments in Ther-
mochemical Biomass ConVersion; Bridgewater, A. V.; Boocock, D. G. B.,
Eds.; Blackie Academic and Professional: London, 1997; Vol. 1, p 1648.
(20) Elliot, D. C.; Schiefelbein, G. F. Liquid hydrocarbon fuels from
biomass. Am. Chem. Soc., DiV. Fuel Chem. 1989, 34 (4), 1160-1166.
(21) Ferrari, M.; Delmon, B.; Grange, P. Influence of the impregnation
order of molybdenum and cobalt in carbon supported catalysts for
hydrodeoxygenation reactions. Carbon 2002, 40, 497-511.
(22) Oasmaa, A.; Boocock, D. G. B. The catalytic hydrotreatment of
peat pyrolysate oils. Can. J. Chem. Eng. 1992, 70, 294-300.
(23) Puente, G.; Gil, A.; Pis, J. J.; Grange, P. Effects of support surface
chemistry in hydrodeoxygenation reactions over CoMo/activated carbon
sulfided catalysts. Langmuir 1999, 15, 5800-5806.
(24) Zhang, S. P.; Yan, Y. J.; Ren, Z.; Li, T. Study of hydrodeoxygenation
of bio-oil from the fast pyrolysis of biomass. Energy Sources 2003, 25,
57-65.
(25) Czernik, S.; Maggi, R.; Peacoke, G. V. C. Review of methods for
upgrading biomass-derived fast pyrolysis oils. In Fast Pryolysis of Biom-
ass: A Handbook; Bridgewater, A. V., Ed.; CPL Press: Newbury, U.K.,
2002; Vol. 2, p 425.
(26) Gagnon, J.; Kaliaguine, S. Catalytic hydrotreatment of vacuum
pyrolysis oils from wood. Ind. Eng. Chem. Res. 1988, 27 (10), 1783-1788.
(27) Elliott, D. C.; Neuenschwander, G. G. Liquid fuels by low-severity
hydrotreating of biocrude. DeV. Thermochem. Biomass ConVers. 1996, 1,
611-621.
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1733
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that lower the overall energy intensity of the biorefinerys unit
and drive down all production costs by maximizing the use of
all feedstock components, byproducts and waste streams,
economies of the scale, common processing operations, materi-
als, and equipment. Details of some of the important value-
added chemicals have been reviewed in a paper published
elsewhere.
28
The NREL and PNNL study has reduced list of
300 initially selected candidates to 30 potential candidates
through an iterative process based on the petrochemical model
using building blocks, chemical data, known market data,
properties, performance of the potential candidates, and the prior
industry experiences of the PNNL and NREL team. The list of
these 30 potential candidates was further reduced to 12 by
evaluating the potential markets for the building blocks and their
derivatives and the technical complexity of the synthesis
pathway.
(28) Aden, A.; Bozell, J.; Holladay, J.; White, J.; Manheim, A. Top Value
Added Chemicals from Biomass; Pacific Northwest National Laboratory
and National Renewable Energy Laboratory: Richland, WA, 2004; p 76.
Table 5. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Four Carbon
1,4-Diacids (succinic, furmaric, and malic acid)
a
a
Family 1, reduction; family 2, reductive aminations; family 3, direct
polymerization.
Table 6. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of 2,5-Furan
Dicarboxylic Acid (FDCA)
a
a
Family 1, reduction; family 2, direct polymerization.
Table 7. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of 3-Hydroxy
Propionic Acid (3-HPA)
a
a
Family 1, reductions; family 2, dehydrations.
Table 8. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Aspartic Acid
a
a
Family 1, selective reductions; family 2, dehydration to anhydrides;
family 3, direct polymerizations.
1734 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.
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4. Top 12 Building Blocks
The following list includes top twelve building blocks
identified by the NREL and PNNL study.
28
1,4-succinic, -fumaric, and -malic acids
2,5-furan dicarboxylic acid
3-hydroxy propionic acid
aspartic acid
glucaric acid
glutamic acid
itaconic acid
levulinic acid
3-hydroxybutyrolactone
glycerol
sorbitol
xylitol/arabinitol
The NREL and PNNL study analyzed the synthesis for each
of the top building blocks and their derivatives as a two-part
pathway, where the first part is the transformation of the sugars
into the building blocks and the second part is the conversion
of the building blocks to secondary chemicals or families of
derivatives. Biological transformations account for the majority
of the routes from plant feedstocks to building blocks, but
Table 9. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Glucaric
Acid
a
a
Family 1, dehydration; family 2, direct polymerizations.
Table 10. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Glutamic
Acid
a
a
Family 1, hydrogenation/reduction.
Table 11. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Itaconic Acid
a
a
Family 1, reduction; family 2, direct polymerization.
Table 12. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Levulinic
Acid
a
a
Family 1, reductions; family 2, oxidations; family 3, condensations.
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1735
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chemical transformations predominate in the conversion of
building blocks to molecular derivatives and intermediates. The
challenges and complexity of these pathways, as briefly
examined by the NREL and PNNL study to highlight R&D
needs that could help improve the economics of producing these
building blocks and derivatives, have been described here for
each of the twelve building blocks (Tables 5-16).
5. Conclusion and Final Remarks
The paper has discussed the concept of biorefineries, different
types of biorefineries, future directions, and associated technical
challenges. The biorefinery concept is still in its infancy. It is
important to formulate standards for the products obtained from
the biorefineries, if not available, starting from the onset of the
technology so that the variability of the intermediate products
is minimal to the streamline with existing technologies. One
factor that needs critical thinking is whether modern biorefineries
should be geared toward producing an entirely new line of
chemicals/products, such as platform chemicals that are precur-
sors to high value chemicals, or to produce raw material that
Table 13. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of
3-Hydroxybutyrolactone
a
a
Family 1, reduction; family 2, direct polymerization.
Table 14. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Glycerol
a
a
Family 1, oxidation; family 2, bond breaking (hydrogenolysis); family
3, direct polymerization
Table 15. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Sorbitol
a
a
Family 1, dehydration; family 2, bond cleavage (hydrogenolysis); family
3, direct polymerization.
Table 16. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of
Xylitol/Arabinitol
a
a
Family 1, oxidation; family 2, bond cleavage (hydrogenolysis); family
3, direct polymerization.
1736 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.
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could be starting feedstock for existing refineries or chemical
plants. The answer to this paradigm will help in long-term
sustainability of the integrated biorefineries and also help in
continual use of the infrastructure network that is already in
place which took decades if not centuries to develop to where
it is today.
EF060097W
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1737
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