Applied Catalysis A: General 219 (2001) 131–140

Low temperature hydrocracking of n-heptane over Ni-supported

catalysts: study of global kinetics
K.I. Alhumaizi a,∗ , V.M. Akhmedov b , S.M. Al-Zahrani a , S.H. Al-Khowaiter b
a Chemical Engineering Department, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia
bPetroleum & Petrochemical Research Institute, KACST, P.O. Box 6086, Riyadh 11442, Saudi Arabia
Received 28 September 2000; received in revised form 2 March 2001; accepted 8 May 2001

Abstract
Two kinetic models were applied to n-heptane hydrocracking on a Ni-Re/ZSM-5 catalyst over a wide range of operating
experimental conditions (temperature = 433–493 K, and pressure = 760 mm Hg). In the first model, the hydrogen is adsorbed
on the catalyst surface without dissociation, while the second model assumes hydrogen dissociation. Both models assume
that the adsorption follows Langmuir isotherm. The molecular hydrogen associated with an active site is most likely involved
in the C–C bond rupture, which is concluded to be the rate controlling step in this work. The extracted intrinsic kinetics
were estimated via the derivation of the reactor model. The apparent activation energy for n-heptane cracking is found to
be 83 kJ/mol. Both models describe well the n-heptane consumption rate. The simulation results revealed that the hydrogen
adsorption constant is smaller than the n-heptane adsorption constant. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Hydrocracking; n-Heptane; Intrinsic kinetics; Nickel-supported catalyst

1. Introduction and selectivity in hydrocracking of saturated hydro-

Hydrocracking reactions are of great importance
in the petroleum refining industry for gasoline pro-
duction [1–4]. These reactions have been investigated
over a variety of catalysts by many authors [5–16].
Current hydrocracking processes are based on com-
mercial catalysts that are effective above 673 K.
Developing a new catalyst which works at lower tem-
perature will increase the operational and economical
benefits of hydrocarcking processes.
Akhmedov and others have used metal vapor
methods to design new transition-metal-supported
catalysts [17–20]. These catalysts posses high activity
∗ Corresponding author. Tel.: +966-1-4676873;
fax: +966-1-4678-770.
E-mail address: humaizi@ksu.edu.sa (K.I. Alhumaizi).
carbons under very mild conditions (less than 473 K
and normal pressure). As reported by Akhmedov
et al. [19], the new approaches to the preparations
of metal-supported systems completely changed the
reactivity and selectivity of nickle-containing cata-
lysts with regard to known successive demethylation
of alkanes [5–9].
n-Heptane has been widely used in catalytic trans-
formations of alkanes as a probe molecule, due to the
variety of reaction paths that it can take on different
catalysts. Rearrangement of n-heptane in the presence
of hydrogen over Ni-Re/ZSM-5 results in formation
of only propane and i-butane. The molar distribution
of the cracked products does not change significantly
even at conversions of n-heptane over 80% [19].
The mechanisms of hydrocracking reactions are
directly related to the structure of the surface inter-

0926-860X/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 6 7 5 - 5
132 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140

mediate species that undergo rupture of C–C bonds.
Based on these facts, it is very important to deter-
mine the kinetics of the hydrocracking and to dis-
cuss the possible reaction mechanisms to develop
these catalytic systems while seeking the optimum
activity.
The purpose of this work is to develop kinetic mod-
els of hydrocracking of n-heptane over Ni-Re/ZSM-5
catalyst, which reflect the physiochemical nature of
the process, in order to provide a better insight into the
C–C bond cleavage in hydrogenolysis reactions. The
developed models will be used to interpret the experi-
mental results via rate equations for the hydrocracking
reactions, which can be used later for reactor design
and optimization.
2. Experimental
The experiments were performed in a flow reaction
apparatus at atmospheric pressure. The metal vapor
method (MVM) was used for preparation of Ni-Re
bimetallic supported catalysts. The previous publica-
tion [19] demonstrated that the MVM is one of the
most promising approaches to the synthesis of the
Ni-Re/ZSM-5 catalyst which possesses unusual low
temperature C–C bond cleavage activity. The details
of the catalyst preparation and characterization of
Ni-Re/ZSM-5 catalyst can be found elsewhere [19].
The conversion rate of n-heptane was obtained by
the summation of the formation rate of all the prod-
ucts. The hydrogen was always kept flowing through
the catalyst bed. Under these conditions, no signifi-
cance deactivation of the catalyst was observed. The
effects of the temperature, hydrogen and n-heptane
flow rates on the conversion rate of hydrocarbon were
investigated.
The following experimental conditions were used
for a typical catalyst run: the fine powder catalyst
sample (0.2 g) was loaded into the micro-flow reac-
tor and a thermocouple was placed on the center of
the catalyst bed to monitor the reaction temperature.
n-Heptane and hydrogen were fed continuously to the
reactor and all the reaction products were analyzed by
an online gas chromatograph (Varian Star 3600 CX)
using a DBI capillary column (30 m long). Under the
given conditions, n-heptane underwent hydrocracking
to propane and i-butane and traces of other alkanes.
The catalyst also causes isomerization of n-heptane
to i-heptane. Tables 1–4 show the hydrocracking and
hydroisomerization activity and selectivity of the stud-
ied catalyst under different reaction conditions.

Table 1
Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at different reaction temperatures
Temperature (K)
433 443 453 463 473 483 493
FC7 (mole/h) 0.024 0.0246 0.0246 0.0246 0.0246 0.0246 0.0246
FH2 (mole/h) 0.162 0.162 0.162 0.162 0.162 0.162 0.162
Rtotal (mole/mole Ni h) 7.61 24.25 74.67 128.4 204.9 313.4 380.4
Rcracking (mole/mole Ni h) 0.68 6.97 34.18 71.19 150.33 240.83 344.64
Risomer (mole/mole Ni h) 6.93 17.28 40.48 57.22 54.65 72.58 35.84
Products
C1 – 0.25 4.76 8.50 23.06 36.04 40.90
C2 – – – – 1.84 6.37 9.13
C3 0.66 6.56 31.23 65.63 130.71 214.62 320.21
i-C4 0.66 6.66 30.61 63.52 129.59 198.75 273.03
n-C4 – – – – 2.19 4.64 22.56
i-C5 – – – – 0.28 0.52 0.84
n-C5 – – – – 2.53 4.13 11.78
i-C6 – 0.09 – – 1.57 3.71 2.65
n-C6 – 0.15 2.25 4.78 10.15 16.5 13.54
i-C7 6.93 17.28 40.48 57.22 54.65 72.58 35.84
2Rcracking + Risomer 8.29 31.22 108.84 199.60 353.31 552.57 725.12
 Products 8.25 30.85 109.33 199.65 356.57 557.86 730.48
 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140 133

Table 2
Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at T = 493 K
Temperature (K)

493 493 493 493 493 493

FC7 (mole/h) 0.0082 0.0164 0.0246 0.0246 0.0246 0.0246

FH2 (mole/h) 0.162 0.162 0.162 0.324 0.486 0.648
Rtotal (mole/mole Ni h) 140.96 275.85 380.48 364.78 325.78 285.74
Rcracking (mole/mole Ni h) 125.23 246.38 344.64 329.91 289.26 247.34
Risomer (mole/mole Ni h) 15.67 29.47 35.84 34.87 36.52 38.50
Products
C1 25.27 30.82 40.90 35.79 28.30 24.48
C2 2.39 6.19 9.13 8.26 5.86 4.85
C3 105.99 213.51 320.21 301.27 264.92 219.49
i-C4 101.69 195.35 273.03 259.05 228.38 207.63
n-C4 2.23 14.46 22.56 27.67 18.86 –
i-C5 0.44 – 0.84 1.01 0.86 –
n-C5 2.60 6.01 11.78 13.83 11.35 10.44
i-C6 3.06 4.17 2.65 3.01 1.59 –
n-C6 7.8115 17.09 13.54 15.95 18.98 22.33
i-C7 15.67 29.47 35.84 34.87 36.52 38.50
2Rcracking + Risomer 266.13 522.23 725.12 694.69 615.04 533.18
 Products 267.15 517.07 730.48 700.71 615.62 527.72

Table 3
Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at T = 483 K
Temperature (K)

483 483 483 483 483 483

FC7 (mole/h) 0.0082 0.0164 0.0246 0.041 0.0246 0.0246

FH2 (mole/h) 0.162 0.162 0.162 0.162 0.405 0.648
Rtotal (mole/mole Ni h) 110.76 226.10 313.42 516.02 286.78 229.27
Rcracking (mole/mole Ni h) 87.16 178.74 240.83 384.59 227.82 185.12
Risomer (mole/mole Ni h) 23.60 47.36 72.59 131.43 58.96 35.15
Products
C1 16.27 30.01 36.04 58.69 29.24 21.89
C2 1.81 4.28 6.37 8.94 6.31 5.94
C3 77.55 151.83 214.62 336.71 199.63 169.39
i-C4 75.19 150.20 198.75 318.24 189.47 158.10
n-C4 1.79 3.11 4.64 7.47 4.15 3.64
mvci-C5 0.32 0.62 0.52 – 0.39 –
n-C5 1.73 2.91 4.13 7.52 2.74 1.65
i-C6 1.14 3.04 3.71 7.14 1.99 –
n-C6 5.17 11.03 16.50 31.20 12.87 5.55
i-C7 23.60 47.36 72.58 131.43 58.96 35.15
2Rcracking +Risomer 197.92 404.84 554.25 900.61 514.6 405.39
 Products 204.48 404.48 557.86 907.34 505.75 401.31
134 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140

Table 4
Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at different reaction temperatures
Temperature (K)

473 473 473 463 463

FC7 (mole/h) 0.0082 0.0164 0.0246 0.0246 0.0328

FH2 (mole/h) 0.162 0.162 0.162 0.162 0.162
Rtotal (mole/mole Ni h) 84.18 145.85 204.89 128.41 172.11
Rcracking (mole/mole Ni h) 61.95 100.45 150.33 71.19 94.82
Risomer (mole/mole Ni h) 22.23 45.40 54.56 57.22 76.29
Products
C1 9.47 14.76 23.06 8.50 11.34
C2 0.77 1.31 1.84 – –
C3 54.70 95.13 130.77 65.63 87.47
i-C4 53.22 89.06 128.66 63.52 84.64
n-C4 0.89 1.51 2.19 – –
i-C5 0.11 – 0.28 – –
n-C5 4.04 1.17 2.53 – –
i-C6 0.64 0.54 1.57 – –
n-C6 4.17 5.95 10.15 4.78 6.37
i-C7 22.43 45.40 54.65 57.22 76.29
2Rcracking + Risomer 146.13 246.3 355.22 199.6 265.93
 Products 150.44 248.83 355.61 199.65 266.11

3. Reaction mechanism and kinetics • surface reaction between the adsorbed reactants
(n-heptane and hydrogen) is the rate-limiting step;
Two kinetic models were investigated to predict and
the overall consumption of n-heptane. Both models • weak adsorption of products.
assume that the surface reaction is the rate-limiting
The proposed reaction mechanism, based on the
step. The major difference between the two models is
Langmuir adsorption isotherm approach consists of
related to the way that hydrogen is adsorbed on the
the following steps:
catalyst surface. In the first model, the hydrogen is ad-
sorbed without dissociation, while the second model (a) Reactant adsorption
assumes hydrogen dissociation.
A + X ⇔ AX
3.1. Kinetic model I H + X ⇔ HX

The first kinetic model is based on a surface reaction (b) Surface reaction
mechanism without hydrogen dissociation. The model AX + HX → Products + 2X
will be used to express the overall rate of consumption
of n-heptane. The following assumptions are used to
Here, A: n-heptane, H: hydrogen, P: product and
derive the kinetic model:
X is the active site. AX and HX are the adsorbed
• equal competition for the active sites between the n-heptane and hydrogen, respectively.
n-heptane and hydrogen in which both adsorbed on
Since the C–C bond rupture is the rate limiting step
the same type of site and according to the Langmuir
(rls), then the reaction rate of n-heptane (i.e. surface
isotherm [21,22];
reaction) is:
• fast chemisorption of the hydrocarbon and hydro-
gen, without hydrogen dissociation; −rA (mole/g cat h) = kr ϑAX ϑHX (1)
 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140 135

where kr is the rate constant of the surface reaction and where i: n-heptane and hydrogen, Eapp the apparent
ϑ AX and ϑ HX are n-heptane and hydrogen coverages, activation energy and Hi is the heat of adsorption
respectively. for component i.
The coverage of the active sites is given by
3.2. Kinetic model II
K A PA
θAX = (2)
1 + K H PH + K A P A This model assumes hydrogen dissociation on the
KH P H active sites. The reaction mechanism consists of the
θHX = (3) following steps:
1 + K H PH + K A P A
(c) Reactant adsorption
Therefore, the reaction rate of n-heptane in terms of
observable gas phase partial pressure will have the A + X ⇔ AX
following form:
H2 + 2X ⇔ 2HX
k r K A K H PA PH
−rA = (4) (d) Surface reaction (rls)
(1 + KA PA + KH PH )2
PA is the partial pressure of n-heptane in the gas phase, AX + 2HX → Products + 3X
PH is the partial pressure of hydrogen in the gas phase.
The consumption rate of n-heptane will have the
This can be written in the form:
following form.
kPA PH √
−rA = (5) kPA PH
(1 + KA PA + KH PH )2 −rA = √ (8)
(1 + KA PA + KH PH )2
where

k = k0 e−Eapp /RT (6)

4. Results and discussion
and
Fig. 1 shows the distribution of the products
Ki = K0i e−Hi /RT (7) obtained by hydrocracking of n-heptane on Ni-Re/

Fig. 1. The product distribution of hydrocracking of n-heptane on Ni-Re/ZSM-5 catalyst vs. the reaction temperature.
136 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140
Fig. 2. Isomerization and cracking products of n-heptane on Ni-Re/ZSM-5 catalyst vs. the reaction temperature.
ZSM-5 catalyst versus the reaction temperature.
This figure reflects the fact that the product contains
almost an equal molar ratio of i-butane and propane.
These hydrocracking products are the major reaction
products as can be seen from Figs. 1 and 2. So the
Ni-Re/ZSM-5 catalyst demonstrates high internal
C–C bond rupture; the total number of moles in the
inlet to the reactor are the same as those exit form the
reactor, as shown in Tables 1–4. Since the tempera-
ture and the pressure along the micro fixed bed can
be assumed to be uniform due to the small amount of
the catalyst used (0.1–0.2 g), the volumetric flow rate
along the reactor will remain constant as illustrated
in Tables 1–4. Fig. 2 illustrates that on increasing the
temperature of the reaction, the cracking selectivity
increases and the fraction of C3 and C4 represent
more than 90% of the all the cracking products. Other
cracking products are also obtained as a result of C–C
bond cleavage in the initial step of the reaction. The
ratio of isomerized to cracked n-heptane decreases
when conversion increases.
Fig. 3 shows the Arrhenius-type diagram of the
Ni-Re/ZSM-5 catalyst (i.e. the natural logarithm of
the n-heptane conversion rate versus 1/T). The slope
of the curve is the same for all the points correspond-
ing to the temperature range investigated in this work;
this indicates that no diffusional phenomenon occurs
( i.e. the potential required to provide the diffusion
flux is insignificant) under the reaction conditions and
that the reaction is kinetic-controlled. Therefore, the
effectiveness factor (η) which accounts for the effect
of diffusion is equal to 1 for such a system. One of
the main causes for such reaction to be controlled by
the kinetics is the usage of small catalyst particle size,
which was used in this work. The results illustrated in
Fig. 3 strength the hypothesis stated in the previous
publications [19] which indicates that the low tem-
perature efficiency of Ni-Re/ZSM-5 catalyst could be
due to the highest dispersed state of supported metal
particles.
In order to estimate the kinetic data, the reactor
model was used. Since the laboratory reactor model
is equivalent to a plug flow reactor, all molecules
have same residence time and concentrations vary only
along the tubular reactor. In this type of reactor, the ef-
fluent composition is an overall integral composition.
The molar balance equation on a differential element
of the reactor is similar to the tubular reactor design
equation [23,24]:
dnA
= −ηrA (9)
dW
where η = 1 as stated above.
 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140 137

Fig. 3. Total consumption rate of n-heptane vs. (1/T) over Ni-Re/ZSM-5 catalyst.

This equation relates the changes of the moles of where Q is the total volumetric flow rate in the
the reactant along the reactor length (in terms of the reactor, T the temperature, and R is the universal gas
catalyst weight) to the rate of consumption of the re- constant.The total pressure is given by
actant. The kinetic model for our system is in the form
Pt Q = nT RT (14)
of a differential equation which in some cases (i.e.
low conversion) can be simplified to algebraic form. Therefore, using Eqs. (13) and (14), the n-heptane
However, in this work the integral from of the above partial pressure can be expressed by
differential equation was used to determine the kinetic
PA = yAf (1 − xA )Pt (15)
parameters because of higher conversion, which was
calculated according to and with the same approach the hydrogen partial
nAf − nA pressure can be expressed by
xA = (10)
nAf PH = yHf − yAf xA Pt (16)
The molar flow rates of A (n-heptane) and hydrogen where yAf and yHf are the mole fractions for n-heptane
(H) are and hydrogen in the feed, respectively. The nonlin-
nA = nAf (1 − xA ), nH = nHf − nAf xA (11) ear differential equation for the reactor needs to be
integrated knowing the initial reactor conditions: at
where nAf and nHf are the number of moles of W = 0; XA = 0.
n-heptane and hydrogen in the feed, respectively. The objective is to determine the kinetic parameters
The reactor model equation in terms of the conver- listed on the rate and reactor design equation, which
sion is given by will be used to predict the reactor output conditions.
dxA rA Therefore, the problem requires a combination of
= (12) nonlinear differential equation solver technique and
dW nAf
nonlinear regression analysis technique. For this ob-
The n-heptane partial pressure can be related to the its
jective, SCIENTIST software was used to solve the
conversion by the following relation:

 problem, it combines Runge–Kutta method with the
RT least square approximation technique to solve for the
PA = nAf (1 − xA ) (13)
Q best fitting kinetic parameters.
138 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140

Fig. 4. Predicted conversion (symbol) using kinetic parameters of model I vs. the experimental conversion.

Fig. 4 shows the predicted conversion using kinetic Fig. 6 shows the conversion predicted using ki-
parameters of model I versus the experimental con- netic parameters of model II versus the experimental
version. The figure indicates that the model I predicts conversion. The figure indicates that model II also
the n-heptane conversion quite well. The simulation predicts the n-heptane conversion quite well. The
results revealed that the hydrogen adsorption constant simulation results of model II also revealed that the
is very small compared to the n-heptane adsorption hydrogen adsorption constant is very small compared
constants, which indicate the weak adsorption of hy- to the n-heptane adsorption constant, which indi-
drogen and strong adsorption of n-heptane. Therefore, cates the weak adsorption of hydrogen and strong
the final consumption rate of n-heptane is found to be: adsorption of n-heptane. In this work, the hydrogen
flow rate was kept much higher than the n-heptane
9.6 × 108 e−9762/T PA PH
−rA = (17)
(1 + 986.88 e−3001/T PA )2
The apparent activation energy for this reaction
is found to be 81.2 kJ/mole. The apparent activation
energy value reported in the literature for n-heptane
hydrocarcking on Ni-Th catalyst for producing
methane and hexane is 160 kJ/mole [15]. Model I
predicts a lower activation energy of n-heptane crack-
ing to propane and butane which is in agreement
with the results reported by Zahraa et al. [15]. Fig. 5
shows the n-heptane conversion versus the tempera-
ture. The solid line represents the model prediction
while the symbols represent experimental data. The
model predictions are very close to the experimen-
tal data specifically at the higher temperature range
where hydrocracking products constitute most of the Fig. 5. n-Heptane conversion vs. reaction temperature, (experimen-
products. tal conversion: symbol, the predicted conversion: line).
 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140 139

Fig. 6. Predicted conversion (symbol) using kinetic parameters of model II vs. the experimental conversion.

flow rate. The objective of using such high ratios of partial pressure of hydrogen. The apparent activation
H2 /n-C7 H16 is to eliminate alkene precursors and to energy of this model is found to be 83.3 kJ/mole.
maintain low coke formation, since the catalyst deac- Table 5 shows the kinetic parameters for both mod-
tivation by coke laydown is minimized by increasing els. The final consumption rate of n-heptane is found
H2 pressure. Therefore, the effect of using excess to be:
amounts of H2 will narrow the differences between √
both models, as reflected on Fig. 7 by plotting the 1.642 × 109 e−10024/T PA PH
−rA = (18)
rates calculated form both mechanisms versus the (1 + 1882.3 e−3206/T PA )2

Fig. 7. Predicted rates form both models vs. the partial pressure of hydrogen.
140 K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131–140
Table 5
Kinetic parameters obtained for both models
Kinetic parameters Model I Model II
k0 (mole/g cat h) 9.6 × 108 1.642 × 109a
Eapp (kJ/mole) 81.2 83.3
KA 986.88 1882.3
HA (kJ/mole) 24.95 26.65
a The value of k for model II is measured in mole atm0.5 /
0
gm cat h
5. Conclusions
Adequate models describing the kinetics of hy-
drocracking and isomerization of n-heptane over
Ni-Re/ZSM-5 catalysts were derived under the as-
sumption that the molecular hydrogen associated with
an active site is most likely involved in the C–C bond
rupture, which is concluded to be the rate controlling
step. Experiments over a wide variety of experimen-
tal conditions were performed in a micro fixed bed
reactor, and kinetic parameters were estimated. The
predicted conversion was found to agree well with
the experimental data, providing evidence for the va-
lidity of C–C bond rapture approach used here. The
apparent activation energy for n-heptane cracking and
isomerization is found to be 83 kJ/mole. It is con-
cluded that the Ni-Re/ZSM-5 catalyst prepared by
MVM possesses high activity and selectivity towards
hydrocracking and isomerization of n-heptane. The
interaction between Ni and Re seems to modify the
electronic properties of Ni. In addition, such catalytic
systems are highly stable with a very good activity
under lower reaction temperature environments.
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