CRITICAL REVIEW
www.rsc.org/csr
Introduction
This journal is
5589
Scheme 1 Comparison of the chemical structure of polysaccharides. (a) cellulose with 1,4 0 -b-glycosidic bonds and intra- and inter-chain hydrogen
bonding,27 Adapted and reprinted with permission from ref. 27. Copyright 2006 American Chemical Society; and (b) starch (amylose) with
1,4 0 -a-glycosidic bonds.28 Adapted and reprinted from ref. 28, Copyright 2003, with permission from Elsevier.
Scheme 2 Potential chemicals and fuels from the catalytic conversion of cellulose. (Route A: chemocatalytic conversion of cellulose into various
chemicals and fuels through glucose, Route B: Conversion of cellulose into various chemicals and fuels by a one-pass catalytic process in the
presence of a multifunctional catalyst).
pyrolysis. An emerging trend is to integrate catalytically thermochemical conversion with selectively catalytic hydrogenolysis
and hydrogenation with the addition of hydrogen.4244 Because
of the advantages of easy recovery and reusability of solid
catalysts, heterogeneous processes have been taking priority
over homogeneous catalytic processes. In addition, increasing
endeavors are being made to integrate the two- or multi-step
batch processes into a one-pass continuous conversion by using
well-designed multifunctional catalysts with an expectation to
transform lignocellulosic biomass into various commodity
chemicals in an ecient and environmentally friendly way
(Scheme 2, Route B).45
5591
Typical hydrolysis of lignocellulosic biomass or pure cellulose with H2O over liquid acid catalysts
Table 1
Catalyst
Feedstock
Reaction conditions
Typical products
Yield (%)
Researchers/Year
Ref.
Wood chips
Xylose
47.054.0
Emmel et al./2003
57
Filter paper
Reducing sugar
46.6
Zhuang et al./2006
53
Cotton
483 K, 2 min
B1.9 MPa
488 K, 35 min
4 MPa (H2O)
473 K, 6 min
0.1 MPa
144
Corn cobs
42.2
26.9
8.8
25.0
Kawamoto et al./2007
Levoglucosenone
Furfural
5-HMF
Xylose
Rivas et al./2008
55
Hu et al./2010
56
De Bari et al./2007
58
Liu et al./2006
59
Sugar maple
wood extract
SO2 impregnation
Aspen chips
HCl (5 wt%)
Walnut shells
Cellulose
Oxalic(0.1M) + NaCl
Cellulose
Cellulose
Cellulose
Potato peel
368 K, 50 min
0.1MPa
478 K, 3 min
1.62 MPa (H2O)
523 K, 430 min
1.58.6 MPa (H2O)
378 K, 24 h
533 K, B2 min
2025 MPa CO2,
373 K, 5 h
408 K, 8 min
403 K, 6 h
3 MPa CO2
1
Xylose
Glucose
Rhamnose
Mannose
Galactose
Glucose
Xylose
Levulinic acid
161.6 g L
13.3 g L1
12.4 g L1
12.9 g L1
5.6 g L1
37.0 (wt%)
10.3 (wt%)
12.0
Glucose
HMF
Glucose
B90.0
57.0
B11.0
Binder et al./2010
68
Rogalinski et al./2008
64
Reducing sugar
35.0
Rinaldi et al./2008
90
Reducing sugar
82.5
Lenihan et al./2010
60
Glucose
2.83.9
67
5-HMF: 5-hydroxymethyl-2-furfural. Reducing sugar: mainly mono- and disaccharides with an aldehyde or a ketone group. [EMIM]Cl: 1-ethyl-3methylimidazolium chloride. C4MIMCl: 1-butyl-3-methylimidazolium chloride.
Table 2
Catalyst
Feedstock
ACSO3H + COOH + OH
Cellulose
ACSO3H + COOH + OH
Cellulose
ACSO3H
Cellulose
Cellulose
BCSO3H
Cellulose
HNbMoO6
Cellulose
H3PW12O40
Cellulose
H3PW12O40
CrCl3/LiCl + [C4MIM]Cl
Cellulose
+CH3OH
Cellulose
Naon/silica
Cellulose
Sulfonated silica/carbon
nanocomposites
Cellouse
Reaction conditions
Typical products
373 K, 3 h
373 K, 3 h
423 K, 24 h
Glucose
b-1,4-glucan
Glucose
b-1,4-glucan
Glucose
423 K, 24 h
MW (350 W),
373 K, 1 h
403 K, 12 h
453 K, 2 h
r473 K, 0.5 h
3 MPa
433 K,10 min
463 K, 24 h
423 K, 24 h
Yield (%)
a
Researchers/Year
Ref.
Suganuma et al./2008
82
Yamaguchi et al./2009
78
Onda et al./2008
79
Glucose
4.0
64.0
B8.1b
0.93
40.5
(C-%)
61.0
Pang et al./2010
83
Glucose
19.8
Wu et al./2010
81
Glucose
21.0
Takagaki et al./2008
88
Glucose
Levulinic acid
HMF
Methyl Glucosides
50.5
0.14
1.6
50.060.0
Tian et al./2010
86
Deng et al./2010
94
5-HMF
62.3
Wang et al./2011
89
Glucose
Levulinic acid
Glucose
9.0
2.0
50.0
Hegner et al./2010
76
73
AC: Active carbon. BC: Biomass char. [C4MIM]Cl: 1-butyl-3-methylimidazolium chloride. MW: Microwave-assisted. a catalyst: 0.300 g; cellulose:
0.025 g; distilled water: 0.7 g. b catalyst: 0.300 g; cellulose: 0.25 g; distilled water: 2.25 g.
Scheme 3 Possible products from acid-catalyzed hydrolysis of cellulose.90 Adapted and reprinted with permission from ref. 90. Copyright 2008
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
5593
Scheme 4
Schematic mechanism of breakage of 1,4 0 -b-glycosidic bonds and formation of glucose in the hydrolysis of cellulose.
Fig. 2 Catalytic hydrolysis of cellulose over various solid acid catalysts at 423 K. Reaction conditions: milled cellulose 45 mg, catalyst
50 mg, distilled water 5.0 mL, 24 h.79 Ref. 79Reproduced by
permission of the PCCP Owner Societies.
5595
The 50 wt% co-solvent of either methanol-water or ethanolwater was found to be an eective mixed solvent for the
liquefaction of eastern white pine sawdust.
Comparatively, the dissolution of lignin and hemicellulose is
easier than that of cellulose owing to the abovementioned
dierences in their chemical structure. Therefore, the solvolysis and degradation of cellulose might be worth being
emphasized in the catalytic solvolysis of lignocellulosic biomass. Yamada et al.96 conducted the acid-catalyzed solvolysis
of cellulose using ethylene carbonate (EC) as an organic
reagent and 97% H2SO4 as catalyst. In comparison with
solvolysis by using polyethylene glycol (PEG), using EC as
a solvolysis reagent lead to a faster reaction rate. It was
suggested that cellulose with EC led rst to the formation of
glucosides, which then decomposed to form HMF derivatives
or levulinic acid as intermediates.96 In particular, HMF
derivatives could be either decomposed or polymerized to
form an insoluble fraction of products. Thereby, to obtain a
desired levulinic acid, how to control the formation of HMF
derivatives might be a critical issue. The solvolysis of lignocellulosic biomass can even proceed in the absence of catalyst
under hydrothermal conditions. The results showed that the
solvent such as acetone, ethylene glycol and toluene have a
profound eect on solvolytic product.97 In addition, solvolysis
can also be used to deal with intermediates from deploymerization or degradation of lignocellulosic biomass, for example
5-HMF, and levulinic acid.98 Thereby it might be applied to
acceleration of a catalytic solvolysis process mainly through
the solvolysis of intermediates.
Recently, Liu et al.99 investigated microwave-assisted organosolvolysis by a pretreatment of recalcitrant softwood in
aqueous glycerol with a series of organic and inorganic acids
with dierent pKa values including sulfuric, hydrochloric acid,
phosphoric, malonic, acetic, citric and lactic acids. It was
found that the eciency of pretreatment correlated linearly
with the pKa of the acids except malonic and phosphoric acids.
Noticeably, the organic acids, for example carboxylic acids,
could act simultaneously as the solvent, the reactant and the
catalyst. Moreover, organic acids can be possibly recovered
and reused by distillation or extraction. In addition to common organic acids like the carboxylic acids and sulfonic acids,
organic compounds bearing an OH or SH group might also
have certain acidity. Thus specic organic compounds can be
judiciously selected for both catalysis and solvolysis of lignocellulosic biomass. The method could provide an economical
alternative route to the selective conversion of cellulose to
small organic molecules.
5597
Table 3
Catalyst
Feedstock
Cellulose
573 K, 120 s
Lactic acid
Cellulose
523 K, 180 s (in N2) Glucose
LaCl3 (0.01 M)
5-HMF
Levulinic acid
Cellulose
423 K, 5 h
Acetic Acid
La/Al2O3 (0.34 wt%)
Malic Acid
Cellulose
573 K, 120 s
Lactic Acid
CoSO4 (400 ppm)
MW (400 W)
5-HMF
CrCl3 (3.6 wt%) + [C4MIM]Cl Cellulose
2 min, 0.1 MPa
Reducing sugar
Pine wood
MW (400 W)
5-HMF
CrCl36H2O+ [C4MIM]Cl
3 min, 0.1 MPa
Furfural
Cellulose
393 K, 8 min
5-HMF
CuCl2/CrCl2 + EMIM]Cl
Sorbitol
Cellulose
473 K, 3 h
Levulinic acid
CrCl3 (0.02 M)
Cellulose
608 K, 4.7 s
bio-oil
K2CO3 (0.5 wt%)
27.6 MPa
Empty palm
543 K, 20 min
Phenolic compounds
K2CO3 (1.0 M)
fruit bunch
2 MPa (H2O)
Corn stalk
647 K
bio-oil
Na2CO3 (1.0 wt%)
25 MPa (H2O)
Woody biomass
653 K, 1620 min
Heavy oil
Na2CO3
8 MPa (H2)
Sawdust
553 K, 15 min
Oil
Ca(OH)2 (0.0243 M)
KOH (0.5 M)
Walnut shells
523 K, 430 min,
Phenolic compounds
1.58.6 MPa
Lignin
573 K, 1 h
Phenolic compounds
Ba(OH)2 or Rb2CO3
2 MPa, H2
and oils
Ba(OH)2 or Rb2CO3
Sawdust/cornstalks 573 K, 1 h
Phenolic compounds
2 MPa, H2
and oils
Waste biomass
673 K, 10 min
Oil
K2CO3 + ZrO2
22.1 MPa
Yield (%)
Researchers/Year
Ref.
B6.6
Kong et al./2008
109
5.8 (wt%)
19.2 (wt%)
2.3 (wt%)
4.0 (wt%)
8.0 (wt%)
B9.5
Seri et al./2002
108
Schutt et al./2002
103
Kong et al./2008
109
Li et al./2009
106
Zhang et al./2010
105
Su et al./2010
107
Peng et al./2011
104
N/a
Kumar et al./2008
124
N/a
Akhtar et al./2008
119
47.2 (wt%)
Song et al./2004
123
53.3
Qian et al./2007
122
9.3 (wt%)
N/a
Karagoz et al./2004
Liu et al./2006
115
59
B53
62.0
20.0
52.0
31.0
57.5
1.27
67.0
[EMIM]Cl: 1-ethyl-3-methylimidazolium chloride. [C4MIM]Cl: 1-n-butyl-3-methylimidazolium chloride. N/a: not available. MW: Microwave
irradiation. a data from reaction without catalysts, and the sum is the data with addition of catalysts.
Scheme 5 Main reaction pathways of degradation of major product, glucose, from cellulose hydrolysis over dierent catalysts.90,102 Adapted and
reprinted with permission from ref. 90. Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Adapted and reprinted from ref. 102,
Copyright 2008, with permission from Elsevier.
Scheme 6 Direct conversion of cellulose to 5-HMF catalyzed with CrCl3 in [C4MIM]Cl (n = 13).106 [C4MIM]Cl: 1-n-butyl-3-methylimidazolium chloride. Reprinted from ref. 106, Copyright 2009, with permission from Elsevier.
and product distribution.113,128 As for the eect of temperature on the reaction rate and the product distribution, for
example, earlier Minowa and co-workers114 showed that in the
presence of 0.826 wt% Na2CO3 under 3 MPa, the decomposition of cellulose started at a reaction temperature lower
than 453 K. Only water-soluble products were obtained at
temperatures below 533 K. The cellulose decomposed quickly
at 533573 K. Bio-oil was formed at temperatures above
533 K and its yield reached the highest values at 593613 K.
Chem. Soc. Rev., 2011, 40, 55885617
5599
Scheme 7 Mechanism of cellulose decomposition promoted in homogeneous and heterogeneous environments in subcritical water. High heating
rates result in glucose char without catalyst, but more oil with Na2CO3 catalyst, and more gas with Ni catalyst.121 Reprinted with permission from
ref. 121. Copyright 2004 American Chemical Society.
5601
The fast pyrolysis reaction of lignocellulosic biomass undergoes a complex mechanism in oxygen-decient conditions at
high temperature, even though the reaction is conducted in an
inert atmosphere. Therefore, presently the investigation into
the mechanism could be simplied through the single use of
cellulose or lignin in a non-catalytic system. As shown in
Scheme 9, earlier Luo et al.137 proposed a fast pyrolysis
model of cellulose in an inert nitrogen atmosphere. Hydroxyacetaldehyde and 1-hydroxy-2-propanone was thought to
be produced from the decomposed fragments of activated
cellulose by competing against levoglucosan formation.
Meanwhile, the intermediate fragments might also decompose
to yield gases (COx). At low temperature, activated cellulose
would also directly decompose to produce char, CO2, and
H2O. A long residence time of intermediates like levoglucosan
in the reactor could lead to the secondary cracking reaction,
thereby leading to the formation of methanol, aldehyde, allyl
alcohol, glyoxal, furfural, 5-HMF and gases.
Regarding the gas products, a possible mechanism for fast
pyrolysis of cellulose in an inert gaseous atmosphere was
proposed by Lanza and co-workers recently,138 with the
following simplied decomposition sequence:
Cellulose - Gm, H2O
(2)
(3)
Cn - CH4
(4)
(5)
Table 4
Feedstock
Catalyst
Reaction conditions
Typical products
Yield (%)
Researchers/Year
Ref.
No
Vacuum pyrolysis
773 K
N/a
Garcia-Perez et al./2007
134
Cellulose
No
135
No
20.045.9
12.5-27.4
60
Piskorz et al./2000
Karagoz/2009
136
Cellulose
No
N/a
Lanza et al./2009
138
Cellulose
0.1wt% sulfuric or
polyphosphoric acid
144
Dobele et al./2005
142
Dobele et al./2005
142
Pretreated by 1wt%
phosphoric acid
Pretreated by 1%
phosphoric acid
NaOH
Chen et al./2008
146
Na2CO3
Chen et al./2008
146
Fe2(SO4)3
Chen et al./2008
146
Cellulose
ZSM-5
Carlson et al./2008
152
Pine sawdust
H-ZSM-5
Olazar et al./2000
150
Wood
Ni-ZSM-5
42.2
26.9
8.8
33.6
14.1
25.2
29.8
53.3
0
2.08(area%)
45.28
1.03
2.58
0
50
0
31.1 (C%)
Kawamoto et al./2007
Wood
Flash pyrolysis
11231473 K, 3575 ms.
Pyrolysis, 773 K
Under N2 ow
Fast pyrolysis
1173 K, Z 3 h
Pyrolysis in tetramethylene
sulfone, 473 K, 6 min,
Under N2 ow
Fast pyrolysis, 773 K
Under He ow
Fast pyrolysis, 773 K
Under He ow
Fast pyrolysis, 773 K
Microwave heating
Parans, sterols
Fatty acid methyl
esters
Soluble solids
Liquid product
Liquid product
French et al./2009
151
Cellulose
15.2 (C%)
15.9
16
3.5
Scheme 9 Modied model of fast pyrolysis of cellulose.137 Adapted and reprinted with permission from ref. 137. Copyright 2004 American
Chemical Society.
5603
Gasication is usually referred to as a process of oxygendecient thermal decomposition of carbonaceous matter such
as coal, petroleum, biofuel, or lignocellulosic biomass with a
major objective to produce valuable gaseous products like
hydrogen or syngas.153155 In particular, the production of
hydrogen, an environmentally clean fuel, from cellulosic
biomass gasication is of much interest to scientists and
engineers. Through FischerTropsch synthesis techniques,
bio-syngas can also be converted into synthetic liquid fuels
and classied as clean and renewable transportation fuels.156
In this context, gasication plus FischerTropsch synthesis are
denoted as indirect liquefaction processes of ignocellulosic
biomass. Gasication of lignocellulosic biomass can also be
This journal is
Org+ refers to an intermediate from the decomposed lignocellulosic biomass. According to such a proposition, CO was
formed through the cyclic oxidation-reduction reaction of
RuO2 with intermediate organics compounds (Org) and then
hydrogen was generated from the reduction of water by Ru2+
(eqn (7) and (8)). The hydrogen and CO could reacted to form
methane (eqn (9) and (10)).
CO + 3H2 - CH4 + H2O
(9)
(10)
RuO2 + Org - Ru
2+
+ Org
+ 2CO
(7)
(8)
3nH2 O
11
5605
Some typical reaction conditions and results in catalytic gasication of cellulose or lignocellulosic biomass in the presence of steam
Table 5
Catalyst
Reactants
Reaction conditions
Typical products
Yield (%)
Researchers/Year
Ref.
Ru/TiO2 (2 wt%)
Cellulose + H2O
44.0
9.0
24.0 (wt%)
171
Sawdust + H2O
CH4
H2
H2
Osada et al./2004
Ru/C (5 wt%)
673 K, 15 min
1 MPa (argon gas)
773 K, 20 min
27 MPa (N2)
723 K, 2 h
44 MPa (argon gas)
623 K, 10 min
30 MPa (N2)
623 K, 3 h
30 MPa (N2)
1106 Ka, 60 ms
0.1 MPa (N2/O2 = 3.76)
623 K, 30 min or 1 h
18 MPa (N2)
973 K, in N2
10231063 K
Air-blown bubbling
Hao et al./2005
173
Izumizaki et al./2005
170
Usui et al./2000
178
Usui et al./2000
178
Dauenhauer et al./2007
188
Minowa et al./1999
192
Richardson et al./2010
Lahijani et al./2011
168
155
RuO2
Cellulose + H2O
Pt/Al2O3 (5 wt%)
Cellulose + H2O
Pd/Al2O3 (5 wt%)
Cellulose + H2O
Rh catalysts
Cellulose + H2O
Ni/SiO2Al2O3
(50 wt%)
Ni NP
Cellulose + H2O
Wood
Palm empty fruit
bunch
CH4
H2
H2
CH4
H2
CH4
H2
CO
CO2 + H2 + CH4
32.1
13.7b
31.3
9.2 (vol%)
42.3
7.7 (vol%)
B52.0
B49.0
88.1
H2-rich gas
Gas
N/a
1.76 m3 gas kg1
biomass
(12)
decomposition
! gasesH2 CO
Ni
13
methanation
! gasesCH4 CO2
Ni
Integrated hydroprocessing
5607
Integrated hydrolysis with hydroprocessing in the conversion of cellulose over supported catalysts
Table 6
Catalyst
Reactants
Reaction conditions
Main products
Yield (%)
Researchers/Year
Ref.
Cellulose + H2O + H2
Sorbitol
0.7
Fukuoka et al./2006
205
Ru/PVP (1 wt%)
Cellobiose + H2O + H2
23.18
1.4
39.3
202
Cellulose + H2O + H2
Sorbitol
Glucose
Hexitols
Yan et al./2006
Ru/C (4 wt%)
Luo et al./2007
206
Ru/C
Cellulose + H2O + H2
Geboers et al./2010
209
Cellulose + H2O + H2
Fukuoka et al./2006
205
Pt/PVPb (1 wt%)
Cellobiose + H2O + H2
Yan et al./2006
202
Cellulose + H2O + H2
Ji et al./2008
214
Pt/g-Al2O3
Cellulose + H2O + H2
Jolle et al./2009
204
HRuCl(CO)(PPh3)3, Rh/C
Cellulose + H2O + H2
Ignatyev et al./2010
208
2%Ni30%W2C/AC
Cellulose + H2O + H2
Ji et al./2008
214
Ni/carbon ber
Cellulose + H2O + H2
15%
14%
65
27
25
6
18.5
42.6
9.5
6.0
14.2
15
o1
26
74
3.9
1.9
61.0
50.0
6.2
12.8
2.5
211
Cellulose + H2O + H2
EG
1,2-PD
Polyol
Sorbitol
Sorbitol
Mannitol
Sorbitol
Glucose
Sorbitol
Mannitol
EG
Sorbitol
Glucose
Glucose
Sorbitol
Sorbitol
Mannitol
EG
Sorbitol
Mannitol
Erythritol
EG
Deng et al./2010
463 K, 24 h
5 MPa (H2)
393 K, 12 h
4 MPa (H2)
518 K, 30 min
6 MPa (H2)
498 K, 5 min
6 MPa (H2) + CH3OH
463 K
5MPa (H2)
463 K, 24 h
5 MPa (H2)
393 K, 12 h
4 MPa (H2)
518 K, 30 min
6 MPa (H2)
de Vyver et al./2010
212
463 K, 24 h
5 MPa (H2)
423 K, 48 h
3.5 MPa (H2) + C4MIMCl
518 K, 30 min
6 MPa (H2)
463 K, 24 h
6 MPa (H2)
HUSY: H form of ultrastable Y zeolite. PVP: poly(Nvinyl-2-pyrrolidone). EG: ethylene glycol. PD: propanediol.
Scheme 10 Catalytic conversion of cellulose into polyols by integrated hydrolysis and hydrogenation.206,214 Adapted and reprinted with
permission from ref. 206. Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Adapted and reprinted with permission from
ref. 214. Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Scheme 11 Cellulose structure and the potential monomers formed following cleavage of the COC bonds at positions a or b.202 Reprinted with
permission from ref. 202. Copyright 2006 American Chemical Society.
as the selectivity to polyols, especially sorbitol.203,204 Moreover, in most cases, the hydrolysis reaction could be a
rate-determining step.203207 Thus an ecient conversion of
cellulose into polyols can be realized through a combination of
hydrolysis and hydrogenation over such a class of bifunctional
supported metal catalysts.
In addition to Pt/g-Al2O3, on the surface of a carbonsupported Ru cluster (Ru/C) catalyst, H+ ions could also be
reversibly formed in situ in hot water, thereby resulting in both
catalytic hydrolysis and instantaneous hydrogenation.205,206
Moreover, integrated depolymerization of cellulose and
hydrogenation can be carried out using ionic liquid C4MIMCl
as a solvent in the presence of hydrogen.207 For example,
Ignatyev et al.208 recently discovered that the combination of a
heterogeneous metal catalyst and a homogeneous Ru catalyst
proved to be eective in such a process in the ionic liquid,
possibly because the Ru compound can enhance the transfer of
hydrogen to the metallic surface.
In addition, heteropoly acids together with supported noble
metal catalysts exhibit good performances in the conversion of
lignocellulosic biomass into valuable platform chemicals via
combined hydrolysis and hydrogenation.209 More recently,
Palkovits et al.210 showed that heteropoly acids together with
supported Ru catalysts show not only high activity but also
remarkable selectivity for sugar alcohols reaching up to 81%
yield of C4 to C6 sugar alcohols at 433 K for 7 h. Noticeably,
over supported Ru catalysts in the presence of basic solution,
an integrated one-pot conversion of cellulose could be developed to produce valuable specic polyols such as ethylene
glycol(EG), 1,2-propanediol, and 1,2,5-pentanetriol.211
Ni supported onto carbon is also an alternative catalyst
for a one-pot process of catalytic cellulose to polyols.212
Interestingly, a series of bimetallic catalysts including Ru-W/
AC, Ir-W/AC, Pd-W/AC, Pt-W/AC, Ni-W/SiC, and Ni-W/
TiO2 proved to be highly active and selective for the formation
of EG from cellulose.213 W was considered as a key component for degradation of cellulose, namely, the CC cracking
reactions, while the transition metals were mainly responsible
for the hydrogenation reactions of unsaturated intermediates.
Recently, Ji et al.214 demonstrated that supported tungsten
carbide catalysts can replace supported noble metal-based
catalysts to catalyze the degradation of cellulose. Moreover,
the use of Ni-W2C/AC catalysts showed remarkable selectivity towards EG with a yield up to 61 wt% after 30 min at
518 K and 6 MPa H2. In addition to integrated hydrolysis and
This journal is
5609
Scheme 12 (A) Reaction scheme and key performance factors for the individual process steps in the formation of valeric biofuels (S: selectivity,
[mol%]; P: productivity, [tproductm3reactorh1]; and C: concentration, [wt%]). LA: levulinic acid; gVL: g-valerolactone; VA: valeric acid; EV: ethyl
valerate; EG: ethylene glycol; PG: propylene glycol; IER: acidic ion-exchange resin. (B) Probable reaction mechanism for the conversion of gVL to
VA over bifunctional catalysts. MTHF: methyl tetrahydrofuran; Pe: 1-pentanol; PV: Pentyl valerate; PeOH: 1-pentanol.218 Adapted and reprinted
with permission from ref. 218. Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
(3) Ecient production of liquid hydrocarbons from lignocellulosic biomass. Firstly, because liquid hydrocarbons can be
directly used in current engines, there is no need for building new
infrastructure for distribution. Secondly, if lignocellulosic biomass
is to replace fossil oils mostly or even completely, similar to
current petroleum industry, the large-scale process of lignocellulosic biomass should, for the most part, produce hydrocarbon-based liquid fuels. In addition to platform chemicals
and ne chemicals, the identication of certain specic chemicals
in the conversion of lignocellulosic biomass as a new type of fuels
or fuel additives is also of much signicance.228,229
All in all, to make the catalytic conversion of lignocellulosic
biomass into valuable products practicable is one of the most
important topics in chemistry. It involves many challenges and
opportunities. Though the studies on the chemocatalytic conversion of cellulose have received intensive attention over the
past few decades and many breakthroughs have been achieved
therein. A noteworthy thing is that besides cellulose, lignocellulosic biomass contains hemicellulose and lignin which are
Chem. Soc. Rev., 2011, 40, 55885617
5611
Acknowledgements
We thank anonymous reviewers for thoroughly reading the
manuscript, providing thoughtful, valuable suggestions and
comments on the early version of this manuscript, which
almost lead to a new version. We would like to thank the
Publishers for granting permissions to reproduce copyright
materials cited or adapted in this manuscript. The results and
illustrations are credited to the original researchers to whom
we would like to express our gratitude. The authors wish to
acknowledge the nancial support from the Distinguished
Young Scholar Grants from the Natural Scientic Foundation
of Zhejiang Province (R4100436), the National Natural
Scientic Foundation of China (20773110, 20541002), Zhejiang
151 talents project, and Project (2009C14G2020021) from
Science and Technology Department of Zhejiang Provincial
Government for the related research and development. The
authors wish to acknowledge the support of the School
of Chemical Engineering and ARC Centre of Excellence
for Functional Nanomaterials, AIBN in the University of
Queensland during the preparation of this work.
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