Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
com
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 emerging economies such as China and India [3,4].
www.sciencedirect.com
Figure 1
transportation biofuels or higher value chemical substrates. Although a fraction (40%) of the dried ligninrich 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
www.sciencedirect.com
Figure 2
Figure 3
Figure 4
OH
OCH3
OH
H3CO
OH
OCH3
OH
OH
Coniferyl
alcohol
Sinapyl
alcohol
OH
Coumaryl
alcohol
Figure 5
HO
H3CO
HO
H 3CO
OCH3
O
HO
H3CO
OH
OCH 3
O
OCH3
O
OCH3
5/4
dibenzodioxocin
HO
HO
O
HO
OCH 3
OCH 3
HO
O
H3CO
OCH 3
O
H 3CO
O
1
45
H3CO
O
5
55
of these changes based on different biomass source/pretreatment 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
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
mmol/g
Phenolic OH
mmol/g
0.60
0.30
0.56
0.24
0.39
0.25
1.00
0.90
1.17
1.00
0.99
0.96
0.20
0.10
0.17
0.13
0.10
0.07
4.20
7.30
4.51
1.86
3.88
2.83
1.00
2.70
0.70
2.73
1.00
1.25
Mw
g/mol
1.35 10 4
5.41 10 3
1.68 10 4
2.49 10 3
5.00 10 3
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.
www.sciencedirect.com
H3 CO
HC
HC
H3 CO
Enol Ether
O-CH 2 O
-H+
HO
CH2
HO
H3 CO
O
HC
H3 CO
CH 2
HC
HC OR
HC
-OR
H3 CO
H3 CO
O
OR=H, Aryl
HO
CH2
HO
S
-S
CH
CH
O-
CH2
H C
- S CH
H3 CO
H3 CO
H3 CO
H3 CO
HO
H3 CO
CH2
CH
HC
+HS-H+
O-
www.sciencedirect.com
7.
8.
9.
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 lignocellulosic 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. However, converting this lignin-rich solid residue to liquid
fuels, is presently possible using various pathways such as
fragmentation and hydroprocessing and thermal depolymerization. Key challenges which remain include sustainable, 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 compounds. These opportunities are especially relevant to
todays cellulosic ethanol plants utilizing an aqueous
acidic aqueous based pretreatment system, whereas organosolv 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.
2.
3.
4.
5.
6.
http://genomics.energy.gov/gallery/brc2009/view.np/
view-08.html.
58. Helle SS, Murray A, Lam J, Cameron DR, Duff SJB: Xylose
fermentation by genetically modified Saccharomyces
cerevisiae 259ST in spent sulfite liquor. Bioresour Technol 2004,
92:163-171.
59. Lawford HG, Rousseau JD: Performance testing of zymomonas
mobilis metabolically engineered for cofermentation of
glucose xylose and arabinose. Appl Biochem Biotechnol 2002,
98100:429-448.
60. Hahn-Haegerdal B, Galbe M, Gorwa-Grauslund MF, Liden G,
Zacchi G: Bio-ethanolthe fuel of tomorrow from the residues
of today. Trends Biotechnol 2006, 24:549-556.
61. Lynd LR, van Zyl WH, McBride JE, Laser M: Consolidated
bioprocessing of cellulosic biomass: an update. Curr Opin
Biotechnol 2005, 16:577-583.
62. Den HR, McBride JE, La Grange DC, Lynd LR, Van Zyl WH:
Functional expression of cellobiohydrolases in Saccharomyces
cerevisiae towards one-step conversion of cellulose to ethanol.
Enzyme Microb Technol 2007, 40:1291-1299.
63. Weimer PJ: Ethanol and co-products from cellulosic biomass.
Int Sugar J 2006, 108:630-633.
Current Opinion in Environmental Sustainability 2010, 2:383393
64.
http://www.eere.energy.gov/biomass/cellulase_cost.html.
http://www.helsinki.fi/orgkm_ww/lignin_structure.html.
www.sciencedirect.com
liquid bio-oil with low oxygen content suitable for blending with conventional transportation fuels. Steam explosion lignin has been used in
this study.
www.sciencedirect.com