Review

The new forestry biofuels sector

Yunqiao Pu, Dongcheng Zhang, Preet M. Singh and Arthur J. Ragauskas, Georgia Institute of Technology, USA

Received October 9, 2007; revised version received November 12, 2007; accepted November 13, 2007
Published online December 19, 2007 in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.48;
Biofuels, Bioprod. Bioref. 2:58–73 (2008)

Abstract: Society’s increasing demand for transportation fuels has assured a viable future for the development of
renewable fuels. Although first-generation biofuels are dependent on starches, sugars and vegetable oils, the need to
generate higher volumes of biofuels at lower cost has shifted the research focus to cellulosic ethanol. The utilization
of lignocellulosics for the sustainable manufacturing of biofuels is critically dependent on the chemical constituents
of the starting biomass and the desired fuel properties. This review examines the major chemical constituents of
biomass and the recent advances in their conversion to biofuels, with a special emphasis on the forest residues and
woody-energy crops to bioethanol. © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd

Keywords: cellulose; hemicellulose; lignin; wood; biorefinery; biofuels; pretreatment; saccharification; fermentation;
pyrolysis; gasification

Introduction processability with conversion processes, with the equip-

ment to produce a range of fuels, power, and chemicals from
he events of the last few years have brought into sharp biomass.6 It fully utilizes all components of biomass to make

T focus the need to develop sustainable green technolo-

gies for many of our most basic manufacturing and
energy needs. Since the beginning of the new millennium,
we have witnessed an ever-increasing merger of technical,
economical and societal demands for sustainable technolo-
gies. Indeed, hardly a day goes by in which the issues of
energy security, climate change, cradle-to-cradle product
development are not discussed in public and professional
forums.1–3 Accompanying these interests, science and engi-
neering have made tremendous strides to begin to answer
these challenges. Indeed, it is the intersection of science,
business and public policy that has launched a new green,
industrial revolution that promises to dramatically alter our
world.4
At the cornerstone of this green industrial revolution is the
integrated biorefinery.5 This is a biomass processing facility
that integrates our ability to tailor biomass productivity and
a range of foods, fuels, chemicals, feeds, materials, heat and
power in proportions that maximizes sustainable, economic
development. As such, this vision seeks to develop a new
‘carbohydrate-lignin economy’ that will initially supplement
today’s petroleum economy and, as these non-renewable
resources are consumed, will become the primary resource
for fuels, chemicals and materials.
Today’s bioethanol and biodiesel plants represent the
first-generation biorefineries that utilize readily proces-
sable bioresources such as sucrose, starches and plant
oils.7–9 As has been highlighted in several reviews, society’s
ability to displace substantial amounts of nonrenewable
petroleum reserves with renewable resources rests on its
ability to secure large amounts of low-cost biomass. For
example, Perlack et al., identified 1.3 billion dry tons of
biomass potential/year in the USA which could be directed
to biofuels production; enough to address approximately

Correspondence to: Arthur J. Ragauskas, School of Chemistry and Biochemistry, Georgia Institute of Technology,

500 10th Street NW, Atlanta, GA 30332. E-mail: arthur.ragauskas@chemistry.gatech.edu

58 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd
Review: New forestry biofuels sector
one-third of current demand for transportation fuels in
the United States.10 A subsequent workshop titled Breaking
the biological barriers to cellulosic ethanol supported this
hypothesis, and with a more aggressive research program on
improving energy crops, the biomass replacement potential
could be even greater.11 An analysis of the US bioresource
basin suggests that approximately 30% of this biomass would
originate from forest resources including: wood from forest-
lands, wood-related mill residues, and terrestrial urban wood
residues. The exact distribution of these resources is clearly
sensitive to geographical locations and the next generation
of biorefineries will need to be engineered to utilize local
bioresources. A unique web resource that summarizes the
theoretical potential ethanol yield from biomass, including
woody plants, is the US Department of Energy, Energy effi-
ciency and renewable energy biomass program website.12 The
theoretical ethanol yields for forest thinnings, hardwood
sawdust and mixed paper were predicted at 81.5, 100.8 and
116.2 gallons/ton of dry feedstock, respectively.
Woody biomass resources
The conversion of these bioresources to value-added mate-
rials and chemicals rests primarily on our abilities to
manipulate the chemistry and biochemistry of cellulose,
hemicellulose and lignin. These three biopolymers are the
main global plant resources and further research is needed
to efficiently convert these bio building blocks to biofuels,
biochemicals, biomaterials and biopower.
Cellulose
Of the three bioresources, cellulose is chemically the
simplest structure as it is a linear polymer of β (1→4)
glucopyranosyl (Fig. 1) with a degree of polymerization (DP)
varying from ~10,000 in cotton to less than 500 in several
industrially processed materials.13
The cellulose chain has a strong tendency to form intra- and
inter-molecular hydrogen bonds by the hydroxyl groups on
HOH2C
OH
HO O HO
O O
O O
O HO
HOH2C OH
Figure 1. The structure of cellulose.
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
these linear cellulose chains, which stiffens the chains and
promotes aggregation into a crystalline structure. These
properties give cellulose a multitude of crystalline fiber
structures and morphologies. The degree of crystallinity of
select cellulose samples are presented in Table 1.14
The ultrastructure of native cellulose (cellulose I) has
been shown to possess an additional complexity in the form
of two crystal phases: Iα and Iβ.15 The relative amounts of
Iα and Iβ have been found to vary between samples from
different origins. The Iα-rich specimens have been found in
the cell wall of some algae and in bacterial cellulose, whereas
Iβ-rich specimens have been found in cotton, wood, and
ramie fibers.16 The crystal and molecular structure of cellu-
lose I has been examined recently by Nishiyama et al., using
atomic-resolution synchrotron and neutron diff raction data
recorded from cellulose isolated from alga and tunicin.17
Most native samples of cellulose also have varying degrees of
amorphous cellulose, which is more reactive to chemical and
enzymatic attack.
Hemicellulose
After cellulose, the next major polysaccharide resource is
plant hemicelluloses. Unlike cellulose, hemicelluloses have
lower DP values (i.e., typically 50–300), frequently have
side chain groups and are essentially amorphous. The main
hemicelluloses of soft wood (SW) are galactoglucomannans
(Fig. 2) and arabinoglucuronoxylan (Fig. 3), while in hard-
wood (HW) it is glucuronoxylan (Fig. 4). Table 2 summarizes
Table 1. X-Ray crystallinity of some cellulose
materials.
Sample X-ray crystallinity (%)
Cotton linters 56–63
Sulfite dissolving pulp 50–56
Prehydrolyzed sulfate pulp 40–45
Viscose rayon 27–40
Regenerated cellulose film 40–45
HOH2C
OH O
O
HO
O
HOH2C OH
59
Y Pu et al. Review: New forestry biofuels sector

HOH2C HOH2C
O RO O RO
O O O OR O
OR O OR
HO O RO
HOH2C O
OH
O
R: H or Ac
HO OH

O
CH2OH
HO

Figure 2. Principal structure of galactoglucomannans in softwood.

OH OH
O OH O OH
O O O
O O
HO O O O
O OH
O
HO OH
OH
H3CO O
HOOC HOH2C

OH

Figure 3. Principal structure of arabinoglucuronoxylan in softwood.

OR OR
O OR O RO
O O O
O RO O
RO O O
O OR
HO OH
R: H or Ac
H3CO O
HOOC

Figure 4. Principal structure of glucuronoxylan in hardwood.

Table 2. The major hemicellulose components in softwood and hardwood.19,20

Composition
Amount
Wood Hemicellulose type (% on wood) Units21 Molar ratios Linkage ~DP
β-D-Manp 4
1→4
β-D-Glcp 1
Galacto-glucomannan 10–15 1→4 100
β-D-Galp 0.1
1→6
SW Acetyl 1
β-D-Xylp 10 1→4
Arabino-glucuronoxylan 7–10 4-O-Me-α-D-GlcpA 2 1→2 100
β-L-Araf 1.3 1→3
β-D-Xylp 10
1→4
Glucuronoxylan 15–30 4-O-Me-α-D-GlcpA 1 200
1→2
HW Acetyl 7
β-D-Manp 1–2 1→4
Glucomannan 2–5 200
β-D-Glcp 1 1→4

the main structural features of hemicelluloses appearing in covalent linkages between lignin and carbohydrates. 22,23
common soft wood and hardwood resources.18 The most frequently suggested LCC-linkages in native
In addition, most sugar components can take part in wood are benzyl ester, benzyl ether, and glycosidic
the formation of lignin-carbohydrate complexes (LCC) by linkages. 24

60 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector Y Pu et al.

Lignin enabled scientists to elucidate the predominant structural

features of lignin. Figure 6 depicts some of the common
This biopolymer is an amorphous, cross-linked, and
linkages found in soft wood lignin.28,29 The typical abun-
three dimensional phenolic polymer.25 The biosynthesis
dance of these types of linkages and functional groups in
of lignin stems from the polymerization of three types of
soft woods are shown in Tables 3 and 4.28 Lignin is much less
phenylpropane units as monolignols: coniferyl, sinapyl,
hydrophilic than either cellulose or hemicelluloses and it
and p-coumaryl alcohol.26,27 Figure 5 depicts these three
has a general effect of inhibiting water adsorption and fiber
structures. Soft wood lignin is composed mainly of coniferyl
swelling.
alcohol units, while hardwood lignin is composed mainly of
coniferyl and sinapyl alcohol units. C C
The polymerization process is initiated by an enzyme- C O C C
C
C C O C
catalyzed oxidation of the monolignol phenolic hydroxyl C O
C O
groups to yield free radicals. A monolignol free radical can
then couple with another monolignol free radical to generate O O
a dilignol. Subsequent nucleophilic attack by water, alco- O
β-O-4 α-O-4
hols, or phenolic hydroxyl groups on the benzyl carbon of dibenzodioxocin

the quinone methide intermediate restores the aromaticity C C

C
of the benzene ring. The generated dilignols then undergo C C C
C O C C
further polymerization to form protolignin.
Although the exact structure of protolignin is unknown,
improvements in methods for identifying lignin-degradation O O O
products and advancements in spectroscopic methods have β-5 5-5

C
C
HO C C C C
γ C
C C C C O
β Coniferyl alcohol/guaiacyl: R1 = OMe, R2 = H C C C C
α Sinapyl alcohol/ syringyl: R1 = R2 = OMe
1 p-Coumaryl alcohol: R 1 = R2 = H
O
6 2

5 3 O O O O
R2 R1 4-O-5 β-β β-1
4
OH
Figure 6. Common linkages between phenylpropane
Figure 5. Three building blocks of lignin. units in softwood lignin.28

Table 3. Proportions of different types of linkages connecting the phenylpropane units in softwood lignin.

Linkage typea Dimer structure Percentage

β-O-4 Phenylpropane β-aryl ether 50

β-5 Phenylcoumaran 9–12

5-5 Biphenyl 15–25

5-5/α-O-4 Dibenzodioxicin 10–15

4-O-5 Diaryl ether 4

β-1 1,2-Diaryl propane 7

β-β β-β-linked structures 2

© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb 61
Y Pu et al. Review: New forestry biofuels sector

Table 4. Functional groups in spruce lignin. of the substrate. The effect of virgin lignin, redeposited
lignin after pretreatment33 and LCC on the bioavailability
Milled wood lignin of other cell-wall components is thought to play a large role
Functional group per 100 C9 units
in the physical restriction mechanism. Other factors have
Carbonyl 0.8
been proposed, including non-specific association between
Olefinic + substituted
39 lignin and deconstruction enzymes (i.e., cellulase, xylanase,
aromatic C
Aliphatic CHx-OR 23.6 etc.).34–36 Interestingly, recent studies at the National Renew-
Methoxyl 11.2 able Energy Laboratory (NREL) have suggested that low
Aliphatic CHx 4.9 levels of lignin may actually enhance cellulose hydrolysis.37
This effect has been attributed to a physical separation of
microcellulose fibrils enhancing cellulase access/activity.
Conversion of biomass to biofuels Recent studies by Pu et al.,38 Hayashi et al.,39 and others
As highlighted by Petrus’s recent renewable fuels article, have demonstrated that depolymerization of fibrous cellu-
the utilization of these primary bioresources for biofuels lose by cellulase exhibits selectivity toward the more reactive
production centers about deoxygenation chemistry.30 Table 5 amorphous, paracrystalline and Iα forms of cellulose leaving
summarizes that cellulose, hemicelluloses and lignin are all behind a more recalcitrant crystalline form of cellulose.
too-rich in oxygen-function groups in comparison to typi- In contrast, other reports have suggested that the cellu-
cally hydrocarbon-based gasoline and diesel fuels. lose crystallinity index after hydrolysis does not change.40
To date, the most successful technological route for the Clearly, selectivity of cellulase hydrolysis and its impact on
conversion of plant biomass to biofuels is the fermentation residual crystalline structure needs further investigation
route, with bioethanol derived from starch and sucrose now since it is well known that fungal cellulase hydrolysis of
becoming a common 5–10% fuel supplement. Although all amorphous cellulose is 3–30 times faster than crystalline
biorefineries are regional and no one technology will address cellulose.41,42 The role of acetylated hemicelluloses for both
all needs, for many geographical locations to attain higher soft woods and hardwoods has also been suggested to impact
levels of renewable fuels this will require the utilization of enzymatic deconstruction of polysaccharides.43 The efficient,
lignocellulosics. This change in bioresource is based on the cost-effective depolymerization of these polysaccharides to
greater availability of lignocellulosic biomass, potential lower monosaccharides remains a key challenge in the utilization
cost and the avoidance of the ‘food or fuel’ arguments.31 of these bioresources for fermentation to ethanol.44,45 To
Currently, the overall cost of converting lignocellulosic date, effective utilization of these bioresources is predicated
material to ethanol is higher than well-established commer- on a pretreatment that reduces biomass recalcitrance.
cial starch to bioethanol technologies. This is primarily due
to the recalcitrance of lignocellulosics.32 Lignin is the most Current pretreatment technologies
recalcitrant component of the plant cell wall. In general, the
The objective of pretreating lignocellulosics is to alter the
higher the proportion of lignin, the lower the bioavailability
structure of biomass in order to make the cellulose and
hemicelluloses more accessible and amenable to hydrolytic
Table 5. General chemical composition of enzymes that can generate fermentable sugars. Effective
bioresources and petroleum. pretreatment technologies need to address several important
Cellulose/starch [C6(H2O)5]n criteria, including: minimization of hemicelluloses degrada-
Hemicellulose [C5(H2O)4]n/[C6(H2O)5]n
tion products, limiting the formation of by-products that
inhibit ethanol fermentation, lignin alterations,46 minimal
SW Lignin [C10H12O4]n
energy, capital and operating costs. Some of the most
Gasoline ~C6H14–C12H26
studied lignocellulosic/wood pretreatments are summarized
Diesel ~C10H22 to C15H32
below:

62 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
Uncatalyzed steam explosion involves rapidly heating
biomass with steam at elevated temperatures (~190–240 oC)
with residence times of ~3–8 min, followed by explosive
decompression. This treatment promotes hemicellulose
hydrolysis and opens up the plant cell structure, although
enhanced digestability of cellulose is only weakly correlated
with the physical effects.47,48 This autohydrolysis procedure
has been shown to be effective with agricultural residues
and hardwoods, but not as beneficial for soft woods.49,50 To
improve the efficiency of this process, several additive tech-
nologies have been examined including pre-impregnation
with SO251 and post-alkaline hydrogen peroxide treatment.52
Hot water autocatalyzed pretreatments at 200–230 oC
for up to 15 minutes can result in extensive hemicellulose
hydrolysis but, the high lignin content biomass reduces
subsequent cellulase hydrolysis.53 Depending on the condi-
tions employed, 30–46% of the lignin of corn stovers could
be removed. The production of possible inhibitors such
as furfural and hydroxymethyl furfural was reported to
account for less than 3% of the original carbohydrates54 as
xylan release frequently results in oligomers. Subsequent
enzymatic hydrolysis of cellulose has been reported to
yield glucose in 25–95% yields, with the latter only being
accomplished with physical milling. The application of this
pretreatment to hardwoods has been reported, resulting in
90% conversion of glucose to ethanol after simultaneous
saccharification and fermentation (SSF).55 Allen et al.,
published a comparison study of a hot-water treatment
versus a dilute-acid pretreatment and both yielded compa-
rable conversion to ethanol under optimized conditions,
although the severity of the former pretreatment had to be
much higher.56
Dilute acid pretreatment has been extensively studied and
typically employs 0.4–2% H2SO4 (note: nitric, sulfur dioxide,
and phosphoric acid have also been studied) at tempera-
tures of 160–220 oC to remove hemicelluloses and enhance
cellulase digestion of cellulose.19 The acidic conditions used
have been shown to enhance total sugar release after enzy-
matic hydrolysis to ~93% for corn stovers and ~82% for
soft wood.57 The pretreatment conditions impact not only
the plant polysaccharides but also lignin.58 For soft woods,
a two-stage acidic pretreatment has been used to tailor
the reactivity of cellulose and hemicellulose. This tailored
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
approach has been reported to increase sugar yields by 10%
and reduces cellulase requirements by about 50%.59 The
use of SO2 on spruce woodchips is of exceptional interest
as it yields a more reactive material with less inhibitory
compounds than dilute acid and this is reflected in higher
ethanol yields after saccharification and fermentation.60
Recently, diethyloxylate has been reported as a potential
acidic pretreatment reagent for wood and other treatments
are also being developed.61
Aqueous lime or NaOH pretreatment has been shown to
be effective for wheat straw and sugar bagasse with lower
temperatures than acid treatments; however, the treatment
times are hours long. For example, Chang et al., used lime
with wheat straw at 85 oC, for 3 h.62 The use of an alkaline
treatment incurs additional capital cost, as the recovery
of salts requires a lime kiln to regenerate the base. The
efficiency of alkaline treatments to convert recalcitrant
biomass for subsequent cellulase treatments has focused on
the application of a supplement oxidant, such as oxygen or
hydrogen peroxide. It has been reported that this protocol
dissolves the hemicelluloses, degrades lignin, and yields
a cellulose fraction that is very accessible to enzymes for
hydrolysis and fermentation to ethanol. An improved
version of this pretreatment is the utilization of oxygen
under alkaline conditions. An oxidative lime treatment63
and other wet-oxidations64 have been shown to improve the
effectiveness of this pretreatment technology especially for
wood-related bioresources.
Ammonia pretreatment involves pretreating biomass with
an aqueous solution (5–15%) at temperatures of 160–180 oC.
The ammonia reacts with lignin causing depolymerization
and cleavage of select lignin-carbohydrate bonds. Agricul-
tural residuals and herbaceous plants treated in this manner
exhibit an excellent response to cellulase.65,66 Unfortunately,
hardwoods and soft woods are not efficiently treated by this
technology, with conversion yields of glucose to ethanol
being reported to be less than 85%.67 In all cases, ammonia
recovery is an additional cost and important consideration.
Organosolv pretreatment of biomass resides on the
use of an organic solvent system (i.e., ethanol/water,68,69
acetone/water,70 methyl isobutyl ketone/ethanol/water71)
with enhanced solubilizing properties, due to the organic
component. Usually, the resultant cellulosic fraction is highly
63
Y Pu et al.
susceptible to enzymatic hydrolysis, generating very high
yields of glucose that can be readily converted to ethanol.
Pan et al., have shown that ~88% of the cellulose could be
recovered after the organosolv pretreatment of hybrid poplar
and 85% was converted to glucose upon subsequent enzyme
hydrolysis.72 Even better results were reported for infected
lodgepole pine.73 Several authors have also indicated that
the wood-based biofinery of the future will garner addi-
tional revenues from the extracted lignin and hemicellulose
streams.74–76
In all these and other pretreatment technologies, differences
in cell-wall structure and chemistry impact how hardwoods
and soft woods respond to chemical pretreatments. Several
authors have indicted that the recalcitrance of soft wood
resources is greater than hardwoods which is exhibited in
reduced digestability by cellulase.77,78 The exact chemical
constituents and ultrastructures that contribute to this effect
are not well understood as recently highlighted by Mosier
et al: ‘Greater fundamental understanding of the chemical
and physical mechanism that occur during pretreatment
along with an improved understanding of the relationship
between the chemical composition and physico-chemical
structure of lignocellulosics on the enzymatic digestion of
cellulose and hemicellulose is required for the generation of
effective pretreatments.’79 Future fundamental research into
these issues promises to have a far-reaching beneficial effect
in accelerating the development of low-cost biofuels.
Plant genetics, recalcitrance and future
pretreatments
The need to improve the effectiveness of pretreatment
technologies for wood is driven primarily by the fact that
it remains the most costly step in the overall conversion of
wood to biofuels. Wyman has perhaps best summarized
the state-of-the-art pretreatment capabilities: ‘The only
step more expensive than pretreatment is no pretreatment,
because of its impact on virtually all other operations.’80
In light of the well-known dependency of biomass recal-
citrance on the plant resource, it is natural to consider the
opportunity of reducing the recalcitrance of wood and other
biomass via the genetic engineering of the biomass. Indeed,
the forest products industry has extensively championed the
use of plant genetics to tailor the composition, structure and
64 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
reactivity of soft wood and hardwood biopolymers, especially
lignin. For example studies by Chiang et al., have inserted
antisense 4CL and sense coniferaldehyde 5-hydroxylase
genes into aspen to yield trees with each or both of these
transgenes. Introduction of the former gene reduced lignin
concentrations by 55% and the latter gave up to a three-fold
increase in syringyl: guiacyl lignin.81 Huntley et al., reported
that increased syringyl-lignin in transgenic poplars, by over-
expressing F5H, increased chemical pulp ability by 60%.82
Likewise, Pilate et al., demonstrated that transgenic poplar
with low CAD activity exhibited improved kraft pulping
properties.83 These results highlight the potential to alter
specific biopolymer constituents in woody plants which
confer benefits in subsequent chemical operations such as
kraft and soda pulping.
It is reasonable to anticipate that as our knowledge of
the beneficial physical-chemical impacts of pretreatments
on the plant cell wall is developed, it will be possible to
genetically engineer low-recalcitrance wood. For example,
reduced lignin content, modifications in cellulose crys-
tallinity, differing hemicellulose structures and reduced
lignin-carbohydrate complexes have all been shown to
decrease plant recalcitrance and it should be possible to
engineer these same properties into woody plants and other
bioresources.84,85 A recent report by Davison et al.,86 has
demonstrated this approach, since changes in lignin content
and syringyl–guaiacyl ratios of a second-generation Populus
significantly benefited xylose release upon dilute sulfuric
acid hydrolysis. Chen and Dixon have also reported compa-
rable results for the acid hydrolysis of a series of alfalfa
lines containing antisensing constructs for downregulating
lignin.87 In brief, the lines with reduced lignin content
released greater amounts of carbohydrates during acid
pretreatment and in subsequent enzymatic hydrolysis. These
results indicate that genetic control of lignin content and
composition influences the hydrolyzability of the biomass
and sets the stage for further developments.
Given recent advances in plant genomics, it is anticipated
that engineered changes in plant cell structure will yield low-
recalcitrant, highly productive agro-energy crops in the near
future. This will have a dramatic impact on pretreatment
technologies reducing the severity, capital and operating costs
of this key stage in the conversion of biomass to biofuels.
Review: New forestry biofuels sector Y Pu et al.

Cellulosic saccharification-fermentation by re-adsorption onto fresh lignocellulosic materials.100 In

technologies addition, it is well known that the lignin fraction in pretreated
lignocellulosics is involved in unproductive binding to cellu-
Current: Following pretreatment, woody biomass can be
losic enzymes that reduces the performance of the enzymes.
converted into simple sugars by enzymatic deconstruction via
The development of additives including proteins101 and
a cellulase treatment. This remains the second most expen-
surfactants102 that disrupt this association has been shown to
sive component in the bioconversion of wood to bioethanol,
enhance the efficiency of deconstruction enzymes.
despite the fact that research studies over the past decade
Future: A process challenge in the conversion of wood to
have decreased cellulase costs by greater than a ten-fold
biofuels is the efficient conversion of all wood sugars (i.e.,
basis.88 Numerous publications and reviews have highlighted
C5 and C6) to ethanol, especially for hardwoods which have
the use of (i) separate hydrolysis and fermentation (SHF) and
greater amounts of pentoses. Microorganisms that are able
(ii) simultaneous saccharification and fermentation (SSF) to
to ferment sugars to ethanol can be either yeasts103,104 or
convert pretreated wood to ethanol.89,90 Ewanick et al., have
bacteria.105 Over the past decades, new methods in molecular
reported that employing SSF on a SO2-steam exploded lodge-
biology, protein chemistry and genetic engineering have led
pole pine provided 61–77% yield of the theoretical maximum
to an increasing number of new strains, exhibiting improved
ethanol yield depending upon the severity of the pretreat-
characteristics to ferment the full spectrum of sugars avail-
ment.91 A two-stage acid treatment of spruce using SO2 or
able in hydrolyzates.106,107 One promising strategy has been
H2SO4 was reported to give ethanol yields of 81 and 70%
to take a natural hexose ethanologen and add the pathways
respectively (i.e., 94 and 79 gallons/dry ton).60,92 Comparable
to convert other sugars. This strategy has been effective in
SSF ethanol yields have also been reported for an organosolv
adding pentose conversion to Saccharomyces cerevisiae, and
pretreated mixed soft wood furnish.93
to Zymomonas mobilis.108,109 These enhancements promise to
The conversion of hardwoods to ethanol has also been
further enhance the overall fermentation of mixed solutions
extensively studied. SSF treatment of steam-exploded poplar
of hexoses and pentoses to ethanol.110–112
and eucalyptus has been reported to provide 71 and 62% of
Although research studies over the past decade have
the maximum theoretical yield of ethanol from glucose.94
decreased cellulase cost by greater than a ten-fold basis,113
Higher SSF ethanol yields of 90% from cellulose have been
they still remain a significant cost for SSF and SHF. An
reported for an acidic hot-water treatment of yellow poplar,
alternative approach to minimize the cost of cellulose
provided that the solids were washed with hot water to
deconstruction and conversion to ethanol is consolidated
remove solubilized lignin.95 The role of inhibitors formed
bioprocessing (CBP). CBP involves (i) bioproduction of
during steam explosion of poplar on SSF has been exten-
cellulolytic enzymes from thermophilic anaerobic microbes,
sively studied. Undetoxified pretreated wood was reported to
(ii) hydrolysis of plant polysaccharides to simple sugars
yield no ethanol even with high loadings of Saccharomyces
and (iii) their subsequent fermentation to ethanol all in one
cerevisiae, whereas water-rinsed biomass provided an 82%
stage.114 This bioprocess is projected to reduce the cost of
yield of ethanol.96 Bari et al., have also reported bioethanol
bioethanol by a factor of four over SSF and these reduced
yields of 85% from steam-exploded97 aspen chips and more
costs and simplicity of operation have heightened research in
recently demonstrated that SO2 impregnation can enhance
this field. To date, the penultimate CBP system has not been
this pretreatment technology.98 Although most authors have
developed but the basic pathways that need to be developed
tailored their SSF stage to their exact bioresource, Berlin et al.,
have been reported and research is ongoing.115,116
have reported that cellulase treatments performed optimally
on hardwood also exhibit superior performance on soft wood
substrates.99
Non-biological pathways of converting
A promising approach to reducing cellulase cost is to
biomass to biofuels
capture and reuse the enzymes. For example, Tu et al., have Although the biological route for converting biomass
shown that 51% of the applied cellulases could be recovered to biofuels is one of the most developed and promising

© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb 65
Y Pu et al.
technologies, several other competing processes are also
being explored and developed. As an alternative approach,
the production of a bio-oil from biomass by pyrolysis
certainly is of the most direct methods of liquidifying
nature’s key bioresources. Typically, this process can be
accomplished with a conventional slow pyrolysis reaction
involving a reactor temperature of ~500 oC and a vapor
residence time of 5–30 min, or fast pyrolysis conditions
involving a temperature range of 425–500 oC with a very
short vapor resident time <2 s.117 Both of these conditions
employ an oxygen-depleted or oxygen-free atmosphere
which leads to the fragmentation of lignin and plant polysac-
charides. The resulting bio-oil has been shown to contain
+200 constituents including substituted phenols, catechols,
pyrones, oligomers of lignin, hydroxyaldehydes/ketones,
sugars, carboxylic acids and water.118,119 Although the appli-
cation of bio-oils as a transportation fuel has been reported,
the complex/variable nature of these oils, their instability,
corrosivity, and relatively high water content have limited
their commercial applications.120–122 In an attempt to address
some of these limitations, several investigators have exam-
ined the application of catalysts on pyrolysis products. For
example, Williams et al., reported the use of a ZSM-5 zeolite
catalyst in the downstream section of a pyrolysis reactor
and demonstrated that the pyrolysis oils were markedly less
oxygenated due to dehydration, decarboxylation and decar-
bonylation reactions.123 A comparable effect was reported
when fast pyrolysis vapors were passed through mesoporous
catalysts.124,125 The use of zeolites for upgrading pyrolysis
bio-oils has been reported to be complicated by the deacti-
vation of the catalyst by reversible coke formation and irre-
versible dealumination.126 Clearly, the search for improved
pyrolysis oils by catalytic upgrading provides much promise
but needs to address catalytic activity and stability under the
conditions employed.
An alternative approach to generate fuels from plant-
derived sugars is based on a series of controlled catalytic
dehydration-hydrogenation reactions which has the ability
to convert C6/C5 sugars to their corresponding hydro-
carbons.127 Of special significance to this aqueous-phase
reforming approach is that the hydrogen needed for hydro-
genation is produced in-situ from the polyol over a catalyst.
The incorporation of additional condensation reactions, such
66 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
as Aldo-condensations into this refining pathway provides
for higher molecular weight hydrocarbons (i.e., C9–C15)
that could be considered as viable components for gasoline
or diesel, depending on the reaction conditions employed.128
These recent developments highlight the potential that cata-
lytic refining of biomass to a biogasoline/diesel resource could
provide an alternative route to renewable fuels.129
The final route for converting biomass to biofuels is via
gasification converting plant biomass to a stream of H2 and
CO (syngas) which can be used for the production of Fischer
Tropsch hydrocarbons. Production of syngas from biomass
is usually accomplished in a gasifier at temperatures between
800 and 1000 oC under 20–30 bar.130 As an alternative to
thermal treatment, a pyrolysis plasma of wood has been
recently developed to yield a syngas stream.131 Although
gasification technologies for biomass are reasonably well
developed, the technical challenges reside in the Fisher
Tropsch catalyzed reactions which are prone to poisoning
from alkali metals, halides, nitrogen and sulfur gases suffi-
ciently abundant in most biomass resources.132 In addition,
the propensity to form tars during biomass gasification
provides additional difficulties and leads to inefficiencies in
the overall process. The most common approach to reduce
tar formation is either a thermal or catalytic treatment.133–135
The remaining contaminants in a biomass syngas need to
be removed using scrubbers, sorbents, oxidative treatments
or catalytic decomposition132 and each of these technologies
adds further cost to the overall process. Once these impuri-
ties are removed, Fischer-Tropsch chemistry can efficiently
convert syngas to aliphatic straight-chain hydrocarbons,
primary alcohols, branched and unsaturated hydrocarbons.
The large hydrocarbons can then be hydrocracked to form a
high-quality diesel fuel.
Integrated pulp-biofuel biorefineries
An interesting alternative to the development of a virgin
wood-based biofuel refi nery is to incorporate these manu-
facturing concepts into an existing pulp mill, as depicted
in Fig. 7.
This approach has several attractive features including
access to established wood resources, wood-handling equip-
ment, transportation systems, environmental permitting
issues and access to a skilled workforce knowledgeable in the
Review: New forestry biofuels sector
Figure 7. The scheme for integrated wood-based biorefinery.
processing of wood. The development of the next generation
‘pulp-biofuel mills’ is being actively investigated on several
fronts.18 For kraft pulp mills, two high-priority opportunities
center about the next generation of chemical recovery opera-
tions and the transition from the conventional Thompson
recovery furnace technologies to gasification of black liquor
which could yield a syngas process stream.136–138 Alterna-
tively, ongoing studies have highlighted the potential to
extract select hemicelluloses from woodchips prior to kraft
pulping. It is well known that kraft pulping conditions extract
select hemicelluloses which do not contribute to final pulp
properties as summarized in Table 6.
These extractable hemicelluloses could provide a valuable,
high-volume resource of sugars for bioethanol production
generating ~20–40 million gallons ethanol/year/mill.140
Thorp has reported that the potential annual production
of ethanol from pre-extraction of hemicellulose could
approach 2 billion gallons of ethanol/year.141 Recent studies
suggest that a pre-extraction of northern hardwood benefits
kraft pulping whereas a soft wood furnish suffers from yield
losses which needs to be addressed.142,143
An alternative resource for bioethanol production is
to utilize waste cellulosic streams from paper recycling
Table 6. Changes in carbohydrate distribution before and after kraft pulping loblolly pine.139
Source Glucose Galactose
Wood 67.9 3.5
Kraft Pulp 84.9 0.3
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
operations.144 Paper-mill sludge typically has a negative
value as it needs to be properly landfi lled and hence is an
attractive resource for SSF conversion to bioethanol.145,146
Furthermore, it has been well documented that this low-cost
bioresource does not need a pretreatment prior to SSF but
the presence of minerals, contaminants and difficulties in
mixing paper-mill sludge provide additional complications
to the overall process. Nonetheless, a recent study by Fan
and Lynd suggested that a viable SSF process could be devel-
oped yielding a +15% internal rate of fi nancial return which
provides a viable treatment option for the ~5 million tons of
paper mill sludge generated annually in the USA.147
Tomorrow’s forest biorefinery
The practical application of the science and engineering
associated with converting wood to biofuels is a rapidly
moving target that will require constant updating. Nonethe-
less, near the end of 2007 several notable industrial develop-
ments have been announced. In the USA, the Department
of Energy recently announced an investment of up to $385
million for six biorefinery projects with an industry cost
share of more than $1.2 billion.148 When fully operational,
these biorefineries are expected to produce more than 130
million gallons of cellulosic ethanol/year. Three of these
plants have announced the utilization of wood as a biore-
source converting it to bioethanol via thermochemical or
biological routes, including:
(1) ALICO, Inc., Florida will produce 13.9 million gallons
of ethanol/year with a proposed 770 tons/day feedstock
from yard, wood, vegetative wastes and eventually
energy cane.
(2) BlueFire Ethanol, Inc., California will site a biorefi nery
on an existing landfi ll and produce about 19 million
gallons of ethanol/year. The proposed plant will consume
700 tons/day feedstock of sorted green waste and wood
waste from landfi lls.
Mannose Arabinose Xylanose
17.7 2.1 8.8
7.1 0.5 7.1
67
Y Pu et al.
(3) Range Fuels, Georgia has begun constructing a plant that
will produce about 40 million gallons of ethanol/year
and 9 million gallons/year of methanol. The plant will
use 1,200 tons/day of wood residues and wood-based
energy crops.
The application of thermal and biological technologies to
convert wood to ethanol clearly suggests that both technology
platforms are viable, each with their own unique strengths
and concerns. It is anticipated that the research developments
described earlier in the review will favorably impact these
commercial developments. Meanwhile, the Tembec Temis-
caming sulfite mill in Quebec is a modern example of how
a pulp mill can grow into a biorefinery.149 Along with pulp
production, the mill ferments spent sulfite cooking liquors
with Saccharomyces cerevisiae to produce 4 million gallons/
year of food-grade ethanol. It has installed an anaerobic
biogas unit that displaces ~80% of the natural gas required
for high-yield pulp flash drying and produces lignosulfonates
for commercial markets. Although the same approach is
much more technically challenging for a kraft pulp mill, its
potential has been noted by several industry leaders.150
Another example is the Flambeau River paper mill in
Wisconsin that has announced a partnership with American
Process Inc., for a cellulosic ethanol biorefinery. The biore-
finery project will be designed to produce 20 million gallons
of cellulosic ethanol/year from the mill’s spent pulping
liquor. 151 Xethanol Corporation has reported that it has
acquired a former medium-density fiberboard factory which
it plans to re-open as a pilot plant to demonstrate the tech-
nical and economic viability of using wood chips for the
production of cellulosic feedstock.152 Additional announce-
ments of research consortiums and pilot plant developments
targeted at utilizing waste streams from virgin and recycled
pulp mills along with wood residues occur virtually on a
monthly basis on the international scene.153 Recent improve-
ments in biorefinery processing technology, energy costs and
favorable government policy will only accelerate these busi-
ness developments in the forest products industry.154
Transportation of bioethanol
With anticipated widespread usage of bioethanol, an efficient
and reliable transportation and distribution system from
68 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
biorefinery to the end-user also needs attention. Pipelines are,
by far, the most cost-effective means of transporting large
quantities of fuel over long distances, whereas tankers are
used to transport fuels, including ethanol, over short distances
such as from small biorefineries to storage and distribution
centers. Use of existing pipeline infrastructure, presently used
to transport gasoline products, as well as new, dedicated pipe-
lines may be considered for ethanol transportation.
Existing gasoline pipelines are made out of carbon steel.
Corrosion and stress-corrosion cracking of carbon steel
structures, especially pipeline steel, are other concerns
for ethanol storage and transportation. A 2003 survey of
industry, reported by the American Petroleum Institute (API
Technical Report 939-D),155 indicates that carbon steel may
undergo stress corrosion cracking (SCC) in certain ethanol
environments. This is not a widespread concern as the cracks
have only been observed primarily in user terminals exposed
to ethanol products, but not in ethanol producer tanks, in
rail/tank car/shipping transportation, or in end-user systems
(e.g., gas tanks). Preliminary studies have shown that certain
minor constituents may affect SCC behavior of carbon steel.
For example, the presence of oxygen and the aging of fuel-
grade ethanol have been reported to increase SCC suscepti-
bility of carbon steel.156,157 However, effects of ethanol source
or aging, and resulting differences in the minor constituents,
on corrosion and stress corrosion cracking of carbon steels
are not very clear. Further work is needed to understand
corrosion mechanisms and to identify fuel-grade ethanol
environments that may cause SCC. This will help us find
mitigation strategies where some chemical additives may be
used or alternative materials may be selected for transporta-
tion and storage structures to reliably distribute ethanol.
Summary and conclusions
In closing, after an extended period of low energy costs
and differing research priorities, a near global emphasis
on renewable biofuels technologies has evolved in the new
millennium. Although differing social, environmental
and economic issues have elevated these needs, there is
no denying this new challenge. Furthermore, advances in
plant genomics, biotechnology, nanotechnology, catalysis,
material science, life-cycle analysis and computational
modeling suggest that advances in the field of renewable
Review: New forestry biofuels sector
biofuels will progress at rates unattainable in past decades.
As these technological advances leave the laboratory and
impact commercial practices, it will bring to the forefront
Morris’ vision of the new carbohydrate-economy in which
major industrial sectors are dependent on the sustainable
utilization of biomass, in harmony with global agricultural
production.158
Acknowledgements
The authors acknowledge the support of key sponsors
including NSF Performance for Innovation Program
(Award # EEC0525746) and National Research Initiative
of the USDA Cooperative State Research, Education and
Extension Service, grant number 2003-35504-13620.
References
1. Holdren JP, Energy and sustainability. Science 315:737 (2007).
2. Chow J, Kopp RJ and Portney PR, Energy resources and global
development. Science 302:1528–1531 (2003).
3. Hoffert MI, Caldeira K, Benford, G, Criswell DR, Green C, Herzog H,
Jain AK, Kheshgi HS, Lackner KS, Lewis JS, Lightfoot HD, Manheimer W,
Mankins JC, Mauel ME, Perkins LJ, Schlesinger ME, Volk T and Wigley
TML, Advanced technology paths to global climate stability: energy for a
greenhouse planet. Science 298:981–987 (2002).
4. Grassian VH, Meyer G, Abruna H, Coates GW, Achenie LE, Allison T,
Brunschwig B, Ferry J, Garcia-Garibay M, Gardea-Torresday J, Grey CP,
Hutchison J, Li CJ, Liotta C, Ragauskas A, Minteer S, Mueller K, Roberts J,
Sadik O, Schmehl R, Schneider W, Selloni A, Stair P, Stewart J, Thorn D,
Tyson J, Voelker B, White JM and Wood-Black F, Chemistry for a sustai-
nable future. Environ Sci Technol 41:4840–4846 (2007).
5. Clark JH, Budarin V, Deswarte FEI, Hardy JJE, Kerton FM, Hunt AJ,
Luque R, Macquarrie DJ, Milkowski K, Rodriguez A, Samuel O, Tavener
SJ, White RJ and Wilson AJ, Green chemistry and the biorefinery: A
partnership for a sustainable future. Green Chem 8:853–860 (2006).
6. Ragauskas AJ, Williams CK, Davison BH, Britovsek G, Cairney J, Eckert
CA, Frederick WJ Jr, Hallett JP, Leak DJ, Liotta CL, Mielenz JR, Murphy
R, Templer R and Tschaplinski T, The path forward for biofuels and
biomaterials. Science 311:484–489 (2006).
7. Bothast RJ and Schlicher MA, Biotechnological processes for conversion
of corn into ethanol. Appl Microbiol Biotechnol 67:19–25 (2005).
8. Gray KA, Cellulosic ethanol – state of the technology. Int Sugar J
109:150–151 (2007).
9. Marchetti JM, Miguel VU and Errazu AF, Possible methods for biodiesel
production. Renew Sust Energ Rev 11:1300–1311 (2007).
10. Perlack R, Wright LL, Turhollow AF, Graham RL, Stokes BJ and Erbach
DC, Biomass as feedstock for bioenergy and bioproducts industry:
The technical feasibility of a billion-ton annual supply, 2005, http://
feedstockreview.ornl.gov/pdf/billion_ton_vision.pdf
11. Breaking the biological barriers to cellulosic ethanol: a joint research
agenda A research roadmap resulting from the biomass to biofuels
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
workshop Rockville, Maryland, 2006, http://genomicsgtl.energy.gov/
biofuels/2005workshop/b2blowres63006.pdf
12. http://www1.eere.energy.gov/biomass/printable_versions/ethanol_yield_
calculator.html
13. Klemm D, Heublein B, Fink HP and Bohn A, Cellulose: fascinating
biopolymer and sustainable raw material. Angew Chem Int Ed
44:3358–3393 (2005).
14. Klemn D, Philipp B, Heinze T, Heinze U and Wagenknecht W,
Comprehensive Cellulose Chemistry, Vol. 1. Fundamentals and analytical
methods, Wiley-VCH, Weinheim (1998).
15. Kadla JF and Gilbert RD, Cellulose structure: a review. Cell Chem
Technol 34:197–216 (2001).
16. Atalla RH and VanderHart DL, Native cellulose: a composite of two
distinct crystalline forms. Science 223:283–285 (1984).
17. (i) Nishiyama Y, Sugiyama J, Chanzy H and Langan P, Crystal structure
and hydrogen bonding system in cellulose I α from synchrotron X-ray
and neutron fibrious diffraction. J Am Chem Soc 125:14300–14306
(2003) (ii) Nishiyama Y, Sugiyama J, Chanzy H and Langan P, Crystal
structure and hydrogen bonding system in cellulose I β from synchrotron
X-ray and neutron fibrious diffraction. J Am Chem Soc 124:9074–9082
(2002).
18. Ragauskas AJ, Nagy M, Kim DH, Eckert CA, Hallett JP and Liotta CL,
From wood to fuels: Integrating biofuels and pulp production. Ind
Biotechnol 2:55–65 (2006).
19. Willfoer S, Sundberg A, Pranovich A and Holmbom B, Polysaccharides
in some industrially important hardwood species. Wood Sci Technol
39:601–617 (2005).
20. Willfoer S, Sundberg A, Hemming J and Holmbom B, Polysaccharides
in some industrially important softwood species. Wood Sci Technol
39:245–257 (2005).
21. See http://www.chem.qmul.ac.uk/iupac/
22. Barakat A, Winter H, Rondeau-Mouro C, Saake B, Chabbert B and
Cathala B, Studies of xylan interactions and cross-linking to synthetic
lignins formed by bulk and end-wise polymerization: a model study of
lignin carbohydrate complex formation. Planta 226: 267–281 (2007).
23. Bunzel M, Ralph J, Lu F, Hatfield RD and Steinhart H, Lignins and
ferulate-coniferyl alcohol cross-coupling products in cereal grains.
J Agric Food Chem 52:6496–6502 (2004).
24. Lawoko M, Henriksson G and Gellerstedt G, Characterization of lignin-
carbohydrate complexes (LCCs) of spruce wood (Picea abies L) isolated
with two methods. Holzforschung 60:156–161 (2006).
25. Davin LB and Lewis NG, Lignin primary structures and dirigent sites. Curr
Opin Biotechnol 16:407–415 (2005).
26. Boerjan W, Ralph J and Baucher M, Lignin biosynthesis. Annu Rev Plant
Biol 54:519–546 (2003).
27. Pu Y, Jiang N and Ragauskas AJ, Ionic liquid as a green solvent for lignin.
J Wood Chem Technol 27: 23–33 (2007).
28. Chakar FS and Ragauskas AJ, Review of current and future softwood
kraft lignin process chemistry. Ind Crop Prod 20: 131–141 (2004).
29. Pu Y, Anderson S, Lucia L and Ragauskas AJ, Investigation of the
photooxidative chemistry of acetylated softwood lignin. J Photochem
Photobio A 163: 215–221 (2004).
30. Petrus L and Noordermeer MA, Biomass to biofuels a chemical
perspective. Green Chem 8:861–867 (2006).
69
Y Pu et al.
31. Dale BE, Cellulosic ethanol and sustainability: There is no ‘ food vs fuel’
conflict, 233rd ACS National Meeting, Chicago, IL (2007).
32. Lynd LR, Wyman CE and Gerngross TU, Biocommodity engineering.
Biotechnol Progr 15:777–793 (1995).
33 Selig MJ, Viamajala S, Decker SR, Tucker MP, Himmel ME and
Vinzant TB. Deposition of lignin droplets produced during dilute acid
pretreatment of maize stems retards enzymatic hydrolysis of cellulose.
Biotechnol Progr ACS ASAP.
34. Berlin A, Balakshin M, Gilkes N, Kadla J, Maximenko V, Kubo S and
Saddler J, Inhibition of cellulase xylanase and β-glucosidase activities by
softwood lignin preparations. J Biotechnol 125:198–209 (2006).
35. Pan X, Xie D, Gilkes N, Gregg D J and Saddler JN, Strategies to enhance
the enzymatic hydrolysis of pretreated softwood with high residual lignin
content. Appl Biochem Biotechnol 121–124:1069–1079 (2005).
36. Yang B and Wyman CE, BSA treatment to enhance enzymatic hydrolysis
of cellulose in lignin containing substrates. Biotechnol Bioeng 94:611–617
(2006).
37. Davis MF, Ishizawa C, Jeoh T, Adney WS, Himmel ME and Johnson DK,
Chemical and physical properties of pretreated biomass that affect
enzyme accessibility and digestibility 233rd ACS National Meeting,
Chicago, IL (2007).
38. Pu Y, Ziemer C and Ragauskas AJ, CP/MAS 13C NMR analysis of
cellulase treated bleached softwood kraft pulp. Carbohydr Res 341:
591–597 (2006).
39. Hayashi N, Kondo T and Ishihara M, Enzymatically produced nano-
ordered short elements containing cellulose I β crystalline domains.
Carbohydr Polym 61:191–197 (2005).
40. Mansfield SD, Mooney C and Saddler JN, Substrate and enzyme charac-
teristics that limit cellulose hydrolysis. Biotechnol Progr 15: 804–816
(1999).
41. Lynd LR, Weimer PJ, van Zyl WH and Pretorius IS, Microbial cellulose
utilization: Fundamentals and biotechnology. Microbiol Molecular Biol R
66(3):506–577 (2002).
42. Zhang YHP, Cui J, Lynd LR and Kuang LR, A transition from cellulose
swelling to cellulose dissolution by o-Phosphoric acid: evidence from
enzymatic hydrolysis and supramolecular structure. Biomacromolecules
7:644–648 (2006).
43. Kim S and Holtzapple MT, Effect of structural features on enzyme
digestibility of corn stover. Biores Technol 97:583–591(2005).
44. Schell DJ, Riley CJ, Dowe N, Farmer J, Ibsen KN, Ruth MF, Toon ST and
Lumpkin RE, A bioethanol process development unit: initial operating
experiences and results with a corn fiber feedstock. Biores Technol
91:179–188 (2004).
45. Eggeman Tim and Elander Richard T, Process and economic
analysis of pretreatment technologies. Biores Technol 96:2019–2025
(2005).
46. Yang B, Gray MC, Liu C, Lloyd TA, Stuhler SL, Converse AO and
Wyman CE, Unconventional relationships for hemicellulose hydrolysis
and subsequent cellulose digestion, in Lignocellulose Biodegradation,
ACS Symposium Series 889, ed by Saha BS and Hayashi K. American
Chemical Society, Washington, pp.100–125 (2004).
47. Glasser WG and Wright RS, Steam-assisted biomass fractionation II
fractionation behavior of various biomass resources. Biomass Bioenerg
14:219–235 (1998).
70 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
48. Ballesteros I, Negro, MJ, Oliva JM, Cabanas A, Manzanares P and
Ballesteros M, Ethanol production from steam-explosion pretreated
wheat straw. Appl Biochem Biotechnol 129–132: 496–508 (2006).
49. Negro MJ, Manzanares P, Oliva JM, Ballesteros I and Ballesteros M,
Changes in various physical/chemical parameters of Pinus pinaster wood
after steam explosion pretreatment. Biomass Bioenerg 25:301–308 (2003).
50. Cantarella M, Cantarella L, Gallifuoco A, Spera A and Alfani F, Effect of
inhibitors released during steam-explosion treatment of poplar wood on
subsequent enzymatic hydrolysis and SSF. Biotechnol Progr 20:200–206
(2004).
51 Boussaid AL, Esteghlalian AR, Gregg DJ, Lee KH and Saddler JN, Steam
pretreatment of douglas-fir wood chips: can conditions for optimum
hemicellulose recovery still provide adequate access for efficient
enzymatic hydrolysis? Appl Biochem Biotechnol 84–86:693–705 (2000).
52. Cara C, Ruiz E, Ballesteros I, Negro MJ and Castro E, Enhanced
enzymatic hydrolysis of olive tree wood by steam explosion and alkaline
peroxide delignification. Process Biochem 41:423–429 (2006).
53. Liu C and Wyman CE, Impact of fluid velocity on hot water only
pretreatment of corn stover in a flowthrough reactor. Appl Biochem
Biotechnol 113–116:977–987 (2004).
54. Allen SG, Spencer MJ, Antal MJ Jr, Laser MS and Lynd LR, Hot liquid
water pretreatment of lignocellulosics at high solids concentrations, in
Developments in Thermochemical Biomass Conversion, Vol.1, ed by
Bridgwater AV and Boocock DGB. Blackie, London, pp. 765–772 (1997).
55. van Walsum GP, Allen SG, Spencer MJ, Laser MS, Antal MJ and Lynd LR,
Conversion of lignocellulosics pretreated with liquid hot water to ethanol.
Appl Biochem Biotechnol 57/58:157–170 (1996).
56. Allen SG, Schulman D, Lichwa J, Antal MJ Jr, Jennings E and Elander R,
A comparison of aqueous and dilute-acid single-temperature
pretreatment of yellow poplar sawdust. Ind Eng Chem Res 40(10):
2352–2361 (2001).
57. Lloyd TA and Wyman CE, Combined sugar yields for dilute sulfuric acid
pretreatment of corn stover followed by enzymatic hydrolysis of the
remaining solids. Biores Technol 96:1967–1977 (2005).
58. Yang B, Gray MC, Liu C, Lloyd TA, Stuhler SL, Converse AO and Wyman
CE Unconventional relationships for hemicellulose hydrolysis and
subsequent cellulose digestion, in Lignocellulose Biodegradation, ACS
Symposium Series 889, ed by Saha BS, Hayashi K. American Chemical
Society, Washington, pp. 100–125 (2004).
59. Kim SB and Lee YY, Diffusion of sulfuric acid within lignocellulosic
biomass particles and its impact on dilute-acid pretreatment. Biores
Technol 83:165–171 (2002).
60. Soederstroem J, Galbe M and Zacchi G, Separate versus simultaneous
saccharification and fermentation of two-step steam pretreated softwood
for ethanol production. J Wood Chem Technol 25:187–202 (2005).
61. Kenealy W, Horn E, Davis M, Swaney R and Houtman C, Vapor-
phase diethyl oxalate pretreatment of wood chips: Part 2 Release of
hemicellulosic carbohydrates. Holzforschung 61:230–235 (2007).
62. Chang VS, Nagwani M and Holtzapple MT, Lime pretreatment of crop
residues bagasse and wheat straw. Appl Biochem Biotechnol 74:135–159
(1998).
63. Chang VS, Nagwani M, Kim CH and Holtzapple MT, Oxidative lime
pretreatment of high-lignin biomass: poplar wood and newspaper. Appl
Biochem Biotechnol 94:1–28 (2001).
Review: New forestry biofuels sector
64. Lissens G, Klinke H, Verstraete W, Ahring B and Thomsen AB, Wet
oxidation pre-treatment of woody yard waste: parameter optimization
and enzymatic digestibility for ethanol production. J Chem Technol
Biotechnol 79:889–895 (2004).
65. Kim TH and Lee YY, Pretreatment and fractionation of corn stover by
ammonia recycle percolation process. Biores Technol 96:2007–2013
(2005).
66. Teymouri F, Laureano-Perez L, Alizadeh H, Dale BE, Optimization of the
ammonia fiber explosion (AFEX) treatment parameters for enzymatic
hydrolysis of corn stover. Bioresour Technol 96:2014–2018 (2005).
67. Oh KK; Kim YS, Yoon HH, Tae, BS, Pretreatment of lignocellulosic
biomass using combination of ammonia recycled percolation and dilute-
acid process. J Ind Eng Chem 8:64–70 (2002).
68. Arato C, Pye EK and Gjennestad G, The lignol approach to biorefining
of woody biomass to produce ethanol and chemicals. Appl Biochem
Biotechnol 121–124: 871–882 (2005).
69. Pan X, Kadla JF, Ehara K, Gilkes N and Saddler JN, Organosolv ethanol
lignin from hybrid poplar as a radical scavenger: relationship between
lignin structure extraction conditions and antioxidant activity. J Agric
Food Chem 54:5806–5813 (2006).
70. Hasegawa I, Tabata K, Okuma O and Mae K, New pretreatment methods
combining a hot water treatment and water/acetone extraction for
thermo-chemical conversion of biomass. Energy Fuels 18:755–760
(2004).
71. Bozell JJ, Black SK and Myers M, Clean fractionation of lignocellulosics -
a new process for preparation of alternative feedstocks for the chemical
industry, 8th International Symposium on Wood and Pulping Chemistry,
Helsinki, Finland Vol. 1, pp. 697–704 (1995).
72. Pan X, Gilkes N, Kadla J, Pye K, Saka S, Gregg D, Ehara K, Xie D, Lam D
and Saddler J, Bioconversion of hybrid poplar to ethanol and Co-products
using an organosolv fractionation process: optimization of process yields.
Biotechnol Bioeng 94: 851–861 (2006).
73. Pan X, Xie D, Yu RW, Lam D and Saddler JN, Pretreatment of lodgepole
pine killed by mountain pine beetle using the ethanol organosolv
process: fractionation and process optimization. Ind Eng Chem Res
46:2609–2617 (2007).
74. Pan X, Arato C, Gilkes N, Gregg D, Mabee W, Pye K, Xiao Z, Zhang X and
Saddler J, Biorefining of softwoods using ethanol organosolv pulping:
preliminary evaluation of process streams for manufacture of fuel-grade
ethanol and co-products. Biotechnol Bioeng 90:473–481 (2005).
75. Pye EK, Industrial lignin production and applications, in Biorefineries,
Industrial Processes and Products, Vol. 2, ed by Kamm B, Gruber PR and
Kamm M. Wiley-VCH, Weinheim, pp.165–200 (2006).
76. Mabee WE, Gregg DJ, Arato C, Berlin A, Bura R, Gilkes N, Mirochnik O,
Pan X, Pye EK and Saddler JN, Updates on softwood-to-ethanol process
development. Appl Biochem Biotechnol 129–132: 55–70 (2006).
77. Zhang Y-HP, Ding S-Y, Mielenz JR, Cui J-B, Elander RT, Laser M, Himmel
ME, McMillan JR and Lynd LR, Fractionating recalcitrant lignocellulose at
modest reaction conditions. Biotechnol Bioeng 97(2): 214–223(2007).
78. Galbe M and Zacchi G, A review of the production of ethanol from
softwood. Appl. Microbiol Biotechnol 59:618–628 (2002).
79. Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M and
Ladisch M, Features of promising technologies for pretreatment of
lignocellulosic biomass. Biores Technol 96: 673–686 (2005).
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
80. Wyman CE, What is (and is not) vital to advancing cellulosic ethanol.
Trends Biotechnol 25:153–157 (2007).
81. Chiang VL, Monolignol biosynthesis and genetic engineering of lignin in
trees, a review. Environ Chem Lett 4:143–146 (2006).
82. Huntley SK, Ellis D, Gilbert M, Chapple C and Mansfield SD, Significant
increases in pulping efficiency in C4H- F5H-transformed poplars:
improved chemical savings and reduced environmental toxins. J Agr
Food Chem 51:6178–6183 (2003).
83. Pilate G, Guiney E, Holt K, Petit-Conil, M, Lapierre C, Leple JC, Pollet B,
Mila I, Webster EA, Marstorp HG, Hopkins DW, Jouanin L, Boerjan W,
Schuch W, Cornu D and Halpin C, Field and pulping performances of
transgenic trees with altered lignification. Nat Biotechnol 20:607–612
(2002).
84. Jeoh T, Ishizawa CI, Davis MF, Himmel ME, Adney WS and Johnson
DK, Cellulase digestibility of pretreated biomass is limited by cellulose
accessibility. Biotechnol Bioeng 98:112–122 (2007).
85. Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR, Brady JW and
Foust TD, Biomass recalcitrance: engineering plants and enzymes for
biofuels production. Science 315:804–807 (2007).
86. Davison BH, Drescher SR, Tuskan GA, Davis MF and Nghiem NP,
Variation of S/G ratio and lignin content in a populus family influences
the release of xylose by dilute acid hydrolysis. Appl Biochem Biotechnol
129–132:427–435 (2006).
87. Chen F and Dixon RA, Lignin modification improves fermentable sugar
yields for biofuel production. Nat Biotechnol 25:759–761 (2007).
88. See http://www.eere.energy.gov/ biomass/cellulase_cost.html
89. Wyman CE, Ethanol from lignocellulosic biomass: technology,
economics, and opportunities. Biores Technol 50:3–15 (1994).
90. Wingren A, Galbe M and Zacchi G, Techno-economic evaluation of
producing ethanol from softwood: Comparison of SSF and SHF and
identification of bottlenecks. Biotechnol Progr 19:1109–1117 (2003).
91. Ewanick SM, Bura R and Saddler JN, Acid-catalyzed steam pretreatment
of lodgepole pine and subsequent enzymatic hydrolysis and fermentation
to ethanol. Biotechnol Bioeng 98: 737–746 (2007)
92. Soderstrom J, Pilcher L, Galbe M and Zacchi G, Combined use of H2SO4
and SO2 impregnation for steam pretreatment of spruce in ethanol
production. Appl Biochem Biotechnol 105–108:127–140 (2003).
93. Pan X, Arato C, Gilkes N, Gregg D, Mabee W, Pye K, Xiao Z, Zhang X
and Saddler J. Biorefining of softwoods using ethanol organosolv
pulping: Preliminary evaluation of process streams for manufacture of
fuel-grade ethanol and co-products. Biotechnol Bioeng 90:473–481
(2005).
94. Oliva JM, Saez F, Ballesteros I, Gonzalez A, Negro MJ, Manzanares P
and Ballesteros M, Effect of lignocellulosic degradation compounds from
steam explosion pretreatment on ethanol fermentation by thermotolerant
yeast Kluyveromyces marxianus. Appl Biochem Biotechnol 105–108:
141–153 (2003).
95. Nagle NJ, Elander RT, Newman MM, Rohrback BT, Ruiz RO and Torget
RW, Efficacy of a hot washing process for pretreated yellow poplar to
enhance bioethanol production. Biotechnol Progr 18:734–738 (2002).
96. Cantarella M, Cantarella L, Gallifuoco A, Spera A and Alfani F, Effect of
inhibitors released during steam-explosion treatment of poplar wood on
subsequent enzymatic hydrolysis and SSF. Biotechnol Progr 20:200–206
(2004).
71
Y Pu et al.
97. De Bari I, Viola E, Barisano D, Cardinale M, Nanna F, Zimbardi F,
Cardinale G and Braccio G, Ethanol production at flask and pilot scale
from concentrated slurries of steam-exploded aspen. Ind Eng Chem
Res 41:1745–1753 (2002).
98. De Bari I, Nanna F and Braccio G, SO2-catalyzed steam fractionation
of aspen chips for bioethanol production: Optimization of the catalyst
impregnation. Ind Eng Chem Res 46:7711–7720 (2007).
99. Berlin A, Gilkes N, Kilburn D, Maximenko V, Bura R, Markov A,
Skomarovsky A, Gusakov A, Sinitsyn A, Okunev O, Solovieva I and
Saddler JN. Evaluation of cellulase preparations for hydrolysis of
hardwood substrates. Appl Biochem Biotechnol 129–132: 528–545
(2006).
100. Tu M, Chandra RP and Saddler JN, Evaluating the distribution of
cellulases and the recycling of free cellulases during the hydrolysis of
lignocellulosic substrates. Biotechnol Progr 23:398–406 (2007).
101. Yang B and Wyman CE. Lignin blocking proteins and their use in
treating lignocellulosics. US Pat. Appl. Publ. US 2006088922 (2006).
102. Boerjesson J, Engqvist M, Sipos B and Tjerneld F, Effect of
poly(ethylene glycol) on enzymatic hydrolysis and adsorption of
cellulase enzymes to pretreated lignocellulose. Enzyme Microb Technol
41:186–195 (2007).
103. Sonderegger M, Jeppsson M, Larsson C, Gorwa-Grauslund M-F,
Boles E, Olsson L, Spencer-Martins I, Hahn-Haegerdal B and Sauer
U, Fermentation performance of engineered and evolved xylose-
fermenting Saccharomyces cerevisiae strains. Biotechnol Bioeng
87:90–98 (2004).
104. Taherzadeh MJ and Niklasson C, Ethanol from lignocellulosic materials:
Pretreatment, acid and enzymatic hydrolyses, and fermentation. ACS
Symposium Series 889, pp. 49–68 (2004).
105. Dien BS, Cotta MA and Jeffries TW, Bacteria engineered for fuel ethanol
production: current status. Appl Microbiol Biotechnol 63:258–266
(2003).
106. Sommer P, Georgieva T and Ahring BK, Potential for using thermophilic
anaerobic bacteria for bioethanol production from hemicellulose.
Biochem Soc T 32: 283–289 (2004).
107. Olsson L and Hahn-Haegerdal B, Fermentation of lignocellulosic
hydrolyzates for ethanol production. Enzyme Microb Technol 18:
312–31 (1996).
108. Helle SS, Murray A, Lam J, Cameron DR and Duff SJB, Xylose
fermentation by genetically modified Saccharomyces cerevisiae 259ST
in spent sulfite liquor. Biores Technol 92:163–171 (2004).
109. Lawford HG and Rousseau JD, Performance testing of Zymomonas
mobilis metabolically engineered for cofermentation of glucose, xylose,
and arabinose. Appl Biochem Biotechnol 98–100:429–448 (2002).
110. Hahn-Haegerdal B, Galbe M, Gorwa-Grauslund MF, Liden G and
Zacchi G, Bio-ethanol – the fuel of tomorrow from the residues of today.
Trends Biotechnol 24:549–556 (2006).
111. Sues A, Millati R, Edebo L and Taherzadeh MJ, Ethanol production from
hexoses, pentoses, and dilute-acid hydrolyzate by Mucor indicus.
FEMS Yeast Res 5:669–676 (2005).
112. Karimi K, Brandberg T, Edebo L and Taherzadeh MJ, Fed-batch
cultivation of Mucor indicus in dilute-acid lignocellulosic hydrolyzate for
ethanol production. Biotechnol Lett 27:1395–1400 (2005).
113. See http://www.eere.energy.gov/ biomass/cellulase_cost.html
72 © 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Review: New forestry biofuels sector
114. Lynd LR, van Zyl WH, McBride JE and Laser M, Consolidated
bioprocessing of cellulosic biomass: an update. Curr Opin Biotechnol
16:577–583 (2005).
115. Den HR, McBride JE, La Grange DC, Lynd R and Van Zyl WH, Functional
expression of cellobiohydrolases in Saccharomyces cerevisiae towards
one-step conversion of cellulose to ethanol. Enzyme Microb Technol
40:1291–1299 (2007).
116. Weimer PJ, Ethanol and co-products from cellulosic biomass. Int
Sugar J 108:630–633 (2006).
117. Mohan D, Pittman CU Jr and Steele PH, Pyrolysis of wood/ biomass for
bio-oil: a critical review. Energy Fuels 20:848–889 (2006).
118. Lesueur D, Castola V, Bighelli A, Conti L and Casanova J, Quantification
of hydroxyacetaldehyde in a biomass pyrolysis liquid using 13C NMR
spectroscopy. Spectrosc Lett 40:591–602 (2007).
119. Debdoubi A, El Amarti A, Colacio E, Blesa MJ and Hajjaj LH, The effect
of heating rate on yields and compositions of oil products from esparto
pyrolysis. Int J Energ Res 30:1243–1250 (2006).
120. Czernik S and Bridgwater AV, Overview of applications of biomass fast
pyrolysis oil. Energy Fuels 18:590–598 (2004).
121. Oasmaa A, Peacocke C, Gust S, Meier D and McLellan R, Norms
and standards for pyrolysis liquids end-user requirements and
specifications. Energy Fuels 19:2155–2163 (2005).
122. Chiaramonti D, Bonini M, Fratini E, Tondi G, Gartner K, Bridgwater A
V, Grimm H P, Soldaini I, Webster A and Baglioni P, Development of
emulsions from biomass pyrolysis liquid and diesel and their use in
engines – Part 2: tests in diesel engines Biomass Bioenerg 25:101–111
(2003).
123. Horne PA and Williams PT, Reaction of oxygenated biomass pyrolysis
model compounds over a ZSM-5 catalyst. Renew Energ 7:131–144 (1996).
124. Adam J, Antonakou E, Lappas A, Stoecker M, Nilsen MH, Bouzga A,
Hustad JE and Oye G, In situ catalytic upgrading of biomass derived
fast pyrolysis vapours in a fixed bed reactor using mesoporous
materials. Micropor Mesopor Mat 96:93–101 (2006).
125. Antonakou E, Lappas A, Nilsen MH, Bouzga A and Stoecker M,
Evaluation of various types of Al-MCM-41 materials as catalysts in
biomass pyrolysis for the production of bio-fuels and chemicals. Fuel
85:2202–2212 (2006).
126. Gayubo AG, Aguayo AT, Atutxa A, Prieto R and Bilbao J, Deactivation of
a HZSM-5 zeolite catalyst in the transformation of the aqueous fraction
of biomass pyrolysis oil into hydrocarbons. Energy Fuels 18:1640–1647
(2004).
127. Huber GW and Dumesic JA, An overview of aqueous-phase catalytic
processes for production of hydrogen and alkanes in a biorefinery. Catal
Today 111:119–132 (2006).
128. Huber GW, Chheda JN, Barrett CJ and Dumesic JA, Production of
liquid alkanes by aqueous-phase processing of biomass-derived
carbohydrates. Science 308:1446–1450 (2005).
129. Chiaramonti D, Bonini M, Fratini E, Tondi G, Gartner K, Bridgwater AV,
Grimm HP, Soldaini I, Webster A and Baglioni P, Development of emulsions
from biomass pyrolysis liquid and diesel and their use in engines – Part 2:
tests in diesel engines. Biomass Bioenerg 25:101–111 (2003).
130. Dasappa S, Paul PJ, Mukunda, HS, Rajan NKS, Sridhar G and Sridhar
HV, Biomass gasification technology – a route to meet energy needs.
Curr Sci 87:908–916 (2004).
Review: New forestry biofuels sector
131. Hrabovsky M, Konrad M, Kopecky V, Hlina M, Kavka T, Chumak O,
van Oost G, Beeckman E and Defoort B, Pyrolysis of wood in arc
plasma for syngas production. High Temp Mater Processes 10:557–570
(2006).
132. Jeczmionek L, Biomass as raw material for production of hydrocarbon
fuels – biomass gasification to produce synthesis gas and its use.
Nafta-Gaz 62:72–82 (2006).
133. Nordgreen T, Liliedahl T and Sjoestroem K, Metallic iron as a tar
breakdown catalyst related to atmospheric fluidised bed gasification of
biomass. Fuel 85:689–694 (2006).
134. Ma L, Verelst H and Baron GV, Integrated high temperature gas
cleaning: tar removal in biomass gasification with a catalytic filter. Catal
Today 105:729–734 (2005).
135. Devi L, Nair SA, Pemen AJM, Yan K, van Heesch EJM, Ptasinski KJ
and Janssen FJJG, Tar removal from biomass gasification processes,
in Biomass and Bioenergy, ed by Brenes MD, Nova Science Publishers
Inc., Hauppauge, NY, pp. 249–274 (2006).
136. Kelley SS, Lignocellulosic biorefineries: reality hype or something in
between? in Materials Chemicals and Energy from Forest Biomass, ACS
Symposium Series 954, ed by Argyropoulos DS, American Chemical
Society, Washington, pp. 31–47 (2007).
137. van Heiningen A, Converting a kraft pulp mill into an integrated forest
biorefinery Pulp Pap Canada 107:38–43 (2006).
138. Farmer MC, Adaptable biorefinery: some basic economic concepts to
guide research selection. TAPPI Engineering Pulping and Environmental
Conference Proceedings, Philadelphia, PA (2005).
139. Kim DH, Allison L, Carter B, Hou Q, Courchene C, Ragauskas AJ and
Sealey J, Profiling the wood and pulping properties of southern pine
thinning resources. Tappi J 4:21–25 (2005).
140. Amidon TE, Francis R, Scott GM, Bartholomew J, Ramarao BV and
Wood CD, Pulp and pulping processes from an integrated forest
biorefinery. Appl. No. PCT/US2005/013216 (2007).
141. Thorp B, Transition of mills to biorefinery model creates new profit
streams. Pulp and Paper, Nov., 35–39 (2005).
142. Amidon TE, Bolton TS, Francis RC and Gratien K, Effect of hot water
pre-extraction on alkaline pulping of hardwoods. TAPPI Engineering
Pulping & Environmental Conference Proceedings. Atlanta, GA
(2006).
© 2007 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 2:58–73 (2008); DOI: 10.1002/bbb
Y Pu et al.
143. Yoon SH, MacEwan K and Heiningen AV, Pre-Extraction of southern
pine chips with hot water followed by kraft cooking. TAPPI Engineering
Pulping & Environmental Conference Proceedings. Atlanta, GA (2006).
144. Kim SB and Jin WC, Pretreatment for enzymatic hydrolysis of used
newspaper, in Lignocellulose Biodegradation, ACS Symposium
Series 889, ed by Saha BS, Hayashi K. American Chemical Society,
Washington, pp. 36–48 (2004).
145. Agblevor FA, Method for producing bioethanol from a lignocellulosic
biomass and recycled paper sludge. US Pat. Appl. Publ. US
2007134781(2007).
146. Kadar Zs, Szengyel Zs and Reczey K, Simultaneous saccharification
and fermentation (SSF) of industrial wastes for the production of
ethanol. Ind Crop Prod 20:103–110 (2004).
147. Fan Z and Lynd LR, Conversion of paper sludge to ethanol II: Process
design and economic analysis. Bioproc Biosyst Eng 30:35–45 (2007).
148. See http://www.energy.gov/news/4827.htm
149. Magdzinski L, Tembec Temiscaming integrated biorefinery. Pulp Pap
Can 107: 44–46 (2006).
150. Perine L, Bio-refineries on the brink, Paper 360 o Dec., 31 (2006);
Raymond D and Closset G, Forest Product Biorefinery: technology for a
new future. Solutions, Sept., 49–53 (2004).
151. See http://www.idahoforests.org/fire_20020033.htm
152. See http://www.tappi.org/s_tappi/doc.asp?CID=183&DID=551863
153. Solomon BD, Barnes JR and Halvorsen KE, Grain and cellulosic
ethanol: history, economics and energy policy. Biomass Bioenerg
31:416–425 (2007).
154. See http://www.tappi.org/s_tappi/doc.asp?CID=183&DID=554165
155. American Petroleum Institute Technical Report 939-D, Second Edition,
Stress corrosion cracking of carbon steel in fuel grade ethanol: review,
experience, survey, field monitoring, and laboratory testing, May (2007).
156. Sridhar N, Price K, Buckingham J and Dante J, Stress corrosion
cracking of carbon steel in ethanol. Corrosion 62:687–702 (2006).
157. Maldonado JG and Sridhar N, SCC of carbon steel in fuel ethanol
service: effect of corrosion potential and ethanol processing source.
Corrosion/2007, Paper No. 07574, Houston, TX: NACE International
(2007).
158. Morris D, The next economy: from dead carbon to living carbon. J Sci
Food Agr 86: 1743–1746 (2006).
73