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Kinetic Modeling of Naphtha Catalytic

Reforming Reactions
CONFERENCE PAPER OCTOBER 2010

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13th Iranian National Chemical Engineering Congress

& 1st International Regional Chemical and Petroleum Engineering
Kermanshah, Iran, 25-28 October, 2010

Kinetic Modeling of Naphtha Catalytic Reforming Reactions

Majid Mohadesi, Chiya Savari, Gholamreza Moradi
Department of Chemical engineering, Faculty of Engineering, Razi University,Tagh Bostan Kermanshah
gmoradi@razi.ac.ir

Abstract
One of the important processes in oil refining industry, is the catalytic naphtha reforming. In this
process naphtha with low octane number converted to gasoline with high octane number. The
major reaction is highly endothermic and results in a large temperature decrease between the inlet
and outlet of the reactor, so a heater is used before each reactor. In this paper, catalytic naphtha
reforming unit in Isfahan Oil Refinery has been investigated. Smiths model for process modeling
has been used. The activation energies have been estimated using plant production data. The
reactor model is validated against plant data. The agreement between predicted results and
observations is generally good. Finally, the effects of inlet temperature and H 2/HC on performance
were investigated. The amount of aromatics increases with increasing temperature and decreasing
H2/HC.
Keywords: Catalytic Raforming, Naphtha, Modeling, Smiths Model

1. Introduction
Catalytic naphtha reformers are an integral part of an oil refinery, converting low octane
naphtha to a high octane reformate, through a series of catalytic reactors. Hydrogen and light
hydrocarbons are also obtained as side products. The normal commercial practice is to operate
a system of 3 or 4 adiabatic reactors in series with intermediate preheaters. The fixed bed
reactors operate adiabatically at temperatures of 450-550C, total pressures of 10-35atm, and
molar hydrogen-to-hydrocarbon ratios (H2/HC) of 3-8. The hydrodesulfurized straight-run
naphtha used as catalytic reforming feedstock. The naphtha feed is very complex consisting of
several hundred components and each of them undergoes various reactions. A detailed model
considering all the components and reactions is very complex and hence a properties and
kinetic behavior would be more convenient [1].
Naphtha being a complex mixture of hydrocarbons, undergoes a variety of reactions such as
dehydrogenation and dehydroisomerization of naphthenes to aromatics, dehydrogenation of
paraffins to olefins, dehydrocyclization of paraffins and olefins to aromatics, isomerization or
hydroisomerization to isoparaffins, isomerization of alkylcyclopentanes and substituted
aromatics and hydrocracking of paraffins and naphthenes to lower hydrocarbons. While it is
not practical to identify all the constituent components of naphtha and account for the
reactions they may undergo, attempts have been made to model naphtha by considering
groups of compounds (or kinetic lumps) taking part in reforming reactions [2].

Kinetic Modeling of Naphtha Catalytic Reforming

The model suggested by Smith [3] is probably the simplest, where naphtha reforming is
considered as a combination of only four reactions. The model published by Bommannan et
al. [2] is a simple kinetic model similar to Smiths model [3], which considers catalyst
deactivation. A simulation model for catalytic reforming was developed by Padmavathi et al.
[1] to monitor commercial plant performance [1]. Kmak and Stuckey [4] studied reforming
over a wide range of operating conditions using pure components, mixtures and naphtha feed
and developed a detailed model. Their model was limited to the representation of isothermal
operation at some point within the experimental temperature range in which they fitted the
parameters [4]. Turpin [5] discussed the typical refinery problems that can be solved
accurately using process simulation model and showed that a reduction of the reaction
pressure results in higher reformate and hydrogen yields [5]. On the basis of Rahimpour's
model [6], the average inlet temperature of reformers can be increased to compensate
aromatic yield. They have shown that the optimum mass of catalyst distribution for maximum
aromatic yield of the Shiraz refinery's reformers was 30, 30, and 40% respectively in three
reactors [6].
In the present study, a somewhat modified Smiths model has been used successfully to
predict plant performance for Isfahan Oil Refinery (Iran). The kinetic parameters have been
estimated from the plant data. Then, the effects of temperature and hydrogen to hydrocarbon
ratio on performance are investigated.
2. Kinetic Model
The complex naphtha mixture is idealized so that each of the three hydrocarbon classes;
naphthenes, paraffins and aromatics is represented by a single compound having average
properties of that class. It is further assumed that each of the three compounds has the same
number of carbon atoms caused by hydrocracking of paraffins and naphthenes are relatively
small [2]. The following four reactions are accounted for this model [2, 7]:
1. Dehydrogenation of naphthenes to aromatics; the dehydrogenation reaction and the relevant
rate equation for naphthenes are:
NaphtheneAromatic+3H2
(1)
3
(2)
r1 k1 PN K1 PA P H2
This reaction is catalyzed by the metal function of the catalyst and it is the fastest of all the
reforming reactions. It is endothermic and increases the octane number of the product. An
increasing amount of naphthenes in the feed stream favors the thermodynamic feasibility of
the formation of aromatics. The reaction is favored at high temperature and low pressure.
2. Dehydrocyclization of paraffins to naphthenes; the dehydrocyclization of paraffins to
naphthenes is a relatively slow reaction. The rate is comparable to that of hydrocracking. The
thermodynamic feasibility of the reaction increases with increasing carbon number. The
reaction is favored at high temperature and low pressure. The rate equation is:
ParaffinAromatic+H2
(3)

(4)
r2 k2 PP K2 PA PH2
3. Hydrocracking of naphthenes to lower hydrocarbons (C1-C5); hydrocracking is an
exothermic reaction and its reaction rate increases with increasing temperature, pressure, and
paraffin carbon number. The rate equation of hydrocracking of naphthenes is:
n 3
n
Naphthene+
H2
3
15

r3 k3 P N

Ptot

C
5

(5)

i 1

(6)

13th Iranian National Chemical Engineering Congress

& 1st International Regional Chemical and Petroleum Engineering
Kermanshah, Iran, 25-28 October, 2010

Which n is the number of carbon atoms in each class and is equal to:
1
(7)
n Mw 2 NP 6 NA
14
4. Hydrocracking of paraffins to lower hydrocarbons (C1-C5); assuming paraffins
hydrocracking to be similar to naphthene hydrocracking with reaction rate constant to be the
same:
Paraffin+

n
n
H2
3
15

C
5

(8)

i 1

r 4 k 4 PP

(9)
Ptot
The cracking of naphthenes and paraffins are irreversible. In these reactions, the forward rate
constants ki and Ki can be expressed as:
Ei

ki ki ,0 exp RT , i 1,2,3,4

(10)

Bi

Ai
(11)
Ki exp T , i 1,2
Values of ki,0, Ai and Bi are obtained from average values of Padmavathi et al. [1] work.
These values are shown in Table 1. Activation energies must be estimated by optimization.

Reaction
1
2
3
4

Table 1: Kinetic and Thermodynamic Parameters

ki,0 [Kmole/(hr.kgcat. kPa)]
A
B
Hi (KJ/mole)
3.055108
60.5011 24639.15
2.0841105
11
3.41110
-11.2422 -5118.471 -0.56446105
17
6.56010
-0.49845105
18
4.72810
-0.51102105

2.1. Mass and Heat Balance

The molar (or mass) flow rate of each component i through the non-isothermal plug flow
reactor including catalyst was determined by mass balance:
d Ni

dw

r
4

(12)

i i

i 1

Based on the Padmavathi et al. [1] model, the height and diameter of the reactor need not be
specified, only the amount of catalyst occupying the reactor volume needs be known. This
makes the model flexible, in order to simulate reformer's reactors of different sizes. The
temperature change through the adiabatic reactors was obtained from energy balance:

H r
N C
4

dT

dw

i i

i 1

(13)

Pi

i N ,P ,A ,H 2

In equation (13) Hi is heat of reaction for each reaction, which obtained from average values
of Padmavathi et al. [1] work. These values are shown in Table 1. Heat capacities of each
class are adopted from table 1 of Liang et al. [8] work.

Kinetic Modeling of Naphtha Catalytic Reforming

3. Experimental Plants Data

Table 2 shows the design parameters and operating conditions of the catalytic reformers of
Isfahan Oil Refinery. Also Table 3 shows the input and output flow rates. The total catalyst
weight was 55910 kg, H2/HC is equal to 4.4 and n is 7.61.

Reactor number
1
2
3
4

Table 2: Operating conditions of reforming unit

Mass of catalyst (kg) Inlet temperature (K) Temperature drop (K)
5666
770
60.5
8368
770
29
13891
770
11
27985
770
4.4

Table 3: Input and output flow rate of reforming unit

Component Input flow rate (kmole/hr) Output flow rate (kmole/hr)
Paraffin
78.21
40.68
Naphthene
46.55
1.68
Aromatic
17.64
63.04
Total
142.4
105.4

4. Estimation of Activation Energies

A constrained optimization procedure was used to find the activation energies which
minimized the difference between the calculated and experimental values of outlet
temperatures of each bed and the aromatics yield simultaneously. The objective function to be
optimized was:
4
Ni ,calc Ni ,exp
Tcalc Texp
(14)
OF

N
T
i
,
exp
i
,
exp
i N ,A ,P
i 1
By using Genetic Algorithm Toolbox in Matlab 7.8 and solving 4th order Runge-Kutta
(equations 12 and 13) contemporarily, the activation energies are obtained. These values are
shown in Table 4.

Table 4: Activation energies from optimization

Reaction number

E
(K ) 10-3
R

1
2
3
4

21.332
33.204
35.335
33.979

5. Result and Discussions

The proposed model was validated against the plant data. Fig. 1 shows the temperature profile
for the reactors versus reactor length in the reformers. For this study, the inlet temperature of
each reactor was fixed at plant conditions. It appears that the temperature decreases smoothly,
in an exponential manner, in all of these reformers. The main reaction of this process is
endothermic. For this reason, heaters are placed between each two reactors.

13th Iranian National Chemical Engineering Congress

& 1st International Regional Chemical and Petroleum Engineering
Kermanshah, Iran, 25-28 October, 2010

Figure 1: Temperature profile in the reformers

The flow rate profile of each lumped versus reactor length was shown in Fig. 2. It can be
observed that naphthene hydrocarbon was disappeared by passing the feedstock through the
unit in steady state conditions. A high rate of conversion of naphthenes was found in the first
reactor. After second reactor, naphthenes concentration approaches to a very low steady-state
value. The concentration of paraffin increases in two first reactors, and then decrease
smoothly in two last reactors. Aromatics increases sharply in first reactor, due to
dehydrogenation reaction. After second reactor, aromatics concentration increases slowly, due
to decrease of paraffin.

Figure 2: Flow rate profiles in the reformers

Kinetic Modeling of Naphtha Catalytic Reforming

Figs. 3 and 4 show the effect of inlet temperature and hydrogen to hydrocarbon ratio of
reactors on performance of catalytic naphtha reformer. As shown in Fig. 3, the flow rare of
aromatic increases with increasing of inlet temperature, but the paraffin content decreaces.
Increases of temperature also increase the amount of coke deposition on catalysts and reduce
the catalyst activity [7]. Changes in the amount of aromatic and paraffin output versus H 2/HC
have been shown in Fig. 4. As may be observed, the amount production of aromatic increases
with decreasing the ratio of H2/HC, while the amount of coke deposition on the catalyst
decreases.

Fig. 3: Effect of inlet temperatures on aromatic and paraffin yields

Fig. 4: Effect of hydrogen to hydrocarbon ratio on aromatic and paraffin yields

13th Iranian National Chemical Engineering Congress

& 1st International Regional Chemical and Petroleum Engineering
Kermanshah, Iran, 25-28 October, 2010

6. Conclusion
Smiths model has been used for modeling of catalytic naphtha reformer. Activation energies
for the four reactions are obtained by optimizing experimental data and results of model. The
modeling results have been found to be in close agreement with plant data. Finally, the effect
of inlet temperature and input H2/HC on the performance process were investigated. Results
indicate that, with increasing temperature and decreasing of hydrogen to hydrocarbon ratio,
the amount of aromatics production increases; while the amount of coke deposition has also
increased. Therefore, the optimized values for temperature and hydrogen to hydrocarbon ratio
must be determined.

Nomenclature
Ai: Constant for reaction i
Bi: Constant for reaction i
CP: Specific heat (KJ/Kmole. K)
Ei: Activation energy for reaction i (KJ/Kmole)
ki: Rate constant ((Kmole/hr. Kg cat. KPa) for reaction 1 and 2, (Kmole/hr. Kg cat) for
reaction 3 and 4)
Ki: Rate constant for reverse reaction ((Kmole/hr. Kg cat. KPa3) for reaction 1 and (Kmole/hr.
Kg cat. KPa2))
ki,0: Constant rate
Mw: Molecular weight (gr/mole)
n: Hydrocarbon with n atoms
Ni: Molar flow rate (Kmole/hr)
OF: Objective function
P: Pressure of process (KPa)
R: Gases constant (8.314KJ/Kmole. K)
ri: Rate of reactions (Kmole/hr. Kg cat)
w: Weight of catalyst (Kg)

Subscripts
A: Aromatic
calc: Calculated
exp: Experimental
N: Naphthene
P: Paraffin
tot: Total

Greek Letters
i: Stoichiometric coefficient for reaction i
Hi: Heat of reaction for reaction i

Kinetic Modeling of Naphtha Catalytic Reforming

Reference
[1] G. Padmavathi, K. Chaudhuw, Modelling and simulation of commercial catalytic naphtha
reformers, Can. J. Chem. Eng., 75 (1997) 930-937.
[2] D. Bommannan, R.D. Srivastava, D.N. Saraf, Modelling of catalytic naphtha reformers,
Can. J. Chem. Eng., 67 (1989) 405-411.
[3] R. B. Smith, Kinetic analysis of naphtha reforming with platinum catalyst, Chem. Eng.
Prog., 55 (1959) 76-80.
[4] W. S. Kmak, A. N. Stuckey, Power forming process studies with a kinetic simulation
model, AIChE National Meeting, New Orleans, 56 (1973) 99.
[5] L. E. Turpin et al., Modelling commercial reformers, Marcel Dekker, New York (1995).
[6] M. R. Rahimpour, S. Esmailian, N. Bagheri-Ghalehghazi, A kinetic and activation model
for industrial catalytic naphtha reforming, Iranian J. Sc. & Tech. Transition B, 27(B2) (2003)
280.
[7] M. R. Rahimpour, Operability of an industrial catalytic naphtha reformer in the presence
of catalyst deactivation, Chem. Eng. Technol., 29 (2006) 616-624.
[8] L. Ke-min, G. Hai-yan, P. Shi-wei, A study on naphtha catalytic reforming reactor
simulation and analysis, J Zhejiang Univ SCI, 6B(6) (2005) 590-596.

13th Iranian National Chemical Engineering Congress

& 1st International Regional Chemical and Petroleum Engineering
Kermanshah, Iran, 25-28 October, 2010

gmoradi@razi.ac.ir

.
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