Available online at www.sciencedirect.
com
Cellulosic biorefineries—unleashing lignin opportunities
Poulomi Sannigrahi, Yunqiao Pu and Arthur Ragauskas
Increasing concerns on global climate change and energy
security coupled with diminishing fossil fuel resources have
spurred a renaissance of interest in the development of
alternative forms of fuel and materials from renewable
resources. Lignocellulosic biomass is a renewable resource,
which can be converted to liquid transportation fuels as well as
used as a platform to produce bio-based materials. Conversion
of biomass to biofuels by biological conversion processes
results in the production of a lignin-rich solid residue, only a
fraction of which is necessary as a heat source for the
pretreatment and ethanol distillation processes. This review
provides an overview of lignin chemistry and the changes
observed after biomass pretreatment. Recent advances in
lignin modification pathways such as fragmentation/
hydroprocessing and thermal depolymerization for green
gasoline and diesel are discussed.
Address
School of Chemistry and Biochemistry, Institute of Paper Science and
Technology, Georgia Institute of Technology, Atlanta, GA 30332, USA
Corresponding author: Ragauskas, Arthur
(arthur.ragauskas@chemistry.gatech.edu)
Current Opinion in Environmental Sustainability 2010, 2:383–393
This review comes from the Open issue
Edited by Rik Leemans and Anand Patwardhan
Received 16 July 2010; Accepted 17 September 2010
Available online 15th October 2010
1877-3435/$ – see front matter
# 2010 Elsevier B.V. All rights reserved.
DOI 10.1016/j.cosust.2010.09.004
Introduction
The need for alternative, sustainable fuels is now well
acknowledged, as global petroleum resources continue to
decline while energy requirements increase. As an
example, the overall US demand for energy has increased
over the past four decades from 66.5 quadrillion kJ in 1970
to 90.7 quadrillion kJ in 2007 of which +50% is secured
from foreign sources [1]. Assuming a long-term growing
demand for oil products under ‘business-as-usual’ policies
and trends, the share of imported hydrocarbon products
for the U.S.A. is projected to reach +65% by 2020. This
dependency on fuel imports yielded an oil import bill of
$60 billion for U.S.A. as of 1999 and is expected to
increase twofold by 2020 [2]. In recent years, there has
also been a tremendous growth in oil demand by emer-
ging economies such as China and India [3,4].
www.sciencedirect.com
Coupled to this increased energy demand are concerns of
increased atmospheric CO2 discharges. For example, in
the past decade the United States increased its GDP by
70% and this was accompanied with a 7% increase in CO2
emissions. By contrast, during the same time period,
Sweden increased its GDP by 42% and decreased its
overall CO2 emissions by 9%. These results provide a
real-life example that countries can improve their stan-
dard of living while reducing their CO2 foot-print [http://
www.swedishenergyagency.se/]. At present, the bioetha-
nol industry in the U.S.A. generates 26 billion liters
annually. The next largest producer is Brazil yielding 19
billion liters ethanol from sugar cane in 2007. The U.S.A.
energy bill (i.e., EISA) contains provisions that increase
the Renewable Fuel Standard (RFS) to 136 billion liters
by 2022. Of that, corn ethanol production is capped at 57
billion liters per year; and by 2015 the remainder is
expected to be provided by ‘advanced biofuels’ the
majority of which are cellulosic biofuels. As summarized
in Figure 1, the current RFS mandates production
volumes for cellulosic ethanol to increase from 0.4 billion
liters per year to 11 billion liters per year by 2013, and 60
billion liters by 2022. This implies that between 60 and
100 new cellulosic biorefineries, with an average pro-
duction capacity of 113–189 million liters per year will
need to be in place (see Figure 2).
The USDA/DOE Billion Ton report [5] reviewed these
demands and concluded that these goals are certainly
attainable provided non-traditional biomass resources are
utilized, including: perennial crops, wheat straw, corn
stover, other agro-energy crops (e.g. switchgrass or mis-
canthus), forest residues, tree farms (i.e., hybrid poplar)
and secondary forest industry waste materials [6].
Although a variety of fuels could be derived from this
bio-based inventory (i.e., biomethanol, biobutanol, bio-
diesel, dimethyl ether and hydrogen) [7], bioethanol will
be the preferred fuel for the near-term for U.S.A. Pre-
viously, Leemans et al. [8] comprehensively assessed the
impacts of large-scale global utilization of biomass on
regional and grid-scale land cover, greenhouse gas emis-
sions and carbon cycle. They concluded that the large-
scale cultivation of non-traditional biomass is feasible on a
global scale.
A key issue in addressing this vision is the need to
effectively utilize low cost, high-volume agricultural
and forest biomass, which will contain varying levels of
cellulose, hemicellulose, and lignin [9]. The processing of
these materials is significantly more technically challen-
ging [10,11] than the bioprocessing of corn starch [12] or
sugarcane [13] into bioethanol. Biofuels produced from
Current Opinion in Environmental Sustainability 2010, 2:383–393
384 Open issue
Figure 1
2007 EISA biofuels production volume mandate.
starch and sugar derived from corn and sugarcane are
collectively termed 1st generation biofuels. Liquid fuels
derived from animal and vegetable fat using conventional
technology can also be included in this category [14].
Biofuels produced from lignocellulosic feedstocks are
considered as 2nd generation, while those from algae
and advanced processing of the 2nd generation biofuels
are defined as 3rd generation biofuels [15].
The natural resistance of lignocellulosic biomass to enzy-
matic and microbial deconstruction is defined as recalci-
trance [16]. To facilitate the enzymatic saccharification of
cellulose, biomass typically requires pretreatment at elev-
ated temperatures (i.e., 150–220 8C) using either acidic
or basic processing conditions [17,18]. Most biomass
pretreatments release some simple sugars from the hemi-
celluloses, which are directly fermented to ethanol. The
pretreated solid material is reacted with cellulase to
hydrolyze cellulose to glucose, which is then fermented
to ethanol [19].
Regardless of the exact bioprocessing technology
employed, almost all biological processing platforms for
the conversion of plant polysaccharides to bioethanol (or
biobutanol) result in the formation of a vast lignin process
stream (25–35% of total biomass) [20]. This material is
frequently utilized as an energy source for power gener-
ation, in part, because there are few efficient chemical
conversion processes available that can convert lignin into
Current Opinion in Environmental Sustainability 2010, 2:383–393
transportation biofuels or higher value chemical sub-
strates. Although a fraction (40%) of the dried lignin-
rich solid stream after ethanol production is necessary to
meet the thermal requirements of bioethanol production
which includes pretreatment and ethanol distillation
[21,22], modern biological cellulosic processing plants
will have 60% excess of lignin that could be utilized as a
feedstock for biogasoline/green diesel and/or green
chemicals, thus offering a significant opportunity for
enhancing the operation of a lignocellulosic biorefinery
[23]. Most techno-economic evaluations of bioethanol
production currently available (e.g. [24,26]) utilize the
residual lignin stream as a green energy source for the
process and do not take in to account the value added by
converting the lignin to liquid fuels or biomaterials.
There is an urgent need for updated techno-economic
evaluations, which take into account the potential for
converting the excess lignin to liquid fuels.
At present, most commercial bioethanol plants employ
simultaneous saccharification and fermentation (SSF), in
which the solid residue is primarily composed of lignin
along with unconverted sugars, unrecovered enzymes and
fermenting microbes and metals or ash. With currently
available technologies, it is often not readily feasible to
purify the fermentation residue to a form suitable for the
production of lignin-based biomaterials. It should be
noted that among current pretreatment technologies,
the organosolv pretreatment produces a relatively pure
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 Cellulosic biorefineries Sannigrahi, Pu and Ragauskas 385

Figure 2 Figure 3

Total number of cellulosic plants needed to comply with Renewable Fuel

Standard (RFS). MLY: million liters per year.

lignin stream as a by-product, which can be converted to

biomaterials. For most other acidic pretreatments, which
do not extract lignin during pretreatment, the conversion
of the residue to liquid fuels is presently a more viable
option. This review is focused on the chemistry of the
conversion of lignin-rich material to fuels using various
pathways. However, with technological advancements in
the production of 2nd and 3rd generation biofuels from
lignocellulosics, we anticipate that new opportunities will
be developed that will facilitate the conversion of lignin
from cellulosic bio-based biorefineries into bio-based
chemicals, materials and fuels. These opportunities
should not be missed by the research and entrepreneurial
Schematic of plant cell wall utilization of lignin, hemicellulose and
community.
cellulose [27].

Bioethanol biorefinery system

The efficient, cost-effective depolymerization of poly-
saccharides in biomass to monosaccharides remains a key
challenge in the utilization of these bioresources for
fermentation to ethanol [25,26]. To date, effective util-
ization of these bioresources through biological routes is
predicated on pretreatment technologies that can reduce
biomass recalcitrance. The objective of pretreating lig-
nocellulosics is to alter the structure of biomass and to
make the cellulose and hemicelluloses more accessible/
amenable to hydrolytic enzymes (see Figure 3) [27,28].
Effective pretreatment technologies need to address
several important criteria, including: minimization of
hemicellulose degradation products, limiting the for-
mation of by-products that inhibit ethanol fermentation,
reducing energy/water use and lowering environmental
impacts, capital and operating costs [29].
Some of the most promising pretreatments include steam
explosion, hot water/auto-catalyzed pretreatment, dilute
acid, aqueous lime or NaOH pretreatment, ammonia, and
organosolv pretreatment. Steam explosion involves rapidly
heating biomass with steam at elevated temperatures
(190–240 8C) with residence times of 3–8 min fol-
lowed by explosive decompression. This treatment pro-
motes hemicellulose hydrolysis and opens up the plant
cell structure, although enhanced digestibility of cellu-
lose is only weakly correlated with the physical effects
[30,31]. Hot water or auto-catalyzed pretreatment can result
in extensive hemicellulose hydrolysis but high residual
lignin content in biomass reduces subsequent cellulase
hydrolysis [32]. The generation of furfural and 5-hydro-
xymethyl furfural has been reported to be detrimental to
subsequent fermentation operations. Dilute acid pretreat-
ment has been extensively studied and typically employs
0.4–2% H2SO4 at temperatures of 160–220 8C to remove
hemicelluloses and enhance cellulase digestion of cellu-
lose [33,34]. This approach is being pursued in some of
the biological conversion demonstration plants being
constructed in the U.S.A. (http://www1.eere.energy.gov/

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386 Open issue
biomass/biochemical_processes.html). Aqueous lime or
NaOH pretreatment has been shown to be effective for
wheat straw and sugarcane bagasse at lower temperatures
than acid treatments; however, the treatment times are in
some cases on the order of hours [35]. The use of an
alkaline treatment also incurs additional capital cost, as
the recovery of salts requires a lime kiln to regenerate the
base. Ammonia pretreatment involves pretreating biomass
with an aqueous ammonia solution causing depolymer-
ization and cleavage of lignin–carbohydrate bonds.
Agricultural residues and herbaceous plants treated in
this manner exhibit an excellent response to cellulase
[36,37]. However, woody biomass is often not efficiently
treated by this technology, and in all cases, ammonia
recovery is an additional cost and important consider-
ation. Organosolv pretreatment of biomass resides on the
use of an organic solvent system [38–41] with enhanced
lignin solubilizing properties. Usually, the resultant cel-
lulosic fraction is highly susceptible to enzymatic
hydrolysis, generating very high yields of glucose that
can be readily converted to ethanol.
After pretreatment, the remaining pretreated material is
reacted with cellulase to hydrolyze cellulose to glucose,
which is then fermented to ethanol [42,43]. An important
consideration during the hydrolysis process is to minimize
formation of compounds that inhibit fermentation [44].
The nature, composition, and concentration of these
compounds are dependent on the hydrolysis conditions
and have a profound influence on the fermentation pro-
duction rate of biofuels from the hydrolyzate [45,46].
Several strategies have been pursued for dealing with
fermentation inhibitors in the hydrolyzates, including
hydrolysis optimization [47], detoxification before fer-
mentation [48–50], genetic engineering of specific strains
[51], and fed-batch fermentation techniques [52]. For
optimal process economics, all available sugars need to
be converted to biofuel. The microorganisms that are able
to ferment sugars to ethanol can be either yeasts [53,54] or
bacteria [55]. Over the past decades, new methods in
molecular biology, protein chemistry and genetic engin-
eering have led to an increasing number of new strains,
exhibiting improved characteristics to ferment the full
spectrum of sugars available in hydrolyzates [56–60]. An
alternative promising approach reported is consolidated
bioprocessing (CBP) which involves, first, bioproduction
of cellulolytic enzymes from thermophilic anaerobic
microbes; second, hydrolysis of plant polysaccharides to
simple sugars; and third, their subsequent fermentation to
ethanol, all in one-stage [61]. CBP is projected to sub-
stantially reduce the cost of bioethanol and these reduced
costs and simplicity of operation have heightened
research in this field [62,63]. Clearly, as advances in
fermentation and cellulase technology develop [64] and
become even less expensive, biological pathways for the
production of 2nd and 3rd generation biofuels are becom-
ing even more economically compelling.
Current Opinion in Environmental Sustainability 2010, 2:383–393
Chemical structure of lignin
Plant cell walls are complex and dynamic structures
comprised primarily of cellulose, hemicellulose and lig-
nin. Of the three major plant biopolymers, lignin is
distinctly different from the other macromolecular com-
ponents of terrestrial biomass. Cellulose consists of long
linear fibrils of b-(1,4)-glucopyranoside chains that have a
native degree of polymerization (DP) of 5000–15,000.
Hemicelluloses exhibit a much broader distribution of
sugars, and frequently are branched polysaccharides com-
posed of 1,4-linked b-D-hexosyl residues with a typical
DP from 70 to 200. Lignin is an irregular polyphenolic
polymer synthesized by dehydrogenative polymerization
of phenyl propanoid units (see Figure 4), namely, con-
iferyl alcohol, sinapyl alcohol and coumaryl alcohol, which
corresponds to guaiacyl (G), syringyl (S) and p-hydroxy-
phenyl (H) structures of lignin, respectively. Softwood
lignin is composed mainly of coniferyl alcohol units, while
hardwood lignin is composed of coniferyl and sinapyl
alcohol units. Grasses contain guaiacyl, syringyl and p-
hydroxyphenyl (H) structural units. Generally, the abun-
dance of lignin in lignocellulosic biomass is softwood 27–
33%, hardwood 18–25% and grass 17–24%.
The lignin macromolecule is biosynthetically polymer-
ized via carbon–carbon and carbon–oxygen (ether) bond
connection of phenyl propanoid building blocks.
Although the exact structure of protolignin is unknown,
improvements in methods for identifying lignin degra-
dation products and advancements in spectroscopic
methods have enabled scientists to elucidate the predo-
minant structural features of lignin. The structure of
lignin, especially in woody biomass, and its chemistry
have been extensively studied by our group and other
researchers and these advances have dramatically
enhanced our understanding of this biopolymer
[65,66,67,68,69]. Some of the common and most import-
ant inter-unit linkages identified in softwood lignin are
shown in Figure 5. Biomass pretreatments result in alter-
ing the structure and molecular weight of lignin and some
Figure 4
OH OH OH
OCH3 H3CO OCH3
OH OH OH
Coniferyl Sinapyl Coumaryl
alcohol alcohol alcohol
Current Opinion in Environmental Sustainability
Phenyl propanoid units employed in the biosynthesis of lignin.
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 Cellulosic biorefineries Sannigrahi, Pu and Ragauskas 387

Figure 5

HO
H3CO
HO O H 3CO OCH3
O O O
O
H3CO HO
OH
O OCH3
OCH 3
O O
O OCH3
β−Ο−4 β−β β−5/α−Ο−4 dibenzodioxocin

HO HO O
O OCH 3
HO HO
O OCH 3
OCH 3
H3CO O

H 3CO H3CO
O O
O O

β−1 4−Ο−5 5−5 β−5

Current Opinion in Environmental Sustainability

Primary inter-unit linkages in softwood lignin.

of these changes based on different biomass source/pre-
treatment processes are summarized in Table 1.
Lignin is the most recalcitrant component of the major
plant cell wall biopolymers. In general, the higher the
proportion of lignin, the lower the bioavailability of the
substrate for bioethanol generation. According to current
understanding lignin, cellulose and hemicellulose are not
just individual units in a plant cell wall but are intimately
interrelated and associated. Lignin is considered the
essential ‘glue’ that holds these three polymers together
and is linked to polysaccharides, mainly hemicellulose in
a plant cell wall. Recent studies have demonstrated that
in grasses, polysaccharide-lignin crosslinking is mediated
by ferulates attached primarily to arabinoxylans [70–73].
The occurrence of stable lignin–carbohydrate crosslin-
kages and bonds in biomass has been extensively inves-
tigated and is considered one of the main reasons
preventing selective separation of the biomass com-
ponents in a biorefinery process [74–76].
Lignin fragmentation and hydroprocessing
The utilization of lignin from a non-thermal based bior-
efinery as a biofuel is contingent on the reduction of its
molecular weight and deoxygenation. The predominant
commercial lignin fragmentation process is kraft pulping

Table 1

Some key structural features in varying biomass lignin before and after pretreatments.

Lignin b-O-4 a Methoxyl b b-b/b-5 c Aliphatic OH Phenolic OH Mw

mmol/g mmol/g g/mol
Loblolly pine [77] 0.60 1.00 0.20 4.20 1.00 1.35  10 4
Loblolly pine EOL after EOP 0.30 0.90 0.10 7.30 2.70 5.41  10 3
Butterfly bush (B. davidii) [78] 0.56 1.17 0.17 4.51 0.70 1.68  10 4
Butterfly bush EOL after EOP 0.24 1.00 0.13 1.86 2.73 2.49  10 3
Switchgrass [79] 0.39 0.99 0.10 3.88 1.00 5.00  10 3
Switchgrass after dilute acid pretreatment 0.25 0.96 0.07 2.83 1.25 4.16  10 3

EOL: ethanol organosolv lignin; EOP: ethanol organosolv pretreatment; Mw: average molecular weight.
a
Cg in b-O-4, #C/aromatic ring.
b
C in OCH3, #C/aromatic ring.
c
Cb in b-b/b-5, #C/aromatic ring.

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388 Open issue

which utilizes NaOH and Na2S to fragment and solubilize
lignin from wood. By employing elevated pulping tem-
peratures (160–175 8C), 80–95% of the lignin in wood
can be relinquished from wood. This process initiates a
series of fragmentation and re-polymerization reactions
[80]. Figure 6 summarizes some of the predominant lignin
fragmentation reactions during kraft pulping [81]. Most
frequently, this material is used as an energy source for
the kraft pulp mill. A variety of other alkaline and acid-
catalyzed systems have been employed to pulp wood
chips but the kraft process has remained the predominant
system for removing lignin from woody feedstock. Sub-
sequent chemical derivatization of this lignin stream is
frequently complicated because of the presence of sulfur
and salts.
Several studies have dealt with a chemical treatment to
fragment lignin into lower carbon chains (i.e., C6–C22)
that could be used to generate a green gasoline and/or
diesel. Recent patents by Shabtai et al. described a two-
step method to yield a reformulated, partially oxygenated
gasoline product which includes a mixture of C7–C10
substituted phenyl/methyl ethers, cycloalkyl methyl
ethers branched paraffins, and alkylated and polyalky-
lated cycloalkanes [82]. The lignin refining process
includes an initial aqueous alkaline-catalyzed depolymer-
ization of lignin present in biomass or industrial lignin-
rich process streams, followed by hydroprocessing of the
depolymerized lignin to C7-10 alkylbenzenes, which
were proposed to be used for improving the octane level
of petroleum-based fuels. Chen [83] has also reported a
patent that combines alkaline fragmentation with metal-
catalyzed hydrogenation to initially yield phenolics fol-
lowed by their conversion to substituted cyclohexanes,
which are also deoxygenated. Yie et al. recognized the
opportunity to integrate this concept into the bioethanol

Figure 6

H3 CO

HC O
HC

H3 CO Enol Ether
O-

-CH 2 O
-H+

HO H3 CO HO H3 CO
CH2 CH 2
HC O HC O
HC OR HC

-OR

H3 CO H3 CO
O- O
R=H, Aryl
+HS-
-H+

HO HO HO H3 CO
H3 CO CH2
CH2 CH2
- H C O
CH
S
CH - O
- S CH
HC CH
-S

H3 CO H3 CO H3 CO
O- O- O-
Current Opinion in Environmental Sustainability

Lignin fragmentation during Kraft pulping.

Current Opinion in Environmental Sustainability 2010, 2:383–393 www.sciencedirect.com


process by treating the lignin-rich phase of biomass after
enzymatic deconstruction and fermentation with an
alkaline hydrogenation stage yielding a green diesel/gaso-
line resource [84].
Prior lignin hydrogenation studies have typically
employed high temperatures (>200 8C) and/or high H2
pressures (>7 MPa), strong acidic or basic media.
Depending on the reaction conditions, up to 60–80%
conversion of the starting lignin to liquefied mixtures
was obtained. These mixtures contained hydrogenated
products and substituted phenols [85–87]. The knowl-
edge gained about the chemical mechanisms involved,
the reusability of the catalyst, and tailoring the selectivity
of the hydrogenation towards specific lignin groups is
leading to improved reaction conditions [88,89].
Recent hydrogenation studies with colloidal Ru or mono-,
di- and tetra-nuclear Ru-Arene complexes as catalyst on
milled wood lignin indicate that a 50% decrease in DP can
be accomplished. These catalyst systems were designed
for the hydrogenation of the aromatic ring in the lignin
polymer. The decrease in DP during the hydrogenation
suggests that hydrogenolysis of the biopolymer may have
also occurred [90,91].
Hydrogenation with phosphine ligand containing ruthe-
nium complexes of carbon–carbon double bond and/or
carbon–oxygen bond containing chemicals has provided
additional insight on how to tailor catalytic selectivity
towards carbon–oxygen bond cleavage over carbon–car-
bon double bond hydrogenation [92]. The expectation is
that selective hydrogenolysis of lignin can lead to poten-
tial fuel precursors or other value-added chemicals by
oxygen decrement and hydrogen increment and to pro-
ducts with lower molecular weight by reductive cleavage
of C–O–C bonds [93].
Recent studies by Nagy and Ragauskas have highlighted
the potential of in situ generated BI3 to catalytically
decrease the molecular weight of softwood organosolv
lignin by 60%, in part by hydrogenolysis [94]. The same
catalyst has been reported to be beneficial to coal lique-
faction by borane-catalyzed hydrogenation and hydroge-
nolysis at 350 -C under H2 pressure. The products were
still solid but could be readily liquefied in a subsequent
conventional Bergius hydrocracking process [95,96]. The
potential for selective degradation of lignin via hydro-
genolysis has also been highlighted by Yan [97]. The use
of dioxane and near-critical water with 1 wt% H3PO4 with
birch sawdust and using either Pt/C or Rh/C, under
hydrogen pressure, yielded approximately 10% lignin
dimers and 45% lignin monomers which were sub-
sequently hydrogenated in a second step to hydrocarbons
[97]. A recent review by Zakzeski et al. has summarized
the advances in catalytic valorization of lignin to chemi-
cals both for model lignin compounds and for isolated
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Cellulosic biorefineries Sannigrahi, Pu and Ragauskas 389
lignin [98]. This combined knowledge points to a rich
future in which combinations of catalysts will be used to
reduce the molecular weight of lignin and yield deoxy-
genated aromatics and aliphatics.
Thermal depolymerization of lignin
An alternative approach for converting lignin into low
molecular weight chemical feedstocks is by pyrolysis.
Depending on the reactor design and operating con-
ditions lignin can be fragmented into a series of phenolic
derivatives [99] and/or converted further into H2, CO,
CO2, CH4, C2H6 and other low molecular weight frag-
ments [100]. The thermal cracking of lignin to low
molecular weight phenolics was practiced in the former
USSR to generate phenolics and activated carbon [101].
The cracking temperature of lignin has been studied from
400 to 1100 8C with yields and products dependent on
reaction temperatures and conditions [102]. The limita-
tion of today’s fast biomass pyrolysis reactor design for
lignin was highlighted in a joint international study which
concluded that for concentrated lignin feedstocks, new
pyrolysis reactor designs will be required other than the
typical fluidized-bed fast pyrolysis systems that are com-
monly used for biomass [103].
Using soda and organosolv lignin, de Wild et al. reported
yields of 10–20% condensable organics using a fast flui-
dized bed pyrolysis unit at 400 8C and this was accom-
panied by 30–35% char formation [100]. Several
investigators have shown that commercial catalysts can
facilitate cracking of lignin at lower temperatures and
influence final product distributions [104]. Common salts
including Fe2O3, ZnCl2, NaCl, KCl, NaOH, K2CO3, and
Na2CO3 have been shown to be beneficial to pyrolysis
although several of these require a co-additive to achieve
these benefits [105].
Recently, Kleinert et al. highlighted an alternative
approach to the depolymerization of lignin using a novel
liquefaction process dependent upon a reductive treat-
ment using formic acid with lignin in ethanol at tempera-
tures of 350–400 8C. During this thermal reductive
treatment both depolymerization and deoxygenation of
lignin occurs [106]. The resulting lignin fragments
separate into two phases, where the lighter organic phase
consists mainly of low molecular weight substituted
phenols and the heavier phase had C8–C10 aliphatics.
A follow-up publication has documented the applicability
of this reductive fragmentation treatment for lignin iso-
lated after enzymatic deconstruction of wood [107]. Gel-
lerstedt et al. examined this treatment using a sample of
spruce sodium lignosulfonate and lignin from steam
exploded birch wood at 380 8C using a mixture of formic
acid and ethanol [108]. The resulting product yielded
little char and the bio-oil consisting of a complex mixture
of aliphatic hydrocarbons and phenolics had an average
DP of 300. These recent results illustrate the potential to
Current Opinion in Environmental Sustainability 2010, 2:383–393
390 Open issue
depolymerize and reduce the oxygen functionality of
lignin. On the basis of these advances and the improved
understanding of biomass pyrolysis we will see an accel-
eration of this technology platform for lignin processing.
Conclusions
The advent of cellulosic biofuels has brought to the
forefront the need for lignin chemistry. All bioconversion
platforms for the production of ethanol from lignocellu-
losic biomass produce a lignin-rich solid residue. While
this solid stream is primarily composed of lignin, the
presence of other components necessitates purification
before their conversion to lignin based materials. How-
ever, converting this lignin-rich solid residue to liquid
fuels, is presently possible using various pathways such as
fragmentation and hydroprocessing and thermal depoly-
merization. Key challenges which remain include sustain-
able, energy/chemical efficient green chemistry to
convert various sources of lignin to low molecular weight
aliphatics and aromatics. Coupled with this challenge is
the need to develop new deoxygenation chemistries that
can reduce hydroxyl groups, methoxyl, ether-linkages,
carbonyl and carboxyl groups of lignin and related com-
pounds. These opportunities are especially relevant to
today’s cellulosic ethanol plants utilizing an aqueous
acidic aqueous based pretreatment system, whereas orga-
nosolv and other pretreatments that aggressively remove
lignin during pretreatment provide the opportunity to
deliver a relatively ‘pure’ lignin stream that could be used
for material applications. In closing, if the first decade of
the new millennium in biofuels research was dominated
by cellulosic research, the second will surely see lignin
research grow to be of equal importance.
Acknowledgment
This project was supported by the Georgia Institute of Technology Focused
Research Program.
References and recommended reading
Papers of particular interest, published within the period of review,
have been highlighted as:
 of special interest
 of outstanding interest
1. US Department of Energy, Energy Information Administration:
Mon Energy Rev2001, October:1-114.
2. US Department of Energy: Annual Energy Outlook 2000. 2000:.
DOE/EIA-0383.
3. IEA, World Energy Outlook, Paris (2004).
4. Yang B, Lu Y: Perspective: the promise of cellulosic ethanol
production in China. J Chem Technol Biotechnol 2007, 82:6-10.
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Current Opinion in Environmental Sustainability 2010, 2:383–393