Catalytic Conversion of Lignocellulosic Biomass To Fine Chemicals and Fuels

5588 Chem. Soc. Rev.
, 2011, 40, 55885617 This journal is c The Royal Society of Chemistry 2011
Cite this: Chem. Soc. Rev., 2011, 40, 55885617
Catalytic conversion of lignocellulosic biomass to ne chemicals and fuels
Chun-Hui Zhou,*
a
Xi Xia,
a
Chun-Xiang Lin,
b
Dong-Shen Tong
a
and Jorge Beltramini
b
Received 5th May 2011
DOI: 10.1039/c1cs15124j
Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for
sustainable production of chemicals and fuels. This critical review provides insights into the state-of
the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals
from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis,
solvolysis, liquefaction, pyrolysis, gasication, hydrogenolysis and hydrogenation are the major processes
presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and
various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast
pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasication is
typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are
the prime factors that aect the yield and composition of the target products. Most of processes yield a
complex mixture, leading to problematic upgrading and separation. An emerging technique is to
integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to
convert lignocellulosic biomass to value-added ne chemicals and bio-hydrocarbon fuels. And the
promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still
exist technological barriers that need to be overcome (229 references).
1 Introduction
The depletion of fossil fuel resources and the resulting adverse
eects on the global environment and climate are of major
academic, economic and political concern worldwide.
13
As supplies of fossil fuels and related petrochemicals may soon
be limited, alternative solutions are sought. One alternative is to
a
Research Group for Advanced Materials & Sustainable Catalysis
(AMSC), Breeding Base of State Key Laboratory of Green
Chemistry Synthesis Technology, College of Chemical Engineering
and Materials Science, Zhejiang University of Technology,
Hangzhou, 310032, China. E-mail: catalysis8@yahoo.com.cn,
chc.zhou@yahoo.com.cn
b
The School of Chemical Engineering, ARC Centre of Excellence for
Functional Nanomaterials, AIBN, The University of Queensland,
St. Lucia, QLD 4072, Australia
Chun-Hui Zhou
Dr Chun-Hui (Clayton) Zhou
is a Professor of Chemical
Engineering and Group
Leader of the Research Group
for Advanced Materials
and Sustainable Catalysis
(AMSC) at Zhejiang Univer-
sity of Technology as well as a
Member of the Editorial
Board of Applied Clay Science
(Elsevier). He worked as a
visiting Academic at the ARC
Center of Excellence for Func-
tional Nanomaterials, AIBN,
the University of Queensland
in 20062007 and as Visiting
Professor at the Centre for Strategic Nano-fabrication, the
University of Western Australia in 2010. His research interests
include clay-based materials for miscellaneous applications,
sustainable catalysis for fuels and chemicals from biorenewable
resources, process intensication and advanced biomaterials.
Xi Xia
Xi Xia has been a postgradu-
ate under the supervision of
Prof. Chun-Hui Zhou in the
Research Group for Advanced
Materials & Sustainable
Catalysis, Zhejiang University
of Technology (ZJUT) since
September, 2008. He obtained
his Bachelors Degree in
Chemistry from Nanyang
Normal University in 2008
and his Masters degree of
Industrial Catalysis at ZJUT
in 2011. His research interests
are in advanced clay-based
materials, catalysts and their
potential for the catalytic conversion of biomass into liquid fuels
and chemicals.
Chem Soc Rev
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This journal is c The Royal Society of Chemistry 2011 Chem. Soc. Rev., 2011, 40, 55885617 5589
develop a series of novel chemical processes based on renewable
feedstocks, typically biomass
4
and biomass-derived chemicals.
57
Biomass generally refers to organic materials such as wood,
grass, algae, agricultural crops and their residues and wastes,
including some animal waste.
8
All of these materials originally
result from biological photosynthesis from readily available
atmospheric CO
2
, water and sunlight. Therefore, biomass is a
sustainable and green feedstock for the production of fuels and
ne chemicals with net zero carbon emission.
Biochemically, living systems produce a large number
of organic molecules such as carbohydrates, fats and oils,
phospholipids and glycolipids, waxes, steroids, proteins and
nucleotides. Among them, carbohydrates are the primary
energy-storage molecules. Carbohydrates are the main struc-
tural components of the cell walls of plants, in which the
carbohydrate polymers, namely cellulose and hemicellulose,
are tightly bound to the lignin.
9
Any materials rich in cellulose,
hemicelluloses, and lignin are commonly referred to as ligno-
cellulosic biomass.
10
For example, wood, bamboo, grass and
their derived pulp and paper, and agricultural residues like
corn stover and sugarcane bagasse are typical sources of
lignocellulosic biomass.
Lignocellulosic biomass has received intensive attention
over the past decade. Many studies have shown that ligno-
cellulosic biomass oers great potential to be used as a renewable
feedstock in abundance with easy availability.
1114
Fig. 1 displays
the weight percentage of cellulose, hemicellulouse and lignin in
some typical biological sources such as pinaster,
15
eucalyptus
globules,
15
wheat straw,
16
sorghum stalks,
17
bamboo
18
and
banana pseudo-stems.
19
Generally, most of the lignocellulosic
biomass contains 3550% of cellulose, 2035% of hemi-cellulose,
and 1025% of lignin. Clearly, the major component of ligno-
cellulosic biomass is cellulose. It is estimated that nearly half of
the organic carbon in the biosphere is present in the form of
cellulose. Therefore, in the context of processing lignocellulosic
biomass into fuels and valuable chemicals, the conversion of
cellulose is of paramount importance and worth being given
priority.
1114
The development of the processes to convert lignocellulosic
biomass to fuels and value-added chemicals, however, remains
a big challenge. Firstly, the complex chemical composition of
lignocellulosic biomass makes it dicult to yield target fuels
and chemicals in a high yield and quality. Comparatively, as
to the three main components in lignocellulosic biomass,
the structure of cellulose is the simplest and most ordered.
Cellulose consists of only anhydrous glucose units, while
hemicelluloses contain many dierent sugar monomers. Con-
sequently, cellulose is crystalline and hemicellulose just has a
random, amorphous structure. Dierent from carbohydrate-
based cellulose and hemicellulose, lignin is a class of complex,
cross-linked, three-dimensional biopolymers with phenyl-
propane units with relative hydrophobic and aromatic properties.
Those dierences in the chemical composition and structure in
lignin, hemicellulose and cellulose lead to their much dierent
reactivity. On one hand, for example, the decomposition of lignin
and hemicellulose is generally easier than that of cellulose.
20,21
In other words, the decomposition and degradation of cellulose is
the most dicult and energy-consuming step in the conversion of
lignocellulosic biomass. As a result, to improving the reactivity of
cellulose is a rst critical point. On the other hand, based on
their dierent reactivity, it is feasible to separate cellulose and
hemicellulose from lignin.
22,23
Therefore, as reported in the
literature and discussed below, besides using the natural ligno-
cellulosic biomass as the reactants, many researchers often choose
pure cellulose, in particular microcrystalline cellulose, as a model
of lignocellulosic biomass.
Over decades, many researchers have endeavored to explore
the production of fuels and chemicals from cellulose, which
is representative of lignocellulosic biomass.
24,25
A cellulose
molecule has the generic chemical formula (C
6
H
12
O
5
)
n
.
It consists of a skeletal linear polysaccharide, in which glucose-
based monomer units are jointed together through b-1,4-glyco-
sidic linkages.
26
The glucose units are further tightly bound by
extensive intramolecular and intermolecular hydrogen bonding
networks (Scheme 1a). The chain length of a cellulose molecule
ranges from about 100 to 14000 units. Accordingly, cellulose has
an average molecular weight in the range of 300000500000.
27
Noticeably, cellulose exists in the form of a robust crystalline
structure. And it is the principle scaolding component of all
plant cell walls. Such a cell wall polymer is neither soluble in water
nor easily digestible in the gastrointestinal tract of humans.
The changes in the types of chemical bonding and the
crystalline structure in polysaccharides, however, have signi-
cant impacts on their physical properties and chemical
reactivity.
23
For example, starch is also a polysaccharide with
the same general formula (C
6
H
12
O
5
)
n
as cellulose. Neverthe-
less, in each starch(amylose) molecule the neighboring glucose
units are linked through the 1,4
0
-a-glycosidic bond (Scheme 1b)
or the 1,6
0
-a-glycosidic bond (amylopectin), rather than the
1,4
0
-b-glycosidic bond in each cellulose molecule.
28
This dier-
ence has a profound eect on the three dimensional structure
and reactivity of the biopolymer molecule. Such 1,4
0
-a-glycosidic
linkages in starch are more easily attacked by acids or enzymes.
Thereby in the presence of acids or enzymes as catalysts starch is
more easily deconstructed into glucose monomers than cellulose.
For instance, starch is more easily fermented to yield ethanol
than cellulose. This is one of the major reasons that starches are
currently used as the starting materials for commercial bio-
ethanol production, instead of cellulose.
29,30
Nonetheless, any
large-scale processing of starch to fuels and chemicals readily
brings about strong competition between chemical production
and food demands.
31
Therefore, in terms of both the abundance
Fig. 1 The weight percentage of cellulose, hemicelluloses and lignin in
some typical biological sources: pine pinaster,
15
eucalyptus globules,
15
wheat straw,
16
sorghum stalks,
17
bamboo
18
and banana pseudo-stems.
19
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5590 Chem. Soc. Rev., 2011, 40, 55885617 This journal is c The Royal Society of Chemistry 2011
and availability from bioresources and little impact on food
supply, cellulosic materials as feedstocks are more practicable
and sustainable for the production of fuels and commodity
chemicals. In this context, the catalytic conversion of cellulose
to fuels and chemicals is more attractive and promising than that
of any other form of biomass like starch to bioethanol and
vegetable oil to biodiesel.
3235
Still, lignocellulosic biomass such as wood, grass and agri-
cultural residues are conventionally used as energy sources
typically by direct combustion.
36
The principal utilization of
cellulose in industry is currently limited to textiles and paper
manufacturing.
37
In some biological processes such as fermen-
tation and enzymic catalysis, peculiar enzymes, bacteria and
other microorganisms are used to break down cellulose
molecules and thus a few commodity chemicals can be
obtained.
38,39
Nevertheless, such biological processes generally
suer from unsolvable problems such as low eciencies,
narrow reaction conditions and limited scale of produc-
tion.
39,40
Chemocatalytic conversion of cellulose has been
around for some time, but it only receives serious attention
with the advent of a series of novel chemocatalytic reaction
routes since the fossil oil crisis in the 1970s.
However, besides the complexity of biological sources,
the inert chemical structure and the compositional ratio of
carbon, hydrogen and oxygen in molecules in lignocellulosic
biomass produce additional diculties in the chemocatalytic
conversion of cellulose to valuable fuels and commodity
chemicals. In this context, the development of a new family
of highly active and selective catalyst systems is an essential
prerequisite for chemoselectively catalytic conversion of
lignocellulosic biomass to desired products.
41
As such, this
article attempts to summarize and review recent advancements
in the dierent catalytic processes for the conversion of
lignocellulosic biomass, in particular cellulose, into potential
fuels and commodity chemicals.
Scheme 2 lists some typical ne chemicals and fuels which
can be produced by chemocatalytic conversion of cellulose
by dierent chemical processes. Clearly, a variety of fuels,
including ethanol, hydrogen, methane and chemicals such as
glucose, fructose, sorbitol, levulinic acid and lactic acid can be
obtained from catalytic conversion of lignocellulosic biomass.
Lignocellulosic biomass can also be used to produce syngas
(CO + H
2
) which can then be transformed into fuels and
myriad chemicals.
In many instances, depolymerization and hydrolysis of
cellulose to monomer glucose is regarded a necessary rst step.
Then glucose is further catalytically degraded into various
intermediates, chemicals and fuels (Scheme 2, Route A). Recent
research has paid much heed to accelerating the conversion
of lignocellulosic biomass in the presence of multifunctional
catalysts. The typical processes can be categorized as direct
liquefaction, gasication and aqueous-phase reforming,
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.
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pyrolysis. An emerging trend is to integrate catalytically thermo-
chemical 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
2 Catalytic hydrolysis of lignocellulosic biomass
Lignocellulosic biomass with cellulose as a main component is
generally resistant to hydrolysis in water. As such, the hydro-
lysis of cellulose in lignocellulosic biomass usually involves the
use of strong liquid acids as catalysts. Cellulose hydrolysis in
the presence of acids primarily yields reducing sugars, which
are a class of compounds that have an open chain with an
aldehyde or a ketone group. Typically, glucose and xylose are
obtained. Interests in such acid-catalyzed hydrolysis have been
reignited because many ne and even platform chemicals can
be obtained from further conversion of reducing sugars.
Moreover, using a multistep fractionation process, various
ne chemicals and potential fuels can also be directly obtained
from acid processing of lignocellulosic biomass.
46
Neverthe-
less, instead of the traditional use of liquid acids, nowadays
much attention is given to the use of solid catalysts such as
solid-supported Brnsted or Lewis acid reagent catalysts, acid-
modied amorphous carbon, layered transition metal oxides,
and acidic resins for the depolymerization of lignocellulosic
biomass by hydrolysis (Tables 1 and 2).
2.1 Liquid acid-catalyzed hydrolysis
Acid-catalyzed hydrolysis of cellulose is a reaction in which
hydrogen cations (H
+
) and hydroxide anions (OH
) from the
splitting of molecules of water react with polymeric cellulose
molecules, thereby yielding hydrolytic products by depolymer-
ization. The discovery of such an acid-catalyzed reaction of
cellulose hydrolysis has a relatively long history.
5577
Commer-
cial microcrystalline cellulose is just a slightly depolymerized
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).
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product of cellulose by liquid acid-catalyzed hydrolysis.
47,48
More importantly, various products such as glucose, xylose,
arabinose and cellobiose and oligosaccharides can be readily
formed from liquid acid-catalyzed hydrolysis of cellulose
(Scheme 3).
Both inorganic liquid mineral acids such as H
2
SO
4
and HCl,
and organic acids such as various carboxylic acids and
p-toluenesulfonic acid can be used as catalysts for the hydro-
lysis of cellulose. Various types of lignocellulosic biomass, for
example wood chips, sawdust, corn-cobs, and walnut shells,
have been tentatively processed by the liquid acid-catalyzed
hydrolysis (Table 1). However, it should be pointed out that
the hydrolysis mainly occurred in the cellulosic components in
these lignocellulosic sources with glucose and xylose as the
main products in most cases.
As summarized in Table 1, thus far H
2
SO
4
has been the
most frequently used liquid acid catalyst in the hydrolysis of
lignocellulosic biomass. The reaction is usually conducted
at temperatures in the range of 363533 K and under atmo-
spheric or higher pressure. In general, when a dilute acid
solution is used, higher temperature and longer reaction
time are necessary.
49
In turn, when the hydrolysis reaction of
cellulose is conducted at low temperature and in a short
reaction time, concentrated acid is favorable. The treatment
of cellulose in a concentrated acid solution remarkably
accelerates such biopolymer molecules to be depolymerized
to monomers.
50,51
Usually, the yield of reducing sugars
increases with increasing acid concentration. However, the
use of concentrated acid solutions could lead to a decrease of
the yield of glucose and xylose due to further degradation.
Consequently, there is a substantial increase in the amount of
products of further degradation of glucose or xylose, for
example 5-hydroxymethyl-2-furfural (5-HMF).
52
In addition,
taking into account the operation safety, equipment corrosion
and waste disposal, dilute acid is preferable for use in the
hydrolysis of cellulose.
53
Furthermore, as for catalytic perfor-
mances in the hydrolysis of lignocellulosic biomass with a high
content of hemicelluloses, dilute acid could be more eective
than concentrated acid.
54
The deep insights into the eect of pressure on the conver-
sion and distribution of products are scarcely reported.
However, it has been revealed that under atmospheric
pressure, catalytic hydrolysis of cellulose is also feasible with
both hydrolytic and dehydrated products.
56
Clearly, under
atmospheric pressure, higher temperature, concentrated acid
and longer residence time are favorable to eectively depoly-
merize and degrade lignocellulosic biomass.
The impregnation of lignocellulosic biomass with acid
solution can lead to partial destruction of the cellulosic parts
in lignocellulosic biomass. Thereby such a pretreatment can
facilitate their further hydrolytic reaction. For example,
Emmel and co-workers
57
reported that the pretreatment of
wood chips by impregnating them in 0.175 wt% H
2
SO
4
led to
the remarkable hydrolysis of hemicellulose after the dilute
acid-catalyzed hydrolysis at 483 K for 2 min in steam. Thus
a yield of xylose up to 70% of its theoretical yield was
obtained in the water-soluble fraction. In this case, the pre-
treatment temperature was found to inuence the yield of
xylose. Interestingly, impregnation with gaseous SO
2
proved
to be more eective than H
2
SO
4
since a higher yield of
Table 1 Typical hydrolysis of lignocellulosic biomass or pure cellulose with H
2
O over liquid acid catalysts
Catalyst Feedstock Reaction conditions Typical products Yield (%) Researchers/Year Ref.
H
2
SO
4
(0.175 wt%) Wood chips 483 K, 2 min Xylose 47.054.0 Emmel et al./2003 57
B1.9 MPa
H
2
SO
4
(0.05 wt%) Filter paper 488 K, 35 min Reducing sugar 46.6 Zhuang et al./2006 53
4 MPa (H
2
O)
H
2
SO
4
(0.1 wt%) Cotton 473 K, 6 min Levoglucosenone 42.2 Kawamoto et al./2007 144
0.1 MPa Furfural 26.9
5-HMF 8.8
H
2
SO
4
(0.5 wt%) Corn cobs 398 K, 165 min Xylose 25.0 Rivas et al./2008 55
H
2
SO
4
(6.2 wt%) Sugar maple
wood extract
368 K, 50 min Xylose 161.6 g L
1
Hu et al./2010 56
0.1MPa Glucose 13.3 g L
1
Rhamnose 12.4 g L
1
Mannose 12.9 g L
1
Galactose 5.6 g L
1
SO
2
impregnation Aspen chips 478 K, 3 min Glucose 37.0 (wt%) De Bari et al./2007 58
1.62 MPa (H
2
O) Xylose 10.3 (wt%)
HCl (5 wt%) Walnut shells 523 K, 430 min
1.58.6 MPa (H
2
O)
Levulinic acid 12.0 Liu et al./2006 59
HCl (20 wt%)/
+ [EMIM]Cl
Cellulose 378 K, 24 h Glucose B90.0 Binder et al./2010 68
HMF 57.0
CO
2
+ H
2
O
(100% saturation)
Cellulose 533 K, B2 min Glucose B11.0 Rogalinski et al./2008 64
2025 MPa CO
2
,
p-toluenesulfonic acid
+ C
4
MIMCl
Cellulose 373 K, 5 h Reducing sugar 35.0 Rinaldi et al./2008 90
H
3
PO
4
(10 wt%) Potato peel 408 K, 8 min Reducing sugar 82.5 Lenihan et al./2010 60
Oxalic(0.1M) + NaCl Cellulose 403 K, 6 h Glucose 2.83.9 Vom Stein et al./2010 67

3 MPa CO
2
5-HMF: 5-hydroxymethyl-2-furfural. Reducing sugar: mainly mono- and disaccharides with an aldehyde or a ketone group. [EMIM]Cl: 1-ethyl-3-
methylimidazolium chloride. C
4
MIMCl: 1-butyl-3-methylimidazolium chloride.
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glucose could be obtained.
58
It was suggested that the addition
of SO
2
catalyst (0.9% w/w dry raw material) reduced the
degree of polymerization of the cellulose by an average of
50%. In addition to the catalytic performances, another
noteworthy feature is that SO
2
is less corrosive than the
H
2
SO
4
solution.
In addition to reaction parameters such as temperature,
pressure, time and the concentration of acids, the type of acid
catalysts is also an inuential parameter for the distribution of
products in the catalytic hydrolysis of lignocellulosic biomass.
For example, in the presence of HCl acid in the hydrolysis
of walnut shells, the yield of levulinic acid could reach 12%.
59
This result might indicate that HCl acid as a catalyst could
promote further catalytic dehydration of hydrolytic compounds,
thereby resulting in the remarkable generation of levulinic
acid. Dilute phosphoric acid is also an alternative catalyst.
60
In a phosphate buer solution at pH 2, the hydrolysis and
dissolution of Japanese red pine wood chips under subcritical
water conditions yielded hydrolytic saccharides and such further
dehydrated products as 5-HMF and furfural.
61
It might indicate
that the presence of phosphate buer could play a pivotal role in
deep degradation of such a lignocellulosic biomass. However, in
the absence of a catalyst, water-soluble saccharides can also be
directly produced from the hydrolysis of lignocellulosic biomass,
for example sugi wood powder, in supercritical and subcritical
water.
62
Despite the relatively high catalytic activity of H
2
SO
4
, HCl
and H
3
PO
4
in the hydrolysis of cellulosic materials, by and large
their uses are still uneconomical because the process suers from
severe corrosion, costly separation and neutralization of waste
acids. These problems could be signicantly addressed provided
that carbonic acid (H
2
CO
3
), present in the form of a solution of
CO
2
in water, can be used as a catalyst.
63,64
First of all, carbonic
acid has little corrosive eect. Secondly, theoretically, it can be
Table 2 Typical hydrolysis of cellulose with H
2
O over solid acid catalysts
Catalyst Feedstock Reaction conditions Typical products Yield (%) Researchers/Year Ref.
ACSO
3
H + COOH + OH Cellulose 373 K, 3 h Glucose 4.0
a
Suganuma et al./2008 82
b-1,4-glucan 64.0
ACSO
3
H + COOH + OH Cellulose 373 K, 3 h Glucose B8.1
b
Yamaguchi et al./2009 78
b-1,4-glucan 0.93
ACSO
3
H Cellulose 423 K, 24 h Glucose 40.5 Onda et al./2008 79
(C-%)
ACSO
3
H (Sulfonation T = 523 K) Cellulose 423 K, 24 h Glucose 61.0 Pang et al./2010 83
BCSO
3
H Cellulose MW (350 W),
373 K, 1 h
Glucose 19.8 Wu et al./2010 81
HNbMoO
6
Cellulose 403 K, 12 h Glucose 21.0 Takagaki et al./2008 88
H
3
PW
12
O
40
Cellulose 453 K, 2 h Glucose 50.5 Tian et al./2010 86
Levulinic acid 0.14
HMF 1.6
H
3
PW
12
O
40
Cellulose r473 K, 0.5 h Methyl Glucosides 50.060.0 Deng et al./2010 94
+CH
3
OH 3 MPa
CrCl
3
/LiCl + [C
4
MIM]Cl Cellulose 433 K,10 min 5-HMF 62.3 Wang et al./2011 89
Naon/silica Cellulose 463 K, 24 h Glucose 9.0 Hegner et al./2010 76

Levulinic acid 2.0
Sulfonated silica/carbon
nanocomposites
Cellouse 423 K, 24 h Glucose 50.0 Van de Vyver et al./2010 73
AC: Active carbon. BC: Biomass char. [C

4
MIM]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.
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easily removed by depressurization and thus it does not
leave any waste acid catalysts after reaction. Therefore, such a
carbonic acid-catalyzed process is environmentally friendly.
Rogalinski et al.
64
reported that for the hydrolysis of cellulose
in subcritical water with pressurized CO
2
at 533 K, the yield of
glucose could be signicantly increased by the acidication of
CO
2
compared with that in pure water. Moreover, the onset of
the formation of glucose is shifted to a shorter residence time
due to the faster cleavage of 1,4
0
-b-glycosidic bonds facilitated
by carbonic acid. As for the catalytic mechanism, CO
2
is
believed to promote the hydrolysis reaction of cellulose by the
formation and then dissociation of carbonic acid in water to give
active H
+
cations, which then attack and break 1,4
0
-b-glycosidic
bonds in cellulose (eqn (1)).
63,64
CO
2
+ H
2
O !H
2
CO
3
!H
+
+ HCO
3
!2H
+
+ CO
2
3
(1)
The avoidance of the use of strong liquid acids oers an
alternative approach to develop a green acid-catalyzed pro-
cess. However, the insolubility of cellulose is another big
barrier that needs to be tackled. In this context, one possible
solution is to choose a suitable solvent. For instance, Recently
Lin et al.
65
investigated the hydrolysis and degradation of
cotton cellulose treated with 1.39% HCl acid either in water or
in ethanol at 338 K for more than 1 h. A higher yield of
hydrolytic products was obtained in ethanol (2.445.04%)
than in water (1.121.50%). Moreover, the eect of the
reaction temperature on the yield of hydrolytic products in
ethanol was much greater than that in water. The phenomena
could be ascribed to the fact that the solubilization of cellulose
is enhanced by ethanol. This might well explain why cellulose
was more easily deconstructed in ethanol than in water.
The other alternative solution is to use a mixture of inorganic
and organic acids as catalysts.
66
It has been found that
dicarboxylic acids, like oxalic and maleic acid, are able to
catalytically depolymerize cellulose, producing oligomers and
glucose.
67
The third solution is to use ionic liquids as the
solvent and/or as the catalyst. Recently Binder and Raines
68
reported a much eective process, in which water was gradu-
ally added to a catalytic system consisting of chloride ionic
liquid and acid catalysts (1-ethyl-3-methylimidazolium chloride,
[EMIM]Cl + H
2
SO
4
or HCl). This method led to a nearly 90%
yield of glucose from cellulose and 7080% yield of sugars from
corn stover in a few hours. In comparison to other conventional
solvents and organic acids, however, the high cost of ionic
liquids and the problematic reusability might still hinder its
scale-up to commercial use.
Finally, in the liquid acid-catalyzed hydrolysis, besides acidic
catalysts, solvents and reaction variables, the source of ligno-
cellulosic biomass is also an important factor. Obviously, the
molecular composition and arrangements of cellulose, hemi-
cellulose and lignin in the plant cell wall changes throughout the
life of the plant. Moreover, they dier among plant species,
among tissues of a single species and even among geographical
regions of the plant. The dierences of chain length and
hydrogen bonding pattern between amorphous hemicellulose
and crystalline cellulose, for example, greatly aected the
distribution of glucose and oligomers in the liquid products
after catalytic hydrolysis.
69
In addition, even the size of biomass
feedstock particles may also be one of the important parameters.
These are also common points worth consideration in any other
processes discussed below.
2.2 Solid acid-catalyzed hydrolysis
Compared with homogeneous catalysts, heterogeneous solid
catalysts have several advantages. In particular, solid catalysts
can be easily separated from the liquid mixture after the
reaction, thereby allowing the possible reuse of catalysts,
along with the minimization of corrosion. Moreover, solid
acid catalysts have the potential to be easily applied to a
continuous ow xed-bed reactor. These merits have stimu-
lated the research and development of recyclable solid acids as
replacements for the unrecyclable liquid acid catalysts in the
catalytic hydrolysis of lignocellulosic biomass.
7072
As such, several types of solid acids, such as Naon,
Amberlyst, SO
3
H functionalized amorphous carbon or
mesoporous silica, H-form zeolites like HZSM-5, hetero-
polyacids and even metal oxides (for example, g-Al
2
O
3
) have
been explored on their catalytic performances in the catalytic
hydrolysis of lignocellulosic biomass. It has been shown that
solid Brnsted acid catalysts are indeed applicable for the
ecient hydrolysis of lignocellulosic biomass.
74,75
Over solid
acid catalysts, the typical hydrolytic products like glucose
and xylose were also obtained, together with other chemicals
such as b-1,4-glucan, furfural, 5-HMF, and levulinic acid.
Furthermore, solid surface supported Lewis acid catalysts,
for example FeCl
3
supported onto amorphous silica, can also
catalyze the hydrolysis of cellulose to glucose and then to
levulinic acid even under relatively mild conditions.
76
How-
ever, in most cases, over solid catalysts the catalytic activity
and the selectivity to the desired products are quite low.
Therefore, a longer reaction time is needed to acquire the high
yield of glucose (Table 2), compared with liquid acid catalysts
(Table 1).
As shown in Scheme 4, a commonplace insight into the
hydrolysis reaction is that it involves the splitting of the
water molecule into hydrogen cations (H
+
) and hydroxide
anions (OH
). In the presence of cellulose, the H

+
attacks the
oxygen atom in the 1,4
0
-b-glycosidic linkage. Thus the 1,4
0
-b-
glycosidic linkage is broken to form a cyclic carbonium cation
with a chair shape. This step is considered as the rate-
determining step.
77
Finally, glucose is formed by rapid ion
transfer of OH
from the dissociation of water molecules to

the glucose unit-based carbonium cation. According to such a
reaction mechanism, that a solid acid catalyst and reaction
conditions favor the splitting of water will favor the hydrolysis
of cellulose. The splitting of a water molecule into hydrogen
cations (H
+
) and hydroxide anions (OH
) can be regarded as
deprotonation. It was discovered that the catalytic activity of a
catalyst in the hydrolysis of cellulose increases with a decrease
in the deprotonation enthalpy (DPE) of water on the surface
of the solid acid catalyst.
85
These ndings suggested that
stronger Brnsted acidity is more favorable to the catalytic
hydrolysis of cellulose. In addition, to some extent, an increase
in the amount of water had a positive eect on the breakage of
1,4
0
-b-glycosidic bonds and intramolecular hydrogen bonds in
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insoluble cellulose, thereby leading to more hydrolytic products.
Clearly, the formation of glucose requires more water than
the formation of b-1,4-glucan. Yamaguchi and co-workers
78
revealed that the amount of water comparable to the solid
catalyst weight could lead to a maximum yield of glucose in
the heterogeneous catalytic hydrolysis reaction of cellulose.
On the one hand, the conditions conducive to splitting of
water molecules are needed. On the other hand, the conditions
should help to avoid deep degradation. Therefore, mildly
hydrothermal conditions were found favorable to the produc-
tion of glucose from the hydrolysis of cellulose over solid acid
catalysts.
78,79
Among a series of typical solid acid catalysts like
H-form zeolite, sulfated zirconia, sulfonated activated carbon
and Amberlyst polymer- based materials (Amberlyst, a com-
mercially available sulfonated resin), as reported by Onda and
co-workers,
79
sulfonated activated carbon showed a remark-
ably high yield of 40.5% of glucose (Fig. 2). Over such
sulfonated activated carbon catalysts, a selectivity of higher
than 90% to glucose was obtained. The catalysts could act in a
way similar to sulfonic acids containing the group SO
3
H,
which has fairly strong acidity. The remarkably catalytic
properties can be ascribed to the strong acidity of SO
3
H
functional groups and the hydrophobic planes on the surfaces
of such a catalyst, as well as its high hydrothermal stability.
Such systematic evaluation of a series of catalysts provided
valuable information and clues for the design and preparation
of a class of eective solid acid catalyst for catalytic hydrolysis
of cellulose by adjusting its surface acidity and hydrophilicity/
hydrophobicity.
It is worth noting that lignocellulosic biomass itself can be
made into carbon materials by carbonization.
80
Bio-char or
activated carbon from lignocellulosic biomass such as bamboo,
wood, and coconut shells are well-documented catalyst sup-
ports. Microwave-assisted hydrolysis of cellulose in water over a
sulfonated bio-char acid catalyst (BC-SO
3
H) even showed a
much higher turnover number (TON, 1.331.73) compared to
that in dilute H
2
SO
4
solution (TON, 0.02).
81
The results were
likely due to the strong anity to 1,4
0
-b-glycosidic bonds of
cellulose on the surfaces of such catalysts, thereby accelerating
the activation of cellulose molecules. Microwave irradiation
could strengthen the collision of cellulose particles in the
reaction system. In addition, the surface of carbon solids can
be functionalized with several functional groups. For example,
Suganuma et al.
82
described that a modied amorphous carbon
material can simultaneously bear SO
3
H, COOH, and OH
groups by means of partial carbonization of cellulose, followed
by sulfonation of the resulting amorphous carbon (Fig. 3).
80
This strategy of catalyst preparation could eciently enhance
the performance of catalysts. Over such a catalyst, for example,
when the hydrolysis of microcrystalline cellulose was conducted
in a Pyrex reactor (catalyst = 0.300 g; cellulose = 0.025 g;
distilled water = 0.700 g) at 373 K for 3 h, the yield of glucose
and b-1,4-glucan reached 4% and 64%, respectively.
82
The yield
of glucose was increased to 8.08% under the optimized condi-
tions (catalyst = 0.300 g; cellulose = 0.25 g; distilled water =
2.25 g).
78
The enhanced catalytic performance is attributed to
the good ability of such a material with a multi-functional
surface to adsorb b-1,4-glucan. This view might be partly
supported by the result that sulfonated silica/carbon nano-
composites exhibited high performance in the selective hydro-
lysis of cellulose into glucose.
73
In this case, the hybrid surface
structure constituted interpenetrated silica and carbon components
which can greatly facilitate the adsorption of b-1,4-glucan on
the solid catalyst. More recently, it was suggested that elevating
the temperature of sulfonation during the preparation of
sulfonated carbon catalysts enhanced their catalytic properties
in the hydrolysis of cellulose.
83
No matter what methods
were used, in essence, the presence of strong, accessible
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 cata-
lysts 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. D
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Brnsted acid sites on catalysts played a crucial role in the
catalytic hydrolysis of cellulose.
In addition to the surface-grafted or supported solid acids,
heteropolyacids such as tungstophosphoric acid H
3
PW
12
O
40
8486
and HNbMoO
6
87,88
can also be used as heterogeneous-like
catalysts for the catalytic hydrolysis of cellulose. For the hydro-
lysis of cellulose samples, H
3
PW
12
O
40
and Sn
0.75
PW
12
O
40
catalysts gave a higher yield of total reducing sugars than
H
2
SO
4
. A 50.5% yield of glucose with a selectivity higher than
90% were achieved over H
3
PW
12
O
40
catalysts at 453 K for 2 h
with a mass ratio of 0.42 of cellulose to H
3
PW
12
O
40
86
Over a
series of catalysts like H
3
PW
12
O
40
, H
4
SiW
12
O
40
and polyvalent
transition metal salts of PW
12
O
40
3
(Ag
+
, Ca
2+
, Co
2+
, Y
3+
,
Sn
4+
, Sc
3+
, Ru
3+
, Fe
3+
, Hf
4+
, Ga
3+
and Al
3+
), the highest
reaction rates were observed for the catalysts with moderate
Lewis acidity, such as Sn
4+
and Ru
3+
-containing catalysts.
86
In addition, layered transition metal oxides, for example
HNbMoO
6
, have also been found to be a class of eectively solid
acid catalyst for the hydrolysis of cellulosic materials to glucose.
88
A 21% of the yield of glucose was obtained over layered
HNbMoO
6
catalysts, even higher than that over Amberlyst-15
(3.4%) under the same reaction conditions (Table 2). The peculiar
layered structure might make facile the accessibility of saccharides
into the interlayer gallery of HNbMoO
6
, where the strong acidic
sites are located. Notably, such a layered structure exhibited good
properties of water tolerance, which is of particular importance in
a hydrolysis reaction.
Nevertheless, in the case of solid acid catalysts, there is a
signicantly poorer solidsolid reaction contact between
catalysts and lignocellulosic biomass as both lignocellulosic
biomass and solid cannot be dissolved in water. As such, either
the H
+
ions from solid Brnsted acids or the active sites from
solid Lewis acid are dicult to access by reactants. Therefore,
the 1,4
0
-b-glycosidic bonds suer from diculty to be acti-
vated, attacked and then opened. Consequently, it results in a
low reaction activity. Moreover, in practice, there is another
diculty in the use of solid catalysts. To determine the true
conversion of lignocellulosic biomass remains an essential task
because it is not easy to separate unreacted cellulose from
sticky residues and various insoluble products that might
readily be adsorbed onto the solid acid catalysts.
79
To tackle
these challenges, integrating the use of ionic liquids for
dissolving microcrystalline cellulose along with solid acids
for catalytic splitting of cellulose into sugars may provide a
possible solution.
89
For example, Rinaldi et al.
90
showed
that the cellulose biopolymers were broken down into oligo-
mers in the form of averaging ten glucose units catalyzed by
Amberlyst catalysts in 1-butyl-3-methylimidazolium chloride
(C
4
MIMCl) ionic liquid after 5 h. It was postulated that the
easy release of H
+
ions into the solvent, the high surface area
and large pores in Amberlyst catalysts were probably crucial
factors to enable the long cellulose chains to be approached
and activated, thereby increasing the reactivity.
Furthermore, to further convert in situ hydrolytic glucose
to value-added commodity chemicals in a one-pot reaction
system is promising. So far the acidic solids have proved
to be eective in many reactions in organic synthesis. For
example, alkylation is also an acid-catalyzed reaction.
91
After acidic resin Amberlyst catalyzed the hydrolysis of the
1,4
0
-b-glycosidic linkages in the cellulose polymeric chain to
give glucose, such acid catalysts could further catalyzed the
in situ alkylation of the hydroxyl groups at the C1 position of
the glucose as an intermediate. Consequently, cellulose
was directly converted into an environmentally friendly alkyl
glycoside surfactant in a one pot transformation.
92
This state-
of-the-art integration of consecutive reactions has also been
demonstrated in a recent work by Ignatyev et al.
93
that
cellulose was fully converted into alkylglycosides under mild
conditions in the C
4
MIMCl ionic liquid in the presence of an
acidic catalyst. Primary alcohols like n-butanol and n-octanol
were used as alkylating reagents. In the reaction with n-butanol,
the yield of butylglucopyranoside isomers reached 86%. Accord-
ing to a well-established concept, the removal of intermediate
glucose by such alkylation can facilitate chemical equilibrium
to move forward, thereby leading to a higher conversion of
cellulose.
3 Catalytic solvolysis of lignocellulosic biomass
Apart from organic ionic liquid, certain organic reagents can
also physically and chemically modify cellulosic materials by
means of solvolysis, thereby promoting the contact between
cellulose molecules and surfaces of a solid acid catalyst. In this
context, the organic molecules act both as the solvents and as
the reactants. Consequently, they can signicantly facilitate
the catalytic conversion of lignocellulosic biomass over a solid
catalyst. Clearly, there is a chemical interaction between the
solvent and the solute lignocellulosic biomass. Therefore, the
inherent properties of solvents have a signicant eect on
products distribution. Moreover, it is also possible that
organic solvents react with intermediates, for example oligo-
saccharides or monomers, to yield secondary products. Deng
et al.
94
reported that for the conversion of cellulose, the use
of methanol as a solvent led to the formation of methyl
glucosides in the presence of dilute H
2
SO
4
, heteropolyacids
or sulfonated solid acid catalysts under mild conditions
(r473 K). H
3
PW
12
O
40
catalysts gave the highest TON
(B73 in 0.5 h) to methyl glucosides. Additionally, methyl
glucosides formed in methanol are more stable against
further degradation than glucose in water. Recently, it was
revealed that alcohol (methanol or ethanol) and water
showed a synergistic eect on direct liquefaction of biomass.
95
Fig. 3 Proposed schematic structure of the prepared carbon material
bearing SO
3
H, COOH, and OH functions.
82
Reprinted with permis-
sion from ref. 82. Copyright 2008 American Chemical Society.
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The 50 wt% co-solvent of either methanol-water or ethanol-
water 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 solvo-
lysis and degradation of cellulose might be worth being
emphasized in the catalytic solvolysis of lignocellulosic bio-
mass. Yamada et al.
96
conducted the acid-catalyzed solvolysis
of cellulose using ethylene carbonate (EC) as an organic
reagent and 97% H
2
SO
4
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 ligno-
cellulosic 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 deploymer-
ization 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 orga-
nosolvolysis by a pretreatment of recalcitrant softwood in
aqueous glycerol with a series of organic and inorganic acids
with dierent pK
a
values including sulfuric, hydrochloric acid,
phosphoric, malonic, acetic, citric and lactic acids. It was
found that the eciency of pretreatment correlated linearly
with the pK
a
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 com-
mon 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 ligno-
cellulosic biomass. The method could provide an economical
alternative route to the selective conversion of cellulose to
small organic molecules.
4 Catalytically hydrothermal liquefaction of
lignocellulosic biomass
As discussed above, over certain acid catalysts, longer reaction
time, higher reaction temperature and pressure can readily
lead to deep degradation and decomposition of glucose,
xylose, arabinose and cellobiose and oligosaccharides which
are yielded from the hydrolysis of lignocellulosic biomass.
Thereby a liquid mixture product mainly consisting of
C
2
C
6
organic compounds are obtained. In this respect, such
a process is usually called the liquefaction of lignocellulosic
materials instead. Clearly, the objective of the liquefaction of
lignocellulosic materials is to produce low molecular-weight
liquid products, instead of glucose and xylose by hydrolysis.
100
The catalytic liquefaction of lignocellulosic biomass is
generally performed in hydrothermal water similar to conditions
for hydrolysis at the temperature of 393653 K (Table 3).
An obvious advantage of the hydrothermal liquefaction process
is that it does not require the lignocellulosic biomass feedstock
to be pre-dried. Dierent from catalytic hydrolysis, however,
the liquefaction process of lignocellulosic biomass targets deep
degradation and decomposition of glucose through dehydration,
isomerization, decomposition and rearrangement, and so forth.
101
The products are greatly changed when the type of catalyst is
substantially changed. For example, over halide catalysts, as
shown in Scheme 5, glucose, 5-HMF and furfural could respec-
tively decompose to liquid products, such as levulinic acid,
5-HMF, furan and formic acid, in a parallel reaction.
102
However,
over alkaline catalysts bio-oils and phenolic compounds are
dominantly produced (Table 3).
4.1 Hydrothermal liquefaction over halide and sulfate
catalysts
Recent literature reports that catalytic liquefaction of ligno-
cellulosic biomass was often carried out over sulfate, halide
and oxide-based catalysts. Lewis acid catalysts could exhibit
good catalytic properties in hydrothermal liquefaction of
lignocellulosic biomass while catalytic hydrolysis is frequently
conducted in the presence of Brnsted acid catalysts (Table 3).
Several studies suggested, for example, that alkali and alkaline
earth metal chlorides were not eective in the conversion of
cellulose, while transition metal chlorides such as CrCl
3
,
FeCl
3
, CuCl
2
and AlCl
3
,
105,106
including a pair of these metal
chlorides (for example CuCl
2
and CrCl
2
),
107
exhibited high
catalytic activity. In particular, CrCl
3
was found to be highly
active in the conversion of cellulose to levulinic acid, reaching
a yield of 67 mol% after 180 min at 473 K with a catalyst
dosage of 0.02 M and substrate concentration of 50 wt%.
104
In
particular, the use of ionic liquids such as [C
4
MIM]Cl
105,106
and [EMIM]Cl
107
can eectively promote cellulose depolymer-
ization, thereby quickening the hydrothermal liquefaction.
Recently, a one-step process for the conversion of lignocellulosic
biomass into valuable furanic compounds in ionic liquids
over CrCl
3
under microwave irradiation was reported.
105
The results showed that CrCl
3
could eectively catalytically
convert lignocellulosic biomass into 5-HMF and furfural with
yields up to 52% and 31%, respectively, within a few minutes
without any pretreatment. It was postulated that CrCl
3
in
[C
4
MIM]Cl might form complexes [C
4
MIM]
n
[CrCl
3+n
]. Thus,
in the presence of ionic liquid, the 1,4-glucosidic bonds were
weakened partially at the cellulose hydrolysis step under
microwave irradiation (400 W) because of coordination with
[CrCl
3+n
]
n
. As a result, it was more easily attacked by water
to form glucose and oligomers (Scheme 6).
106
This coordina-
tion then promoted rapid mutarotation of the a-glucopyranose
anomer of glucose to the b- glucopyranose anomer of glucose
through hydrogen bonds of chloride anions with the hydroxyl
groups of glucose. The hemiacetal portion of b-glucopyranose
with [CrCl
4
]
then formed a Cr
3+
enolate anion complex and
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it aroused the isomerization of glucose into fructose. Finally,
fructose is dehydrated to 5-HMF.
106
Nonetheless, the heating
by microwave irradiation could also have an eect on cellulose
decomposition and 5-HMF formation. Though microwave
irradiation is facile at the laboratory scale, it might still be
dicult at large scale-up in industry. Furthermore, it cannot
be ignored that ionic liquids may also play a role in catalysis,
in addition to their role in facilitating the dissolution of
cellulose.
107
Rare-earth metal salts or ions, for example lanthanum(III)
ions, which retain Lewis acid reactivity even in aqueous
solutions, have been used to catalyze the degradation of ligno-
cellulosic biomass, typically cellulose.
103
Earlier, Seri et al.
108
showed that the conversion of cellulose degradation in water at
523 K in the presence of LaCl
3
reached 80.3% after 180 s.
A 54.2 wt% yield of a water-soluble product mainly containing
5-HMF glucose and levulinic acid was obtained. In addition to
metal halides, sulfates can also be used as catalysts for the
catalytic liquefaction of cellulose. Furthermore, the reaction can
be directed towards a specic target product other than 5-HMF,
glucose and levulinic acid. Kong et al.
109
revealed, for example,
that lactic acid can be produced from the catalytic hydrothermal
liquefaction of lignocellulosic biomass in the presence of dierent
transition metal ions like ZnSO
4
, NiSO
4
, CoSO
4
or Cr
2
(SO
4
)
3
.
In comparison to a non-catalytic process, the addition of 400 ppm
Ni
2+
catalyst evidently increased the yield of lactic acid
from 3.25% to 6.62% at 573 K for 120 s in the hydrothermal
liquefaction microcrystalline cellulose samples in subcritical
water. It is noteworthy that lactic acid can also act as a platform
chemical from which lots of ne chemicals can be obtained.
6
4.2 Hydrothermal liquefaction over alkaline catalysts
One of the important features of lignocellulosic biomass is that
it mainly contains two types of biopolymers, namely cellulosic
polymer and lignin polymer. Relatively speaking, the former
readily interacts with acid while the latter is apt to interact
with alkali. Therefore, in the presence of alkaline catalysts,
liquefaction of lignocellulosic biomass mainly leads to oil-like
products, although this process is usually conducted thermally
in an aqueous medium.
110,111
In a sense, this process mimics
the conversion of ancient plant material into the crude oil.
112
So far, various carbonates like Na
2
CO
3
, K
2
CO
3
, and hydroxides
such as KOH or Ca(OH)
2
as catalysts have been evaluated
in the hydrothermal liquefaction for wood, agricultural
and civic wastes such as sugar cane bagasse and corn stalk
as sources of lignocellulosic biomass (Table 3). The so-called
bio-oil product is actually a complicated liquid mixture with a
wide range of compositions. It typically consists of glycoalde-
hyde dimers, 1,3-dihydroxyacetone dimers, anhydroglucose,
Table 3 Catalytically hydrothermal liquefaction of lignocellulosic biomass or pure cellulose in an aqueous medium
Catalyst Feedstock Reaction conditions Main products Yield (%) Researchers/Year Ref.
NiSO
4
(400 ppm) Cellulose 573 K, 120 s Lactic acid B6.6 Kong et al./2008 109
LaCl
3
(0.01 M) Cellulose 523 K, 180 s (in N
2
) Glucose 5.8 (wt%) Seri et al./2002 108
5-HMF 19.2 (wt%)
Levulinic acid 2.3 (wt%)
La/Al
2
O
3
(0.34 wt%) Cellulose 423 K, 5 h Acetic Acid 4.0 (wt%) Schutt et al./2002 103
Malic Acid 8.0 (wt%)
CoSO
4
(400 ppm) Cellulose 573 K, 120 s Lactic Acid B9.5 Kong et al./2008 109
CrCl
3
(3.6 wt%) + [C
4
MIM]Cl Cellulose MW (400 W) 5-HMF 62.0 Li et al./2009 106
2 min, 0.1 MPa Reducing sugar 20.0
CrCl
3
6H
2
O+ [C
4
MIM]Cl Pine wood MW (400 W) 5-HMF 52.0 Zhang et al./2010 105
3 min, 0.1 MPa Furfural 31.0
CuCl
2
/CrCl
2
+ EMIM]Cl Cellulose 393 K, 8 min 5-HMF 57.5 Su et al./2010 107
Sorbitol 1.27
CrCl
3
(0.02 M) Cellulose 473 K, 3 h Levulinic acid 67.0 Peng et al./2011 104
K
2
CO
3
(0.5 wt%) Cellulose 608 K, 4.7 s bio-oil N/a Kumar et al./2008 124
27.6 MPa
K
2
CO
3
(1.0 M) Empty palm
fruit bunch
543 K, 20 min Phenolic compounds N/a Akhtar et al./2008 119
2 MPa (H
2
O)
Na
2
CO
3
(1.0 wt%) Corn stalk 647 K bio-oil 47.2 (wt%) Song et al./2004 123
25 MPa (H
2
O)
Na
2
CO
3
Woody biomass 653 K, 1620 min Heavy oil 53.3 Qian et al./2007 122
8 MPa (H
2
)
Ca(OH)
2
(0.0243 M) Sawdust 553 K, 15 min Oil 9.3 (wt%) Karagoz et al./2004 115
KOH (0.5 M) Walnut shells 523 K, 430 min, Phenolic compounds N/a Liu et al./2006 59
1.58.6 MPa
Ba(OH)
2
or Rb
2
CO
3
Lignin 573 K, 1 h Phenolic compounds
and oils
B53 Tymchyshyn et al./2010 126
2 MPa, H
2
Ba(OH)
2
or Rb
2
CO
3
Sawdust/cornstalks 573 K, 1 h Phenolic compounds
and oils
B32
a
+ 30/ Tymchyshyn et al./2010 126
2 MPa, H
2
32
a
+ 25
K
2
CO
3
+ ZrO
2
Waste biomass 673 K, 10 min Oil 913% Hammerschmidt
et al. /2011
125
22.1 MPa
[EMIM]Cl: 1-ethyl-3-methylimidazolium chloride. [C
4
MIM]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.
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soluble polyols, 5-HMF, furfural, organic acids, phenolic
compounds and even hydrocarbons. Therefore, an ecient
hydrothermal liquefaction process of lignocellulosic biomass
over alkaline catalysts oers remarkable potential for
simultaneously producing biofuels and value-added chemicals
by integrating it with proper separation and extraction
techniques.
Clearly, the reaction temperature and time and the type of
alkaline medium have a signicant eect on the reaction rate
and product distribution.
113,128
As for the eect of tempera-
ture on the reaction rate and the product distribution, for
example, earlier Minowa and co-workers
114
showed that in the
presence of 0.826 wt% Na
2
CO
3
under 3 MPa, the decomposi-
tion 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.
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 CrCl
3
in [C
4
MIM]Cl (n = 13).
106
[C
4
MIM]Cl: 1-n-butyl-3-methylimidazo-
lium chloride. Reprinted from ref. 106, Copyright 2009, with permission from Elsevier.
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No cellulose remained after reaction at temperatures greater
than 573 K. Later, Karagoz and colleagues
115
used a 0.0243 M
Ca(OH)
2
solution as a solvent instead of pure water a in
liquefaction reaction of wood biomass. The results also
revealed that increasing the reaction temperature increased
the conversion of wood biomass and the total bio-oil yield.
Maximum bio-oil yield was found to be 8.5 wt% for a reaction
at 553 K for 15 min. Regarding these ndings, in general, an
obvious reason is that decomposition temperature for cellulose
and lignin is inherently dierent. Moreover, decomposition of
cellulose tends to yield polyols, alcohols and carboxylic acids
while decomposition of lignin principally leads to phenolic
compounds.
However, at elevated temperatures or over longer reaction
times, the occurrence of secondary reactions of bio-oil
products is increased so much that the yield of the bio-oil
decreases. In particular, for most of the lignocellulosic bio-
mass treated at a temperature higher than 573 K a carboniza-
tion process tends to readily take place.
116
The carbonization
could be eectively avoided at lower reaction temperature
in the presence of an appropriate catalyst. With regard to
low-temperature catalytic hydrothermal treatment of wood
biomass, several studies showed that the use of alkaline
catalysts increased the formation of the compounds such as
4-methyl-2-methoxy-phenol, 4-ethyl-2-methoxy-phenol and
benzenediol derivatives and decreased the solid residues, tar
and biochar.
117,118
The role of catalysts in directing product
distribution is clearly proved by the observation that the furan
derivatives obtained from the thermal run were not observed
for the catalytic run. Moreover, the conversion and yield of
liquid products decreases in the following order: K
2
CO
3
4
KOH 4 Na
2
CO
3
4 NaOH.
117119
It is most likely that the decomposition of lignocellulosic
biomass in water inhibits char formation. In particular, such a
process is conducted under subcritical or supercritical water
conditions. It is well-documented that near the critical point of
water (647 K, 22.1 MPa), the ionic concentration (K
w
= [H
+
]
[OH
]; [H
+
] = [OH
]) increases and water behaves as a

weakly polar solvent. Therefore, subcritical and supercritical
water conditions are often considered to be applied to the
liquefaction of lignocellulosic biomass. Earlier, Demirbas
120
found that the yield of bio-oil from catalytic supercritical uid
extraction of oriental beech reached 68.6% at 573 K after
30 min in the presence of 20% wt NaOH. However, there are
also disadvantages in the use of subcritical or supercritical
water. Typically, the equipment corrosion by caustic hydroxides
is severely enhanced under subcritical and supercritical
water conditions. Therefore, in this aspect, alkali and alkaline
earth carbonate salts are favorable for use as catalysts. When
cellulose liquefaction is carried out in the presence of Na
2
CO
3
under subcritical water and at a reaction temperature of 623 K,
bio-oil and gas were the main products, with little solid residue
formed.
121
Qian et al.
122
reported that when woody biomass
was liqueed at 653 K in the presence of Na
2
CO
3
as a catalyst,
a yield of 53.3% of bio-oil, mainly composed of hydrocarbon,
aldehyde, ketone, hydroxybenzene and ester, was obtained.
However, Song et al.
123
showed that in the case of isothermal
liquefaction of corn stalks in water without a catalyst, the
conversion was also very high, reaching 95.4 wt% with a liquid
yield of 77.6% and gas production of 17.9%. When 1.0 wt%
Na
2
CO
3
was added as a catalyst, the conversion rate remained
unchanged (95.7%), but the catalytic reaction favored the yield
of liquid products which increased to 88.0% and the gas
production decreased to 6.8%. Moreover, in the presence of a
catalyst, the bio-oil content in the liquid products sharply
increased from 33.4 wt% to 47.2 wt%. Clearly, not only does
the catalyst change the rate of the liquefaction reaction, but it
can also change the direction of the liquefaction reaction
towards dierent types of products.
The hydrothermal liquefaction is almost all conducted in a
batch reactor. However, it can be carried out in a continuous
ow reactor. For example, Kumar et al.
124
revealed that when
using K
2
CO
3
as a catalyst in a continuous ow reactor,
increasing the reaction temperature to the supercritical region,
or increasing the reaction time, hydrolytic oligomers and
monomers of cellulose samples were further degraded into
glycoaldehyde dimer, D-fructose, 1,3-dihydroxyacetone dimer,
anhydroglucose, 5-HMF, and furfural, thereby yielding bio-
oils. To improve the selectivity to target compounds in the
bio-oil, Hammerschmidt and co-workers
125
recently described
a continuous one-step process making use of two kinds of
catalysts, a homogeneous K
2
CO
3
catalyst and a heterogeneous
ZrO
2
catalyst. Such combination of a homogeneous system
with a heterogeneous system provides new ways to realize a
more ecient continuous process.
It should be noted that thermal liquefaction in an aqueous
solution might also undergo hydrolysis, pyrolysis and steam
gasication, in particular in super- or subcritical water. Such
complex reaction networks for cellulose decomposition in
homogeneous and heterogeneous reaction conditions under
subcritical water using Na
2
CO
3
, and Ni as catalysts and with-
out catalysts, have been proposed by Fang and co-workers, as
shown in Scheme 7.
121
In the course of the reaction, dissolved
compounds, for example part of cellulose, oligomers, glucose,
and levoglucosan and non-dissolved feedstock cellulose and
compounds, might undergo dierent reaction mechanisms,
thereby resulting in dierent intermediates and nal products.
At a high heating rate, a Na
2
CO
3
catalyst resulted in more oil
while a Ni catalyst produced more gas. The dissolved reaction
paths in the homogenous phase were homogeneously hydro-
lyzed to glucose and other soluble pyrolytic products (e.g.
levoglucosan), which then further decomposed to acids, alde-
hydes, and alcohols of C
1
C
3
. Part of the glucose degraded to
furfurals and 5-HMF, which ultimately condensed to phenols
and dehydrated to levulinic and formic acids. The non-
dissolved reaction fraction in the heterogeneous phase possibly
underwent pyrolysis to yield a mixture of hydrocarbons,
aromatic derivatives and tar, randomly linked oligosaccharides,
light volatiles and gases via dehydration, cracking and ssion,
and rearrangement of the sugar units. Even for single cellulose as
a feedstock, the reaction mechanism is extraordinarily compli-
cated. For lignocellulosic biomass, the presence of lignin and
hemicellulose certainly make it much more perplexing.
Among the components in bio-oils, phenolic compounds are
one type of typical, important product from the liquefaction
of lignocellulosic biomass after treatment with alkali. It is well-
documented that alkalis are exceptionally eective to extract and
convert lignin lignocellulosic biomass. Liu et al.
59
showed that
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the products from the hydrothermal conversion of walnut shells
catalyzed by 0.5 M KOH at 573 K were mainly phenol
derivatives, especially the methoxy phenolic compounds.
Clearly, these chemicals are readily derived from lignin. Owing
to the inherent multicomponent plant cells, small amounts
of cyclopentene derivatives and C
1218
fatty acids were also
detected. Recently Tymchyshyn and colleagues
126
described a
series of direct liquefaction of lignocellulosic wastes like sawdust
and cornstalks, and model biomass compounds like lignin and
cellulose in hot-compressed water at temperatures from 523 to
623 K in the presence of 2 MPa H
2,
with the addition of
Ba(OH)
2
and Rb
2
CO
3
catalysts. Signicant quantities of
phenolic compounds such as 2-methoxy-phenol, 4-ethyl-2-
methoxyphenol, and 2,6-dimethoxy-phenol were obtained from
the two lignocellulosic wastes and pure lignin. Yet the liquid
products from cellulose contained essentially carboxylic acids
and neutral compounds. Such experimental data evidently
revealed that lignin and cellulose inherently tend to result in
dierent categories of products. To bear this in mind is of much
importance in designing and developing a catalytic system for
hydrothermal liquefaction of lignocellulosic biomass to the
target products based on dierent goals.
As discussed above, catalytically hydrothermal liquefaction
of lignocellulosic biomass produces a very complex mixture of
liquid products along with some gases and solid residues and
tars. It makes the production of bio-oil from hydrothermal
liquefaction of lignocellulosic biomass very uneconomical at
present when compared to the costs of diesel or gasoline
production from fossil oils. Scheme 8 shows the separation
and extraction procedure proposed by Karagoz et al.
117
It involves the complicated multistep extraction by several
types of solvents. Moreover it needs inorganic acids for
neutralization and the separation of water-soluble organic
compounds in the water phase. Therefore, in addition to the
technical need for the improvement of the activity and selectivity
of catalysts, the novel technology for separation and extraction
of downstream products from hydrothermal liquefaction of
lignocellulosic biomass need to be developed.
127,128
On the other
hand, such complexity in products is a reection of the complex
reaction mechanism in catalytic liquefaction of lignocellulosic
biomass. Thus far, researchers have not acquired in-depth
understanding of the reaction mechanism yet. To disclose it
certainly is conducive to developing such a process for the
commercial use. Finally, generally speaking, hydrothermal
liquefaction is relatively time-consuming and energy-intensive.
In this context, comparatively, fast pyrolysis, as discussed below,
is more promising.
5 Catalytic pyrolysis of lignocellulosic biomass
Pyrolysis of lignocellulosic biomass is generally a process of
thermal chemical decomposition in the absence of oxygen to
convert biomass into liquid products (bio-oils) together with
some gases and solid chars. Such a thermolysis process
simultaneously involves various reactions such as depolymer-
ization, dehydration, decarboxylation, esterication,
condensation, cyclization, and so forth.
27,129,130
However,
dierent from catalytic liquefaction at lower temperature in
the aqueous phase, pyrolysis is usually conducted at tempera-
tures greater than 773 K (Table 4). The liquid products are
commonly referred to as pyrolysis oils, which have been
identied as promising alternative renewable liquid fuels.
131,132
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 Na
2
CO
3
catalyst, and more gas with Ni catalyst.
121
Reprinted with permission from
ref. 121. Copyright 2004 American Chemical Society.
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Similar to the liquid products from thermal liquefaction, the
pyrolysis oil is a complicated mixture of oxygenated and
deoxygenated compounds, typically consisting of organic
acids, aldehydes, ketones, esters, aromatic and phenolic deri-
vatives, and even hydrocarbons. Accordingly, liquid pyrolysis
oils are normally acidic and emulsion-like uids containing
both aqueous phases and phenolic phases. Thus it is impera-
tive to further upgrade pyrolysis oil so as to get useful liquid
hydrocarbon-like fuels and fuel additives.
Pyrolytic processing of lignocellulosic biomass can be
roughly classied into steam pyrolysis, fast pyrolysis in the
ow of an inert gas and vacuum pyrolysis. For all of these
approaches, a major, common objective is to improve the
selectivity of low molecular-weight substances with great
potential as fuels. As seen in Table 4, fast pyrolysis has been
the attractive subject of a lot of research over the past decade
because it is proven to be two to three times more economical
than liquefaction and gasication processes.
133
Generally, four
parameters play a pivotal role in the catalytic activity and
selectivity of targeted pyrolysis oils. They are (1) the catalysts,
(2) heating rate of lignocellulosic biomass, (3) residence time of
reactants and the products inside the reactor, and (4) reaction
temperature.
130
In addition, the atmosphere in the reactor is
inuential. For example, if the pyrolysis is conducted in the
presence of hydrogen, more hydrogenated products will be
obtained. Such an integrated pyrolysis with hydrogenation
process will be discussed in detail in Section 7.
5.1 Fast pyrolysis mechanism
The fast pyrolysis reaction of lignocellulosic biomass under-
goes 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. Hydroxy-
acetaldehyde 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 (CO
x
). At low temperature, activated cellulose
would also directly decompose to produce char, CO
2
, and
H
2
O. 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, H
2
O (2)
where Gm = short oligomers.
Gm, H
2
O -C
n
, CO, H
2
O (+CO
2
, H
2
), with n r 4 (3)
C
n
-CH
4
(4)
CH
4
+ H
2
O -CO + 3H
2
(5)
As depicted by the reaction paths in eqn (2)(5), cellulose
decomposes primarily to H
2
O and short oligomers (Gm),
which is then broken down to levoglucosan. The levoglucosan
easily breaks down to mainly form CO, H
2
O and hydro-
carbons up to C
4
, along with minor CO
2
and H
2
. In these
sequential reactions, butadiene was identied as a key inter-
mediate. The hydrocarbons undergo further thermal cracking
reactions to yield CH
4
. The presence of H
2
O steam and
hydrocarbons results in a reforming reaction, nally leading
to chemical equilibrium composition among syngas and CH
4
.
According to this mechanism, H
2
and CO can form in two
dierent reaction routes in eqn (2) and (5), respectively. And
the dierent pathways and rates in the formation of CO and
H
2
explain why the ratio of CO to H
2
is not constant under
dierent conditions, particularly at short residence time.
Therefore, it could be reasonably deduced that a longer
contact time is required if the aim is to produce syngas from
the fast pyrolysis of cellulose.
Although all of the abovementioned mechanisms have
proposed relatively simple reaction routes and identied key
intermediates in the non-catalyst system,
137,138
it is evident
that fast pyrolysis involves a series of consecutive and parallel
reactions competing against each other among liquid products
and gaseous products. Nevertheless, as such reactions are
frequently conducted either in the gas or liquid phase in the
presence of homogenous and heterogeneous catalysts,
139,140
the reaction mechanism might undergo far more complicated
Scheme 8 Separation and extraction procedure.
117
Reprinted with
permission from ref. 117, Copyright 2005, with permission from
Elsevier. WSH: Water soluble hydrocarbons (WSH and others in
wt% = 100 (oil1 + oil2 + oil3 + solid + gas). (Typical products
in oil 1: 2-Furancarboxaldehyd, 2-Methoxy-phenol, 4-Methyl-phenol,
4-Hydroxy-3-methoxy-benzeneacetic acid, 2-Hydroxy-3-methyl-2-
cyclopenten-1-one and Butylated hydroxytoluene; oil 2: 3-Methoxy-1-
propene, 4-oxo-Pentanoic acid, 5-Ethyldihydro-2(3H)-furanone;
oil 3: 2-Furancarboxaldehyde,2-Methoxy-phenol, 3-Methyl-phenol or
4-methyl-phenol, Eugenol, 4-Hydroxy-3-methoxy-benzeneaceticacid-
methyl ester, 3-Acetyl-7,8-dimethoxy-2-methyl-1H-naptho[2,1-b]pyran-1-
one.
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steps and reaction networks. Furthermore, many intermediate
products are more active than cellulose itself and polyols,
thereby making the reaction more perplexing. Such complex
reaction networks are still a puzzle and a barrier on the way to
understanding and utilizing cellulose by pyrolysis conversion
in a more ecient, economical way.
5.2 Catalytic fast pyrolysis
To increase the pyrolysis eciency and the content of the target
compounds in bio-oils, liquid acid such as H
2
SO
4
, hydrochloric
acid, phosphoric acid and Lewis acids can be used as a specic
pretreatment for pyrolysis of lignocellulosic biomass.
141
For example, Dobele et al.
142
reported that the pretreatment
of pine wood sawdust and microcrystalline cellulose samples
with phosphoric acid or iron(III) sulfate drastically increased
the contents of levoglucosenone and levoglucosane in volatile
products obtained by a subsequent fast pyrolysis (Table 4).
These results were attributed to the catalysis of the cellulose
depolymerization and dehydration in the presence of acids
from the pretreatment. As for the use of iron ions, possibly
the cleavage of glycoside bonds were catalyzed by iron
oxihydroxide which formed during pretreatment of ligno-
cellulosic biomass. As a result, such a pretreatment had a
positive eect on the yield of 1,6-anhydrosaccharides. With
regards to lignocellulosic biomass with a higher content of
Table 4 Typical pyrolysis of lignocellulosic biomass in the presence or absence of catalysts
Feedstock Catalyst Reaction conditions Typical products Yield (%) Researchers/Year Ref.
Softwood bark and
Hardwood
No Vacuum pyrolysis Parans, sterols N/a Garcia-Perez et al./2007 134
773 K Fatty acid methyl
esters
Cellulose No Flash pyrolysis Soluble solids 20.045.9 Piskorz et al./2000 135
11231473 K, 3575 ms. Liquid product 12.5-27.4
Soybean oil cake No Pyrolysis, 773 K Liquid product 60 Karagoz/2009 136
Under N
2
ow
Cellulose No Fast pyrolysis CO, H
2
, CH
4
,
hydrocarbons
N/a Lanza et al./2009 138
1173 K, Z 3 h
Cellulose 0.1wt% sulfuric or
polyphosphoric acid
Pyrolysis in tetramethylene
sulfone, 473 K, 6 min,
Under N
2
ow
Levoglucosenone,
furfural
42.2 Kawamoto et al./2007 144
26.9
5-HMF 8.8
Wood Pretreated by 1wt%
phosphoric acid
Fast pyrolysis, 773 K Levoglucosane 33.6 Dobele et al./2005 142
Under He ow Levoglucosenone 14.1
Cellulose Pretreated by 1%
phosphoric acid
Fast pyrolysis, 773 K Levoglucosane 25.2 Dobele et al./2005 142
Under He ow Levoglucosenone 29.8
Pine wood sawdust NaOH Fast pyrolysis, 773 K Acetol 53.3 Chen et al./2008 146
Microwave heating Furfural 0
2-furanmethanol 2.08(area%)
Pine wood sawdust Na
2
CO
3
Fast pyrolysis, 773 K Acetol 45.28 Chen et al./2008 146
Microwave heating Furfural 1.03
2-furanmethanol 2.58
Pine wood sawdust Fe
2
(SO
4
)
3
Fast pyrolysis, 773 K Acetol 0 Chen et al./2008 146
Microwave heating Furfural 50
2-furanmethano 0
Cellulose ZSM-5 Fast Pyrolysis, 873 K,
240 s
Aromatic
compounds
31.1 (C%) Carlson et al./2008 152
Under He ow CO 15.2 (C%)
Pine sawdust H-ZSM-5 Flash pyrolysis, 673773 K,
50 ms, under N
2
ow
C
4
-hydrocarbons 15.9 Olazar et al./2000 150
Wood Ni-ZSM-5 Fast pyrolysis, 873 K Hydrocarbons 16 French et al./2009 151
Under He ow Toluene 3.5
n/a: no available. No. without catalyst.
Scheme 9 Modied model of fast pyrolysis of cellulose.
137
Adapted and reprinted with permission from ref. 137. Copyright 2004 American
Chemical Society.
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lignin, higher concentration of phosphoric acid or iron(III)
sulfate was needed for pretreatment. Clearly, directly employ-
ing catalysts in the fast pyrolysis of lignocellulosic biomass can
remarkably improve the conversion and selectivity to targeted
products. As for the catalytic fast pyrolysis of microcrystalline
cellulose at 7731073 K by on-line analysis of the pyrolysis
vapors, Lu et al.
143
revealed that SO
4
2
/SnO
2
was the most
eective catalyst to yield 5-methyl furfural. The selectivity was
evidently changed with the change of catalyst support. For
example, the SO
4
2
/TiO
2
catalyst favored the formation of
furfural, while SO
4
2
/ZrO
2
favored the formation of furan.
143
In addition, it is noteworthy that the type of solvent used
during the pyrolysis reaction also has a signicant impact on
the distribution of products. Kawamoto et al.
144
depicted
the catalytic pyrolysis of cellulose catalyzed by H
2
SO
4
in
tetramethylene sulfone (C
4
H
8
O
2
S) and found that the yield
of levoglucosenone, furfural, and 5-HMF reached up to 42.2%,
26.9%, and 8.8% (as mol% yield based on the glucose unit),
respectively, at 473 K for 6 min.
144
Remarkably, the cellulose
pyrolysis in tetramethylene sulfone suered so little from carbo-
nization reactions that the residues obtained from pyrolysis in
sulfolane were colorless. There, levoglucosan was identied as
the major anhydromonosaccharide formed during the pyrolysis
of cellulose.
145
Tetramethylene sulfone is an aprotic polar solvent
and it could dissolve anhydromonosaccharides, therefore it could
prevent the polymerization and carbonization reaction. As such,
cellulose completely decomposed into soluble products in tetra-
methylene sulfone.
145
In contrast, pyrolysis under nitrogen or in
dioctyl phthalate (a poor solvent for levoglucosan) produced
brown/black solid residues. The ndings indicated that the solvent
is also inuential in pyrolysis and it can be properly selected in
view of promoting dissolution of lignocellulosic biomass and/or
intermediates.
At present, the catalytic pyrolysis of lignocellulosic biomass
is often conducted in the presence of acid or alkaline catalysts
such as carbonates and hydroxides. Because the pyrolysis oils
yield various organic acids, the presence of alkaline species in
the reaction system has an important eect on the stability of
bio-oil. Phosphates, sulfates and chlorides also have certain
catalytic activity in the catalytic pyrolysis of lignocellulosic
biomass. With regard to the catalytic fast pyrolysis of pine
wood sawdust by microwave heating in a uidized reactor,
alkaline sodium compounds like NaOH, Na
2
CO
3
and Na
2
SiO
3
catalytically resulted in bio-oils rich in acetol, and to some
extent favored H
2
formation while the use of the Fe
2
(SO
4
)
3
catalyst favored the formation of fufural and 4-methyl-2-
methoxy-phenol.
146
In addition, phosphates, sulfates and
chlorides could be used to replace corrosive alkaline catalysts
or corresponding acid catalysts. Other than catalysis, diammonium
phosphate (NH
4
)
2
HPO
4
and diammonium sulfate (NH
4
)
2
SO
4
could act as dehydrating agents upon heating during pyrolysis.
Therefore, at reaction temperatures of about 650750 K, a
pretreatment of water-extracted re wood by the impregnation
in about 1% of (NH
4
)
2
HPO
4
or (NH
4
)
2
SO
4
solution before
pyrolysis is able to increase the yields of levoglucosan,
5-methyl-2-furaldehyde and 2-acetylfuran in the range of
25%.
147
Furthermore, alkali and alkaline earth metal
chlorides have also been investigated as catalysts. Shimada
and co-workers
148
showed that the use of alkaline earth metal
chlorides could substantially reduce the reaction temperature
from 673 to 423 K.
Recently, the catalytic pyrolysis of lignocellulosic biomass
over zeolites and supported solid catalysts have received
serious attention. In particular, it is attractive to employ
continuous fast pyrolysis of lignocellulosic biomass catalyzed
by solid catalysts which has obvious advantages over the use
of liquid acid catalysts in a batch reactor. More importantly,
the most desired product from the catalytic pyrolysis of
lignocellulosic biomass should be directed to hydrocarbons-
containing pyrolysis oils with high yield, similar to petrol
presently in use with easy storage and transportation. In
response, recent advances have shown that hydrocarbons
can indeed be produced in considerable quantities by fast
pyrolysis of biomass over zeolite and mesoporous catalysts
such as ZSM-5, Al-MCM-41.
149
Such a catalytic fast pyrolysis
demonstrated an optimistic prospect for direct production of
high-octane pyrolysis oils from biomass for practical applica-
tions. For instance, Olazar et al.
150
studied the fast pyrolysis of
pine sawdust with ZSM-5 in a spouted-bed reactor using
nitrogen as the carrier gas and observed a yield of aromatic
compounds of 12% (carbon). By using a semi-continuous ow
reactor with helium as carrier gas, French et al.
151
revealed
that lignocellulosic biomass could be pyrolyzed at tempera-
tures ranging from 673 to 873 K with a catalyst-to-biomass
ratio of 510 by weight over nickel, cobalt, iron, or gallium-
substituted ZSM-5, leading to an approximately 16 wt% yield
of hydrocarbons. Aromatic compounds like toluene
151
and
even gasoline-like products
152
can be obtained in remarkable
quantities even without using the hydrogen. However, over
solid catalysts at high temperature, the cracking and deoxygen-
ating activity might decrease with time because of the coke
deposits formed on the solid catalyst.
152
Finally, it should be
noted that the distribution of the pyrolysis products such as
charcoal, liquids and gaseous products are also strongly
inuenced by the physical and chemical characteristics of
the raw materials of lignocellulosic biomass. Therefore, the
cellulosic sources with adequate chemical composition should
be selected for the specic desired product, together with the
search for optimal reaction conditions and the catalysts. In this
context, the growth and productivity, ecological inuence and
cost of plant sources of lignocellulosic biomass should be taken
into consideration.
6 Catalytic gasication of lignocellulosic biomass
Gasication is usually referred to as a process of oxygen-
decient 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
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performed at high temperatures with a controlled amount of
oxygen like catalytic partial oxidation.
157
Provided that air is
used, the resultant products will contain nitrogen, thereby
leading to an additional problem of separation and purica-
tion. In many instances, gasication also produces small
amounts of tar, mainly composed of highly condensed poly-
aromatic hydrocarbons.
158,159
To avoid such a problem and to
increase the eciency, biomass gasication in supercritical
water is of growing scientic and technical interest.
160162
This
so-called steam gasication of cellulose, can be described by
the following reaction (eqn (6)).
163165
0.59C
6
H
12
O
6
+ 0.7H
2
O -1.42CH
4
+ 2.12CO
2
+ 1.4H
2
(6)
Table 5 lists some typical reaction conditions and results in
catalytic gasication of lignocellulosic biomass in the presence
of steam. The possibly improved solubility of cellulosic mate-
rials in the supercritical water employed can greatly reduce
mass-transfer limitation. In addition, it can prevent catalyst
deactivation due to coke deposition by means of extracting the
coke precursor from the catalyst surface in the supercritical
water.
166
Moreover, the use of supercritical water might
improve the hydrolysis and saccharization of cellulose in
extremely short residence times. Furthermore, Fushimi et al.
recently revealed that the evolutions of water-soluble tar and
gaseous products (CO, H
2
, CH
4
and C
2
H
4
) are signicantly
suppressed by the interaction between cellulose and lignin.
167
6.1 Gasication over supported noble metal catalysts
Supported Ru, Pt or Pd catalysts appear promising in
the catalytic gasication of lignocellulosic biomass under
supercritical conditions (Table 5). In addition, these catalysts
are commonly active for hydrogenation. Therefore, the H
2
produced from gasication in turn might be a reactant for
in situ consecutive hydrogenation.
Various Ru-based catalysts such as RuO
2
, Ru/TiO
2
and
Ru/C have been explored as catalysts in the catalytic gasica-
tion of lignocellulosic biomass. Earlier, Park et al.
169
reported
the production of hydrogen from sewage disposals in super-
critical water using RuO
2
as the catalyst. The reaction was
more eective than conventional steam reforming to produce
hydrogen. Izumizaki and co-workers
170
chose RuO
2
as a
catalyst for the production of hydrogen from biomass in
supercritical water under argon atmosphere of 44 MPa at
723 K for 120 min. The amount of hydrogen in gaseous
mixtures was 15.0% from cellulose, 14.1% from pulp, 21.0%
from the mixture of cellulose and lignin, 16% from waste
paper and 27% from paper sludge, respectively. RuO
2
evidently accelerated the thermal decomposition for cellulose
and pulp. However, for lignin, the catalytic performance could
be greatly suppressed because of the quick deactivation of the
RuO
2
catalyst by coke and char formation.
A possible reaction model over such a RuO
2
catalyst is
proposed as below.
170
RuO
2
+ Org -Ru
2+
+ Org
+
+ 2CO (7)
Ru
2+
+ 2H
2
O -RuO
2
+ 2H
+
+ H
2
(8)
Org
+
refers to an intermediate from the decomposed ligno-
cellulosic biomass. According to such a proposition, CO was
formed through the cyclic oxidation-reduction reaction of
RuO
2
with intermediate organics compounds (Org) and then
hydrogen was generated from the reduction of water by Ru
2+
(eqn (7) and (8)). The hydrogen and CO could reacted to form
methane (eqn (9) and (10)).
CO + 3H
2
-CH
4
+ H
2
O (9)
2CO + 2H
2
-CH
4
+ CO
2
(10)
According to this reaction mechanism, a higher hydrogen ratio
in the product stream is subject to low methane formation. In
this case, the desired catalyst is the one which can signicantly
enhance the overall conversion of lignocellulosic biomass
whilst hindering reduced methane formation so that the yield
of hydrogen can be increased. Osada et al.
171
showed that the
gasication of cellulose over Ru/TiO
2
in supercritical water
conducted at 673 K for 15 min led to a high gas yield of
74.4 C% (calculation based on the carbon balance). Never-
theless, using the same reaction conditions without the pre-
sence of a catalyst, the gas yield and the water-soluble yield
were 11.3 C% and 39.0 C%, respectively. In this case, it is
reported that in the catalytic reaction no solid product was
formed.
In addition to the use of supercritical water conditions, to
tackle the insolubility of cellulosic materials in gasication,
there are a few reports suggesting that the derivative of
cellulose, carboxymethylcellulose (CMC) and acetyl cellulose,
can be mixed with particulate biomass and water to form a
uniform and stable viscous paste. Such a mixture can then be
gasied in a continuous ow system more eciently.
172,173
Hao et al.
173
found that the 10 wt% cellulose or sawdust
sample mixed with CMC (23 wt%) can be completely gasied
in supercritical water at 773 K, 27 MPa and for 20 min
residence time in the presence of a Ru/C catalyst. And the
experimental results suggested the catalytic activities in the
order as follows: Ru/C 4 Pd/C 4 nano-(CeZr)
x
O
2
4 nano-
CeO
2
4 CeO
2
.
When acidic solid support, for example in a Pt/Al
2
O
3
catalyst, was used, the catalytic gasication of lignocellulosic
biomass could consist of two main steps: (1) Al
2
O
3
with
surface acidity could eectively act as a catalyst in the rst
step for the depolymerization of a lignocellulosic biomass
feedstock, similar to acid-catalyzed hydrolysis. As mentioned
previously, in supercritical water this depolymerization can
also occur to some extent even without catalysts. (2) The next
step is the gasication of water-soluble depolymerized pro-
ducts over Pt/Al
2
O
3
in a catalytic reactor, producing H
2
, CO
2
,
and CH
4
(eqn (11)).
174,175
Similarly, in the case of Pt/C
catalyst in conversion of cellulose into hydrogen by aqueous
phase reforming process, it was proposed that this process
might involve slow hydrolysis of cellulose to glucose which
was catalyzed by the H
+
reversibly formed in water during the
reaction and followed by rapid reforming of glucose to H
2
.
176
Cellulose !
H
2
O
C
6
H
12
O
6
!
3nH
2
O
6nC
3n
H
2
O 11
Gasication of cellulose by the reforming reaction with H
2
O under
high temperature can be regarded as catalytic wet oxidation.
103,177
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Usui et al.
178
studied how cellulose is gasied in hot-compressed
water at 623 K in the presence of a series of supported catalysts
(2 wt% loading) using Zr(OH)
4
, (CH
3
COCHQC(O)CH
3
)
3
Fe,
ferrocene, Ru
3
(CO)
12
, (CH
3
COCHQC(O)CH
3
)
2
Co, NiC
2
O
4
,
NiO, Ni(OH)
2
, 2NiCO
3
3Ni(OH)
2
, PdI
2
, CuCO
3
Cu(OH)
2
,
(CH
3
CO
2
)
2
CuH
2
O, (CH
3
COCHQC(O)CH
3
)
2
Cu, and
Cu(OH)
2
. Among these catalysts, after reaction for 3 h,
5 wt% Pd supported on Al
2
O
3
particularly showed the highest
catalytic activity, leading to a yield of H
2
at 42.3 vol% and
CH
4
at 7.7 vol%, respectively (Table 5). A possible two-step
mechanism is also proposed. Namely, rst the C
2
C
10
unit
aldehydes, ketones, and organic acids were formed from
cellulose in hot compressed water and then these intermediates
were catalytically decomposed to give gaseous products mainly
consisting of H
2
, CH
4
, CO, and CO
2
. It is noteworthy that
using transition metal complexes as catalysts for the gasica-
tion of cellulose, oil and char were mainly produced with few
gaseous products.
Many studies have shown that the deactivation of a catalyst
in gasication of lignocellulosic biomass is often related to
the amount of coke deposition.
179
In addition to catalyst
deactivation, the formation of tar readily causes trouble in
downstream equipment such as blocking and fouling. There-
fore, a good catalyst should be multifunctional, including the
conducive roles in further catalytic steam reforming tar to
syngas and in the removal of the inactive biochar by catalytic
combustion. For example, Miyazawa et al.
180
demonstrated
catalytic partial oxidation of tar over a multicomponent
Rh/CeO
2
/SiO
2
catalyst for syngas production from ligno-
cellulosic biomass. In addition, Asadullah and coworkers
181
conducted a series of experiments on Rh-based catalysts
for gasication of cellulose and found that the Rh loading of
1.2 10
4
mol g
1
catalyst supported on CeO
2
exhibited
multiple functions during the gasication of microcrystalline
cellulose. The Rh/CeO
2
catalysts remarkably increased the
conversion and inhibited the formation of methane, thereby
enhancing the yields of CO and H
2
, compared to Ru/CeO
2
,
Pd/CeO
2
, Ni/CeO
2
, Rh/Al
2
O
3
and Rh/TiO
2
. These studies
suggested that Rh/CeO
2
has great potential to be developed
as a catalyst for complete gasication of cellulose.
Finally, in addition to the catalysts and reaction variables,
the reactor also plays a role in gasication eciency and
product distribution.
182186
Kaewluan et al.
187
depicted a
bubbling uidized bed gasier having a high carbon conver-
sion eciency (97.3%) and gasication eciency (80.2%) to
syngas from rubber wood chip. Dauenhauer and co-workers
188
reported millisecond reforming, by which cellulose particles can
be converted extremely quickly into syngas on a hot Rh surface
without detectable deactivation from carbon formation.
6.2 Gasication over non-noble metal catalysts
It is well-documented that Ni, Fe, Co, and Cu-based catalysts
are eective for the water-gas shift reaction in which carbon
monoxide reacts with water to form CO
2
and hydrogen
(eqn (12)).
189
Therefore, when such kinds of solid catalysts
exist in the gasication of cellulose in the presence of steam,
the yield of hydrogen can be increased (eqn (13)), possibly
following a model involving in the watergas shift reaction
(eqn (12)).
190
CO + H
2
O -CO
2
+ H
2
(12)
Cellulose !
decomposition
water-soluble products
!
gasfication
Ni
gasesH
2
CO
!
methanation
Ni
gasesCH
4
CO
2
13
However, the H
2
is readily released from the liquid phase to
the gas phase. As a result, the catalyst cannot be in contact
with a large concentration of hydrogen. This might prevent the
methanation reaction from occurrence although methanation
is readily catalyzed by such types of catalysts (eqn (9) and
(10)). Recently, Sinag et al.
191
compared the eect of nano-
sized and bulky ZnO and SnO
2
on the water-gas shift reaction
in gasication of cellulose. The results showed that at 573 K
the watergas shift reaction proceeded faster over ZnO
catalysts than that over SnO
2
catalysts. Therefore, a higher
yield of hydrogen was obtained in the presence of ZnO.
Table 5 Some typical reaction conditions and results in catalytic gasication of cellulose or lignocellulosic biomass in the presence of steam
Catalyst Reactants Reaction conditions Typical products Yield (%) Researchers/Year Ref.
Ru/TiO
2
(2 wt%) Cellulose + H
2
O 673 K, 15 min CH
4
44.0 Osada et al./2004 171
1 MPa (argon gas) H
2
9.0
Ru/C (5 wt%) Sawdust + H
2
O 773 K, 20 min H
2
24.0 (wt%) Hao et al./2005 173
27 MPa (N
2
)
RuO
2
Cellulose + H
2
O 723 K, 2 h CH
4
32.1
b
Izumizaki et al./2005 170
44 MPa (argon gas) H
2
13.7
b
Pt/Al
2
O
3
2
O 623 K, 10 min H
2
31.3 Usui et al./2000 178
30 MPa (N
2
) CH
4
9.2 (vol%)
Pd/Al
2
O
3
2
O 623 K, 3 h H
2
42.3 Usui et al./2000 178
30 MPa (N
2
) CH
4
7.7 (vol%)
Rh catalysts Cellulose + H
2
O 1106 K
a
, 60 ms H
2
B52.0 Dauenhauer et al./2007 188
0.1 MPa (N
2
/O
2
= 3.76) CO B49.0
Ni/SiO
2
Al
2
O
3
(50 wt%)
Cellulose + H
2
O 623 K, 30 min or 1 h CO
2
+ H
2
+ CH
4
88.1 Minowa et al./1999 192
18 MPa (N
2
)
Ni NP Wood 973 K, in N
2
H
2
-rich gas N/a Richardson et al./2010 168
Palm empty fruit
bunch
10231063 K Gas 1.76 m
3
gas kg
1
biomass
Lahijani et al./2011 155
Air-blown bubbling
a
Temperature measured at 10 mm from the top of the catalytic bed.
b
L/per 100 g feedstock. NP: nanoparticles.
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The methanation reaction could be also suppressed under
subcritical and supercritical conditions. Minowa et al.
192
reported that cellulose was gasied to hydrogen-rich gas over
a nickel catalyst supported on kieselguhr in hot-compressed
water at around 623 K and 18 MPa (subcritical conditions).
During gasication, the steam reforming reaction and metha-
nation reaction both occurred. The gas phase equilibrium
composition was 4146 mol% CH
4
, 4749 mol% CO
2
and
611 mol% H
2
. Recently, a series of catalysts such as nickel,
iron, copper, zinc, zirconium, ruthenium and RANEY
s
nickel
slurry were evaluated by Resende and Savage in the gasica-
tion of cellulose and lignin in supercritical water.
193
The results
revealed that the metallic catalysts played a critical role in the
formation of gaseous product and the selectivity. The yield of
hydrogen gas could be increased to some degree over nickel or
copper by optimizing catalyst loading and the catalyst surface
area/biomass weight ratio. However, it is worth noting that, in
addition to the active component in a catalyst, usually the
acidity and basicity of a support is also an inuential factor
on product distribution and coke formation. Interestingly,
Tasaka and co-workers disclosed that steam reforming of tar
derived from cellulose gasication was eciently catalyzed
by 12 wt% Co/MgO catalyst at 873 K in a uidized bed
reactor. Over such a type of MgO supported catalysts, the
conversion of tar was found to increase with the amount of
Co loading.
194,195
Those ndings indicate that the eciency
of gasication of lignocellulosic biomass could be greatly
enhanced by endowing the catalysts an additional function
of in situ removal of tar by catalytic steam reforming.
7 Integrated hydroprocessing
Because the dominant components in lignocellulosic biomass
are oxygen-rich cellulosic carbohydrates, the deploymerization
and degradation of lignocellulosic biomass by catalytic hydro-
lysis, solvolysis, liquefaction and pyrolysis primarily leads to
oxygenated molecules with carboxyl, keto, and/or hydroxyl
groups. Therefore, to yield targeted value-added chemicals
and liquid hydrocarbons as transportation fuels, most oxygen-
ated molecules should be further deoxygenated along with
the formation of new CC bonds. In other words, an addi-
tional hydrogenation or hydroprocessing is needed.
196
When
hydrogen is present in the reaction system over multi-
functional catalysts, the partial or thorough removal of
oxygen from the oxygenated molecules and the formation
of CC bonds by hydrogenation and aldol condensation,
alkylation, or ketonization could occur simultaneously or
in situ consecutively.
197
In addition, the catalytic hydrogeno-
lysis of the glucosic carbonoxygen (CO and CQO) bonds in
cellulose and hemicelluloses and aromatic carbonoxygen
(CO) bonds in lignin may also take place in the presence
of hydrogen.
198
Therefore, the technology of integrating
hydroprocessing with hydrolysis, solvolysis, liquefaction and
pyrolysis has increasingly received attention over the past decade.
And it has shown great potential for the production of the
commodity chemicals and fuels from lignocellulosic biomass.
199
In the context of catalytic hydrogenation, supported metal
catalysts, for example Pt, Ru, Pd or Ni catalysts convention-
ally possess superior catalytic properties. Moreover, these
supported metal catalysts have relatively large surface areas
with well-dispersed active metal sites. In addition, metal-
support interactions might signicantly contribute to the
activity, selectivity and stability of a catalyst. The introduction
of metal ions to a catalyst support can also modulate the
acidity/basicity on the surfaces, thereby possibly facilitating
the degradation of lignocellulosic biomass and reducing
carbon deposition by both the support and the active metal sites.
Over these supported catalytic metal catalysts, the eciency of
converting lignocellulosic biomass into hydrogenated products
can be greatly enhanced through complicated reaction networks
consisting of dehydration, dehydrogenation, hydrogenation,
isomerization, oligomerization, decarbonylation and decarboxy-
lation, and so forth.
7.1 Integrated hydroprocessing to produce commodity
chemicals
As summarized in Table 6, presently many researchers use
cellulose as a model of lignocellulosic biomass for investigation
of the integrated hydroprocessing with hydrolysis to produce
commodity chemicals. A typical method is the combination of
supported Pt, Pd or Ru catalysts for hydrogenation with liquid
acid catalysts for hydrolysis. It oers a more ecient route to the
conversion of cellulose in a one-pot process reaction in the
aqueous phase to form C
4
to C
6
sugar alcohols, in particular
sorbitol, mannitol, and even ethylene glycol (Scheme 10, Table 6).
In particular, sorbitol can be transformed to fuels (hydrogen, light
alkanes and liquid alkanes) by aqueous-phase reforming or
to a number of high value-added chemicals by aqueous-phase
hydrodeoxygenation.
200
The type of noble metal and support, the type of acid, acid
concentration and reaction time signicantly inuence cellu-
lose conversion, carbon eciency and product distribution.
201
Notably, the breakage of cellulose involves the cleavage of two
types of COC bonds: the 1,4-b-glycosidic bond connecting
two adjacent glucose monomers and the COC bond within
the glucose ring. Scheme 11 illustrates that over a ruthenium
nanocluster catalyst the cleavage of the 1,4
0
-b-glycosidic bond
at a dierent position will result in two dierent products:
202
Cleavage at the C
1
O bond (position a) leads to dehydrated
sorbitol, while cleavage at the position b gives dehydroxyed
glucose. Therefore, to design a catalyst for a precise COC
cleavage is much conducive to the selectivity of the desired
product.
In addition, when noble metals are supported onto acidic
solids, possibly there is no need for the use of liquid acid. For
example, over Pt/g-Al
2
O
3
catalysts, the surfaces of g-Al
2
O
3
support have acidic sites, which can catalyze the hydrolysis of
cellulose to glucose, and then the CQO group in the glucose
molecule can be catalytically reduced by H
2
over Pt species on
the surface of g-Al
2
O
3
, thereby leading to the formation
of hydrogenated products like sorbitol or mannitol.
203,204
Nevertheless, g-Al
2
O
3
itself is not acidic enough to eciently
hydrolyze cellulose.
118
The additional acidity can be produced
from the interaction between Pt/Al
2
O
3
and hydrogen.
28
Under
the reaction conditions H
2
may undergo heterolytic dissocia-
tive chemisorption of hydrogen on platinumatoms. Moreover,
hydrogen molecules activated on the platinum surface are able
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to exchange with protons of the hydroxy groups on the surface
of support Al
2
O
3
.
203
These resultant H
+
species can reversibly
spill over onto the surface of the catalyst support.
203,204
Consequently, more Brnsted acid sites formed on the support
which can then catalyze the hydrolysis of cellulose to glucose,
followed by metal-catalyzed hydrogenation. This is part of the
reasons that the presence of Pt/g-Al
2
O
3
was found to signi-
cantly increase the initial rate of dissolution-conversion as well
Table 6 Integrated hydrolysis with hydroprocessing in the conversion of cellulose over supported catalysts
Catalyst Reactants Reaction conditions Main products Yield (%) Researchers/Year Ref.
Ru/HUSY (2.5 wt%) Cellulose + H
2
O + H
2
463 K, 24 h Sorbitol 0.7 Fukuoka et al./2006 205
5 MPa (H
2
)
Ru/PVP (1 wt%) Cellobiose + H
2
O + H
2
393 K, 12 h Sorbitol 23.18 Yan et al./2006 202
4 MPa (H
2
) Glucose 1.4
Ru/C (4 wt%) Cellulose + H
2
O + H
2
518 K, 30 min Hexitols 39.3 Luo et al./2007 206
6 MPa (H
2
)
Ru/C Cellulose + H
2
O + H
2
498 K, 5 min EG 15% Deng et al./2010 211
6 MPa (H
2
) + CH
3
OH 1,2-PD 14%
H
4
SiW
12
O
40
and Ru/C
catalysts
Cellulose + H
2
O + H
2
463 K Polyol 65 Geboers et al./2010 209
5MPa (H
2
) Sorbitol 27
Pt/g-Al
2
O
3
(2.5 wt%) Cellulose + H
2
O + H
2
463 K, 24 h Sorbitol 25 Fukuoka et al./2006 205
5 MPa (H
2
) Mannitol 6
Pt/PVP
b
(1 wt%) Cellobiose + H
2
O + H
2
393 K, 12 h Sorbitol 18.5 Yan et al./2006 202
4 MPa (H
2
) Glucose 42.6
Pt/Al
2
O
3
(2.5 wt%) Cellulose + H
2
O + H
2
518 K, 30 min Sorbitol 9.5 Ji et al./2008 214
6 MPa (H
2
) Mannitol 6.0
EG 14.2
Pt/g-Al
2
O
3
Cellulose + H
2
O + H
2
463 K, 24 h Sorbitol 15 Jolle et al./2009 204
5 MPa (H
2
) Glucose o1
HRuCl(CO)(PPh
3
)
3
, Rh/C Cellulose + H
2
O + H
2
423 K, 48 h Glucose 26 Ignatyev et al./2010 208
3.5 MPa (H
2
) + C
4
MIMCl Sorbitol 74
2%Ni30%W
2
C/AC Cellulose + H
2
O + H
2
518 K, 30 min Sorbitol 3.9 Ji et al./2008 214
6 MPa (H
2
) Mannitol 1.9
EG 61.0
Ni/carbon ber Cellulose + H
2
O + H
2
463 K, 24 h Sorbitol 50.0 de Vyver et al./2010 212
6 MPa (H
2
) Mannitol 6.2
Erythritol 12.8
EG 2.5
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.
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as the selectivity to polyols, especially sorbitol.
203,204
More-
over, 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-Al
2
O
3
, on the surface of a carbon-
supported 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 C
4
MIMCl
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 C
4
to C
6
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 devel-
oped 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/
TiO
2
proved to be highly active and selective for the formation
of EG from cellulose.
213
W was considered as a key compo-
nent 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-W
2
C/AC catalysts showed remarkable selec-
tivity towards EG with a yield up to 61 wt% after 30 min at
518 K and 6 MPa H
2
. In addition to integrated hydrolysis and
hydrogenation, integrated aldol-condensation and hydro-
genation of lignocellulosic biomass (corncobs) to produce
water-soluble C
5
C
15
compounds was recently developed in
a single reactor system over Pd/WO
3
ZrO
2
catalysts.
215
The
promising progress means that there is still plenty of scope
to design more ecient catalysts for the one-pot catalytic
conversion of cellulose into value-added polyols and other
ne chemicals.
7.2 Integrated hydroprocessing to produce fuels
Another major objective of integrating hydroprocessing is to
convert lignocellulosic biomass to liquid hydrocarbons so that
they can directly replace the present gasoline or diesel fuels in
transportation applications. In this context, the processes of
hydrogenating hydrolytic compounds and hydrogenating
pyrolysis oil have been intensively investigated. Moreover,
lignocellulosic biomass is used more often as a starting
material, rather than pure cellulose model samples.
Studies have shown the possibilities for yielding diesel
and gasoline from lignocellulosic biomass by integrated
hydrogenation with acid-catalyzed hydrolysis. Recently it was
revealed, for example, that an integrated process can produce
gasoline with high octane numbers from maple wood.
216
Such a process involves dilute acid-catalyzed (H
2
SO
4
, oxalic
acid) hydrolysis of maple wood into aqueous carbohydrate
solutions at 433 K, followed by aqueous phase hydro-
deoxygenation of the resulting sugar solutions. Thus it led to
a product similar to gasoline with a carbon yield of up to 57%
and an estimated octane number of 96.5. Because of the compli-
cated compositions of hydrolytic products, hydrogenation
deoxygenation of aqueous carbohydrate stream was realized
by a two-stage selectively catalytic process: rst the catalyst bed
contained a Ru/C catalyst at 393 K and the second catalyst
bed contained a Pt/zirconium phosphate catalyst at 518 K.
As discussed previously, pretreatment by organic solvent can
be signicantly helpful to dissolve or solvolyze lignin, cellulose
or hemicellulose in lignocellulosic biomass. Clearly, it is also
conducive to the integrated process of hydrolysis and hydro-
genation. It was demonstrated that the pretreatment of cellu-
lose in 1-hexanol at 623 K, followed by hydrocracking catalyzed
by Pt/HZSM-5(23) at 673 K in the presence of hydrogen,
produced C
2
C
9
alkanes with a remarkable yield up to 89%.
217
Compounds other than hydrocarbons from lignocellulosic
materials also have potential for use as fuels. For example,
Lange and co-workers
218
reported that over bifunctional
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.
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catalysts Pt/TiO
2
and Pt/ZSM-5 valeric esters as biofuels were
produced from lignocellulosic materials. The synthesis of
valeric biofuels consisted of acid hydrolysis of lignocellulosic
materials to levulinic acid, hydrogenation of the levulinic
acid to g-valerolactone (gVL) and valeric acid (VA), and its
subsequent esterication to valeric biofuels (Scheme 12A).
According to the proposed mechanism for the conversion of
gVL to VA over bifunctional catalysts (Scheme 12B), the
optimal production of VA requires a balancing of the acidic
and hydrogenation functionalities of the bifunctional metal/
zeolite catalyst. Therefore, changing the ratio of metal to
zeolite led to dierent intermediates and products. Low metal
loading onto zeolite resulted in an increase in the coproduction
of pentenoic acid. High metal loading favored the formation
of methyl tetrahydrofuran (MTHF), pentanal/pentanol,
and/or pentane/butane. In particular, it is noteworthy that
valeric biofuels were found to be fully compatible for blending
with gasoline or diesel. More recently, Serrano-Ruiz et al.
described
219,220
that the deconstruction of cellulose in an
aqueous solution of H
2
SO
4
yielded an equimolar mixture of
levulinic acid and formic acid. The formic acid could then be
decomposed into H
2
and CO
2
and thus H
2
was consumed
to reduce levulinic acid to GVL in the H
2
SO
4
solution over a
Ru/C catalyst. Moreover, the formation of GVL brought
about easy separation and recycling of the used H
2
SO
4
in
the cellulose deconstruction reactor. Remarkably, in a single
reactor by means of a dual catalyst bed of Pd/Nb
2
O
5
and
ceria-zirconia; levulinic acid and GVL could be catalytically
upgraded to 5-nonanone and then liquid hydrocarbon fuels
similar to diesel and gasoline.
In addition to hydrotreating hydrolytic products, hydro-
processing of the pyrolysis oil of lignocellulosic biomass is also
a promising option for the production of CH-rich fuels from
lignocellulosic biomass. One example is the extraordinary nd-
ing by Vispute and co-workers documenting that the further
hydroprocessing of the pyrolysis oil greatly increased its intrinsic
hydrogen content, thereby leading to light olens and aromatic
hydrocarbons.
221
Over zeolite catalyst, the yield of aromatic
hydrocarbons and light olens could be tuned through the
amount of hydrogen added to the biomass feedstock during
hydroprocessing. As discussed, fast pyrolysis of lignocellulosic
biomass is a relatively economical way to produce pyrolysis
oil. As such, an ecient integrated hydrotreating denitely
oers remarkable potential for production of renewable liquid
bio-based diesel and gasoline from lignocellulosic biomass.
8 Prospects and concluding remarks
The limitation in the availability and sustainability of fossil
fuels such as coal, petroleum and natural gas, along with the
negative ecological and environmental impacts of their uses
compel many researchers to develop new environmentally
friendly processes on the basis of renewable feedstocks.
222
Lignocellulosic biomass, in particular plant cell wall-based
cellulose, is the most abundant and bio-renewable resource
on earth. It has been considered as one of the most attractive
alternatives to replace fossil resources for the production of
fuels, fuel additives and ne chemicals.
Over the past decades, several catalytic systems, namely
hydrolysis, liquefaction, gasication, pyrolysis and deoxy-
genation/hydrogenation for the catalytic conversion of ligno-
cellulosic biomass have increasingly received attention.
Generally, acid catalysts are primarily used in the catalytic
hydrolysis of lignocellulosic biomass to produce glucose and
xylose; metal supported catalysts and zeolites are primarily
evaluated in the gasication of lignocellulosic biomass to
produce H
2
or syngas; and alkaline catalysts are dominantly
investigated in the fast pyrolysis. Over multifunctional
catalysts, the integrated hydroprocessing of lignocellulosic
biomass specically lead to sorbitol and mannitol, EG or
hydrocarbon-based diesel and gasoline.
Theoretically, the scale-up of a chemocatalytic process of
lignocellulosic biomass can produce fuels and chemicals in
large quantities in a short reaction period. However, no matter
what type of catalytic processes employed, present techniques
have not yet met the required level for commercialization in an
economical and environmentally stable fashion. The present
liquefaction, gasication and pyrolysis of lignocellulosic
biomass yield very complicated products in most cases. The
upgrading and separation of products requires high energy
consumption. The invention of a heterogeneously solid
catalyst with extraordinary activity and selectivity remains
an essential task of paramount importance. A paradoxical,
challenging issue is that the heterogeneous reaction over solid
catalysts commonly suers from low catalytic activity due to
the solidsolid contact between the insoluble lignocellulosic
biomass and solid catalyst. The utilization of ionic liquids as
solvents and/or as catalysts provides an alternative solution.
However, the use of the ionic liquids might bring about new
problems such as separation and extraction of the targeted
products and increased cost.
Fast pyrolysis of lignocellulosic biomass has proven to be
more ecient than liquefaction and gasication. It is expected
that upgraded pyrolysis oils can act as fuels directly. However,
provided that gasication processes can selectively produce
syngas with cost-eective cleaning technology, it is also
certainly of great commercial value because syngas can be
converted to clean fuels and ne chemicals by currently
available catalytic technologies, for example syngas to methanol
and ethanol and then to hydrocarbons and olens.
223
Also, it
is much desired to directly gasify and pyrolyze wet ligno-
cellulosic biomass because drying lignocellulosic biomass is an
energy-intensive and time-consuming operation.
224
In the short term, fossil crude oils are still available in large
quantities. Therefore, the overall costs for production of
commodity fuels and chemicals from lignocellulosic biomass
processes by the present catalytic techniques are indeed
less competitive in comparison with large-scales petroleum
industries. In the long run, integrated production of fuels
and ne commodity chemicals from lignocellulosic biomass
feedstocks could be the most economical and renewable alter-
native in a sustainable society. To put the catalytic processes
of lignocellulosic biomass into use, some key points to be
addressed in the years ahead include:
(1) In-depth understanding of the mechanism of the hetero-
geneously catalytic conversion of lignocellulosic biomass. It is
necessary to identify the specic features of each component
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such as cellulose, lignocelluloses and lignin in the reaction
networks. It includes the interrelationship among the feed-
stock, the catalyst, the reaction conditions and the product
distribution. In addition, the specic sources of lignocellulosic
biomass to the desired products should also be established
more clearly in each process.
225
In-depth insights into the
structure of cellulose and lignin biopolymers from the inter-
disciplinary sciences of plant and chemistry are surely useful to
develop a strategy to convert it.
226,227
(2) Strategic design and preparation of multifunctional cata-
lysts for highly active and selective conversion of lignocellulosic
biomass. This involves acidity, basicity, metal-support interac-
tions, the shape of catalyst particles, mechanical and chemical
stability, deactivation and reusability. Because of the peculiar
features of lignocellulosic biomass and its degraded products,
novel reactors and separation systems, including process intensi-
cation, for continuous one-pass or one-pot operation should be
developed so as to reduce the cost, minimize waste disposal and
energy consumption, and maximize the productivity.
(3) Ecient production of liquid hydrocarbons from ligno-
cellulosic 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 ligno-
cellulosic biomass should, for the most part, produce hydro-
carbon-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 con-
version 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, ligno-
cellulosic biomass contains hemicellulose and lignin which are
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, [t
product
m
3
reactor
h
1
]; 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.
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still less investigated. Moreover, the most workable and
economical way could be to use lignocellulosic biomass
directly, rather than pure cellulose. It might be right to say
that the technology of catalytic conversion of lignocellulosic
biomass to fuels and chemicals remains in its infancy. Recent
advances have shown an exciting prospect of putting catalytic
conversion of lignocellulosic biomass to good use. The next
decades will certainly witness the use and growth of catalytic
production of fuels and chemicals from lignocellulosic
biomass with continual technological innovations.
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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Catalytic Conversion of Lignocellulosic Biomass To Fine Chemicals and Fuels

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5588 Chem. Soc. Rev.

Oxalic(0.1M) + NaCl Cellulose 403 K, 6 h Glucose 2.83.9 Vom Stein et al./2010 67

Naon/silica Cellulose 463 K, 24 h Glucose 9.0 Hegner et al./2010 76

AC: Active carbon. BC: Biomass char. [C

). In the presence of cellulose, the H

from the dissociation of water molecules to

]) increases and water behaves as a

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