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Cite this: Catal. Sci. Technol., 2012, 2, 1852–1858

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Conversion of cellulose to polyols over promoted nickel catalystsw
Abhijit Shrotri,za Akshat Tanksale,z*b Jorge Norberto Beltramini,a
Hanmant Guravc and Satyanarayana V. Chilukuric
Received 27th February 2012, Accepted 14th May 2012
DOI: 10.1039/c2cy20119d

Sorbitol is one of the key platform chemicals that can be applied to several industrial
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applications, including bio-fuels and hydrogen production. Presently there is no commercial

heterogeneous catalytic process to produce sorbitol from cellulose due to the low yield and high
cost of noble metals required for the conversion. In this paper we describe an aqueous phase
hydrolysis–hydrogenation process to convert cellulose to sorbitol using a cheap Ni based catalyst.
Monometallic Ni catalysts showed little activity for the reaction, but with the addition of a small
amount of Pt to the Ni catalyst (Ni : Pt = 22 : 1 atom ratio), the activity was greatly enhanced.
Results showed that the bimetallic Ni–Pt catalysts supported on mesoporous alumina gave a hexitol
(sorbitol + mannitol) yield of 32.4% compared to only 5% with a Ni catalyst. Moreover, Ni–Pt
supported on a mesoporous beta zeolite support provided even higher yield of 36.6%. These results
were obtained after only 6 hours of run at 200 1C and 50 bar H2 pressure (at room temperature).
The presence of a small amount of Pt promotes the protonation of water and hydrogen molecules,
which spill over to Ni sites creating in situ acid sites to catalyse hydrolysis of cellulose.

1. Introduction feedstock for selective conversion to desired products. In this

Carbohydrates are one of the most abundant and economical
bio-materials available in Nature, yet their non-food utilization
is confined to textile, paper and coating industries. As carbo-
hydrates are nontoxic, and biodegradable compounds, they can
provide important environmental benefits to synthesise new
platform chemicals.1 Carbohydrates form a large family of
compounds with considerable structural variety that combines
a number of carbon atom backbones with a high density of
functional groups. Polysaccharides form the bulk of the
renewable lignocellulosic biomass. However, the key platform
chemicals1 are usually made of low molecular weight
compounds (rC6), so they are more readily obtained from
low molecular weight carbohydrates such as C5 or C6 sugars.
The challenge therefore is to utilise the polysaccharides like
cellulose, starch, inulin and xylan that are inexpensive and
available in large quantities but difficult to process as a
paper we describe a method for converting cellulose into key
platform chemicals – sorbitol, mannitol and glycerol, which
can be further converted to make value added chemicals,
liquid fuels or hydrogen (Fig. 1). Sorbitol is an important
platform chemical1 because it can be converted to several
value added chemicals like iso-sorbide2,3 or renewable fuels
like hydrogen4 and can be used unmodified as a sweetener in
consumer products like toothpaste.
Traditionally, cellulose has been converted to glucose by
dilute or concentrated acid hydrolysis.5–7 However, this pro-
cess suffers from acid corrosion and glucose degradation at
high acid concentration. Recently, several researchers have
focused on using heterogeneous catalysts for hydrolysis of
cellulose, following initial reports by Dhepe et al.8,9 whereby
cellulose can be directly converted to sorbitol over a supported
metal catalyst, in the presence of a hydrogen rich gas. This
process has several advantages over the conversion of cellulose

a
ARC Centre of Excellence for Functional Nanomaterials,
University of Queensland, Brisbane, QLD 4072, Australia.
E-mail: a.tanksale@uq.edu.au; Fax: +61 7 3346 3973;
Tel: +61 7 3346 3807
b
Department of Chemical Engineering, Monash University, Clayton,
VIC 3800, Australia. E-mail: akshat.tanksale@monash.edu;
Fax: +61 3 9905 5686; Tel: +61 3 9902 4388
c
National Chemical Laboratory, Dr Homi Bhabha Road,
Pune 411008, India. E-mail: sv.chilukuri@ncl.res.in;
Fax: +91 20 2590 2633; Tel: +91 20 2590 2019
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c2cy20119d Fig. 1 Conversion of cellulose to key platform chemical sorbitol,
z Equal contribution from AS and AT. which can be converted to hydrogen and value added chemicals.

1852 Catal. Sci. Technol., 2012, 2, 1852–1858 This journal is c The Royal Society of Chemistry 2012

to glucose. In the presence of acids and under hydrothermal
conditions, glucose is not stable and leads to the formation of
various by-products, mainly due to the dehydration reaction.
By using a hydrogen rich environment, glucose is rapidly
converted to sorbitol, which is relatively stable under these
conditions. Various types of supported metal catalysts have
been tested for this reaction. Initially zeolite supports were
considered for the reaction,8 but they are not very active due to
the large number of pores in the microporous range. Most of
the mesoporous catalysts require acid functionalization with
sulphonic groups such as sulphonated silicas9 and carbon.10
However, under hot compressed water conditions the function-
alised mesoporous silicas are not stable.11,12 Fukuoka and
Dhepe reported that Pt and Ru supported on g-alumina and
SiO2–Al2O3 were among the best supports for high sorbitol
yield.8 Ru supported on nitric acid functionalised carbon
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nanotubes has also been reported with some success.13 How-
ever, there is a need for a low cost catalyst, which can
effectively replace or reduce the precious metal catalysts. In
this regard we tested Ni-based catalysts, which are widely used
in existing industries due to their low cost and availability. Ni
is known to be a good hydrogenation catalyst, therefore, it is
expected that Ni may perform well as a catalyst for glucose
hydrogenation to sorbitol, as glucose is an intermediate
product in this reaction. However, since the rate determining
step is cellulose hydrolysis which forms glucose,14 an acid site
is required to catalyse the hydrolysis reaction. Molecular
hydrogen is known to dissociatively adsorb on transition
metals and produce hydrogen atoms. These atoms spill over
on supports and migrate away from the metal site where the
atom donates its electron to a Lewis acid site to form a
proton.15,16 This proton acts as an active site for many acid
catalysed reactions.17 Dhepe and Fukuoka14 recently demon-
strated that supported precious metals such as Pt and Ru can
protonate hydrogen and water molecules during the reaction
to produce in situ acid sites, which may catalyse the hydrolysis
reaction. Therefore, in this research we tested the effect of Pt
promotion on Ni catalysts supported on alumina nano-fibre,
mesoporous alumina and mesoporous beta zeolites with
different ratios of Si/Al. These supports were chosen because
of their different level of acidity. We prepared monometallic
catalysts of Pt and Ni and co-impregnated Ni–Pt catalysts on
these supports. In an earlier study we reported the promoting
effect of Pt and Pd on Ni catalysts supported on alumina
nano-fibre for the aqueous phase reforming of sorbitol to
produce hydrogen.4,18 It showed that when Ni and Pt are
co-impregnated on an alumina support, the catalytic activity is
enhanced significantly. This is due to the increased reducibility
of Ni, reduction in the heat of CO-chemisorption, and promo-
tion of the water gas shift reaction.4 In this study we report the
synergistic effect of Ni–Pt bimetallic catalysts on hydrolysis–
hydrogenation of cellulose to produce sorbitol.
2. Experimental
2.1 Catalyst preparation and testing
Alumina nano-fibre (Alnf) was prepared using the method
described in our previous report.4 Mesoporous alumina (Al2O3)
This journal is c The Royal Society of Chemistry 2012
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was prepared by sol–gel synthesis. 4 g of Laponite clay, which
was used as a pillaring agent, was suspended in 200 mL of
water and stirred until a clear solution was achieved. 20 g of
polyethylene oxide surfactant Tergitol 15-S-9 was added to the
solution and stirred for 2 hours. To this solution 20 mL
of Locron-L solution was added drop-wise with continuous
stirring. The resulting solution was transferred to an autoclave
to age for 2 days at 100 1C. The resulting white precipitate
was centrifuged and washed with deionised water six times.
The resulting white cake was calcined at 500 1C for 2 hours with
a heating rate of 2 1C min1. A beta zeolite (Beta_N, where
N = Si/Al) with N = 38 was acquired from M/s Zeolyst
International, PA, USA. To increase the Si/Al ratio dealumina-
tion was carried out by steam treating the as received beta
zeolite followed by removal of dislodged aluminium. Three
types of Beta_N supports with different Si/Al ratios – 38, 75
and 150 – were used in this research. Ni, Pt and Pd metals were
impregnated using appropriate quantities of their chemical
precursors, Ni(NiO3)26H2O (Univar), 8 wt% H2PtCl6 in water
(Sigma) and 10 wt% Pd(NO3)2 in 10 wt% HNO3 (Sigma),
respectively. The precursors were added to the supports and
heated to 50 1C in the presence of a small amount of water and
stirred constantly for 5–6 hours. The resultant solution was
dried overnight in a 90 1C oven and calcined at 500 1C for 5 h.
The catalysts were then reduced in a fixed bed reactor at 400 1C
for 5 h prior to the catalytic run.
Catalysts were tested for cellulose conversion in a Parr high
pressure batch reactor at 50 bar H2 pressure (at room tempera-
ture) and 200 1C for 6 hours. 20 g L1 of Sigmacell Cellulose
20 mm (Sigma) was prepared in 300 mL of deionised water and
1.5 g of catalyst was added to the reactor before pressurising
and heating. After the reaction was complete, the resulting
solution was filtered using a 0.45 mm filter to recover the catalyst
mixed with unconverted cellulose. The solution was filtered
again with a 0.22 mm filter for HPLC analysis.
2.2 Post run characterisation
HPLC analysis was carried out in a Shimadzu Prominence
HPLC system using a Rezex RCM Monosaccharide column
(7.8  300 mm) with 8% Ca cross linking with an oven
temperature set at 65 1C and a water (mobile phase) flow rate
of 0.6 mL min1. The products from the reaction were
detected using a Shimadzu low temperature ELSDII detector
at 40 1C and 370 kPa N2 pressure. The sorbitol and mannitol
yield was calculated by dividing the measured concentration of
sorbitol or mannitol (in mg L1) by 20 000 mg L1, which was
the initial cellulose concentration.
Carbon conversion was calculated using two methods –
Total Organic Carbon (TOC) analysis in the aqueous phase
and elemental carbon analysis in the solid residue. TOC was
measured using a Shimadzu TOC-VCHS analyser. The total
carbon content was analysed by injecting 50 mL of solution
and oxidising in the presence of a catalyst at 680 1C to produce
CO2, which was detected on a non-dispersive infrared (NDIR)
detector. Total inorganic carbon was analysed by reacting
50 mL of solution with HCl, which is volatilised by sparging,
and the emitted CO2 detected on an NDIR detector. TOC is
calculated by subtracting total inorganic carbon from the total
Catal. Sci. Technol., 2012, 2, 1852–1858 1853
 View Article Online

carbon content. TOC conversion was calculated using the
following formula
TOCmeasured ðmg
LÞ
TOC Conversion ¼  100%
8000ðmg
L Þ
where 8000 mg L1 = TOC value for 100% conversion.
Solid carbon content in the catalyst residue was measured
using a Thermo Electron Corporation FlashEAs 1112 series
CHNS-O analyser. 2–3 mg of sample was placed in a tin
container, which was combusted in a furnace at 900 1C. The
product gases were separated in a chromatographic column
and analysed on a Thermal Conductivity Detector. The ‘C’
conversion, based on solid elemental analysis, was calculated
using the following formula
Ccellulose  Cresidue
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remove physisorbed NH3. The TPD experiments were carried
out in the temperature range of 100 1C to 600 1C at a heating
rate of 10 1C min1. The resultant peaks were integrated in the
instrument software and the amount of NH3 desorbed was
calculated against a calibration curve, which is made by
passing pulses of known NH3 standard.
Carbon monoxide (CO) TPD was carried out to determine
the dispersion of metals on a bimetallic beta zeolite catalyst. In
a typical method about 200 mg of catalyst was loaded on the
reaction cell and was reduced at 400 1C for 4 hours using a
hydrogen and nitrogen gas mixture (50 mL min1). The
catalyst was purged with helium at 400 1C to remove adsorbed
H2. The sample was cooled to room temperature under He
flow. A 10% CO–He mixture was passed for 15 min to
complete adsorption of CO on metal sites. Residual CO was
purged with helium until CO base line reading was constant.

0
C 0 Conversion ¼  100%
Ccellulose
where Ccellulose is the amount of carbon in the starting cellulose
material and Cresidue is the amount of carbon in the residue
after reaction. Note that the residue also contains the used
catalyst and therefore we adjusted the measured carbon content
from the CHNS-O analyser by subtracting the weight of the
catalyst used.
2.3 Fresh catalyst characterisation
The supports were characterised with N2 physisorption using a
Quantachrome Quadrasorb SI instrument at liquid nitrogen
temperature, for pore size distribution, pore volume and
surface area. Powder X-Ray Diffraction (XRD) of the calcined
catalysts was carried out in a Rigaku MiniFlex instrument to
analyse the support and metal particle size and phases. These
XRD results were also used as a reference for the post run
XRD of the used catalysts, which contained unconverted
cellulose particles. The metal content of fresh and used
catalysts was analysed by digesting 40 mg of catalyst in
5 mL of nitric acid and 4 mL of hydrofluoric acid using a
CEM MSP 1000 microwave digester. Samples were diluted to
50 mL. Digested solid samples were analysed using a Varian
Vista Pro ICPOES instrument.
Ammonia (NH3) Temperature Programmed Desorption
(TPD) measurements were carried out using Micromeritics
Autochem 2920. About 100 mg of catalyst was activated in a
helium flow for 2 hours at 550 1C. The sample was then cooled
to 100 1C for the NH3 sorption. Mixed gas containing 10%
NH3 in helium (20 mL min1) was passed through the sample
for 0.5 hour, followed by passing pure helium for 0.5 hour to
Temperature programmed desorption was carried out in
the temperature range of 30 1C to 500 1C at a heating rate
of 10 1C min1 under He flow of 40 mL min1. The desorbed
gas was detected using a thermal conductivity detector. Metal
dispersion was calculated assuming that surface concentration
of metals was equal to bulk concentration.19
3. Results and discussion
3.1 Catalyst properties
The catalyst properties shown in Table 1 include support
acidity, BET surface area, BJH pore volume and catalyst
metal loadings. The BET surface area does not change much
with the changing Si/Al ratio in the beta zeolites. The N2
adsorption isotherm of beta zeolites (Fig. 2) shows that
the catalyst is microporous and there is increased adsorption
in the mesoporous range after the dealumination process.
Appearance of large pores in Beta_75 and Beta_150 suggested
significant changes in structure of catalysts after dealumina-
tion. High resolution TEM images of beta zeolites (see Fig S1,
ESIw) show an increase in the pore width after the dealumina-
tion treatment. TEM images also inferred that the large pores
seen in N2 adsorption analysis were interparticle channels
formed due to breaking and loose agglomeration of particles
during the dealumination process. Results in Table 1 show
that reducing the alumina concentration has a reducing effect
on the acidity of the beta zeolite supports. The highest total
acidity (weak + strong acidity) was 0.794 mmol g1 for
Beta_38 (Si/Al = 38), which reduces to less than 1/3rd to
0.226 mmol g1 for Beta_150 (Si/Al = 150). The metal

Table 1 Catalyst physical properties – metal loading, Al concentration (in beta zeolites), pore volume, width, surface area and acidity measured
by NH3 TPD

Metal loading (% w/w) Support

Bi-metallic Acidity by NH3 TPD,
Co-impregnated (Ni–Pt) mmol g1
Al in sample, BJH pore BET surface
Support Mono-metallic (Pt) Ni Pt mmol g1 volume, cm3 g1 area, m2 g1 Weak Strong
Alnf 2.91 6.50 0.96 — 1.19 303 0.106 0.091
Al2O3 3.08 7.32 0.98 — 0.93 531 0.103 0.090
Beta_38 2.72 7.67 0.90 0.839 0.71 524 0.502 0.292
Beta_75 3.44 7.31 0.86 0.434 0.63 538 0.256 0.215
Beta_150 3.16 8.22 1.17 0.219 0.64 535 0.142 0.084

1854 Catal. Sci. Technol., 2012, 2, 1852–1858 This journal is c The Royal Society of Chemistry 2012
 View Article Online

Fig. 4 Rate of CO desorption for bimetallic catalysts on beta zeolite

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supports. Ni–Pt/Beta_38 (J), Ni–Pt/Beta_75 (&), Ni–Pt/Beta_150 (n).

Fig. 2 N2 physisorption isotherm of beta zeolite supports with various
Si/Al ratios; the inset shows pore size distribution of these supports – circles:
Si/Al = 38, squares: Si/Al = 75 and triangles: Si/Al = 150.
formation of large metal particles on the outer surface of the
catalyst as the micropores in beta zeolites are too small
for particle formation inside via the impregnation method.
Dealumination treatments of the Beta_38 support increased
the pore width and also created interparticle channels which
assisted in formation of smaller particles, increasing the metal
surface area. The metal dispersion of the catalysts was in the
following increasing order – Ni–Pt/Beta_38 (3.90%) o Ni–Pt/
Beta_150 (5.00%) o Ni–Pt/Beta_75 (5.75%).

3.2 Cellulose conversion over alumina supported catalysts

The yields of sorbitol and mannitol as determined by HPLC
analysis; and cellulose ‘‘C’’ conversion as determined by
carbon elemental analysis from the solid residue are shown
in Fig. 5. The Ni monometallic catalysts did not show good
activity for the conversion of cellulose, which was less than
24% for both the Ni catalysts. The Pt supported catalysts
Fig. 3 XRD patterns of catalysts supported on beta zeolites with Si/Al showed higher conversion of cellulose with 36.4% and 40.7% for
ratios of 38 (Beta_38), 75 (Beta_75) and 150 (Beta_150). Alnf and mesoporous Al2O3 supported catalysts, respectively. At
the same time, the yields of sorbitol and mannitol also increased
concentration as calculated from the ICPOES analysis is substantially to a combined yield of 26.8% and 32.1% for Alnf
approximately the same for all the catalysts. The Pt loading
was kept at 3% w/w approximately and in the bi-metallic
Ni–Pt catalyst Ni and Pt loadings were equal to 7% w/w and
1% w/w, respectively.
XRD diffraction patterns of all the catalysts supported on
the beta zeolite supports with different Si/Al ratios are shown
in Fig. 3. The large peaks at 2y values of 8.81 and 26.251 match
the beta zeolite peaks according to JCPDS cards and also
those reported in the literature.20,21 The peaks at 2y values of
46.61, 54.51 and 80.31 correspond to PtO2, while the peaks at
43.21, 50.81 and 74.31 correspond to NiO. PtO2 peaks are not
visible for the bi-metallic catalysts due to the relatively low
concentration of loading. These catalysts were not reduced
before the XRD run; therefore the active metal species are
present in their oxide form.
CO TPD results of bimetallic catalysts on beta zeolite
supports show the CO desorption peak centered at about Fig. 5 Sorbitol and mannitol yield and cellulose ‘C’ conversion
150 1C (Fig. 4). These peaks represent the active metal sites (circles) from the aqueous phase hydrolysis–hydrogenation of cellulose
with low heat of adsorption.4 Ni–Pt/Beta_38 showed least at 200 1C and 50 bar H2 pressure (at room temperature) for 6 hours,
activity for CO adsorption in this region. This may be due to using supported alumina catalysts.

This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 1852–1858 1855

and Al2O3 supported catalysts, respectively. If the selectivity
of C6 polyols (hexitols) is defined as
YieldðSorbitol þ MannitolÞ
S¼ 0 C 0 Conversion
 100%
then we find that the selectivity for the two Pt supported
catalysts is 74% and 79% respectively. The conversion, yield
and selectivity values for the Al2O3 supported catalyst are
slightly higher than those for the Alnf supported catalyst. This
may be due to the higher surface area of the support, which
may provide higher Pt particle dispersion. Bi-metallic Ni–Pt
catalysts provided the highest conversion of 44.0% and 48.7%
for the Alnf and Al2O3 supported catalysts, respectively.
However, the selectivity is lower compared to that of Pt
catalysts of 65.8% and 66.5%, respectively. Despite lower
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selectivity, the overall yield is slightly higher due to the higher
conversion. XRD analysis was done on the used catalysts
(Fig. 6) which contained unconverted cellulose to confirm
the cellulose conversion results (also see Fig. S2, ESIw). The
bottom curve shows the XRD pattern of the feed cellulose powder,
which shows a microcrystalline structure with three prominent
peaks at 2y = 18.21, 26.11 and 40.31. The corresponding peak
intensities reduce in the order of Ni/Alnf 4 Pt/Alnf and Ni–Pt/Alnf
for the used catalysts. For the Ni–Pt/Alnf catalyst the cellulose
peaks are not visible at this scale. This indicates that the
amount of microcrystalline cellulose is very small compared
to the other two catalysts, which supports the ‘C’ conversion
results.
Hexitol yield obtained with the bimetallic Ni–Pt catalysts is
significantly higher than that with the Ni catalysts. Therefore
it shows that a small amount of Pt promotes the Ni catalyst
significantly to improve its catalytic activity. This is due to the
synergistic effects between Pt and Ni particles when they are in
close vicinity.4,18,22
In previous studies it was shown that the bi-metallic catalysts
showed very different properties than the corresponding mono-
metallic catalyst, which changes the binding energies of the
adsorbed species.22–24 Supported Pt particles are known to
Fig. 6 XRD pattern of 20 mm cellulose powder and the used Ni, Pt and
Ni–Pt catalysts supported on alumina nano-fibre (Alnf). After the
reaction is complete the used catalysts were filtered with a 0.45 mm filter
and then washed with deionised water to remove soluble products.
1856 Catal. Sci. Technol., 2012, 2, 1852–1858
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assist in the protonation of water and molecular H2 by the
hydrogen spillover effect, which provides in situ acidic sites for
hydrolysis of cellulose.14
Our results suggest that the Ni monometallic catalyst is
unable to generate this acidity and therefore the cellulose
conversion is low. In Ni–Pt bimetallic catalysts Pt atoms
promote protonation of water and H2 to initiate hydrolysis.
In the H2 rich atmosphere Pt sites dissociate molecular H2 into
atomic hydrogen (H+), which spills over to the Ni sites to create
in situ acidity for hydrolysis reaction. The role of Pt promotion
studied earlier showed that bi-metallic Ni–Pt catalysts have
lower reduction temperature than Ni catalysts.4 Pt is able to
react with molecular H2 at a lower temperature than Ni and the
resultant adsorbed H+ reacts with Ni particles at significantly
lower temperatures. In the absence of Pt particles much higher
temperatures are required for Ni particles reduction.
Ni and Pt are known hydrogenation catalysts, with Ni showing
slightly better activity than Pt in a gas phase reaction.23 Under
hydrothermal conditions at low temperature however, Ni is not
very active as shown in our previous results with aqueous phase
reforming of oxygenated hydrocarbons.4,25 With a Pt promoter
the spillover hydrogen adsorbed on the Ni site is able to hydro-
genate the intermediate glucose. Therefore conversion of glucose
into sorbitol happens rapidly. This is indicated from the fact that
we did not detect any glucose in the product mixture in the HPLC
analysis. The results in this paper show some improvement over
the the reported literature in terms of the residence time of the
reactants. Each of our experiments was carried out over 6 hour
duration, while previous reports have used a 24 hour run.8,10,13,26
3.3 Cellulose conversion over beta zeolite supported catalysts
Fig. 7 shows sorbitol and mannitol yields and cellulose conversion
using the beta zeolite supported catalysts. The reaction conditions
were identical to those of the alumina supported catalysts;
however, for HPLC analysis the ELSDII temperature was
reduced to 30 1C to detect volatile species produced during the
reaction. As a result we were able to detect glycerol in the
Fig. 7 Sorbitol, mannitol and glycerol yields and cellulose ‘C’ conver-
sion (circles) and TOC conversion (triangles) from the aqueous phase
hydrolysis–hydrogenation of cellulose at 200 1C and 50 bar H2 pressure
(at room temperature) for 6 hours. ELSD temperature was lowered to
30 1C to detect glycerol during HPLC analysis.
This journal is c The Royal Society of Chemistry 2012

product which was not detected earlier when ELSDII was
operated at 40 1C. The ‘‘C’’ conversion values in Fig. 7
obtained using the elemental carbon analysis were validated
against those obtained using liquid TOC analysis and were
found to be similar within the range of errors in the instrument
precision and accuracy of manually handling the samples.
The results show similar trends as obtained with alumina
catalysts. The beta zeolite support also showed highest cellulose
conversion and hexitol yield with the bi-metallic Ni–Pt catalyst.
The metal dispersion and support acidity, which were a result
of the different Si/Al ratios in the samples, both affected the
conversion. The cellulose ‘‘C’’ conversion and hexitol yield
were in the following increasing order – Ni–Pt/Beta_38 (46.5%
and 25.5%) o Ni–Pt/Beta_150 (48.2% and 30.3%) o Ni–Pt/
Beta_75 (51.3% and 36.6%), respectively. The metal dispersion
of the catalysts is in the following increasing order – Beta_38 o
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Beta_150 o Beta_75. This suggests that cellulose conversion is
directly associated with the number of active metal sites
present on the catalyst. These metal sites assist in formation
of protonic acid sites via dissociation of molecular hydrogen
by spillover.
These acid sites increase the rate of cellulose hydrolysis,
increasing the overall conversion. It is also important to note
that an optimum level of support acidity is required for higher
yield of hexitols. If the acidity is too low the rate of hydrolysis
is low. Whereas, higher acidity leads to degradation of glucose
by dehydration reaction, lowering the hexitol yield. Therefore
we find that the hexitol selectivity is in the following increasing
order – Ni–Pt/Beta_38 (54.8%) o Ni–Pt/Beta_150 (62.9%) o
Ni–Pt/Beta_75 (71.3%).
To confirm the synergistic effect of bi-metallic Ni–Pt
catalysts, where Ni and Pt particles are in close proximity
due to co-impregnation, a control run was performed where a
physical mixture of Pt/Beta_75 and Ni/Beta_75 was put into
the reaction mixture under identical reaction conditions. The
metal loading of the mono-metallic catalysts in the control
reaction mixture was chosen carefully to match the mass
composition of the metals and supports used in the reaction
mixture with bi-metallic Ni–Pt/Beta_75. From the results, as
shown in Fig. 7, it is clear that the yield of hexitols and glycerol
is significantly lower with a physical mixture of the mono-
metallic catalysts compared to all the bi-metallic catalysts
studied. This is not surprising since we know from our
previous reports4,18,25 that Pt promotes the Ni sites during
reduction of the catalysts thereby increasing the active metal
surface area and dispersion. Therefore, we can conclude that
the active sites of Ni and Pt have to be in close proximity to
enhance the catalytic activity due to the synergistic effect of
Ni–Pt interaction.
Glycerol is a product of sorbitol hydrogenolysis which takes
place in the presence of an H2 rich atmosphere on a metal
site (Scheme 1). Other products of sorbitol hydrogenolysis
are propylene glycol, ethylene glycol, erythritol and xylitol
(in decreasing order of their selectivity27). The reaction conditions
in our study favour glycerol production through hydrogenolysis of
sorbitol.27,28 A study by Clark27 showed that the rate of sorbitol
hydrogenolysis is inversely proportional to the reaction pressure.
Clark reported that the reaction follows first order kinetics and at
200 1C and 138 bar (2000 psi) the rate constant is 0.0112 min1.
This journal is c The Royal Society of Chemistry 2012
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Scheme 1 Hydrogenolysis of sorbitol to produce glycerol, propylene
glycol and ethylene glycol.
Since the reaction pressure in our study at 200 1C is B80 bar
we expect the glycerol production rate will be higher than that
reported by Clark.
Since propylene glycol and ethylene glycol are more volatile
than glycerol they could not be detected in HPLC analysis.
The presence of erythritol and xylitol in the product could not
be confirmed due to their concentration being under the
detection limit. Inclusion of the glycerol yield with that of
hexitol does not change the trend in Fig. 7. The maximum
polyol yield (glycerol + hexitol) in the product mixture was
achieved by Ni–Pt/Beta_75 (46%) followed by Ni–Pt/
Beta_150 (44.8%) and Ni–Pt/Beta_38 (40.1%).
Confirmation of the extent of cellulose conversion is
provided by the XRD patterns of the used catalysts (Fig. 8).
All the catalysts show only traces of cellulose microcrystalline
peaks. The absolute intensity of the cellulose peaks in Fig. 6 is
lower than that in Fig. 4, but since the scale of Fig. 6 is smaller,
the apparent height of the peaks appears to be the same.
Additionally, the cellulose peak at 26.11 overlaps with the beta
zeolite peak at 26.251 making it undiscernible from each other
and may give a false impression of high cellulose content.
Overall, we can conclude that all the beta zeolite catalysts
showed higher cellulose conversion by looking at the lower
intensity of the XRD peaks.
Recycling experiments were performed using Ni–Pt/Beta_75
to study the loss of catalytic activity. The used catalyst
was calcined to remove unreacted cellulose, which was then
reduced and tested again under the same reaction conditions
by adding fresh cellulose feed. The results show reduction in
catalytic activity after the 1st run. Cellulose conversion of
36.97% was obtained which is lower than the initial result of
Fig. 8 XRD patterns of the used Pt and Ni–Pt catalysts supported on
beta zeolites with Si/Al ratios of 38 (Beta_38), 75 (Beta_75) and 150
(Beta_150). After the reaction was complete the used catalysts were
filtered with a 0.45 mm filter and then washed with deionised water to
remove soluble products.
Catal. Sci. Technol., 2012, 2, 1852–1858 1857

51.3%. The yield of hexitols also reduced to 16.7%. Selectivity
towards hexitols reduced from 71.3% to 45.17%. This
reduction in activity and selectivity of catalyst is attributed
to the loss of metal from the catalyst after the 1st run. Metal
content of Beta_75 reduced to 0.28% Pt and 6.34% Ni. A
significant decrease in platinum from the support surface
resulted in reduction of the promoter effect in the bimetallic
catalyst which caused a loss in activity. It is important to note
that the catalyst support structure itself is not changed after
the reaction. The XRD patterns of fresh and used catalysts are
very similar. Therefore, it may be possible to reuse the
catalysts in multiple runs by reducing the loss of metals via
improved catalyst preparation techniques.
4. Conclusions
Published on 14 May 2012. Downloaded on 31/01/2014 11:08:33.
Hydrolysis of cellulose is one of the key steps in converting
biomass to fuels and chemicals. However a cheap and reliable
catalyst is required to utilise this technology on a large
commercial scale. In this regard this report shows that Ni
based catalysts can be used with high efficiency on non-
functionalised supports, which are often used in current industries.
Beta zeolite supports used in this study were modified
by dealuminating the original Si/Al = 38 support, which
increased the mesopores in the resulting samples. Supported
bimetallic Ni–Pt catalysts on the modified beta zeolites showed
a maximum conversion of 51.3% and a maximum polyol yield
of 46%, which gives a selectivity of 90%. Moreover, this result
was achieved in only 6 hours of the catalytic run. The
bimetallic Ni–Pt catalysts, supported on the alumina nanofibre,
mesoporous alumina and beta zeolites, all provided slightly
better yield of hexitols when compared to the corresponding Pt
catalysts with significant reduction in the Pt loading on these
supports. Ni monometallic catalysts did not show good activity
for cellulose conversion and hexitol yield. We believe this is due
to the lack of in situ acid sites created in the absence of noble
metal active sites. In the case of the bi-metallic catalysts the
presence of a small amount of Pt promotes the protonation of
water and molecular hydrogen, which then spills over to Ni sites
creating a large amount of in situ acid sites. With the develop-
ment of a much cheaper catalyst, the challenge now is to
develop a continuous heterogeneous catalytic process for the
conversion of cellulose to sorbitol to make this process viable
for commercial application.
1858 Catal. Sci. Technol., 2012, 2, 1852–1858
View Article Online
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