Académique Documents
Professionnel Documents
Culture Documents
Laboratory of Surface Chemistry and Catalysis, National Research Center (NRC), Dokki, Cairo, Egypt
b
Egyptian Petroleum Research Institute (EPRI), Nasr City, Cairo, Egypt
c
Faculty of Science, Department of Chemistry, Zagazig University, Zagazig, Egypt
Received 6 January 2003; accepted 10 June 2003
Abstract
Cumene hydrocracking was carried out over pure and doped Ni/Al2O3 solids and also, on these solids after exposure
to different doses of g-rays between 0.4 and 1.6 MGy. The dopant concentration was varied between 1 and 4 mol%
CeO2. Pure and doped samples were subjected to heat treatment at 400 C and cumene hydrocracking reaction was
carried out using various solids at temperatures between 250 C and 400 C by means of micropulse technique. The
results showed that both CeO2 doping and g-irradiation of the investigated system brought about an increase in its
specic surface area. g-irradiation of pure samples increased their catalytic activities effectively. However, the doping
caused a decrease in the catalytic activity. g-irradiation of the doped samples brought about a net decrease in the
catalytic activity.
The catalytic reaction products over different investigated solids were ethylbenzene as a major product together with
different amounts of toluene, benzene and C1C3 gaseous hydrocarbons. The selectivity towards the formation of
various reaction products varies with the reaction temperature, doping and g-irradiation.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: g-irradiation; CeO2 doping; Cumene hydrocracking; Ni/Al2O3
1. Introduction
Transition metals or metal oxides on support are
commonly employed to catalyze several reactions
including oxidationreduction, dehydration, dehydrogenation, cracking, alkylation, etc. (Muradov, 1993; Dos
Santos et al., 1997; Zhang and Amiridis, 1998; Velu and
Swamy, 1997; El-Shobaky and Al-Noaimi, 1987a; Luo
et al., 1997; El-Shobaky et al., 1997, 2001; Golchet and
White, 1978; Youssef et al., 1992; Mendes and Schmal,
1997; Li and Ding, 2000). The activities and selectivities
for these variety of solids could be modied by doping
with certain foreign oxides (El-Shobaky et al., 1988,
1989, 2000, 2002, 2003; El-Boohy et al., 2002; Doheim
et al., 2001a, b, 2002).
0969-806X/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0969-806X(03)00444-4
ARTICLE IN PRESS
32
excess oxygen and fragmentation of its crystallites (ElShobaky et al., 1987c). However, these catalysts undergo
deactivation due to the formation of cobalt aluminate
via metal oxidealumina interactions (Bolt et al., 1993).
The present work aimed at investigating the role of
doping Ni/Al2O3 system with CeO2 and treating the
same with g-irradiation on its surface and catalytic
properties. The techniques employed were XRD, nitrogen adsorption isotherm measured at 196 C and
cumene hydrocracking at 250400 C.
2. Experimental
2.1. Materials
3. Results and discussion
Nickel oxide supported on g-alumina was prepared by
treating a calculated amount of nely powdered
Al(OH)3 with a known amount of Ni(NO3)2 dissolved
in the least amount of distilled water. The obtained
solids were dried at 110 C to constant weight, then
subjected to thermal treatment at 500 C for 5 h. The
composition of the prepared solids after calcination was
0.1NiO/Al2O3, the NiO content was 10%. Three doped
samples were prepared by treating the Al(OH)3 support
material with cerium nitrate dissolved in the least
amount of distilled water. The obtained solids were
dried at 110 C to constant weight then treated with
Ni(NO3)2 dissolved in the least amount of distilled
water, dried and then calcined at 500 C for 5 h. The
amounts of dopant added, expressed as mol% CeO2
were 1, 2 and 4. The chemicals employed Ni(NO3)2,
Al(OH)3 and cerium nitrate were of analytical grade
supplied by BDH company, analar cumene was supplied
by Merck.
The calcined samples were exposed to different doses
of g-rays using a 60Co source. The doses were 0.2, 0.4,
0.8 and 1.6 MGy at a dose rate of 2.7 107 MGy s1.
The irradiated samples were left 2 weeks in sealed tubes
before the different measurements were carried out.
The reduction of the investigated samples was done by
heating at 400 C in a current of hydrogen owing at a
rate of 30 ml min1, followed by cooling to the reaction
temperature of the catalytic reaction. The reduction
process was conducted for 1 h.
2.2. Techniques
An X-ray powder diffraction was conducted over pure
and variously doped solids precalcined at 500 C and
also those exposed to g-irradiation using a Shimadzu
diffractometer type (D-D1). The patterns were run with
( at 60 kV
nickel-ltered copper radiation (l 1:5405 A)
and 25 mA with a scanning speed of 8 in 2y min1.
The specic surface areas of the various prepared
catalyst samples were determined from nitrogen adsorp-
Dose of
g-rays (MGy)
0.0
2
4
8
0.0
2
4
8
0.0
2
4
8
0.0
2
4
8
0.0
0.0
0.0
0.0
0.4
0.4
0.4
0.4
0.8
0.8
0.8
0.8
1.6
1.6
1.6
1.6
153
160
164
168
170
172
180
185
192
194
199
203
210
215
227
232
ARTICLE IN PRESS
G.A. El-Shobaky et al. / Radiation Physics and Chemistry 69 (2004) 3137
0.0 MGy
0.4 MGy
0.8 MGy
1.6 MGy
% Conversion
95
75
55
35
250
300
350
Temperature C
400
(a)
0.0 MGy
1.6 MGy
0.0 MGy
300
350
Temperature C
0.4 MGy
0.8 MGy
10
5
0
300
350
Temperature C
1.6 MGy
5
0
250
(b)
1.6 MGy
0.8 MGy
15
10
400
15
250
0.4 MGy
20
0.0 MGy
% Selectivity
% Selectivity
0.8 MGy
50
40
30
20
10
0
250
(c)
0.4 MGy
% Selectivity
% Selectivity
0.0 MGy
33
400
0.4 MGy
0.8 MGy
400
1.6 MGy
100
80
60
40
20
0
250
(d)
300
350
Temperature C
300
350
Temperature C
400
Fig. 2. (a) Effect of g-irradiation on the selectivity towards the ethylbenzene formation for the catalytic reaction conducted over pure
catalyst; (b) g-irradiation on the selectivity towards the toluene formation for the catalytic reaction conducted over pure catalyst;
(c) g-irradiation on the selectivity towards the benzene formation for the catalytic reaction conducted over pure catalyst; and
(d) g-irradiation on the selectivity towards the gases formation for the catalytic reaction conducted over pure catalyst.
ARTICLE IN PRESS
G.A. El-Shobaky et al. / Radiation Physics and Chemistry 69 (2004) 3137
34
0.0 mol%
1 mol%
2 mol%
4 mol%
% Conversion
100
80
60
40
(a)
0.0 mol%
300
350
TemperatureC
1 mol%
400
C6 H5 CHCH3 2
- C6 H5 CH3 gases;
2 mol%
Cumene
4 mol%
Toluene
C6 H5 CHCH3 2
Cumene
120
% Conversion
20
0
250
- C6 H5 gases:
Benzene
100
80
60
C6 H5 CH2 CH3
Ethylbenzene
40
20
0
250
(b)
C6 H5 CHCH3 2
Cumene
300
350
TemperatureC
C6 H6 CH4
Benzene
400
0.0 MGy
- C6 H5 CH3 gases;
Toluene
- C6 H5 CH3 :
Toluene
1 mol%
2 mol%
- C6 H6 gases;
Benzene
4 mol%
% Selectivity
50
40
30
20
10
0
250
% Selectivity
0.0 MGy
350
400
1 mol%
2 mol%
4 mol%
80
70
60
50
40
30
20
10
0
250
(b)
300
Temperature C
(a)
300
350
400
Temperature C
Fig. 4. (a) Effect of dopant concentration on the selectivity towards the ethylbenzene formation for the catalytic reaction conducted
over CeO2-doped catalyst; and (b) effect of 1.6 MGy dose of g-rays on the selectivity towards the ethylbenzene formation for the
catalytic reaction conducted over CeO2-doped catalyst.
ARTICLE IN PRESS
G.A. El-Shobaky et al. / Radiation Physics and Chemistry 69 (2004) 3137
0.0 MGy
1 mol%
2 mol%
35
4 mol%
% Selectivity
20
15
10
5
0
250
300
0.0 MGy
% Selectivity
350
400
Temperature C
(a)
1 mol%
2 mol%
4 mol%
14
12
10
8
6
4
2
0
250
300
350
400
Temperature C
(b)
Fig. 5. (a) Effect of dopant concentration on the selectivity towards the toluene formation for the catalytic reaction conducted over
CeO2-doped catalyst; and (b) effect of 1.6 MGy dose of g-rays on the selectivity towards the toluene formation for the catalytic reaction
conducted over CeO2-doped catalyst.
% Selectivity
0.0 MGy
1 mol%
2 mol%
4 mol%
12
10
8
6
4
2
0
250
300
350
400
Temperature C
(a)
0.0 MGy
1 mol%
2 mol%
4 mol%
% Selectivity
15
10
5
0
250
(b)
300
350
400
Temperature C
Fig. 6. (a) Effect of dopant concentration on the selectivity towards the benzene formation for the catalytic reaction conducted over
CeO2-doped catalyst; and (b) effect of 1.6 MGy dose of g-rays on the selectivity towards the benzene formation for the catalytic
reaction conducted over CeO2-doped catalyst.
ARTICLE IN PRESS
36
0.0 MGy
1 mol%
2 mol%
4 mol%
% Selectivity
100
80
60
40
20
0
250
(a)
0.0 MGy
300
350
Temperature C
1 mol%
2 mol%
400
4 mol%
% Selectivity
80
60
40
20
0
250
(b)
300
350
Temperature C
400
Fig. 7. (a) Effect of dopant concentration on the selectivity towards the gases formation for the catalytic reaction conducted over
CeO2-doped catalyst; and (b) effect of 1.6 MGy dose of g-rays on the selectivity towards the gases formation for the catalytic reaction
conducted over CeO2-doped catalyst.
C6 H5 CH3
Toluene
- C6 H6 gases:
Benzene
4. Conclusions
The results obtained lead to the following main
conclusions:
1. XRD-investigation of 0.1 Ni/Al2O3 system showed
its amorphous nature.
2. CeO2 doping and g-irradiation of Ni/Al2O3 increased
the specic surface area in proportion to the amount
of dopant added and the dose of g-irradiation.
3. CeO2 doping of the investigated solids brought about
a signicant decrease in their catalytic activities in
hydrocracking of cumene. The hydrocracking of
cumene led to the formation of ethylbenzene as a
ARTICLE IN PRESS
G.A. El-Shobaky et al. / Radiation Physics and Chemistry 69 (2004) 3137
References
Andreev, A., Kafedzhiiski, V., Kunev, T., Kalchev, V., 1991.
Rany type copperzincaluminum catalyst for water gas
shift reaction. Appl. Catal. A 78, 199213.
Benson, S.W., 1976. Thermochemical Kinetics. Wiley, New
York, USA.
Bolt, P.H., Lobner, S.F., Bout, T.P., Geus, J.W., Habarken,
F.H.P.M., 1993. Interfacial reactions of transition metal
oxides on alumina. Appl. Surf. Sci. 70/71, 196208.
Doheim, M.M., El-Boohy, H.A., El-Shobaky, G.A., 2001a.
Catalytic conversion of ethanol and isopropanol on
g-irradiated Co3O4/Al2O3. Adsorp. Sci. Technol. 19 (8),
635643.
Doheim, M.M., El-Boohy, H.A., Mokhtar, M., El-Shobaky,
G.A., 2001b. Surface and catalytic properties of g-irradiated
ZnO-treated Co3O4/Al2O3. Adsorp. Sci. Technol. 19 (9),
751764.
Doheim, M.M., Ahmed, A.S., El-Boohy, H.A., El-Shobaky,
G.A., 2002. Activity and selectivity of manganese oxides in
alcohol conversion as inuenced by g-irradiation. J. Radioanal. Nucl. Chem. Art. 254 (3), 583588.
Dos Santos, A.C.B., Kover, W.B., Faro, A.C., 1997. Transition
metal oxides addivated with sulphate or phosphate as
catalysts for cracking of cumene. Appl. Catal. A 153,
83101.
El-Boohy, H.A., Doheim, M.M., El-Shobaky, G.A., 2002.
Effect of g-irradiation on catalytic conversion of ethanol
and isopropanol over pure and Na2O-doped Mn2O3/Al2O3.
AFINIDAD 19, 4550.
El-Shobaky, G.A., Al-Noaimi, A.N., 1987a. Catalytic oxidation of CO of sodium oxide treated-NiO/Al2O3 solids. Appl.
Catal. 29, 235242.
El-Shobaky, G.A., Fagal, G.A., Petro, N., Dessouki, A.M.,
1987b. Effect of g-irradiation on surface and catalytic
processes of Co3O4 supported on Al2O3. Radiat. Phys.
Chem. 29, 3943.
El-Shobaky, G.A., El-Shaabiny, A.M., Ramadan, A.A.,
Dessouki, A.M., 1987c. Effect of g-irradiation on microstrain and lattice parameter of Co3O4 loaded on Al2O3.
Radiat. Phys. Chem. 30, 233236.
El-Shobaky, G.A., El-Nabarawy, Th., Fagal, G.A., Dessouki,
A.M., 1988. Surface and catalytic processes of g-irradiated
CuO/Al2O3. Radiat. Phys. Chem. 32, 773778.
El-Shobaky, G.A., El-Shaabiny, A.M., Ramadan, A.A.,
Dessouki, A.M., 1989. Some structural characteristics of
37