765

Vapour phase By P.Sangeetha et al.
, Bulletin of the Catalysis Society of India, 8 (2009) 52-63

52

Vapour phase hydrogenation of furfural over palladium supported catalysts

P. Sangeetha
a #
, B.M. Nagaraja
b
K. Shanthi
a *
, K.S. Rama Rao
b
, S. Narayanan
b

a
Department of Chemistry, Anna University, Chennai-600 025, India.
b
Inorganic and Physical Chemistry Division, Indian Institute of Chemical
Technology,Hyderabad-500 007, India.
# Department of Chemical and Materials Engineering, National Central University,
Chungli, Taiwan.

Calcined samples of Mg-Al hydrotalcite prepared by co-precipitation at high
supersaturation conditions (pH=11-13), Mg-Al and Mg-Cr mixed oxides prepared by co-
precipiation method at low supersaturation conditions(pH=10) were employed as
supports and were impregnated with required amount of Pd for 1% from aq.PdCl
2

solution. The supports were characterised by XRD, FT-IR, TGA, BET surface area and
SEM. Supported palladium catalyst was characterised by TPR and CO chemisorption.
Vapour phase hydrogenation of furfural at atmospheric pressure was carried over the
supported palladium catalysts in the temperature region of 453-523 K. 1 wt.% Pd
supported on Mg-Al hydrotalcite, prepared at high supersaturation conditions, shows
>95% selectivity for furfuryl alcohol with about 15% conversion of furfural at 498 K.
The conversion and selectivity variations among the palladium catalysts are discussed on
the basis of structural differences of the supports.
Keywords: Hydrotalcite; palladium; hydrogenation; furfural; furfuryl alcohol

1 Introduction

Selective hydrogenation of
unsaturated organic molecules is an
important reaction in the synthesis of
fine chemicals. Selective hydrogenation
of aldehyde and ketonic groups in
presence of unsaturated C=C bonds is a
challenging proposition. Generally a,
unsaturated aldehydes and ketones are
hydrogenated to yield predominantly the
saturated aldehydes and ketones
respectively by preferential reduction of
C=C bonds. It is also thermodynamically
favourable to obtain the saturated
alcohols by the hydrogenation of both
C=O as well as C=C bond. It is therefore
desirable to design catalyst which will
control the intramolecular selective
hydrogenation of aldehyde or the ketonic
group, preferentially keeping the C=C
bond intact [1]. Such selective
hydrogenation of a, unsaturated
aldehydes and ketones are important
from the perfumery industry. There are
several examples of this reaction such as
hydrogenation of crotonaldehyde,
cinnamaldehyde, maleic anhydride over
supported metal catalysts [2-10].
Selective hydrogenation of furfural
yields furfuryl alcohol, which is an
important chemical in polymer industry.
Furfuryl alcohol is used in the
production of dark thermostatic resins,
resistant to acids, bases and various
solvents. The uses include the
production of resins for bonding foundry
sand to produce cores and molds for
metal casting, and as a solvent for
pigment or phenolic resins. It is a non-
reactive diluent for epoxy resins,
modifier for phenolic and urea resins,
oil-well sand consolidation, production
of tetrahydrofurfuryl alcohol and in the
Vapour phase By P.Sangeetha et al., Bulletin of the Catalysis Society of India, 8 (2009) 52-63

53

synthesis of other chemicals. It is also an
essential intermediate for the
manufacture of lysine, Vitamin C,
lubricant, dispersing agent and
plasticizer [11]. Copper chromite
catalysts have been used for partial
hydrogenation of vegetable oils and fatty
acids as well as for the hydrogenation of
furfural [12]. Recently Nagaraja et al.
[13,14] have reported Cu/MgO catalyst
for the vapour phase hydrogenation of
furfural with high conversion (98%) and
selectivity towards furfuryl alcohol
(98%) at GHSV of 0.05 molh
-1
g
-1
at 453
K. Rao et al. [15] have studied furfural
hydrogenation over Cu dispersed on
three forms of carbon namely activated
carbon, diamond and graphitised fibres.
Activity and selectivity over Cu catalysts
have been described on the basis of
availability of Cu
0
and Cu
+
species for
the reaction. Baijun et al. [16] have
reported that among the transition metal
salts, copper salt is superb in
performance. In liquid phase selective
hydrogenation of furfural on Raney
nickel catalyst, modified by
impregnation of copper containing
heteropolyacid, gave furfural conversion
and furfuryl alcohol selectivity as high
as 98%. Cu-Ca/SiO
2
catalyst prepared by
sol-gel technique showed higher copper
dispersion and higher activity as well as
selectivity in the hydrogenation of
furfural to furfuryl alcohol compared
with Cu-Ca/SiO
2
catalyst prepared by
impregnation method [17]. There are
several systems involving Ni-Ce-B
amorphous alloy catalyst and polymer
stabilized Ni-B catalyst, which have
been used for liquid phase
hydrogenation of furfural [18,19].
Platinum deposited on monolayer
supports has also been successfully used
for the furfural hydrogenation reaction
[20]. The role of both strong metal
support interaction [SMSI] and strong
oxide -oxide interaction [SOOI] have
been invoked for in explaining the
enhanced catalytic activity of platinum
supported on reducible oxides such as
titania [11]. Clays, especially synthetic
anionic clays of hydrotalcite type, have
found application as catalyst support for
precious metals. Hydrotalcite based
metal catalysts have been used in several
hydrogenation reactions [21-27]. It has
been found that the basic nature of the
hydrotalcite as well as the exchangeable
property of cation in the brucite layer are
useful in metal dispersion which is
responsible for hydrogenation reaction.
Narayanan et al. [22-26] have studied
the hydrogenation of phenol to
cyclohexanone over Pd hydrotalcite
catalysts with very high conversion and
nearly 100% selectivity towards
cyclohexanone. They have reported that
hydrogenation of phenol depends on the
availability of metal and the selectivity
for cyclohexanone is independent of
phenol conversion. Unnikrishnan and
Narayanan [27] have reported synthesis
of methyl isobutyl ketone (MIBK) from
acetone over metal loaded hydrotalcite.
The hydrogenation of furfural has been
studied mostly over copper based
catalysts. However, examples of furfural
hydrogenation over hydrotalcite based
metal catalysts especially involving
palladium loaded hydrotalcite are rare in
literature. In this study palladium
supported on Mg-Al hydrotalcite (HT) is
used as catalyst for the selective
hydrogenation of furfural. The activity
of Pd hydrotalcite catalyst is compared
with that of Pd on mixed oxides as well
as Pd on MgO catalysts.

2 Experimental
2.1 Support preparation
2.1.1 Preparation of Mg-Al hydrotalcite
(Support A)

54

Mg-Al HT {X=Al (III)/Al(III) +
Mg(II) = 0.33}was prepared according
to the method reported by Reichle [28].
Solution A was prepared by dissolving
256 g of Mg (NO
3
)
2
.6H
2
O (1 mol) and
185.7 g of Al(NO
3
)
3
.9H
2
O (0.5 mol) in
700 cm
3
distilled water, maintaining a
Mg/Al molar ratio of 2. Solution B was
prepared by dissolving 280 g of 50%
NaOH (140 g in 140 cm
3
distilled water)
and 100 g of Na
2
CO
3
in 1000 cm
3

distilled water. HT was prepared by
adding solution A to solution B in 3-4 h
with constant stirring while maintaining
the pH between 11-13. The resulting gel
was transferred to an autoclave and
allowed to crystallize at 333 K for 18 h.
The sample was filtered and washed
several times with hot distilled water
until pH of the filtrate is neutral and also
to remove any free sodium ions that may
be present. The sample was dried in an
oven for 12 h at 373 K and then calcined
at 723 K in air for 18 h.
2.1.2 Preparation of MgAl Mixed oxide
(Support B)
MgAl mixed oxide is prepared
by co-precipitation method at low
supersaturation condition (pH=10).
About 576 g of Mg(NO
3
).6H
2
O and 36.8
g of Al(NO
3
)
3
.9H
2
O were dissolved in
~2.25 l distilled H
2
O, keeping a molar
ratio of Mg/Al~22.8. To this solution, a
mixture of 50% aqueous solution of
NaOH (60.4 g in 603 ml distilled H
2
O)
and aqueous Na
2
CO
3
solution (60.4 g in
603 ml of distilled water) was added
drop wise with constant stirring. The gel
formed was transferred to an autoclave
and allowed to crystallize at 333 K for
18 h. The sample was filtered and
washed several times with hot distilled
water until pH of the filtrate is neutral
and to remove excess sodium ion. The
sample was dried in an oven for 12 h at
373 K and then calcined at 723 K in air
for 18 h.
2.1.3 Preparation of MgCr Mixed oxide
(Support C)
MgCr mixed oxide is prepared
by co-precipitation method at low
supersaturation condition (pH=10).
About 576 g of Mg (NO
3
).6H
2
O and
26.3 g of Cr (NO
3
)
3
.9H
2
O were
dissolved in 2.23 l distilled water,
maintaining a molar ratio of
Mg/Al~34.5. A mixture of 50% aqueous
solution of NaOH (90.1g in 90.1ml of
distilled water) and aqueous Na
2
CO
3
solution (59.7 g in 597 ml of distilled
water) was prepared. The metal nitrate
solution and alkali solution were added
simultaneously into a beaker containing
about 2 l distilled water and stirred
continuously. The pH was maintained at
10. The resulting gel was transferred to
an autoclave and allowed to crystallize at
333 K for 18 h. The solid sample was
filtered and washed several times with
hot distilled water until the pH of the
filtrate is neutral to remove any sodium
ions that may be present. The sample
was dried in an oven for 12 h at 383 K
and then calcined at 723 K in air for 18
h.
2.1.4 Preparation of MgO (Support D)
Magnesium carbonate was
precipitated from a solution of
magnesium nitrate (1mol) using K
2
CO
3

solution (1 mol). The carbonate samples
was filtered and washed several times
with hot distilled water in order to
remove excess potassium ions and dried
in an oven at 383 K for 12 h. The dried
sample was then calcined at 773 K for
18 h to get MgO.
2.1.5 Wet Impregnation Method
1 wt.% Pd on support A was
prepared by incipient wet impregnation
method, using an aqueous solution of
palladium chloride acidified with HCl

55

(to effect the complete dissolution of the
salt). Required amount of palladium
chloride was taken so as to obtain the
desired Pd concentration on Support and
the solution was mixed with Support A
in distilled water. The resulting slurry
was stirred well and subsequently dried
in an oven at 373 K for 12 h. The solid
residue was then crushed and calcined in
air at 723 K for 5 h. A similar method is
used for loading Pd on supports B, C and
D as well.
2.1.6 Characterization
X-ray powder diffraction (XRD)
patterns of all the four supports were
recorded on a Rigaku Miniflex (M/s
Rigaku Corporation, Japan) X-ray
diffractometer using Ni filtered Cu K a
radiation (. = 1.5406 ) with a scan
speed of 2 min-1 and a scan range of 2-
80 at 30 kV and15 mA in order to
identify the phase present. The x-ray
diffraction data were collected in the
step scan mode. Temperature
Programmed Reduction (TPR) profiles
were obtained using a flow system. A
5% H2/Ar mixture gas was introduced
into the reactor at a flow rate of 30
ml/min with a temperature ramp of 10 K
min
-1
. Before the TPR analysis the
catalyst (about 100 mg) was pretreated
in a flow of Ar at 523 K for 2 h. The
consumption of hydrogen was monitored
using a thermal conductivity detector.
FT-IR spectra was recorded on Digilab
(USA). For FT-IR study, the powdered
samples were mixed with KBr and
compressed into thin disk-shaped pellets.
BET surface area was obtained on
Autosorb Automated Gas Sorption
System (M/S. quantachrome, USA) with
N
2
as adsorbate at liquid nitrogen
temperature. SE micrographs were
recorded in a LEO STEREO SCAN,
Model No: 440. CO Chemisorption and
calculation of Pd dispersion as well as
the metal crystallite size are described in
detail by Narayanan and Krishna (22-
26).
2.1.7 Furfural Hydrogenation
Vapour phase hydrogenation of
furfural was studied over calcined 0.5 g
of supported Pd catalysts at 453 K in a
vertical down flow reactor. The catalyst
sample was supported by plugs of quartz
wool in the middle portion of the reactor.
Glass beads on top of catalyst sample act
as preheater. Details of the experimental
set up is given in ref 29.Before carrying
out experiment, the samples were
reduced in hydrogen at 523 K for 4 h in
hydrogen flow of 0.9 lh
-1
. The reactant,
furfural was added from the top of the
reactor at a controlled rate with the help
of a calibrated motorized syringe. The
liquid products, collected for every hour
in a trap cooled in ice, were analyzed on
a Shimadzu GC-MS (Model 17A) with a
carbowax packed (20 m long) column.
The product analysis revealed traces of
tetrahydrofuran, minor quantities of
ethanone 1-2 furan and 5-methyl furan.
However the major products identified
were furfuryl alcohol and
tetrahydrofurfurylalcohol.
3. Results and Discussion
3.1 Characterization
X-ray diffraction patterns of the
support materials A, B, C, D dried and
calcined are given in Figs1 and 2.
Support A (MgAlHT) is very crystalline
and has all the
characteristic peaks expected of
hydrotalcite. Sharp and symmetrical
peaks for (003), (006), (110) and (113)
are observed, and the peaks
corresponding to (102), (105) and (108)
are diffused and asymmetrical [24].
XRD pattern confirms the HT type
structure of support A. Supports B and C
show a relatively less crystalline
characteristics. Support D is a pure

56

magnesium oxide and has the crystalline
peaks corresponding to that of MgO with
2 values = 42.5, 61.5 and 77.3.
Thermogravimetric analysis of
MgAlHT (Support A) was carried out by
calcining the sample (723 K for 18 h)
from 323 1023 K at the heating rate of
10min
-1
. TGA curve shows, three
distinctive temperature regions
accompanied with weight loss. The first
region between 323 523 K may
correspond to the loss of physisorbed
water as well as the interlayer water. The
weight loss in this region corresponds to
nearly 12.5%. In the second region
between 523 723 K, there is a weight
loss of 12.5%, beyond which
temperature the sample stabilizes. The
weight loss in the temperature region
523 723 K may be ascribed to
dehydroxylation of hydrotalcite and to
the loss of structural water, as well as
due to the liberation of carbondioxide
from the interlayer carbonate anion.
Dehydroxylation may lead to structural
disturbances. However, the third weight
loss seems to be stabilized beyond 723
K, indicating that there is no structural
variation or due to loss of structural
water. TGA profiles and the weight
changes are typical of Mg-Al
hydrotalcite with carbonate interlayer
anion [24,28,31]. SEM picture of Mg-
AlHT (support A) in Fig3 shows
agglomerated particles with almost
spherical morphology. Many surfacial
crevices are also present which are
attributed to crater formation sites during
calcination that helps the elimination of
carbondioxide and watervapour.

Figure 1 : XRD patterns of as-synthesised support
A= MgAlHT; B= MgAl mixed oxide; C= MgCr mixed oxide; D= MgO


57

FT-IR spectra of Mg-Al HT
(support A) is shown in Fig. 4. It shows
a strong absorption band at 3357cm
-1
for
OH stretching, indicating that hydroxyl
groups of a brucitelike layer are
hydrogen bonded. A weak band at 3080
cm
-1
is due to the water molecule
hydrogen bonded to the carbonate ion
present in the interlayer. Water bending
occurs at 1600 cm
-1
. The bands around
3100 and 1600 cm
-1
correspond to
hydrogen bonding between interlayer
water and carbonate ions present in
support A. The three absorption bands
observed at 1365, 868, and 644 cm cm
-
1
indicates that the carbonate anion is an
asymmetric environment characterised
by D
3
h planar symmetry. Some of the
peaks in the 400-1000 cm
-1
region are
assigned due to lattice vibrations such as
M (II)-M (III)-O, M-O bending and
stretching vibrations [30] Analysis of the
spectra in the 3400-3800 cm
-1
region
shows that the hydrotalcite prepared at
high supersaturation and crystallized at
373 K, the band due to OH is broad and
asymmetrical

Figure 2 : XRD patterns of calcined support


58

TPR profiles of calcined Pd catalysts
supported on different supports are
shown in Fig 5. A two-stage reduction is
observed in 1 wt.% Pd/Mg-Al HT
catalyst. The first stage reduction gives
rise to a strong positive hydrogen
consumption peak at T
max
~ 450 K. This
represents PdO reduction and/or
hydrogen chemisorption on the metallic
palladium that is formed and/or
hydrogen adsorption that is known to
occur directly on the support as well as
spillover species.The second stage of
hydrogen consumption occurs at higher
temperatures. This indicates further
consumption of hydrogen by all the
catalysts, which can be attributed to the
spill over of hydrogen activated on
metallic palladium on to the support. No
negative peak corresponding to -PdHx
decomposition is observed over Pd/Mg-
Al HT catalysts. In the case of 1 wt.%
Pd/MgCr catalyst, one stage reduction is
found to occur at 550 K. In the case of 1
wt.% Pd/MgAl mixed oxide catalyst,
there is found to be negative peak at
lower temperature. In 1 wt.% Pd/MgO
catalyst, one negative peak due to -
PdHx is observed at lower temperature,
and then a positive peak is found to
occur around 750 K.

Figure 3 : SEM pattern of MgAlHT (support A)


59

Figure 4 : IR spectra of MgAlHT (support A)

Figure 5 : TPR pattern of 1 wt.% Pd on support

60

3.2. Catalytic Activity
As described in earlier section
four different supports, namely A, B, C,
D were prepared and loaded on with 1
wt.% Pd by wet impregnation method.
Support A is Mg-Al hydrotalcite with
surface area 190-200 m
2
g
-1
. Support B
and C as indicated by XRD have only
mixed oxide characteristics of MgO
andAl
2
O
3
with surface area 80 m
2
g
-1
)
and MgO and Cr
2
O
3
(support C, Surface
area = 60 m
2
g
-1
). They have lower
surface area than support A. Support D
on the other hand is a pure MgO having
surface area around 35 m
2
g
-1
. The four
catalysts with different support
properties and having same metal
content of 1wt% Pd are evaluated for
their catalytic property. Hydrogenation
of furfural (Scheme 1) under vapour
phase conditions was carried out over
0.5 g of each of the catalyst in the
temperature region 450-530 K. Furfural
was added at a WHSV of 0.012 molh
-1
g
-
1
, while H
2
flow was maintained at 0.9
lh
-1
during the reaction. In Fig.7 the
effect of temperature on furfural
hydrogenation over 1 wt.%Pd on
supports A, B, C, D are shown. Pd/Mg-
AlHT (support A) shows a conversion of
about 15% at 453 K and it is more or
less maintained throughout the
temperature region studied. Of the mixed
oxides based catalysts, Pd/MgAl
(support B) shows a conversion of 20-
25% in the same temperature region. In
contrast Pd/MgCr (support C) shows a
much lower conversion (2-7%)
compared to Pd/Mg-AlHT. 1 wt.%
Pd/MgO (support D) starts with furfural
conversion of 35% at 453 K and it is
lowered to 20% at 523 K. As can be seen
from fig.6 the conversion is more or less
steady between 470 and 520 K on all the
catalysts. Therefore, the reaction
temperature of 498 K is chosen for
comparison of catalysts from the point of
view of furfural conversion and furfuryl
alcohol selectivity as well as other
products.

Figure 6: Effect of temperature on furfural conversion over 1 wt.% Pd on different
supports :A= MgAlHT; B= MgAl mixed oxide; C= MgCr mixed oxide; D= MgO
Catalyst= 0.5 g; WHSV= 0.012 molh-1g-1; H2 flow= 0.9 lh
-1


61

In Fig.7, the activity for furfural
hydrogenation over 1 wt.% Pd on
supports A, B, C and D are compared at
the reaction temperature of 498 K.
Conversion follows the order Pd/MgAl >
Pd/MgO > Pd/Mg-AlHT >> Pd/MgCr.
Palladium on MgCr mixed oxide catalyst
shows a conversion of less than 3%. The
selectivity for furfuryl alcohol on
catalysts follows the order Pd/Mg-AlHT
>> Pd/MgO > Pd/MgAl > Pd/MgCr. Of
all the catalysts, 1 wt.% Pd/MgAlHT
shows nearly 95 % selectivity compared
to 50%, 40% and 15% on other Pd
catalysts based on supports D, B and C
respectively. Another interesting factor
is that the selectivity of THFA and other
products are lower (less than 5%) on
Pd/supportA compared to on other
catalysts. The higher conversion of
furfural over Pd on supports B and D
(Palladium on MgAl mixed oxide and
MgO) results in the formation of THFA
and other products apart from furfuryl
alcohol. The reason for high selectivity
of nearly 95% over 1wt% PdMg-AlHT
(support A) may be due to the well
dispersed Pd on MgAl hydrotalcite
structure. Eventhough supports B, C and
D contain 1 wt.% Pd, the physical
properties of these oxides are different
and probably the low surface area also
contribute to the poor dispersion of
metal and correspondingly to the
selectivity for furfuryl alcohol. It has
been observed that there is no direct
dependence of Pd dispersion and the
surface area of support indicating that
the structural properties may decide the
metal dispersion [32]. Nevertheless, it
may be said that Pd disperses well on
Mg-Al hydrotalcite support rather than
on mixed oxides of Mg/Al or Mg/Cr or
on pure MgO. In addition the basicity
differences of the support materials
would also contribute to metal
dispersion as well as product selectivity.
It has been reported that in the case of
phenol hydrogenation over palladium
hydrotalcite, the conversion is dependent
on availability of metal. Selectivity for
cyclohexanone is always higher than
96% and is independent of the
conversion. It may be true that furfural
hydrogenation also depends on the
available metal. The selectivity for
furfuryl alcohol is high on a well
dispersed Pd on Mg-Al HT support. Pd
dispersion on support with required
basicity contribute to conversion and
selectivity of product.

Scheme 1.

4. Conclusion
Hydrogenation of furfural is
studied over 1 wt.% Pd on different
supports with varying structural and
physical characteristics. Pd disperses
much better on a Mg-Al hydrotalcite that

62

on mixed oxides of Mg/Al and Mg/Cr
or pure MgO support. Physical
characteristics of support contribute to
the Pd dispersion and the particle size.
Both the structure and metal crystallite
size affect furfural conversion and
selectivity for furfuryl alcohol. It seems
well dispersed palladium gives high
selectivity for furfuryl alcohol though
conversion is low. Pd on hydrotalcite
gives selectively furfuryl alcohol (nearly
95%) at a conversion of nearly 15% at
498 K. Hydrotalcite may be an alternate
preferred support for palladium, useful
for selective hydrogenation of furfural to
furfuryl alcohol.
Acknowledgement
PS thanks DRDO, New Delhi for
a research fellowship. SN thanks UGC,
New Delhi for the award of Emeritus
Project Scheme

Figure 7: Furfural hydrogenation over 1wt% Pd on different supports
A = MgAlHT; B= MgAl mixed oxide; C= MgCr mixed oxide; D= MgO
T= 498 K; Catalyst= 0.5 g; WHSV= 0.012 molh-1g-1; H2 flow= 0.9 lh-1

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Vapour phase By P.Sangeetha et al.

, Bulletin of the Catalysis Society of India, 8 (2009) 52-63

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