i ~ APPLI

CATALEYDSIS
A: GENERAL

ELSEVIER

Applied Catalysis A: General 163 (1997) 101-109

Selective hydrogenation of cyclopentadiene to cyclopentene

over an amorphous NiB/SiO2 catalyst
Wei-Jiang

Wang, Ming-Hua

Qiao, Jun Yang, Song-Hai

Xie, Jing-Fa Deng*

Department of Chemistry, Fudan Universi~, Shanghai 200433, China

Received 5 December 1996; received in revised form 6 March 1997; accepted 11 March 1997

Abstract

An amorphous NiB/SiO2 catalyst, with a large specific surface area, was prepared by a reductive-impregnation method. The
selective hydrogenation of cyclopentadiene to cyclopentene was carried out in a continuous flow fix-bed reactor at
atmospheric pressure and with 10 g g cat -I h -l of cyclopentadiene feed. The catalyst showed high selectivity and stability.
Cyclopentene was obtained in 96--100% yield at complete conversion of cyclopentadiene at temperatures ranging from 80C
to 200C and no significant decrease of the activity was observed during the reaction period of 500 h. The catalyst sample was
characterized by ICP, XRD, DSC, SEM, XPS, BET and 02 adsorption. XRD measurement revealed that the amorphous state
was kept after catalytic reaction. Differential kinetic study showed that the hydrogenation proceeded according to a RidealEley mechanism. 1997 Elsevier Science B.V.

Keywords: Supported amorphous alloy; Nickel-boron alloy; Cyclopentadiene hydrogenation; Catalytic activity; Differential
kinetics

1. Introduction

The selective hydrogenation of cyclopentadiene to

cyclopentene is of great synthetic and industrial interest, because cyclopentene with a highly reactive double bond could be used as a basic material in industry
[1-3]. The hydrogenation of cyclopentadiene is a
consecutive reaction. The activation energy of the first
stage is higher than that of the second one [4--6], so
that it is impossible to convert cyclopentadiene to
cyclopentene completely, especially under the g a s -

*Corresponding author. Tel.: +86 21 65492222x3792; fax: +86

21 65341642; e-mail: knfan@fudan.ihep.ac.cn
0926-860X/97/$17.00 ~"~
~c5) 1997 Elsevier Science B.V. All rights reserved.
PII S0926-860X(97)00
125-7

solid phase reaction conditions used widely in industry. For most hydrogenation catalysts such as Pd, Pt,
Ni, Cu [7-10], at the low ratio of PH2/PD(Po: the
pressure of cyclopentadiene), cyclopentene is produced with 100% selectivity at low conversion of
cyclopentadiene, whereas the increase in P~:/Po or
W/Fo decreases the selectivity. The unconverted
cyclopentadiene at low conversion is easily polymerized on catalysts at the reaction temperature, which
leads to the deactivation of the catalysts and also to
low yields of cyclopentene. These phenomena are
commercially impracticable. For these reasons, it is
a crucial subject to prepare special catalysts in order to
obtain cyclopentene at nearly 100% selectivity at
complete conversion of cyclopentadiene.

102

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

It is well known that amorphous metal alloy

catalysts exhibited attractive selectivity and activity
for some reactions due to their isotropic structure,
devoid of any long-range ordering of the constituents
[11,12]. The application of these materials in
catalysis, however, is severely limited, since the
amorphous state is metastable, and thus is very
difficult to maintain under conditions where catalytic
reactions are carried out. Furthermore, the surface
area of amorphous films prepared by rapid-quenching
methods is too low and the shape of amorphous
alloy prepared by wet chemical reduction methods
is powder, which are both inconvenient for use of
the catalytic potential of these materials in technical
catalysis. One of the promising routes to solve
these problems has been developed by depositing
the amorphous alloys in high dispersion on a
suitable support. For example, the preparation
of amorphous nickel-(cobalt)-phosphorus alloys
deposited on silica has been reported previously
[13,14]. The results showed that these supported
amorphous alloy catalysts exhibited higher activity
and selectivity for the hydrogenation of styrene
with higher thermal stability than unsupported
counterparts.
Unfortunately,
the
phosphorus
component in amorphous alloys is easily lost during
catalytic runs [14] and the preparation methods
are unsuitable for supporting highly reactive
amorphous nickel-boron alloy on a support due to
the too rapid reduction of nickel ion by potassium
borohydride in water.
In this paper, the preparation of amorphous
nickel-boron alloy supported on silica by a new
method is reported. Its catalytic properties in the
hydrogenation of cyclopentadiene and characterization results obtained by ICR XRD, XPS, SEM,
DSC, BET and 02 adsorption methods are
discussed in detail. The reaction mechanism is
proposed on the basis of the differential kinetic
results.

2. Experimental
2.1. Materials
All chemicals employed were of reagent grade and
were used without further purification.

2.2. Catalyst preparation

The supported amorphous NiB/SiO2 catalyst
was prepared by a reductive impregnation method.
The impregnation was carried out by immersing 10 g
silica gel (200 m 2 g-1 surface area, 17.5 nm pore
diameter and 40-60 mesh, i.e., 0.45-0.30mm
particle size) in a 1 M potassium borohydride
solution (pH=13) for 2 h and then taking the silica
gel out of the solution. To remove the excessive
solution, the silica gel was washed with 10 ml of
95% ethanol and then dried under air at room temperature. Subsequently, the silica gel which had
adsorbed potassium borohydride was added into
10ml of 2 M nickel chloride solution at room
temperature with continuous stirring for 4 h. The
black particles obtained were washed with 15 ml of
0.01 M potassium borohydride aqueous solution and
then washed thoroughly with a large amount of
distilled water. Finally, the catalyst was dried in
nitrogen at 70C for 2 h.
Elemental analysis of the catalyst determined by
inductively coupled plasma (ICP) showed that the
nickel content was 4.3% by weight and the elemental
composition was NisoB2o (mol%).

2.3. Activity measurements and differential kinetic

experiment
Hydrogenation of cyclopentadiene was carried out
in a tubular glass fix-bed reactor (0.8 cm i.d.) in
continuous flow conditions and under atmospheric
pressure. The weight of catalyst was 1 g for each
experiment. Liquid cyclopentadiene, diluted with solvent to keep from polymerization (commonly with
95% ethanol and 1 : 1 volume ratio), was vaporized in
a bubbling-type evaporator at 95C, and then passed
through the reactor using nitrogen and hydrogen
mixture as the carrier gas.
Differential kinetic experiment was also carried out
under the same reaction conditions as those for activity measurements, but the weight of catalyst was 0.1 g
for each kinetic experiment.
The effluent was analyzed by a gas chromatographic method. The conversion and selectivity are
defined as follows:
Conversion(%) = [CPD]conv./[CPD]feed x 100,

(1)

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

Selectivity(%) = [CPE]/[CPD]conv. x 100.

(2)

103

3. Results and discussion

Here CPD and CPE stand for cyclopentadiene and

cyclopentene, respectively.

3.1. Catalytic activity

As mentioned above, the products of cyclopentadiene hydrogenation were cyclopentene and cyclopentane. To obtain cyclopentene as much as possible
at complete conversion of cyclopentadiene, the catalytic reactivity of amorphous NiB/SiO2 catalyst was
concerned about both selectivity to cyclopentene and
conversion of cyclopentadiene.
This catalyst did not need any activation process
before catalytic runs and immediately showed high
activity and selectivity once the hydrogenation started.
Since the cyclopentadiene hydrogenation is very
exothermic (AH1=-99.35 kJ tool J, AH2=-112.24
kJ mol-t), nitrogen together with 95% ethanol was
also mixed as heat transfer gas into the reactant feed.
Nitrogen, showing no significant effect on the cyclopentadiene hydrogenation (Fig. I) with its flow-rate in
the range 40-160 ml min-', was used to adjust the contact time of the reactant with the catalyst in the reaction.
The effects of PH2/PDratio at different Fo (cyclopentadiene feed) values on the catalytic activity were

2.4. Characterization of catalyst

X-ray diffraction (XRD) patterns of support and
the NiB/SiO2 catalysts were performed using a
Rigaku Dmax-rA with nickel filtered Cu Ks
radiation. Differential scanning calorimetry (DSC)
measurements were conducted under nitrogen
(99.99%) atmosphere on a Dupont 9900 computerthermal analysis system. The morphology of the
samples was determined by scanning electron
microscopy (SEM) performed on a Hitachi HUl lB STEM and H600 STEM instruments. X-ray
photoelectron spectroscopy (XPS) spectra were
recorded with a PHI-5000C ESCA system using A1
K,~ radiation. The base pressure of the analysis
chamber was 10 -8 Pa and the energy was 46.95 eV.
All binding energies were calibrated using contaminated carbon (Cls=284.6 eV). The metallic specific
surface areas of the samples were measured according
to a method described in [15].

"- ~

100

I00

90.0

90.0

80.0

80 0

..~
8

~2

70.0

70.0

20

40

60

80

100

120

140

160

I80 2 0 0

Feed-rate(ml.min"t)
Fig. 1. Effect of N2 feed-rate on CPD conversion and CPE selectivity (CPD feed=10 g cat-t h , H2 : CPD=I.4, temperature

120C).

W.-J. Wanget al./Applied Catalysis A." General 163 (1997) 101-109

104

O ~ O O O O O

q
r.,,i

I00

100

90.0

90.0

80.0

80.0

II

G~

g g g g g g g g ~

qq
o

~
0

gga~ggggg

0q.

~[

(.9

oo oo ooo oo oo ooo o~ o q q

'R.

80

110

140

]70

200

Temperature(C)
0 0 0 0

Fig. 2. Effect of reaction temperature on CPD conversion and

CPE selectivity (CPD f e e d = 1 0 g cat 1 h - l , H 2 : C P D = I . 6 : 1
( G H S V = 2 4 000-1).

g g g g g g g ~ >
=o
e~
o

~gggggggg
II

ggggggg~gg

7
o

~ggg~ggggg
e'~
o

=
Q q o q q q o q

~ g g g g g g g g

"2.

gggggggggg

r.~

II

G)
o

"7
eq

studied, as shown in Table 1. The suitable PH2/PD ratio

in order to maintain the selectivity to cyclopentene
higher than 96% at complete conversion of cyciopentadiene varied with changing the cyclopentadienefeed. Clearly, the increase in the cyclopentadiene feed
required high H 2 : cyclopentadiene ratio to maintain
the 100% conversion, but the selectivity slightly
decreased. At the highest cyclopentadiene feed,
16 g g cat t h-~, the selectivity was about 96%, but
the optimum cyclopentadiene feed was 1 0 - 1 2 g g
cat-t h i. Thus, in the present work, the cyclopentadiene feed was controlled at 10 g cat t h-i for most
catalytic runs.
The variation of reaction temperature from 80C to
200C showed little effect on the catalytic reactivity,
as shown in Fig. 2. A further increase in temperature
led to a decrease in the reactivity, which was due to
cyclopentadiene polymerization on the catalyst.
These results indicate that the amorphous NiB/SiO2
catalyst has high selectivity and activity compared
with other commonly used hydrogenation catalysts in
the present reaction conditions. For example, on Pd/
A1203 (Pd: 0.5 wt%), the selectivity and conversion
are 33% and 70% in the present work; and also 90%
and 92.5% at higher pressure in Ref. [7]; on Ni/SiO2
(Ni: 4.6 wt%) 84% and 100% in the present work; on
NiS/SiO2 93.5% and 99% in Ref. [9] (no LHSV value
was given, but according to our knowledge, it may be
0.5 h-t), respectively. If the amorphous NiB/SiO2 was

105

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

treated at 400C for 2 h in nitrogen, its activity and

selectivity remained unchanged, while in the case of
the treatment at 450C for 2 h in nitrogen, the best
selectivity was 94% at 100% conversion.
The stability of the catalytic activity was also very
excellent. For about 500 h, a 97-100% yield of cyclopentene was obtained at 120C and 10 g g cat -~ h -1 of
cyclopentadiene was kept. This shows a possibility to
apply the amorphous NiB/SiO2 catalyst to commercial
cyclopentene production.

488.9 C
437.5 C ~

210C

3.2. Characterization
BET nitrogen surface area of the catalyst sample
was about 180 m 2 g-t. Its nickel dispersion measured
by oxygen uptake at 25C using a pulse chromatographic technique was 0.30. These results show that
the amorphous NiB/SiO2 has larger surface area and
higher nickel dispersion.
Fig. 3 shows the XRD patterns of four NiB/SiO2
samples. The patterns of (b) and (c) were almost the
same. After subtracting the background spectrum of
SiO2, a broad peak at 20=45 was observed. This was
attributed to the NiB alloy in the amorphous state. The
pattern of (d) indicated that the amorphous state still
remained, but on the pattern of (e), the diffraction
peaks of some crystal, which was analyzed to be
nickel crystallite, had appeared. DSC spectra, as

_=

20

40

60

80

20()
Fig. 3. X-ray diffraction patterns of (a) SiO2, (b) original NiB/
SiO> (c) NiB/SiO2 after 500 h of hydrogenation at 120C, (d) NiB!
SiO2 treated in N2 for 2 h at 400C, and (e) NiB/SiO2 treated in N2
for 2 h at 450C.

100

200

300

400

500

600

Temperature(C)
Fig. 4. DSC spectra of NiB/SiO2.

shown in Fig. 4, exhibited that there were three

exothermic peaks at 412.7C, 437.5C and 488.9C,
while on the unsupported counterpart at 144.1C,
253.4C and 341.4C, respectively [16]. This illustrates that the crystalline transformation temperature
of the amorphous NiB/SiO2 is higher than that of the
unsupported counterpart. The SEM photograph in
Fig. 5 shows the surface morphology of three NiB/
SiO2 samples. Pictures (a) and (b) revealed that the
NiB alloy was cottony, which was considered to be the
amorphous state, but the density of the amorphous
alloy on picture (b) seemed to be larger than that on
picture (a). Picture (c) indicated that NiB alloy was
slightly agglomerated, thus we concluded that some
crystallization had occurred. These phenomena were
exactly corresponding to those in the XRD and DSC
experiments. All these results indicate that the supported amorphous nickel-boron alloy has much higher
thermal stability. This property is considered to be
mainly due to the lower metal loading and high alloy
dispersion, the results are meaningful for the application of amorphous alloys in catalysis.
XPS spectra of Ni2p3/2 and B l s in the amorphous
NiB/SiO2 catalyst are shown in Fig. 6. Compared with
the spectra of pure nickel metal foil (852.8 eV) and
nickel oxide (854.5 eV), the peak at 852.0 eV in the
NiEp3/2 level is ascribed to metallic Ni and that at
855.4 eV to oxidized nickel. In the B l s level, two kinds
of higher binding energy than 189.4 eV for elementary

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

106

Magnific~ion:100~.~

B were assigned to boron interacting with nickel

(191 eV) and to oxidized boron (194 eV), respectively
[16-19]. From these results, it can be immediately
concluded that the boron donates electrons to nickel.
The same results were obtained on the amorphous NiB
alloy powder [ 16].
The surface composition calculated from the XPS
spectra using the relative peak area sensitivities was
Niv0B3o (mol%). Compared with the bulk composition
of NisoB2o determined by ICP spectrometry, the surface of the catalyst is metalloid rich.
The results in the characterization mentioned above
could explain the good catalytic properties of the
catalyst obtained in cyclopentadiene hydrogenation;
the high activity is attributable to high dispersed
metallic nickel and the active site of the amorphous
nickel-boron is also metallic nickel [t6]. The higher
selectivity is ascribed to the amorphous state of nickel
which makes the active site of the catalyst chemically
and structurally isotropic [ 11,12]. When the catalyst is
crystallized, the activities of active sites at different
faces would be different, which results in a decrease of
the selectivity. The excellent stability of the catalytic
reactivity seems to result from the high crystalline
transformation temperature of the nickel-boron alloy
supported on silica.
3.3. K i n e t i c s t u d i e s

Magnii]cati~ln ~0 0 ( ~ [11)

Kinetic studies were carried out under differential

conditions, i.e., the conversion was maintained at
approximately 5%. When GHSV>5000 h -], the external diffusion was negligible and the intraparticle
diffusion was completely eliminated, if the particle
size was reduced to 40 mesh in the present work.
The dependence of the cyclopentadiene hydrogenation rate on the partial pressure of cyclopentadiene and
hydrogen was investigated. In the present studies, the
selectivity to cyclopentene was 100%. Furthermore,
the addition of 10 mol% of cyclopentene or cyclopentane into the feed did not influence the reaction rate.
Therefore, the reaction rate re) can be expressed as
m 11

$q~Or~m

Magnil]clllof~ IO00o O0

Fig. 5. SEM pictures of (a) original NiB/SiO2 sample, (b) NiB/

SiO2 sample treated in N2 for 2 h at 400C, and (c) NiB/SiO2
sample treated in N2 for 2 h at 450C.

rD = F D X = kDPDPH2,

(3)

where FD is the cyclopentadiene feed in mol s- 1, X the

conversion in percent of cyclopentadiene converted
and PD is the pressure of cyclopentadiene, respectively. If GHSV in the reactor is fixed by adjusting the

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

Ni2v3t2

107

Bls

852.0 eV
194.0 eV

Binding Energy(eV)
Fig. 6. XPS spectra of Nizp3/2 and BI~ in the NiB/SiO2 catalyst.

nitrogen flow-rate

simply by

PD oc VD :x FD,

(4)

rD = kDPn2 = k e x p ( - E / R T ) P H : ,

Plq2 :x v~q2,

(5)

where k is the pre-exponential factor, and E is the

activation energy. The activation energy was measured
between 80C and 160C and found to be 6.93
kJ mol - l . The average pre-exponential factor k was
calculated to be 2.610 -3 mol g cat - t atm -~ s
Hence the rate of the reaction can be rewritten as

where VD and VH2 are the flow-rate of cyclopentadiene

and hydrogen, respectively. Then
rD = F D X = k v ~~mvn
D
H2
or
X

1 ~m--I
n
= tc~r
D v.2.

(6)

When vH2 remained constant, then

log X oc (m - 1) log FD.

(7)

The logarithm of the conversion is plotted against

the logarithm of the cyclopentadiene feed in Fig. 7,
which exhibits a series of parallel lines depending on
the reaction temperature. Their slope, - 1 , indicates
that the reaction rate upon the cyclopentadiene is zero
order. If FD is constant, then
logX oc n log Vn~.

(8)

Fig. 8 shows the plots of log X to log vIq2, which

also exhibits a series of parallel lines related with
the reaction temperature. The slope, 1, indicates
that the reaction rate upon hydrogen velocity is
the first order, thus the reaction rate ro is expressed

(9)

rD = 2.6 10 -3 e x p ( - 8 3 5 / T ) P m

(10)

with E / R = 8 3 5 mol -j K -1 if E is in J and R in

J mol - t K -1.
Table 2 gives the rates of cyclopentadiene consumption calculated from Eq. (10) at several reaction
temperatures, when hydrogen pressure and cyclo-

Table 2
Observed and calculated rates of reaction as a function of the
reaction temperature
T(C)

robs (10 6 m o l s - l )

real (10 6 m o l s 1)

80
100

3.03
3.78

3. l 8
3.61

120

4.17

4.05

140
160

4.38
4.78

4.48
4.92

PHi_=0.13 atm, PCVD=0.25 atm, 0.1 g of catalyst.

108

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

1.0

0.8

0.6

0.4

0.2

1.1

1.2

1.3

1.4

1.5

1.6

Log Pm
Fig. 7. The logarithm of the CPD conversion vs. the logarithm of the CPD feed plots (conditions: PH2=0.2 atm, GHSV=24000 1).

0.8

0.6
X
o

0.4

0.2

140"C
o 160 C

NN~.%NN~eNN~Q

1.2

1.6

1.4

1.8

2.0

2.2

Log FCI,D
Fig. 8. The logarithm of the CPD conversion vs. the logarithm of the PH2 plots (conditions: P0=0.25 atm, GHSV=24000 i).

pentadiene pressure are 0.13 and 0.25 atm, respectively. Very good agreement was found between the
calculated and observed rates of reaction.

According to rate-equation (10), which is different

from those obtained on NiS [5] and on Pd [20] but
similar to that on Cu/A1203 [21 ], for the bimolecular

W.-J. Wang et al./Applied Catalysis A: General 163 (1997) 101-109

reaction studied here we propose a Redeal-Eley (R-E)

type mechanism. For a Langmuir-Hinshelwood (L-H)
type mechanism, we must suppose that the adsorption of hydrogen and cyclopentadiene are non-competitive, and assume that the adsorption of hydrogen is
weak and cyclopentadiene strong, thus we could
obtain Eq. (10). As the active sites of the amorphous
NiB/SiO2 catalyst are all elemental nickel and isotropic, such non-competitive adsorption is not realistic. Based on the R-E type mechanism, i.e., strongly
adsorbed cyclopentadiene reacting with hydrogen
directly from the gas phase [22], our mechanism,
which is identical with that on Cu/A1203 [21], can
be written as follows:
CPD + catalyst = CPD-catalyst

(11)

CPD-catalyst + H2 --~ CPE + catalyst

(12)

If ~D and KD are the surface coverage and adsorption coefficient of cyclopentadiene, respectively, and
the rate-determining step is Eq. (12), one may
write
(13)

~)D = K D P D / ( I + K D P D ) ,
rD = kD~DPH2 = kDKDPDPH2 / (1 + KDPD ).

Assuming that cyclopentadiene

adsorbed, i.e., KDPD>>I,
rD = kDP.2.

is

strongly
(14)

This is identical with the rate equation obtained in

kinetic experiments.

4. Conclusions
It was shown that an amorphous nickel-boron alloy
supported on silica was very helpful for selective
hydrogenation of cyclopentadiene to cyclopentene
at low temperature in gas-solid phase. The catalyst
activity was very stable for a long time on stream. The
results in catalyst characterization showed that the
amorphous state was maintained over 80-120C. The
differential kinetic study revealed that the reaction
mechanism was of the Rideal-Eley type with cyclopentadiene strongly adsorbed on the catalyst. To our

109

knowledge, the present report is the first one on the

behavior of amorphous alloy catalyst which may be
applied to commercial catalytic processes in gas-solid
phase reaction.

Acknowledgements
This work was supported by the National Natural
Science Foundation of China and China Petrochemical Corporation.

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