Catalytic hydrogenation of xylose to xylitol using ruthenium catalyst on NiO modified TiO2 support

Article abstract of DOI:10.1016/j.apcata.2012.03.007

The activity of Ru catalyst on a new class of NiO modified TiO₂ support, Ru/(NiO-TiO₂), was studied in the liquid phase catalytic hydrogenation of xylose to xylitol. The TiO₂ support was modified by simple impregnation method using nickel chloride precursor and subsequent oxidation. Various catalysts with different targeted compositions of Ru (1.0 and 5.0 wt%) and NiO (1.0, 5.0 and 10 wt%) in NiO-TiO₂ were prepared. These catalysts were characterized by using energy dispersive X-ray analysis (EDX/EDS), temperature-programmed reduction (TPR), inductively coupled plasma (ICP) mass spectrometry, transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and CO chemisorption. The novel catalysts are evaluated for selective hydrogenation of xylose and the results compared with those obtained from conventional Raney Ni, Ru/C and Ru/TiO₂ catalysts carried out under identical reaction conditions. The effect of NiO additive in the catalyst Ru/(NiO-TiO₂), clearly found to enhance the conversion, yield and selectivity to xylitol. Furthermore, the order of catalytic activity may be given as Ru (1.0%)/NiO (5.0%)-TiO₂ > Ru (1.0%)/TiO₂ > Ru (1.0%)/C> Raney Ni. The effects of Ru and NiO loading, xylose concentration (2.5, 15 and 30 wt%) and temperature (100, 120 and 140°C) were studied. Although at higher temp 140 °C, the conversion of xylose was increased to optimum level, xylose to xylitol selectivity decreased due to formation of by-products.

Full text of DOI:10.1016/j.apcata.2012.03.007

Applied Catalysis A: General 425–426 (2012) 110–116
Contents lists available at SciVerse ScienceDirect
Applied Catalysis A: General
journal homepage: www.elsevier.com/locate/apcata
Catalytic hydrogenation of xylose to xylitol using ruthenium catalyst on NiO
modified TiO support
2
∗
Mithilesh Yadav, Dinesh Kumar Mishra, Jin-Soo Hwang
Biorefinery Research Center, Korea Research Institute of Chemical Technology (KRICT), Daejeon 305-600, Republic of Korea
a r t i c l e i n f o
a b s t r a c t
Article history:
The activity of Ru catalyst on a new class of NiO modified TiO2 support, Ru/(NiO–TiO ), was stud-
ied in the liquid phase catalytic hydrogenation of xylose to xylitol. The TiO2 support was modified by
simple impregnation method using nickel chloride precursor and subsequent oxidation. Various cat-
alysts with different targeted compositions of Ru (1.0 and 5.0 wt%) and NiO (1.0, 5.0 and 10 wt%) in
NiO–TiO2 were prepared. These catalysts were characterized by using energy dispersive X-ray analysis
2
Received 13 September 2011
Received in revised form 2 March 2012
Accepted 3 March 2012
Available online 11 March 2012
(
EDX/EDS), temperature-programmed reduction (TPR), inductively coupled plasma (ICP) mass spectrom-
Keywords:
Hydrogenation
Xylose
Xylitol
Ruthenium
etry, transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and CO chemisorption. The
novel catalysts are evaluated for selective hydrogenation of xylose and the results compared with those
obtained from conventional Raney Ni, Ru/C and Ru/TiO2 catalysts carried out under identical reaction
conditions. The effect of NiO additive in the catalyst Ru/(NiO–TiO2), clearly found to enhance the con-
version, yield and selectivity to xylitol. Furthermore, the order of catalytic activity may be given as Ru
NiO modified TiO2 support
(
1.0%)/NiO (5.0%)–TiO2 > Ru (1.0%)/TiO2 > Ru (1.0%)/C> Raney Ni. The effects of Ru and NiO loading, xylose
◦
concentration (2.5, 15 and 30 wt%) and temperature (100, 120 and 140 C) were studied. Although at
higher temp 140 C, the conversion of xylose was increased to optimum level, xylose to xylitol selectivity
◦
decreased due to formation of by-products.
©
2012 Elsevier B.V. All rights reserved.
1
. Introduction
traditionally carried out in a three-phase slurry batch reactor over
Raney nickel catalysts [12]. The principal advantages of the use of
nickel catalysts are its lower price, ease of use as suspended slurry
in typical batch reactions, good activity and selectivity [11,13]. Nev-
ertheless, the major drawback of Raney Ni catalysts, usually, is their
relatively fast deactivation due to accumulation of organic impuri-
ties (from the starting material) on the catalyst surface, leading to
poisoning of the active sites, and metal leaching [1,14–16]. Conse-
quently, conversion rates and process selectivity are jeopardized. In
addition, it is most important that Ni must be completely removed
from hydrogenated xylitol solution when it is used in the food
industry, or as medicine or cosmetics, which adds further costs
since expensive purification steps such as ion-exchange, filtering
and crystallization are involved [15]. The past few years have seen
a variety noble (Pt, Pd, Ru) metals with some supports, but among
them Ruthenium based catalysts which show much less or no deac-
tivation, have been found as alternative to Ni based catalysts for
hydrogenation processes in recent years [17–21]. Investigations
are under progress for proper metal-support systems for the direct
hydrogenation of xylose-rich solutions (Scheme 1) leading to high
activity and selectivity levels towards xylitol production, while
being less sensitive to the deactivation of catalyst surface by fouling
species. Although some reports are available on the applications of
Ru on activated carbon and TiO2 support, there is no systematic
study using modified TiO2 support.
The selective catalytic hydrogenation of naturally occurring
sugar molecules to their corresponding sugar alcohols is an
environment friendly route for the production of alternative
sweeteners: solid metal-based catalysts are used in an aqueous
environment and the hydrogen addition is brought about through
catalytic reactions, thus avoiding the use of stoichiometric reduc-
ing agents and the subsequent formation of inorganic salts as
waste material [1–3]. Xylitol, a penta carbon sugar alcohol with
interesting properties, is an excellent artificial sweetener gaining
large importance in recent years. The annual xylitol market is esti-
mated to be around $340 million priced at ∼$5/kg indicating its
significance in many food and other value added chemical indus-
tries. It is highly soluble in water, does not caramelize at elevated
temperatures, its sweetening capacity exceeds that of sugar and
has lower insulin requirements, thus being especially suitable for
usage by diabetics. Over the last few years, the demand for xylitol
has increased enormously [4–7]. Xylitol also finds applications in
several other industries such as in pharmaceutical, cosmetic, and
synthetic resin [8–11]. The hydrogenation of xylose to xylitol is
∗ Corresponding author. Tel.: +82 42 860 7382; fax: +82 42 860 7676.
E-mail address: jshwang@krict.re.kr (J.-S. Hwang).
0
926-860X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2012.03.007

M. Yadav et al. / Applied Catalysis A: General 425–426 (2012) 110–116
111
Inc., USA and used as such. De-ionized water was used as solvent
for making all solutions.
2
.2. Catalyst Ru/(NiO–TiO ) preparation
2
The preparation of catalyst, Ru/(NiO–TiO ), was carried out by
2
impregnation method using ruthenium (III) chloride hydrate and
new class of support, NiO modified TiO . The proposed novel sup-
2
port material, was prepared by the following procedure: required
amount (4.8 g) of TiO2 was immersed into aqueous solution nickel
chloride (0.55 g) under magnetic stirring. Then, the resulting mix-
◦
ture was dried at 110 C overnight and after complete drying the
◦
sample was oxidized in air at 500 C for 10 h to obtain NiO modi-
fied TiO support (NiO–TiO ). The calculated amount of (NiO–TiO ),
2
2
2
was further re-impregnated with aqueous solution of ruthenium
◦
(
III) chloride hydrate (0.52 g) and was kept in an oven at 110 C
overnight. The catalyst Ru/(NiO–TiO ) thus prepared was reduced
2
◦
in a continuous flow of (5.0%) H /Ar at 200 C for 3 h and then
2
used immediately for the hydrogenation reactions. The catalysts Ru
(
1.0%)/C and Ru (1.0%)/TiO were also prepared by abovementioned
2
impregnation method.
2.3. Liquid phase hydrogenation of xylose
The hydrogenation experiments of xylose were conducted in a
2
00 mL SS autoclave. The catalyst was screened with xylose solu-
◦
tion (20 wt%) prepared in water at approximately (60–65 C). The
hydrogen gas was purged into the reactor at 2.0 MPa H2 pressure
to deoxygenate the reaction mixture followed by stirring (400 rpm
for 30 min) at room temperature and then pressure was released.
The hydrogenation was initiated by stirring the reaction mixture
◦
at 1200 rpm impeller speed and 120 C for 120 min at 5.5 MPa. The
product components were analyzed using a HPLC (Younglin Instru-
ment, Acme 9000) equipped with refractive index (RI) detector and
Sugar-Pak column. Deionized water was used as an eluent for the
◦
analysis at a flow rate of 0.4 mL/min at 70 C. The temperature of RI
◦
detector was maintained at 35 C throughout the analysis. Before
◦
starting the TPR experiments, the samples were dried at 120 C
for 1 h under Ar flow and then cooled to room temperature. The
(
1
10%) H /Ar was used as reducing gas at a continuous flow rate of
0 mL/min.
2
Scheme 1. Mechanism of reduction of xylose.
In the present investigation, a new class of NiO modified TiO2,
2.4. Catalysts characterization
(
NiO–TiO ), supports are prepared by simple impregnation method
2
using nickel chloride precursor salt and subsequent oxidation.
Various ruthenium catalysts of intended compositions are fur-
ther prepared by re-impregnating these NiO modified supports in
aqueous solution of hydrated ruthenium (III) chloride. The novel
catalysts are evaluated for liquid phase hydrogenation of xylose
and the results obtained are presented and discussed with conven-
tional Raney Ni, Ru (1.0%)/C & Ru (1.0%)/TiO2 catalysts carried out
under identical reaction conditions.
The metal contents (amount of Ru loading) of the catalysts were
determined by using EDX, Quantax 200 Energy Dispersive X-ray
Spectrometer, Bruker. The stability of catalysts (before and after
reactions) was determined with X-ray diffraction (RIGAKU, Mini-
flex Instruments). The amount of metal ions present in the reaction
mixture after hydrogenation was analyzed with an inductively
coupled plasma-atomic emission spectrometry (Thermo Scientific
ICAP 6500 duo). Both, morphology and particle size were deter-
mined by the transmission electron microscopy (Maker FEI, Model
Technai G2). For the electron microscopy examination, the catalyst
samples were dissolved in 2-propanol, dispersed carefully in an
ultrasonic bath, and then deposited on carbon-coated copper grids.
BET surface area was determined by N2 adsorption–desorption
at 77 K liquid N2 temperature with a MICROMETRICS, Tristar II
analyzer. For each measurement, the sample was degassed at
2
. Experimental
2.1. Materials
Hydrated ruthenium (III) chloride (RuCl ·xH O) was purchased
3
2
from Strem Chemicals, Newburyport, MA01950 (USA). The nickel
chloride, xylose and xylitol were purchased from Sigma–Aldrich
company, Inc., USA. The supports titanium (IV) oxide (rutile type)
◦
250 C for 3–4 h, then analyzed at 77 K with N2 gas at relative
pressures (P/P0) from 0.005 to 1.0 (adsorption) and 1.0 to 0.1
(desorption). CO chemisorption was carried out by using an instru-
ment model ASAP 2020C V1.09 G. Before adsorption of the CO, the
catalysts (weighed approximately 0.12 g) were pre-treated in He
for 35 min, and in O2 for 15 min, and were then reduced for 30 min
(
TiO ), purity – 99.9%, shape fine powder ca. 1–2 micron purchased
2
from Degussa and active carbon (C) from Sigma–Aldrich company,
◦
Inc., (USA) are used after drying at 110 C. Raney Nickel (50%
slurry in water, active catalyst), pore size (∼50 ␮), surface area
2
(
80–100 m /g) was purchased from Aldrich Chemical company,
in a (5.0%) H /Ar gas flow of 50 mL/min, and in He gas flow for
2

1
12
M. Yadav et al. / Applied Catalysis A: General 425–426 (2012) 110–116
Table 1
Catalytic activity of different Ru & Raney Ni catalysts.
Catalysts
% Conc.
Xylitol
Selc.
Arabinitol
NI
%
% Yield
% Selc.
% Yield
Ru (1.0%)/NiO (5.0%)–TiO2
Ru (1.0%)/TiO2
Ru (1.0%)/C
99.9
97.1
96.5
96.9
99.8
99.0
97.5
96.7
99.7
96.1
94.0
93.7
0.1
0.1
0.2
1.0
0.1
0.1
0.2
0.9
0.0
1.0
2.3
2.4
Raney Ni
NI: not identified.
◦
1
5 min at 400 C in a reaction chamber. After this pre-treatment,
hydrogenation processes practiced. As mentioned in the experi-
mental section, the hydrogenated product was analyzed using HPLC
technique using Sugar-Pak column and RI detector and typical HPLC
chromatogram obtained is shown in Fig. 1. As anticipated the main
peak due to xylitol and very small fractions of arabinitol, xylose and
furfural are explicitly seen in the chromatogram.
◦
the samples were cooled down to 50 C under He gas flow and CO
pulse measurements were carried out using (5.0%) CO/He gas flow
of 50 mL/min. Finally, the surface concentration and dispersion of
metallic Ru were obtained from the CO pulse analysis data.
The catalytic activity of novel Ru catalysts prepared was stud-
ied for liquid phase hydrogenation of xylose; results are presented
in Table 1. Reactions carried out under identical conditions using
Raney Ni & other Ru catalysts are included in the table for com-
parative purposes. The results, characteristically, indicate higher
3
. Results and discussion
Novel Ru catalysts were prepared by simple impregnation
method and characterized for their physico-chemical properties.
The Ru loading in the catalysts were estimated by EDX and their
leaching properties examined. The novel catalysts were evaluated
for liquid phase hydrogenation of xylose and the results compared
with those obtained from conventional Raney Ni, Ru (1.0%)/C and
selectivity of all Ru catalysts [Ru/C, Ru/TiO2 and Ru/(NiO–TiO )]
2
compared to conventional Raney Ni catalyst due to higher reac-
tivity of Ru than Ni. It is also seen from the table that values of
conversion of xylose, yield and selectivity to xylitol with respect to
Ru (1.0%)/TiO2 are higher than those obtained with Ru (1.0%)/C.
Most importantly, the novel catalyst prepared in this study [Ru
Ru (1.0%)/TiO catalysts carried out under identical reaction condi-
2
tions. The effects of varying metal content and NiO loading, xylose
concentration and temperature were studied. The results obtained
from these studies are presented and discussed below.
(
1.0%)/NiO (5.0%)–TiO ], distinctively showed optimum conversion
2
of xylose (99.9%) with the yield (99.7%) and the selectivity to xylitol
99.8%). Based on the above results, the order of catalytic activ-
ity (with reference to selectivity) may be given as Ru (1.0%)/NiO
5.0%)–TiO > Ru (1.0%)/TiO > Ru (1.0%)/C > Raney Ni.
(
3.1. Liquid phase hydrogenation of xylose
(
2
2
Liquid phase catalytic hydrogenation of xylose, in principle, is
The physico-chemical properties of the two Ru catalysts pre-
pared were characterized using various methods and the values
are given in Table 2
simple but the formation of small amounts of by-products e.g.
xylulose (through isomerization) complicates the process since
xylulose may be hydrogenated further to arabinitol and xylitol
(
Scheme 2). In some cases under severe conditions, (at high tem-
peratures and high concentrations of alkali) there is a possibility of
formation of furfural and xylonic acid as by-products. It is known
that alkali-catalyzed Cannizzaro reaction is normally responsible
for formation of xylonic acid. In general, the reaction conditions are
chosen in such a way that the formation of xylonic acid and furfural
is prohibited. Thus the main by-products are xylulose and arabinitol
and their generation is suppressed by using low temperature and
high hydrogen pressure [22], which is not realistic in many catalytic
Scheme 2. Main and side reactions in xylose hydrogenation.
◦
Fig. 1. A typical HPLC chromatogram of hydrogenated products, Reaction conditions: [xylose] = 20 wt%, temperature = 120 C, time = 120 min, pressure = 5.5 MPa, stirring
speed = 1200 rpm.

M. Yadav et al. / Applied Catalysis A: General 425–426 (2012) 110–116
113
Table 2
Characteristic properties of the catalysts Ru (1.0%)/NiO (5.0%)–TiO2 and Ru (1.0%)/TiO2.
SBETa (m /g)
2
[Vmicro
SRub (m /g
2
Dispersionb
(%)
Particle
Catalysts
Precursors
a
2
sizec (nm)
pore ] × 10
catalyst)
3
(
cm /g)
d
Ru (1.0%)/NiO (5.0%)–TiO2
Ru (1.0%)/TiO2d
(RuCl3·xH2O)
42.5
57.6
0.31
0.43
1.9
4.3
63.2
97.8
2.0
2.5
–
a
Determined by N2 adsorption–desorption at 77 K.
Determined by CO adsorption–desorption.
Obtained by transmission electron microscopy (TEM).
b
c
d
◦
Reduction with a continuous flow of H2/Ar (5.0%) at 200 C.
Table 3
Ruthenium content and study of leaching property.
Catalysts
Precursors
Ru contenta (wt%)
Ru loadingb (wt%)
Leachingc (mg/L)
Ru
Ti
Ni
d
Ru (1.0%)/NiO(5.0%)–TiO2
Ru (1.0%)/TiO2d
(RuCl3·xH2O)
1.0
1.0
1.2
0.9
0.31
0.34
N.D.
N.D.
11.0
0.0
–
a
Ru content (1.0 wt%) loaded on NiO modified TiO2 support experimentally.
Obtained by energy dispersive X-ray (EDX) analysis.
b
c
Obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES).
d
◦
Reduction with a continuous flow of H2/Ar (5.0%) at 200 C.
Table 4
The effect of ruthenium and NiO (%) loading on the conversion of xylose, yield and selectivity to xylitol.
Catalysts of ruthenium on NiO
modified TiO2 support
% Conv.
Xylitol
Arabinitol
% Selc.
NI
Ru (%)
NiO (%)
% Selc.
% Yield
% Yield
% Selc.
1.0
1.0
1.0
5.0
1.0
5.0
10
98.8
99.9
98.4
100
98.8
99.8
98.4
100
98.1
99.7
97.1
99.8
0.2
0.1
0.3
0.1
0.2
0.1
0.3
0.1
0.5
0.0
1.1
0.0
5.0
NI: not identified.
.
It is clear from the table that, although the
The second and fourth entries (Table 4) refer to experiments
with constant (5.0 wt%) NiO and varying Ru (1.0 and 5.0 wt%) in the
catalyst. It is observed that there is negligible increase in the values
of conversion of xylose (99.9–100%), yield (99.7–99.8%) and selec-
tivity to xylitol (99.9–100%). Although the above values catalyzed
by 5.0 wt% Ru in the catalyst sample are highest, incorporation of
1.0 wt% Ru is more than enough for all practical purposes as metal
Ru is expensive.
dispersion of Ru on (NiO–TiO ) support and the SBET are lower
than that of Ru (1.0%)/TiO , the catalyst Ru (1.0%)/NiO (5.0%)–TiO2
demonstrated excellent results towards selective hydrogenation of
xylose to xylitol. The lower values of dispersion may be attributed
due to slightly higher loading of Ru metal (1.2% compared to 0.9%)
in Ru (1.0%)/NiO (5.0%)–TiO2 causing aggregation of particles.
2
2
The leaching properties of the two Ru catalysts Ru (1.0)/TiO , Ru
2
(
1.0%)/NiO (5.0%)–TiO2 were examined by analyzing the product
Based on the above results, it may be stated that 1.0 wt% Ru
and 5.0 wt% NiO in the catalyst i.e. the catalyst [Ru (1.0%)/NiO
solutions; details of the methods used and the results are summa-
rized in Table 3. The extent of Ru metal leaching in modified catalyst
was observed to be lower than Ru (1.0%)/TiO2 thus, signifying its
better stability.
(5.0%)–TiO ] is capable enough to produce the best possible values
2
of conversion of xylose, yield and selectivity to xylitol.
3.2. The effect of ruthenium and NiO (%) loading
3.3. Effect of xylose concentrations and temperatures
As mentioned earlier, catalysts with different targeted compo-
As the combination of 1.0 wt% Ru and 5.0 wt% NiO in the cat-
sitions [Ru (1.0 and 5.0 wt%) and NiO (1.0, 5.0 and 10 wt%)] were
used to study their effects on hydrogenation of xylose and observed
results are given in Table 4. The first three entries refer to exper-
iments with constant (1.0 wt%) Ru and varying NiO (1.0, 5.0 and
alyst, [Ru (1.0%)/NiO (5.0%)–TiO ], showed better activity and
2
hence was employed to study the influence of xylose concentra-
tion and temperature on hydrogenation of xylose. The influence
of xylose concentration was studied by carrying out the reaction
using three different concentrations ranging from 2.5 to 30 wt%
and the results are shown in Fig. 2. With 2.5 wt%, the results
explicitly show that the conversion of xylose and selectivity to
xylitol is highest (100%). Strong adsorption of xylose molecules
during hydrogenation reaction is speculated for the optimum val-
ues observed. However, it is noticed that with further increase in
xylose concentration (15–30 wt%), the xylose conversion decreased
continuously to 96.6%. The low conversions observed may be due
to relatively weak adsorption of xylose molecules at higher xylose
concentrations [23,24].
1
0 wt%). It is seen from the table that low values of conversion
of xylose, yield and selectivity to xylitol 98.8%, 98.1% and 98.8%,
respectively, are observed with (1.0 wt%) NiO and attributed to for-
mation of ∼0.2% arabinitol as by-products. The values increased
to their optimum with (5.0 wt%) NiO in the catalyst [conver-
sion (98.8–99.9%), yield (98.1–99.7%) and the selectivity to xylitol
(
98.8–99.8%)] by minimizing the formation of arabinitol and other
by-products. However, with further increasing of NiO to 10 wt%
the values decreased may be due to formation of large amount of
arabinitol and other by-products.

1
14
M. Yadav et al. / Applied Catalysis A: General 425–426 (2012) 110–116
1
00
9
9
8
6
4
9
4
Conv. of xylose
Selec. to xylitol
0
0
0
5
10
15
20
25
30
35
Xylose (wt.%)
Fig. 2. The effect of xylose concentration on the conversion of xylose and the selec-
tivity to xylitol.
Fig. 4. XRD profile of NiO (shown for reference peaks) (a), TiO2 (b), (NiO–TiO2) (c),
Ru (1.0%)/NiO (5.0%)–TiO2 (fresh sample) (d), and Ru (1.0%)/NiO (5.0%)–TiO2 (after
hydrogenation) (e).
1
00
◦
are nearer to 100%. On further increasing the temperature to 140 C,
9
9
8
6
4
it is evident that although the conversion of xylose reached 100%,
the selectivity to xylitol decreased since it is known that higher
the temperature, the more prominent is formation of by-products
[
arabinitol (0.5%) and other by-products (1.3%)] [27].
9
4
3.4. Characteristic properties of the catalyst
0
0
Conv. of xylose
Selec. to xylitol
The X-ray diffraction patterns of neat NiO (a); given as for refer-
ence, neat TiO2 (b), modified NiO–TiO2 (c), catalyst Ru/(NiO–TiO2)
(d) and catalyst Ru (1.0%)/NiO (5.0%)–TiO2 (after hydrogenation) (e)
are shown in Fig. 4. It is seen from this figure that the XRD profiles
of TiO2 support (b: red colour) and NiO modified TiO2 support (c:
blue colour) have obvious differences. The presence of character-
9
0
105
120
Temperature ( C)
135
150
o
Fig. 3. The effect of temperature on the conversion of xylose and the selectivity to
xylitol.
◦
istics NiO peaks (in profile c) which appeared at 2Â values of 37 ,
◦ ◦ ◦ ◦
3 , 62 , 75 and 79 indicate successful modification of TiO sup-
2
4
The effect of temperature on hydrogenation of xylose was stud-
ied by varying the reaction temperature from 100 to 140 C and the
port with nickel chloride. In addition, the XRD profiles of NiO–TiO2
(c, blue color) and its catalyst of Ru (d, green color) look alike. The
metallic Ru in the catalyst could not be detected as Ru loadings less
◦
results are shown in Fig. 3 where both conversion and the selectiv-
ity values are plotted against reaction temperature. It is seen from
the figure that the xylose conversion increased gradually in the
investigated temperature range. This may be due to the fact that
the activity of NiO modified TiO2 support to cleave C–O bond was
obviously increased with increasing reaction temperature [25,26].
It is clear from the figure that the optimum reaction temperature
than 5.0% are always covered by NiO modified TiO support making
2
it difficult to determine [28]. The XRD profile of fresh catalyst sam-
ple i.e. before hydrogenation Ru/(NiO–TiO ) (d: green color) and
2
after hydrogenation (e: pink color) unambiguously demonstrates
that the catalyst is absolutely stable during hydrogenation reaction.
Fig. 5 presents TEM images of the catalysts Ru (1.0%)/TiO2 and
◦
lies very close to 120 C as both conversion and selectivity values
[Ru (1.0%)/NiO (5.0%)–TiO ]. The dark portion of the image (Fig. 5a)
2
Fig. 5. TEM images of the catalysts Ru (1.0%)/TiO2 (a) and Ru (1.0%)/NiO (5.0%)–TiO2 (b).

M. Yadav et al. / Applied Catalysis A: General 425–426 (2012) 110–116
115
Fig. 6. EDX spectrum of the catalyst Ru (1.0%)/NiO (5.0%)–TiO2.
temperature of ∼200 C is enough for the reduction of Ru → Ru0
◦
3+
reveal the presence of particles of size ∼2.5 nm, which correspond
to the Ru particles dispersed on large flakes (gray portion) of TiO2
support. Whereas, Fig. 5(b) displays the particles with slightly
higher size range from 10 to 12 nm corresponding to NiO particles
without affecting the NiO modified TiO2 support.
4. Conclusions
interacted with TiO support. However, the presence of Ru particles
2
though they are present along with NiO particles on the NiO–TiO2
support could not be identified clearly. In order to confirm their
presence EDX analysis was carried out and the spectrum is pre-
sented in Fig. 6. The spectrum undoubtedly shows the presence of
all three components Ru, Ni and Ti of the catalyst [Ru (1.0%)/NiO
Catalytic liquid phase hydrogenation of xylose to xylitol using
a Ru catalyst on NiO modified TiO2 support was examined. A
variety of Ru catalysts with predetermined compositions were
prepared and used to study the hydrogenation of xylose and
the results compared with Ni and other Ru catalysts carried out
under identical reaction conditions. The catalyst [Ru (1.0%)/NiO
(
5.0%)–TiO ].
2
The reducibility of the catalysts prepared was examined by TPR;
(5.0%)–TiO ], unequivocally showed optimum conversion of xylose
2
the profiles of the catalysts Ru/TiO , NiO modified TiO2 support,
(99.9%) with the yield (99.7%) and the selectivity to xylitol (99.8%).
The order of catalytic activity was observed to be [Ru (1.0%)/NiO
(5.0%)–TiO ] > [Ru (1.0%)/TiO ] > [Ru (1.0%)/C] > [Raney Ni]. The per-
2
(
NiO–TiO ) and Ru/NiO–TiO are shown in Fig. 7. Two TPR peaks
2
2
◦
◦
observed at 170 C and 320 C in red profile (curve a) are attributed
2
2
3+
0
to the respective reduction of ruthenium chloride (Ru → Ru ) and
cent NiO incorporated in modified support (NiO–TiO ) played an
2
4+
0
(
Ru → Ru ) oxidized ruthenium on TiO surface. A main peak
important role to minimize arabinitol and other by-products, which
generally form during hydrogenation of xylose. Although the values
of conversion of xylose, yield and selectivity to xylitol with incor-
poration of 5.0 wt% Ru in the catalyst are maximum, the results
obtained with 1.0% Ru are close to 100% and hence is more than
enough for all industrial applications as metal Ru is expensive.
2
◦
2+
0
observed at 378 C (in curve b) is due to conversion of Ni to Ni ,
which is in accordance with Richardson et al. findings as NiO needs
to reduce into Ni at higher temperature [29]. On the other hand, the
profile of [Ru (1.0%)/NiO (5.0%)–TiO ] (curve c) displayed a peak
2
◦
3+
0
at 150 C which is attributed to the reduction of Ru → Ru and
◦
2+
0
the second peak at 360 C is due to the reduction of Ni → Ni .
◦
There is an additional peak observed at 425 C which is attributed to
Acknowledgements
delayed reduction of Ni2 → Ni . It is clear from the TPR data that a
+
0
This work was supported by the Institutional Research Program
of KRICT (SI-1201) and by a grant (B551179-10-03-00) from the
cooperative R&D Program funded by the Korea Research Council
Industrial Science and Technology, Republic of Korea.
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