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Cellulosic biorefineries—unleashing lignin opportunities
Cellulosic biorefineries—unleashing lignin opportunities
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Increasing concerns on global climate change and energy Coupled to this increased energy demand are concerns of
security coupled with diminishing fossil fuel resources have increased atmospheric CO2 discharges. For example, in
spurred a renaissance of interest in the development of the past decade the United States increased its GDP by
alternative forms of fuel and materials from renewable 70% and this was accompanied with a 7% increase in CO2
resources. Lignocellulosic biomass is a renewable resource, emissions. By contrast, during the same time period,
which can be converted to liquid transportation fuels as well as Sweden increased its GDP by 42% and decreased its
used as a platform to produce bio-based materials. Conversion overall CO2 emissions by 9%. These results provide a
of biomass to biofuels by biological conversion processes real-life example that countries can improve their stan-
results in the production of a lignin-rich solid residue, only a dard of living while reducing their CO2 foot-print [http://
fraction of which is necessary as a heat source for the www.swedishenergyagency.se/]. At present, the bioetha-
pretreatment and ethanol distillation processes. This review nol industry in the U.S.A. generates 26 billion liters
provides an overview of lignin chemistry and the changes annually. The next largest producer is Brazil yielding 19
observed after biomass pretreatment. Recent advances in billion liters ethanol from sugar cane in 2007. The U.S.A.
lignin modification pathways such as fragmentation/ energy bill (i.e., EISA) contains provisions that increase
hydroprocessing and thermal depolymerization for green the Renewable Fuel Standard (RFS) to 136 billion liters
gasoline and diesel are discussed. by 2022. Of that, corn ethanol production is capped at 57
billion liters per year; and by 2015 the remainder is
Address expected to be provided by ‘advanced biofuels’ the
School of Chemistry and Biochemistry, Institute of Paper Science and majority of which are cellulosic biofuels. As summarized
Technology, Georgia Institute of Technology, Atlanta, GA 30332, USA in Figure 1, the current RFS mandates production
Corresponding author: Ragauskas, Arthur
volumes for cellulosic ethanol to increase from 0.4 billion
(arthur.ragauskas@chemistry.gatech.edu) 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-
Current Opinion in Environmental Sustainability 2010, 2:383–393
duction capacity of 113–189 million liters per year will
This review comes from the Open issue need to be in place (see Figure 2).
Edited by Rik Leemans and Anand Patwardhan
The USDA/DOE Billion Ton report [5] reviewed these
Received 16 July 2010; Accepted 17 September 2010
Available online 15th October 2010
demands and concluded that these goals are certainly
attainable provided non-traditional biomass resources are
1877-3435/$ – see front matter utilized, including: perennial crops, wheat straw, corn
# 2010 Elsevier B.V. All rights reserved.
stover, other agro-energy crops (e.g. switchgrass or mis-
DOI 10.1016/j.cosust.2010.09.004 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-
Introduction diesel, dimethyl ether and hydrogen) [7], bioethanol will
The need for alternative, sustainable fuels is now well be the preferred fuel for the near-term for U.S.A. Pre-
acknowledged, as global petroleum resources continue to viously, Leemans et al. [8] comprehensively assessed the
decline while energy requirements increase. As an impacts of large-scale global utilization of biomass on
example, the overall US demand for energy has increased regional and grid-scale land cover, greenhouse gas emis-
over the past four decades from 66.5 quadrillion kJ in 1970 sions and carbon cycle. They concluded that the large-
to 90.7 quadrillion kJ in 2007 of which +50% is secured scale cultivation of non-traditional biomass is feasible on a
from foreign sources [1]. Assuming a long-term growing global scale.
demand for oil products under ‘business-as-usual’ policies
and trends, the share of imported hydrocarbon products A key issue in addressing this vision is the need to
for the U.S.A. is projected to reach +65% by 2020. This effectively utilize low cost, high-volume agricultural
dependency on fuel imports yielded an oil import bill of and forest biomass, which will contain varying levels of
$60 billion for U.S.A. as of 1999 and is expected to cellulose, hemicellulose, and lignin [9]. The processing of
increase twofold by 2020 [2]. In recent years, there has these materials is significantly more technically challen-
also been a tremendous growth in oil demand by emer- ging [10,11] than the bioprocessing of corn starch [12] or
ging economies such as China and India [3,4]. sugarcane [13] into bioethanol. Biofuels produced from
Figure 1
starch and sugar derived from corn and sugarcane are transportation biofuels or higher value chemical sub-
collectively termed 1st generation biofuels. Liquid fuels strates. Although a fraction (40%) of the dried lignin-
derived from animal and vegetable fat using conventional rich solid stream after ethanol production is necessary to
technology can also be included in this category [14]. meet the thermal requirements of bioethanol production
Biofuels produced from lignocellulosic feedstocks are which includes pretreatment and ethanol distillation
considered as 2nd generation, while those from algae [21,22], modern biological cellulosic processing plants
and advanced processing of the 2nd generation biofuels will have 60% excess of lignin that could be utilized as a
are defined as 3rd generation biofuels [15]. feedstock for biogasoline/green diesel and/or green
chemicals, thus offering a significant opportunity for
The natural resistance of lignocellulosic biomass to enzy- enhancing the operation of a lignocellulosic biorefinery
matic and microbial deconstruction is defined as recalci- [23]. Most techno-economic evaluations of bioethanol
trance [16]. To facilitate the enzymatic saccharification of production currently available (e.g. [24,26]) utilize the
cellulose, biomass typically requires pretreatment at elev- residual lignin stream as a green energy source for the
ated temperatures (i.e., 150–220 8C) using either acidic process and do not take in to account the value added by
or basic processing conditions [17,18]. Most biomass converting the lignin to liquid fuels or biomaterials.
pretreatments release some simple sugars from the hemi- There is an urgent need for updated techno-economic
celluloses, which are directly fermented to ethanol. The evaluations, which take into account the potential for
pretreated solid material is reacted with cellulase to converting the excess lignin to liquid fuels.
hydrolyze cellulose to glucose, which is then fermented
to ethanol [19]. At present, most commercial bioethanol plants employ
simultaneous saccharification and fermentation (SSF), in
Regardless of the exact bioprocessing technology which the solid residue is primarily composed of lignin
employed, almost all biological processing platforms for along with unconverted sugars, unrecovered enzymes and
the conversion of plant polysaccharides to bioethanol (or fermenting microbes and metals or ash. With currently
biobutanol) result in the formation of a vast lignin process available technologies, it is often not readily feasible to
stream (25–35% of total biomass) [20]. This material is purify the fermentation residue to a form suitable for the
frequently utilized as an energy source for power gener- production of lignin-based biomaterials. It should be
ation, in part, because there are few efficient chemical noted that among current pretreatment technologies,
conversion processes available that can convert lignin into the organosolv pretreatment produces a relatively pure
Figure 2 Figure 3
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
of these changes based on different biomass source/pre- in grasses, polysaccharide-lignin crosslinking is mediated
treatment processes are summarized in Table 1. by ferulates attached primarily to arabinoxylans [70–73].
The occurrence of stable lignin–carbohydrate crosslin-
Lignin is the most recalcitrant component of the major kages and bonds in biomass has been extensively inves-
plant cell wall biopolymers. In general, the higher the tigated and is considered one of the main reasons
proportion of lignin, the lower the bioavailability of the preventing selective separation of the biomass com-
substrate for bioethanol generation. According to current ponents in a biorefinery process [74–76].
understanding lignin, cellulose and hemicellulose are not
just individual units in a plant cell wall but are intimately Lignin fragmentation and hydroprocessing
interrelated and associated. Lignin is considered the The utilization of lignin from a non-thermal based bior-
essential ‘glue’ that holds these three polymers together efinery as a biofuel is contingent on the reduction of its
and is linked to polysaccharides, mainly hemicellulose in molecular weight and deoxygenation. The predominant
a plant cell wall. Recent studies have demonstrated that commercial lignin fragmentation process is kraft pulping
Table 1
Some key structural features in varying biomass lignin before and after pretreatments.
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.
which utilizes NaOH and Na2S to fragment and solubilize that could be used to generate a green gasoline and/or
lignin from wood. By employing elevated pulping tem- diesel. Recent patents by Shabtai et al. described a two-
peratures (160–175 8C), 80–95% of the lignin in wood step method to yield a reformulated, partially oxygenated
can be relinquished from wood. This process initiates a gasoline product which includes a mixture of C7–C10
series of fragmentation and re-polymerization reactions substituted phenyl/methyl ethers, cycloalkyl methyl
[80]. Figure 6 summarizes some of the predominant lignin ethers branched paraffins, and alkylated and polyalky-
fragmentation reactions during kraft pulping [81]. Most lated cycloalkanes [82]. The lignin refining process
frequently, this material is used as an energy source for includes an initial aqueous alkaline-catalyzed depolymer-
the kraft pulp mill. A variety of other alkaline and acid- ization of lignin present in biomass or industrial lignin-
catalyzed systems have been employed to pulp wood rich process streams, followed by hydroprocessing of the
chips but the kraft process has remained the predominant depolymerized lignin to C7-10 alkylbenzenes, which
system for removing lignin from woody feedstock. Sub- were proposed to be used for improving the octane level
sequent chemical derivatization of this lignin stream is of petroleum-based fuels. Chen [83] has also reported a
frequently complicated because of the presence of sulfur patent that combines alkaline fragmentation with metal-
and salts. catalyzed hydrogenation to initially yield phenolics fol-
lowed by their conversion to substituted cyclohexanes,
Several studies have dealt with a chemical treatment to which are also deoxygenated. Yie et al. recognized the
fragment lignin into lower carbon chains (i.e., C6–C22) 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
process by treating the lignin-rich phase of biomass after lignin [98]. This combined knowledge points to a rich
enzymatic deconstruction and fermentation with an future in which combinations of catalysts will be used to
alkaline hydrogenation stage yielding a green diesel/gaso- reduce the molecular weight of lignin and yield deoxy-
line resource [84]. genated aromatics and aliphatics.
depolymerize and reduce the oxygen functionality of 7. (a). Schaub G, Vetter A: Biofuels—a review. Chem Ing Tech
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The land cover and carbon cycle consequences of large-scale
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Conclusions Change 1996, 6:335-357.
The advent of cellulosic biofuels has brought to the 9. Ragauskas AJ, Williams CK, Davison BH, Britovsek G, Cairney J,
forefront the need for lignin chemistry. All bioconversion Eckert CA, Frederick WJ, Hallett JP, Leak DJ, Liotta CL et al.:
The path forward for biofuels and biomaterials. Science 2006,
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losic biomass produce a lignin-rich solid residue. While
10. Wyman CE: Production of low cost sugars from biomass:
this solid stream is primarily composed of lignin, the progress opportunities and challenges. In Proceedings of
presence of other components necessitates purification the biomass conference of the Americas, 1; Oakland, CA:
1999:867-872.
before their conversion to lignin based materials. How-
ever, converting this lignin-rich solid residue to liquid 11. Galbe M, Zacchi G: A review of the production of ethanol from
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fuels, is presently possible using various pathways such as
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the need to develop new deoxygenation chemistries that
14. Sims REH, Mabee W, Saddler JN, Taylor M: An overview of
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Acknowledgment strategic perspective on the US. Department of Energy’s
This project was supported by the Georgia Institute of Technology Focused Research and Development Activities for Bioethanol.
Research Program. Biotechnol Prog 1999, 15:817-827.
20. Wyman CE: What is and is not, vital to advancing cellulosic
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