2008 - Cellulose Conversion Under Heterogeneous Catalysis

DOI: 10.1002/cssc.
200800129
Cellulose Conversion under Heterogeneous Catalysis

Paresh L. Dhepe[b] and Atsushi Fukuoka*[a]
In view of current problems such as global warming, high oil researchers to develop environmentally benign processes that
prices, food crisis, stricter environmental laws, and other geopol- lead to selective formation of value-added products from cellu-
itical scenarios surrounding the use of fossil feedstocks and lose under relatively mild conditions. This Minireview gives insight
edible resources, the efficient conversion of cellulose, a non-food into the importance of biomass utilization, the current status of
biomass, into energy, fuels, and chemicals has received much at- cellulose conversion, and further transformation of the primary
tention. The application of heterogeneous catalysis could allow products obtained.
1. Introduction
It is broadly believed that the huge amount of carbon dioxide is the utilization of biomass. Figure 1 shows a schematic of
(CO2) released in the atmosphere is a main culprit for global how we can utilize biomass for our diverse requirements.
warming, as it is a greenhouse gas.[1] The exponential increase Biomass is defined as a living or dead material derived from
in the use of fossil feedstocks for the production of chemicals, plants, waste, and animal dunk and their body parts. In a bio-
energy, and fuels in recent times has not only contributed to refinery, which is similar to an oil refinery, biomass (either
increasing the total accumulated CO2 in the atmosphere sixfold plant- or animal-derived) is converted into chemicals, energy,
(at 6 billion metric tons in 2000) in nearly 75 years but also has and fuels by various platforms. The CO2 produced is released,
caused an increase in the price of crude oil to US$ 140 per only to be trapped again by plants to make carbohydrates
barrel at present. At this point in time, there are sufficient with the help of water and solar energy in the photosynthesis
amounts of oil reservoirs to satisfy our current needs even if process. In this Minireview, we focus the discussion on plant-
the utilization of oil is on the verge of becoming uneconomi- derived biomass and concentrate on the production of chemi-
cal, but surely one must think about how to develop new re- cals.
sources/methods to replace the current resource or at least to
compensate its consumption in some percentage.[1, 2]
There are several options open to us, but these may not be
as practical as they seem at first glance. For instance, resources 2. Plant-Derived Biomass
such as wind, hydro (including tidal), nuclear (fission or fusion),
Plants produce carbohydrates such as starch, cellulose, and
solar, and biomass are available to produce energy. In continu-
hemicellulose and fix C, H, and O in the form of C5 and C6
ation, for the production of fuels, or in other words to run our
sugar molecules. Starch is a main constituent of food material
machines, we can opt for hydrogen, solar, and biomass resour-
such as potato, rice, and maize. Cellulose, hemicellulose, and
ces. For the production of chemicals, however, we need some
lignin (lignocelluloses) are constituents of wood and are non-
kind of resource that can give us basic elements such as C, H,
food materials. Starch is a polymer made up of glucose units
and O in abundant amounts. For this, the only foreseen option
linked together through a-1,4 or a-1,6 linkages to form amy-
lose and amylopectin, respectively, whereas cellulose is a poly-
mer of glucose linked together in a b-1,4 fashion (Figure 2 and
Figure 3). The difference in the bonding of glucose units be-
tween starch and cellulose gives rise to very different proper-
ties. For example, starch is soluble in hot water, but cellulose is
insoluble in common solvents and is soluble only in concen-
trated aqueous solutions of zinc chloride, ammoniacal copper
hydroxide,[3] and ionic liquids.[4]
[a] Prof. A. Fukuoka

Catalysis Research Center, Hokkaido University
Sapporo 001-0021 (Japan)
Fax: (+ 81) 11-706-9139
E-mail: fukuoka@cat.hokudai.ac.jp
[b] Dr. P. L. Dhepe
Figure 1. Biomass utilization for the production of chemicals, fuels and Inorganic and Catalysis Division, National Chemical Laboratory
energy. Pune 411 008 (India)
ChemSusChem 2008, 1, 969 – 975 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 969
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A. Fukuoka and P. L. Dhepe
solvent extraction that operates at temperature as low as

50 8C.[5]
3. Conversion of Biomass
For the production of chemicals either from a mixture of ligno-
celluloses or separated polymers, the main route involves the
breaking down of these polymers to sugar molecules. Other al-
ternative routes also convert biomass into chemicals (see
Scheme 1). Much work has been done on the conversion of
starch into chemicals, but starch is a food material. The use of
starch for the production of chemicals has been recently criti-
Figure 2. Structure of starch molecules. cized in view of increasing food prices all over the world. We
concentrate our discussion on the utilization of non-food cellu-
lose.
3.1. Properties of Cellulose and Characterization Techniques

Before discussing the different methods to convert cellulose,
first we look into structural aspects that influence the course
of the reaction. The conversion of cellulose is dependent on
various factors such as the crystallinity index (CrI), the degree
of polymerization (DP), and the fraction of reducing ends (FRE)
associated with the substrate.[3, 6–8] Among these, the CrI is a
major factor, because if cellulose has a perfect crystal structure
it is very difficult for a catalyst to have the interaction with the
interior sites of the crystal. Indeed, owing to the rigidity of its
structure (see below), cellulose is rather difficult to degrade. As
shown in Figure 4, d-anhydroglucopyranose units are joined
together through ether linkages (sharing one oxygen) to form
a long chain. The repeating unit in the chain is anhydrocello-
biose. Because of b-type bonding between two adjacent glu-
cose units, alternate glucose units in the chain are rotated by
1808. This arrangement makes the system very symmetric
when two chains run parallel or anti-parallel to each other. As
a result, hydrogen bonding is possible with the same number
of oxygen and OH groups present on both the chains. Thus,
Figure 3. Structure of cellulose molecules.
the network of inter- and intramolecular hydrogen bonds
formed hold large number of chains of cellulose together, and
the intersheet hydrogen bonding also binds various sheets.
Owing to such a large network of hydrogen bonds, cellulose
Hemicellulose is another polymer which is made up of vari- forms a crystalline structure. Molecular simulations predict that
ous monosaccharides such as xylose, arabinose, mannose, glu- in the crystalline form a total of eight hydrogen bonds are
cose, and glucuronic acid, depending on the source, and these present per repeat unit, while in the amorphous form this
monomers are linked together in various fashions. Woods and number is 5.3. These results indicate that the amorphous form
grass plants contain cellulose (40–50 %), hemicellulose (25– of cellulose is more susceptible to hydrolysis than the crystal-
30 %), lignin (25–30 %) and some other ingredients such as line form.
minerals and organic compounds (wax, proteins, fatty acids, There are two types of crystalline structures for cellulose, Ia
etc.). For the use of cellulose in the pulp and paper industries, and Ib, and these forms are part of cellulose-I type.[9] Here, Ia is
its separation from hemicellulose (xylans, mannans, galactans) less stable to chemicals than Ib as a result of differences in
and lignin (phenolic polymer) is performed by steam explosion, inter- and intramolecular hydrogen bonding depending on the
mild oxidation, and treatment with dilute alkali. The two different crystal lattice present. Structure Ia is predominantly
known methods for separation are the Kraft process and the present in algae, while the Ib structure is naturally present in
organosolv process. The Kraft process uses sodium hydroxide higher plants. Cellulose-I can be converted into other types of
and sodium sulfide, whereas in the organosolv process organic cellulose, namely II, III, and IV, upon particular treatment. With
solvents (alcohols) are used for lignin separation.[2] Recently, a enzyme-catalyzed processes, the problem of restricted reactivi-
new method was reported based on acid pretreatment and ty persists even after many decades of research work and has
970 www.chemsuschem.org 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2008, 1, 969 – 975
[Eq. (1)], where I002 represents

the maximum intensity of the
(002) lattice diffraction (2q =
22.58) and IAM represents the in-
tensity of diffraction scatter for
the amorphous part at 2q = 188
in cellulose-I.[10]
CrI ¼ ðI002 IAM Þ=I002 100 % ð1Þ
Furthermore, the crystallinity

index can be calculated in
13
C NMR spectroscopy by using
Equation (2), which is based on
the ratio between the peak
areas (A) of C4 peaks.[11, 12] The
peak at d = 86–92 ppm is as-
signed to crystalline cellulose,
and the peak at d = 79–86 ppm
Scheme 1. Various routes for the conversion of biomass. is assigned to amorphous cellu-
lose.
CrI ¼ A8692ppm =ðA7986ppm þ A8692ppm Þ 100 % ð2Þ
The degree of polymerization can be defined as the

number-average (DPN) or weight-average (DPW), or by viscosity
(DPV). Measurement of DP is possible by dissolution of cellu-
lose in an aqueous solution of cupric ammonium hydroxide or
by the formation of cellulose derivatives with organic solvents
or by dissolving it in ionic liquids. Care must be taken that al-
teration of chain length does not take place during dissolution.
Membrane or vapor pressure osmometry, crystallography, or
electron microscopy can be used to measure the DP.[6, 8] Light
scattering and XRD analyses as well as measurement of the
sedimentation equilibrium give values for DPW. The viscosity
Figure 4. Hydrogen bonding in cellulose.
variant DPV can be calculated by measuring the viscosity of so-
lution.
Even though cellulose looks a very simple molecule, various
parameters make it a very complicated substrate on the mo-
eventually lead to the development of a number of pretreat- lecular level. Hence, to check the activity of different catalysts,
ment procedures to loosen the cellulose structure, that is, to it is rather preferred to use a model substrate. Several model
convert crystalline cellulose into amorphous cellulose. The vari- substrates are known, and to prepare them wood is first con-
ous methods known are divided into two main categories: verted into wood pulp by cutting, delignification (remove
physical (milling, grinding, steaming, irradiation, etc.) and lignin from lignocelluloses), bleaching (change the color), and
chemical (dissolution, alkali, acid, swelling, gas, oxidation, sol- washing processes. Spruce pulp is bleached with SO2 and ball-
vent, etc.). These methods are also responsible to decrease the milled to give Solka Floc. A widely used model cellulose is
degree of polymerization and increase the fraction of reducing Avicel, which is commercially available and is prepared by par-
ends. tial acid hydrolysis of wood pulp. This microcrystalline sub-
Characterization tools such as X-ray diffraction (XRD) and strate contains a substantial amount of the amorphous form as
NMR spectroscopy are generally used to establish the crystal- a result of the hydrolysis step. Filter papers are normally pre-
linity of cellulose and are very useful in determining the extent pared from cotton pulp.[6] The values of DP, CrI, and FRE for
of reaction. The most commonly used method to measure native cotton cellulose and Avicel cellulose are as follows:
crystallinity is based on XRD, as it allows monitoring of struc- DPN = 1000–3000, CrI = 0.8–1.0, and FRE = 0.1–0.03 % for native
tural changes brought about by a certain treatment. Segal cotton cellulose; DPN = 300, CrI = 0.6–0.7, and FRE = 0.3 % for
et al. proposed a formula to calculate the crystallinity index Avicel.
ChemSusChem 2008, 1, 969 – 975 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 971
3.2. Methods for the Conversion of Lignocelluloses vious disadvantages of this method are low activity, the use of
buffers to adjust the pH to that at which the enzymes work,
3.2.1. Thermochemical Transformation
and the high cost of enzymes which makes such a process un-
Among the various known methods to convert cellulose and economical. Also, separation of the product from the enzyme
hemicellulose into chemicals, thermochemical transformation is difficult as they are both soluble in water.
of cellulose is possible above 700 8C to give various chemicals.
As for gasification, cellulose or lignocellulose can be decom-
3.2.5. Other Platforms
posed with restricted amounts of oxygen to give syngas (CO +
H2).[1, 13, 14] Several reports on this process are available, and Direct heating or burning of lignocelluloses is perhaps the
both CHOREN and Shell have demonstrated processes where- oldest known method for using these materials to produce
by after gasification the product stream is exposed to Shell’s energy. Besides this, an agrochemical method is also known in
Fischer–Tropsch technology to clean up the syngas.[2, 15, 16] If which seeds are extracted for the production of oil, which in
lignocelluloses are heated in the absence of oxygen, then a turn can be used to produce biodiesel. The above-discussed
mixture of gases, oils, tar, and char are generated.[2, 17] Even methods are applicable for the conversion of lignocelluloses
though these technologies have been known for a while, they into chemicals.
present several drawbacks and are not commonly used on an Knowing the disadvantages of the various methods, there is
industrial scale. It is hard to gain good selectivity for any com- a need for the development of a new “green” economical pro-
pound as the temperatures employed are too high for sugars cess for the conversion of cellulose into monomers under mild
or other compounds to remain stable. Formation of low-value conditions with high selectivity. With this in mind, we have
char, tar, and oils is also a problem. Another drawback is its shown that supported metal catalysts are able to hydrolyze
cost-efficiency owing to the high energy input. cellulose. Heterogeneous catalysis already plays a vital role in
oil refineries, thanks to the continuous efforts in this area by
researchers worldwide. The story can be repeated for the bio-
3.2.2. Hot Compressed Water
refinery concept by developing various processes that are
The conversion of cellulose using hot and compressed water, based on heterogeneous catalysts for the conversion of bio-
that is, sub- and supercritical water, has been reported.[18–21] In mass-derived products into chemicals.
this method, cellulose is treated in the absence of a catalyst at
200–400 8C and above 20 MPa for a short period of time to
4. Heterogeneous Catalysis
give hydrolysis products. The use of this method is confined
by the low selectivity toward any particular product owing to Supported metal catalysts were shown for the first time recent-
further degradation reactions and the high energy input. As is ly to be active for their hydrolysis of cellulose to glucose and
known, supercritical water displays superacidity and thus the its further conversion into sugar alcohols (sorbitol and manni-
reactor material is significantly prone to corrode. As a result, tol) in a one-pot reaction (Scheme 2).[28] The importance of this
the process has high capital costs associated with it and re- method lies in the fact that no mineral acids or buffers are
quires heavy investment. used to adjust the pH of the solution, essentially making the
whole system corrosion-free and simple to handle. Moreover,
separation of the catalyst from the product is effortless as the
3.2.3. Mineral Acids
catalyst is insoluble in water, the media used for the reaction,
The hydrolysis of cellulose with dilute or concentrated HCl and whereas the products, sorbitol and mannitol, are water-soluble.
H2SO4 has been used for a long time.[22–24] However, its com- A similar route was previously proposed but was only applica-
mercial use is obstructed by problems in stopping the further ble to starch as a starting material owing to its relative ease of
degradation of monomers, corrosion risk, the handling and hydrolysis compared to cellulose.[29] The reactions were typical-
storage of acids, and generation of neutralization waste. Under ly carried out in a batch-type reactor at 150–250 8C under 1–
reaction conditions of 200 8C and above in the presence of 5 MPa hydrogen pressure for 24–48 h.
acids, the structure of cellulose is modified and frequently it Developing on from earlier reports on the acid-catalyzed hy-
becomes more difficult to degrade.[25] drolysis of cellulose, efforts were later put into using solid acid
catalysts. Various solid acids were tested for this reaction, but
they gave only low activity (Figure 5). The most active solid
3.2.4. Enzymes
acid was zeolite HZSM-5 with Si/Al = 20. Compared to conven-
Cellulase is an enzyme complex consisting of endoglucanase, tional acid-catalyzed reactions, the yields were so low that ef-
cellobiohydrolase, and b-glucosidase which catalyzes the hy- forts to make this system viable were abandoned. The reasons
drolysis of cellulose to glucose.[3, 6, 26] Endo- and exo-xylanase behind this low activity are that the solid–solid reaction is diffi-
and b-xylosidase are enzymes typically used for the hydrolysis cult and that protons (H + ) are not freely available to interact
of hemicellulose.[27] In enzymatic hydrolysis, the transfer and with the oxygen atom in the ether linkage of cellulose, point-
adsorption of enzymes onto the surfaces of substrates to form ing to the generation of a large amount of H + in the system.
complexes is essential. This step is followed by hydrolysis, and This may solve the problem of having freely available protons
desorption of products in the water phase takes place. The ob- in the vicinity of the catalyst and the substrate. To achieve a
autoclave with a supported metal catalyst.[30] This approach

gave good results and led to the formation of sugar alcohols
from cellulose (Figure 6).
Figure 6. Supported metal catalyzed conversion of cellulose into sugar alco-

hols. Conditions: cellulose (0.68 g), Pt catalyst (0.21 g), Ru catalyst (0.11 g),
water (60 mL), hydrogen pressure (5 MPa at RT), 190 8C, 24 h.
From Figure 6, it can be seen that Pt and Ru supported on

various supports are active catalysts for the conversion of cel-
lulose (metal loading 2.5 wt % with dispersion in the range of
Scheme 2. Catalytic conversion of cellulose into sorbitol. 10–40 %). The Pt/g-Al2O3 catalyst gave a maximum 31 % yield
of sugar alcohols, namely sorbitol (25 %) and mannitol (6 %).
The overall selectivity for formation of the sugar alcohols was
88 %. The formation of mannitol is explained by isomerization
of glucose during the course of reaction owing to availability
of the acid catalyst. Pt/HUSY (Si/Al = 40) and Ru/HUSY (Si/Al =
20) gave yields of the sugar alcohol of almost 25 %. The amor-
phous supports, SiO2-Al2O3, also showed good activity. Other
metals (Ni, Pd, Ir, Rh) gave low yields of product, implying that
their activity for hydrogen-splitting is lower than that of Pt and
Ru.
Metals supported on a range of supports display different
activities, highlighting the fact that the nature of the support
has a strong influence on the conversion of cellulose. Among
the supports tested, g-Al2O3, HUSY (Si/Al = 40), SiO2-Al2O3, and
HUSY (Si/Al = 20) displayed higher activities than HZSM-5, Hb,
HMOR, SiO2, FSM-16, ZrO2, TiO2, and C. No particular relation-
ship between the activity and the acidity of the supports was
evident from this study, however, further studies are required
to understand this phenomenon.
To make the whole process more attractive and industrially
viable, the catalyst must have a long life and show consistently
high activity. This was studied by separating the catalyst from
Figure 5. Solid acid catalyzed conversion of cellulose into glucose. Condi-
tions: cellulose (0.16 g), catalyst (0.068 g), water (20 mL), hydrogen pressure the reaction mixture and then using it directly in further reac-
(5 MPa at RT), 190 8C, 24 h. tions without any pretreatment. The data for the recycle ex-
periments confirmed that the catalysts could be showed a sim-
ilar activity to the first cycle in subsequent cycles. Moreover,
large amount of H + , and as hydrogen splitting on various when the reaction was carried out with the addition of cellu-
metals is well-established, hydrogen gas was pressurized in the lose to the filtrate solution from a previous reaction, no con-
version was observed. This result confirmed that the metal is

neither leached out during the reaction nor does it form any
adducts with products/substrates.[31]
Ru/C promotes almost complete conversion of cellulose at
an increased reaction temperature of 260 8C.[32] This increased
temperature, however, leads to some loss in selectivity for
sugar alcohols. Besides the desired products, also sorbitan, xyli-
tol, glycols, alcohols, and methane are obtained. The best
result is a selectivity of about 61 % for formation of the sugar
alcohol at 240 8C. The conversion of the model substrate cello-
biose into sugar alcohols was also studied, and almost 100 %
conversion was found to be possible at pH 2. Cellobiose is a
dimer of glucose, soluble in water, and easy to hydrolyze. The
conversion of maltose, sucrose, and starch over metal-free
solid acids has already been reported.[34–37]
Mechanistically, these reactions proceed through various
steps as shown in Figure 7, whereby cellulose is first broken
down into water-soluble oligosaccharides, and then the forma-
tion of glucose proceeds. The metal-catalyzed method involves
the in situ formation of H + by the splitting of hydrogen or
water on the metal surface.[30] The formed proton is reversibly
spilled over onto the support surface and is stabilized. Next,
protonation of the glycosidic O atom takes place and the C1
O bond is broken. The carbocation formed at C1 is then at-
tacked by water, and an OH group is introduced to give glu-
cose. Once glucose forms, it is then readily converted into
sugar alcohols by hydrogenation on the metal.
The proposed mechanism includes the in situ formation of
H + in large excess as hydrogen pressure is applied and a suffi-
cient amount of metal is present to dissociate it. This H + ion
may interact with the cellulose molecule on the external sur-
face of the support. Moreover, as smaller oligomers/glucose
molecules enter the pores of the zeolite they will come into
contact with the metal catalyst inside the pores.
Gasification of cellulose also has been reported by various
groups, and it combines heterogeneous catalysis and supercrit-
ical water conditions.[38–41] Most of the reports on these reac-
tions involve the use of Ru either as an oxide or supported on
Figure 7. Proposed mechanism for the conversion of cellulose.
C and TiO2. Although there are several reports on non-catalytic
gasification reactions under supercritical water conditions, the
use of Ru enhances the conversion of cellulose and the selec- ble because of methanation reactions. The role of Ru is still
tivity for gaseous products. Besides Ru, many other catalysts under investigation, but preliminary suggestions are that it
have been used for this reaction, including Ni/TiO2, Pd/C, CeO2, aids the gasification of several water-soluble compounds.
(CeZr)xO2, and ZrO2.[40, 41] It is well known that supercritical
water acts as a superacid under critical conditions, and so it is
5. Conclusions and Outlook
reasoned that the reaction proceeds like a reaction catalyzed
by a mineral acid. However, under such extreme conditions, The biorefinery concept is increasing the value of biomass to
the sugars formed are readily converted into gaseous products produce multiple products ranging from bulk and fine chemi-
such as H2, CO, CO2, and CH4. It was reported that in the ab- cals to fuels. The use of glucose from the food industry to
sence of a catalyst at 400 8C, the yields of gaseous products, manufacture chemicals has received a lot of attention from re-
water-soluble products, and water-insoluble products are search teams and also from industry. In our work, however,
11.3 %, 39 %, and 29 %, respectively.[40] However, in the pres- glucose is further converted into sugar alcohols such as sorbi-
ence of Ru/TiO2 as catalyst, no water-insoluble products were tol in the presence of metals and hydrogen. At present, sorbi-
obtained while gaseous products were obtained in yields of tol is industrially produced from glucose by hydrogenation[42]
up to 74 %.[40] Similarly, Ni/Al2O3 as catalyst also enhances the and finds use as a low-calorie sweetener, thereby allowing dia-
yields of gaseous products as compared to the catalyst-free re- betic patients to eat sweets. Other possible derivatives from
action. With the Ru/TiO2 catalyst, a higher yield of CH4 is possi- sorbitol are sorbitan, isosorbide, glycols, glycerols, lactic acid,
and l-sorbose.[31, 43] Glycols have a very large market potential [8] H. A. Krssig, Cellulose—Structure, Accessibility and Reactivity, Gordon
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This work was supported by CREST, the JST and KAKENHI
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2008 - Cellulose Conversion Under Heterogeneous Catalysis

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DOI: 10.1002/cssc.

Cellulose Conversion under Heterogeneous Catalysis

[a] Prof. A. Fukuoka

solvent extraction that operates at temperature as low as

3.1. Properties of Cellulose and Characterization Techniques

[Eq. (1)], where I002 represents

CrI ¼ ðI002 IAM Þ=I002 100 % ð1Þ

Furthermore, the crystallinity

CrI ¼ A8692ppm =ðA7986ppm þ A8692ppm Þ 100 % ð2Þ

The degree of polymerization can be defined as the

autoclave with a supported metal catalyst.[30] This approach

Figure 6. Supported metal catalyzed conversion of cellulose into sugar alco-

From Figure 6, it can be seen that Pt and Ru supported on

version was observed. This result confirmed that the metal is

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