Energy & Fuels 2006, 20, 1727-1737 1727

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 Figure 1. Simple three-step biomass-process-products procedure.4
facility that integrates conversion processes and equipments to
produce fuels, power, and chemicals from biomass”.2 To achieve fossil fuels are used as input, is relatively new. Biomass consists
the goals of sustainable development, biorefineries have to play of carbohydrates, lignin, proteins, fats, and to a lesser extent,
a dominant role in the coming millennia. An effort has been various other chemicals, such as vitamins, dyes, and flavors.3
made in this paper to review the biorefinerys’ development to The goal of a biorefinery is to transform such plentiful biological
date and its future directions. 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
2. The Biorefinery Concept
various useful products such as fuel, power, and chemicals using
The concept of producing products from agricultural com- biological and chemical conversion processes.
modities (i.e., biomass) is not new. However, using biomass as The main goal of a biorefinery is to produce high-value low-
an input to produce multiple products using complex processing volume (HVLV) and low-value high-volume (LVHV) products
methods, an approach similar to a petroleum refinery where using a series of unit operations. The operations are designed
to maximize the valued extractibles while minimizing the waste
* To whom correspondence should be addressed. Phone: +1 662 325 streams by converting LVHV intermediates into energy. The
3282. Fax: +1 662 325 3853. E-mail: [email protected]. high-value products enhance the profitability, while the high-
(1) Lynd, L. R.; Jin, H.; Michels, J. G.; Wyman, C. E.; Dale, B. volume fuels help to meet the global energy demand. The power
Bioenergy: background, potential, and policy. Available from http://
rmtools.org/ref/Lynd_et_al_2002.pdf (June 24, 2005). produced from a biorefinery also helps to reduce the overall
(2) National Renewable Energy Laboratory. Conceptual biorefinery.
Available from http://www.nrel.gov/biomass/biorefinery.html (August 1, (3) Askew, M. The biorefinery concept. Available from http://europa.e-
2005). u.int/comm/research/energy/pdf/renews3.pdf (August 1, 2005).

10.1021/ef060097w CCC: $33.50 © 2006 American Chemical Society

Published on Web 06/27/2006
1728 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.

Figure 2. Dry mill ethanol process plant.8

Figure 3. Representation of whole-crop biorefinery process and products.6

cost.2 In contrast to a petroleum refinery, a biorefinery uses I biorefinery plant has fixed processing capabilities and uses
renewable resources and produces fuels and chemicals that grain as a feedstock. A dry mill ethanol plant, illustrated in
contribute less to environmental pollution. Table 1 depicts the Figure 2, is an example of a phase I biorefinery which produces
increase in biobased products sales worldwide from 1983 to a fixed amount of ethanol, other feed products, and carbon
1994. This clearly shows there is a growing interest in biobased dioxide and has almost no processing flexibility.6,7
products. Similarly, Table 2 depicts the United States targets A process involving current wet milling technology could
for biobased products in the selected years. be considered a phase II biorefinery which uses grain feedstock
as input similar to dry milling. However, it has the capability
3. Types of Biorefineries
(5) Biobased Industrial Products: Research and Commercialization
Three types of biorefineries known as phase I, II, and III have Priorities; The National Academies Press: Washington, DC, 2000.
(6) Kamm, B.; Kamm, M. Principles of biorefinery. Appl. Microbiol.
been described by Kamm et al.6 and Van Dyne et al.7 A phase Biotechnol. 2004, 64, 137-145.
(7) Dyne, D. L. V.; Blase, M. G.; Clements, L. D. A strategy for returning
(4) Sokhansanj, S.; Cushman, J.; Wright, L. Collection and delivery of agriculture and rural America to long-term full employment using biomass
biomass for fuel and power production. Available from http://www.ten- refineries. In PerspectiVes on New Crops and New Uses; Janick, J., Ed.;
nesseebiomass.com/storage.php (June 27, 2005). ASHS Press: Alexandria, VA, 1999.
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1729

Figure 4. Representation of green biorefinery process and products.6

Table 1. Worldwide Sales of Biotechnology Products, 1983 and yields an array of products by employing combination of
1994a technologies.6 It allows a mix of agricultural feedstocks, has
1983 ($ millions) 1994 ($ millions) the ability to use various types of processing methods, and has
fuel and industrial ethanol 800 1500 the capability to produce a mix of higher-value chemicals while
high-fructose syrups 1600 3100 coproducing ethanol.9 It is based on both the HVLV and LVHV
citric acid 500 900 principles. The Phase III biorefineries, namely, whole-crop,
monosodium glutamate 600 800
lysine 200 700 green, and lignocellulose feedstock (LCF) biorefineries, are still
enzymes 400 1,000 in research and development.6
specialty chemicals 1300 3000 3.1. Whole-Crop Biorefinery. A whole-crop biorefinery
total 5400 11 000
a
processes and consumes the entire crop to obtain useful products.
Table excludes pharmaceutical products.5
Raw materials such as wheat, rye, triticale, and maize can be
Table 2. United States Biobased Industry Targets5 used as input in the feedstock in the unit operations of a whole-
biobased production levels
crop biorefinery as depicted in Figure 3. The process of
converting biomass into energy is initiated by mechanical
biobased future target future target
product current level intermediate (2020) ultimate (2090)
separation of biomass into different components that are then
treated separately. Biomass is the starting material for the
liquid fuelsa 1-2% 10% up to 50%
organic 10% 25% >90% production of syngas where syngas can be used as the basic
chemicalsb material for the synthesis of fuels and methanol using the Fischer
materialsc 90% 95% 99% Tropsh process.6 Corn either can be used directly after grinding
a Large-scale production of biobased ethanol is a long-term possibility to meal or can be converted to starch. Further processing can
and the projection assumes advanced technologies are in place for processing be carried out as follows: (i) breaking up, (ii) plasticization,
lignocellulosic materials. b Include oxygenated chemicals such as butanol (iii) chemical modification, and (iv) biotechnological conversion
or butyl butyrate that can be processed into other intermediate and specialty
chemicals traditionally dependent on fossil fuel feedstocks. c Include via glucose.
traditional forest products such as lumber, as well as novel biopolymers, 3.2. Green Biorefinery. A green biorefinery is a multiproduct
such as bioplastics. Many new products in this market will be high-value system which handles its refinery cuts, product, and fractions
materials that cannot be produced from petroleum feedstocks.
(8) Lasure, L. L.; Zhang M. Bioconversion and biorefineries of the future.
to produce various end products and far more processing Available from http://www.pnl.gov/biobased/docs/biorefineries.pdf (August
flexibility6,7 depending upon a product demand, prices, and 1, 2005).
contract obligations. The typical products are starch, high- (9) Tyson, K. S.; Bozell, J.; Wallace, R.; Petersen, E.; Moens, L. Biomass
oil analysis: research needs and recommendations. NREL Technical Report.
fructose corn syrup, ethanol, and corn oil. A phase III, the most Available from http://www.eere.energy.gov/biomass/pdfs/34796.pdf (August
developed biorefinery, uses a mix of biomass feedstocks and 1, 2005).
1730 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.

Figure 5. Representation of LCF biorefinery process and products.6

Figure 6. Sugar-lignin platform biorefinery.12

in accordance with the physiology of the corresponding plant untreated products, such as grass, green plants, or green crops
material as described by Kamm et al.6 and illustrated in Figure as inputs, which are produced in large quantities in green plants.
4. A green biorefinery uses natural wet feedstocks derived from The first step of the refinery is to treat the green biomass
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1731

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

substances in their natural form using wet-fractionation to polymer of only glucose, a hemicellulose is a polymer of five
produce a fiber-rich press cake and a nutrient-rich green juice. different sugars. It contains five-carbon sugars (usually D-xylose
The press cake contains cellulose, starch, valuable dyes and and L-arabinose), six-carbon sugars (D-galactose, D-glucose, and
pigments, crude drugs, and other organics, whereas the green D-mannose), and uronic acid. The hydrolysis process of hemi-
juice includes proteins, free amino acids, organic acids, dyes, cellulose results in aforementioned sugars. The following
enzymes, hormones, other organic substances, and minerals. The chemical reactions provide a general overview of the conver-
pressed cake can be also used for the production of green feed sions that take place in a LCF biorefinery.
pellets, as a raw material for the production of chemicals, such
as levulinic acid, and for conversions to syngas and synthetic lignocellulose + H2O ) lignin + cellulose + hemicellulose
fuels.6
3.3. Lignocellulose Feedstock (LCF) Biorefinery. LCF hemicellulose + H2O ) xylose
consists of three basic chemical fractions: (i) hemicellulose, xylose (C5H10O5) + acid catalyst )
five carbon sugar polymers, (ii) cellulose, six carbon glucose
polymers, and (iii) lignin, phenol polymers.9 A LCF biorefinery furfural (C5H4O2) + 3H2O
as depicted in Figure 5 uses hard fibrous plant materials cellulose (C6H10O6) + H2O ) glucose (C6H12O6)
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 The xylose fraction from hemicellulose is important because
hydrolysis. Hemicellulose and cellulose can be produced by it can be converted to furfural which is one of the starting
alkaline (caustic soda) and sulfite (acidic, bisulfite, alkaline, etc.). materials for nylon 6.6 Furthermore, furfural has many uses: it
Lignin in plant materials is broken down with enzymes such as can be used in the refining of motor oils, as a precursor of certain
ligninases, lignin peroxidases, laccases, and xylanolytic en- plastics, and as cleaning agents in liquid fuels.
zymes. The sugar polymers (hemicellulose and cellulose) are The hydrolysis of cellulose to glucose can be carried out either
converted to their component sugars (Figure 5) through hy- by enzymatic processing or chemical processing7 which pro-
drolysis. In the case of hemicellulose, it consists of short, highly duces useful products, such as ethanol, acetic acid, acetone,
branched chains of sugars. In contrast to cellulose, which is a 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 ×
Figure 7. Conceptual map of SPB and syngas platform-based 106 tons of ethanol and 323 × 103 tons of furfural annually
biorefinery.2 from daily feedstock consumption of 4000 tons.7 If substantial
1732 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.

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 hydroxyacetaldehyde 0.9-13
oxygenates
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 0.7
cyclopentene
syringal dehyde 0.1-1.5 R-pinene
4-propenyl syringol 0.1-0.3 dipentene

microbial conversion of glucose can be carried out, it can be power. Five platforms have been suggested: sugar platform
used as an alternative route 6,10,11 for the petrochemically biorefineries (SPBs), thermochemical or syngas platform, biogas
produced substances, such as hydrogen, methane, propanol, and platform, carbon-rich chains platform, and plant products
acetone. platform. The “sugar platform” focuses on the fermentation of
In a more modern approach, the U.S. Department of Energy/ sugars extracted from biomass feedstocks. The objective is to
NREL have described conversion technologies for expanded biologically process the sugars to produce fuel, such as ethanol,
biomass based on the “platforms” because the basic technology or other building block chemicals. SPBs are closely related to
would generate base or platform chemicals from which industry LCF biorefineries in the conventional nomenclature. The unit
could make a wide range of fuels, chemicals, materials, and operation of a SPB is provided in Figure 6.
(10) Zeikus, J. G.; Jain, M. K.; Elankovan, P. Biotechnology of succinic The thermochemical or syngas platform focuses on the
acid production and markets for derived industrial products. Appl. Microbiol. gasification of the biomass feedstocks. This approach converts
Biotechnol. 1999, 51, 545-552. the solid biomass into gaseous and liquid fuels by mixing it
(11) Willke, T.; Vorlop, K. D. Industrial bioconversion of renewable
resources as an alternative to conventional chemistry. Appl. Microbiol. with limited oxygen prior to combustion. Various components
Biotechnol. 2004, 66, 131-142. produced through this process can be separated into fuels or
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1733

valuable chemicals. NREL’s main focuses are on the SPB and petroleum industry refinery infrastructure that is set up for
“syngas” platforms. The concept of these two biorefinery hydrodesulfurization (HDS) process.16 HDO treatment of bio-
platforms is described in Figure 7. oils with metallic catalysts, such as sulfated Co, Mo, W, or Ni,
The biogas platform is a widely used technology particularly have been adopted from the petroleum industry.16-25 It has been
in developing countries for producing cooking gas. This platform shown that a two-stage process is required.17,26 The first stage
decomposes biomass with natural microorganisms in closed applies a mild hydrogenation at relatively low temperatures
tanks known as anaerobic digesters. The process produces below about 270 °C. Full HDO of bio-oils requires temperatures
methane and carbon dioxide. The carbon-rich chains platform above 300 °C which results in polymerization of the highly
uses plant oils, such as soybean, corn, palm, and canola oils, oxygenated compounds in raw bio-oils.27
which are presently used for food and chemical production. It is also important to standardize the quality requirements
Transesterification of the vegetable oil or animal fat produces of biorefinery products at the onset of this technology to
fatty acid methyl esters, commonly known as biodiesel. Biodie- minimize variability. Such standardization will help focus future
sel is already in use as an important commercial air-emission research to attain products with specific quality. As an example,
reducing additive or substitute for petroleum diesel. Selective 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
breeding and genetic engineering can be used to develop plant
refinery. Identifying these minimum qualities is a challenge,
strains that produce greater amounts of desirable feedstocks,
especially, because of the multidisciplinary nature of the subject
chemicals, or even compounds that the plant does not naturally
and should be done in close collaboration with petroleum
produce. The intention is to perform the biorefining in the
engineers, bioenergy engineers, chemists, and biologists.
biological plant itself rather than in an industrial plant. This
As with petrochemical refineries, the main objective of the
approach is known as the plant products platform.
bio-oil-based biorefinery is to produce multiple products,
3.4. Integrated Biorefinery. The biorefinery types that we including higher-value chemicals, as well as fuels and power.
discussed previously are based on one conversion technology Hence, it is important to look at the value-added chemicals
to produce various chemicals. A biorefinery is a capital-intensive produced from the integrated biorefinery, which economically
project, and when it is based on just one conversion technology, and technically support the production of fuel and power
as is the case for the previously described biorefineries, it produced from these refineries. NREL and PNNL (Pacific
increases the cost of outputs (or products) generated from such Northwest National Laboratory) researchers carried out an
biorefineries. Hence, several conversion technologies (thermo- exhaustive study to identify valuable sugar-derived chemicals
chemical, biochemical, etc.) are combined together to reduce and materials that could serve as an economic driver to the
the overall cost, as well as to have more flexibility in product integrated biorefinery.28 Increased productivity, lower production
generation and to provide its own power. Figure 8 provides a cost, and efficiency could be achieved by employing operations
schematic of an integrated biorefinery. Three different platforms,
namely: thermochemical, sugar, and nonplatform or existing (15) Scholze, B. Long-term stability, catalytic upgrading, and application
technologies are integrated. An integrated biorefinery produces of pyrolysis oilssimproving the properties of a potential substitute for fossil
fuels. Dissertation, Department of Physical Chemistry, University of
various products, which include electricity produced from Hamburg, Hamburg, Germany, 2002.
thermochemical and bioproducts from the combination of sugar (16) Bridgewater, A. v.; Cottam, M. L. Opportunities for biomass
and other existing conversion technology platforms. pyrolysis liquids production and upgrading. Energy Fuels 1992, 6, 113-
120.
An emerging concept in the biorefinery arena is conversion (17) Baker, E. G.; Elliott, D. C. Catalytic hydrotreating of biomass-
of bio-oil, the product from biomass pyrolysis, which could be derived oils. In Pyrolysis Oils from Biomass; Soltes, E. J., Milne., T. A.,
routed via a conventional petrochemical refinery (Figure 8) to Eds.; American Chemical Society Symposium Series 376; American
Chemical Society: Washington, DC, 1988; p 353.
generate various chemicals. The advantage of this route is that (18) Centeno, A.; David, O.; Vanbellinghen, C.; Maggi, R.; Delmon, B.
all necessary infrastructures for the separation and purification Behaviour of catalysts supported on carbon in hydrodeoxygenation reactions.
of products generated are already in place. This concept makes In DeVelopments in Thermochemical Biomass ConVersion; Bridgewater,
A. V., Boocock, D. G. B., Eds.; Blackie Academic and Professional:
perfect sense since most petroleum refineries are well equipped London, 1997; Vol. 1, p 1648.
to handle variable feedstock with the assumption that no two (19) Conti, L.; Scano, G.; Boufala, J.; Mascia, S. Bio-crude oil hy-
batches of crude oil are the same. drotreating in a continuous bench-scale plant. In DeVelopments in Ther-
mochemical Biomass ConVersion; Bridgewater, A. V.; Boocock, D. G. B.,
Tables 3 and 4 give the composition of bio-oil compounds. Eds.; Blackie Academic and Professional: London, 1997; Vol. 1, p 1648.
Bio-oil chemical properties vary with the feedstock but woody (20) Elliot, D. C.; Schiefelbein, G. F. Liquid hydrocarbon fuels from
biomass. Am. Chem. Soc., DiV. Fuel Chem. 1989, 34 (4), 1160-1166.
biomass typically produces a mixture of 30% water, 30% (21) Ferrari, M.; Delmon, B.; Grange, P. Influence of the impregnation
phenolics, 20% aldehydes and ketones, 15% alcohols, and 10% order of molybdenum and cobalt in carbon supported catalysts for
miscellaneous compounds.14 A process known as hydrodeoxy- hydrodeoxygenation reactions. Carbon 2002, 40, 497-511.
(22) Oasmaa, A.; Boocock, D. G. B. The catalytic hydrotreatment of
genation (HDO) could be applied to replacing oxygen by peat pyrolysate oils. Can. J. Chem. Eng. 1992, 70, 294-300.
hydrogenation of the raw bio-oils. After several HDO treatment (23) Puente, G.; Gil, A.; Pis, J. J.; Grange, P. Effects of support surface
steps the bio-oil could be transformed into a liquid hydrocarbon chemistry in hydrodeoxygenation reactions over CoMo/activated carbon
sulfided catalysts. Langmuir 1999, 15, 5800-5806.
with properties similar to those of petroleum crude oil.15 The (24) Zhang, S. P.; Yan, Y. J.; Ren, Z.; Li, T. Study of hydrodeoxygenation
deoxygenated bio-oils can potentially be refined in existing of bio-oil from the fast pyrolysis of biomass. Energy Sources 2003, 25,
petroleum refineries, with only minor adjustments to the current 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-
(12) National Renewable Energy Laboratory. Available from http:// ass: A Handbook; Bridgewater, A. V., Ed.; CPL Press: Newbury, U.K.,
www.eere.energy.gov/biomass/pdfs/sugar_enzyme.pdf (August 1, 2005). 2002; Vol. 2, p 425.
(13) Energy Efficiency and Renewable Energy, Office of the Biomass (26) Gagnon, J.; Kaliaguine, S. Catalytic hydrotreatment of vacuum
Program. Multiyear Analysis Plan (FY04-FY08). (August 15, 2005). pyrolysis oils from wood. Ind. Eng. Chem. Res. 1988, 27 (10), 1783-1788.
(14) Bridgewater, A.; Czernik, C.; Diebold, J.; Mekr, D.; Radlein, P. (27) Elliott, D. C.; Neuenschwander, G. G. Liquid fuels by low-severity
Fast Pyrolysis of Biomass: A Handbook; CPL Scientific Publishing hydrotreating of biocrude. DeV. Thermochem. Biomass ConVers. 1996, 1,
Services, Ltd: Newbury, U.K., 1999; p 188. 611-621.
1734 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.

Table 5. Building Blocks, Pathways, Their Transformation to Table 7. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Four Carbon Derivatives, Technical Barriers, and Potential Uses of 3-Hydroxy
1,4-Diacids (succinic, furmaric, and malic acid)a 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 Acida

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, selective reductions; family 2, dehydration to anhydrides;

family 3, direct polymerizations.

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
a Family 1, reduction; family 2, direct polymerization. through an iterative process based on the petrochemical model
using building blocks, chemical data, known market data,
that lower the overall energy intensity of the biorefinery’s unit properties, performance of the potential candidates, and the prior
and drive down all production costs by maximizing the use of industry experiences of the PNNL and NREL team. The list of
all feedstock components, byproducts and waste streams, these 30 potential candidates was further reduced to 12 by
evaluating the potential markets for the building blocks and their
(28) Aden, A.; Bozell, J.; Holladay, J.; White, J.; Manheim, A. Top Value
Added Chemicals from Biomass; Pacific Northwest National Laboratory derivatives and the technical complexity of the synthesis
and National Renewable Energy Laboratory: Richland, WA, 2004; p 76. pathway.
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1735

Table 9. Building Blocks, Pathways, Their Transformation to Table 11. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Glucaric Derivatives, Technical Barriers, and Potential Uses of Itaconic Acida
Acida

a Family 1, reduction; family 2, direct polymerization.

Table 12. Building Blocks, Pathways, Their Transformation to

Derivatives, Technical Barriers, and Potential Uses of Levulinic
Acida

a Family 1, dehydration; family 2, direct polymerizations.

Table 10. Building Blocks, Pathways, Their Transformation to

Derivatives, Technical Barriers, and Potential Uses of Glutamic
Acida

a Family 1, hydrogenation/reduction.

4. Top 12 Building Blocks

The following list includes top twelve building blocks
identified by the NREL and PNNL study.28 a Family 1, reductions; family 2, oxidations; family 3, condensations.
• 1,4-succinic, -fumaric, and -malic acids
• 2,5-furan dicarboxylic acid • sorbitol
• 3-hydroxy propionic acid • xylitol/arabinitol
• aspartic acid The NREL and PNNL study analyzed the synthesis for each
• glucaric acid of the top building blocks and their derivatives as a two-part
• glutamic acid pathway, where the first part is the transformation of the sugars
• itaconic acid into the building blocks and the second part is the conversion
• levulinic acid of the building blocks to secondary chemicals or families of
• 3-hydroxybutyrolactone derivatives. Biological transformations account for the majority
• glycerol of the routes from plant feedstocks to building blocks, but
1736 Energy & Fuels, Vol. 20, No. 4, 2006 Fernando et al.

Table 13. Building Blocks, Pathways, Their Transformation to Table 15. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of Derivatives, Technical Barriers, and Potential Uses of Sorbitola
3-Hydroxybutyrolactonea

a Family 1, dehydration; family 2, bond cleavage (hydrogenolysis); family

a Family 1, reduction; family 2, direct polymerization. 3, direct polymerization.

Table 14. Building Blocks, Pathways, Their Transformation to

Derivatives, Technical Barriers, and Potential Uses of Glycerola Table 16. Building Blocks, Pathways, Their Transformation to
Derivatives, Technical Barriers, and Potential Uses of
Xylitol/Arabinitola

a Family 1, oxidation; family 2, bond breaking (hydrogenolysis); family

3, direct polymerization
a Family 1, oxidation; family 2, bond cleavage (hydrogenolysis); family

chemical transformations predominate in the conversion of 3, direct polymerization.

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 challenges. The biorefinery concept is still in its infancy. It is
needs that could help improve the economics of producing these important to formulate standards for the products obtained from
building blocks and derivatives, have been described here for the biorefineries, if not available, starting from the onset of the
each of the twelve building blocks (Tables 5-16). 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
5. Conclusion and Final Remarks
should be geared toward producing an entirely new line of
The paper has discussed the concept of biorefineries, different chemicals/products, such as platform chemicals that are precur-
types of biorefineries, future directions, and associated technical sors to high value chemicals, or to produce raw material that
Biorefineries Energy & Fuels, Vol. 20, No. 4, 2006 1737

could be starting feedstock for existing refineries or chemical place which took decades if not centuries to develop to where
plants. The answer to this paradigm will help in long-term it is today.
sustainability of the integrated biorefineries and also help in
continual use of the infrastructure network that is already in EF060097W