Modeling of Naphtha Reforming Unit Applying Detailed 2014 Chemical Engineer

CHEMICAL ENGINEERING RESEARCH AND DESIGN 9 2 ( 2 0 1 4 ) 1704–1727
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Chemical Engineering Research and Design
journal homepage:www.elsevier.com/locate/cherd
Modeling of naphtha reforming unit applying detailed

description of kinetic in continuous catalytic
regeneration process
a,c a a a
Davood Iranshahi , Mohsen Karimi , Shahram Amiri , Mitra Jafari ,
Razieh Rafiei a, Mohammad Reza Rahimpour a,b,∗
a
Dept. of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran
b
Department of Chemical Engineering and Materials Science, University of California, Davis, 1 Shields Avenue, Davis,
CA 95616, United States
c
Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran
A B S T R A C T
Naphtha reforming is one of the most important processes in refineries in which high value-added reformate for gasoline pool and
aromatics such as benzene, toluene, and xylene are produced. It is necessary to establish new naphtha reforming units and develop the
traditional units to increase the efficiency of the processes. In this study, according to the recent progresses in the naphtha reforming
technology, mathematical modeling of this process in continuous catalyst regeneration mode of operation is accomplished in two
dimensions (radial and axial) by consider-ing cross flow pattern. In addition, a new catalyst deactivation model has been proposed and a
new reaction network model based on 32 pseudo-components with 84 reactions is investigated. Then, this model has been validated by
comparing with industrial data, and its results have acceptable agreement.
© 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Catalytic naphtha reforming process; Continuous catalytic regeneration; Two dimensional mathematical modeling; Reaction
network; Catalyst deactivation model.
1. Introduction 1. Semi regenerative.

2. Cyclic.
Naphtha reforming process is one of the key processes in petroleum 3. Continuous regenerative (moving bed).
refining for providing high value-added reformate for the gasoline pool. It
is also used for producing BTX (ben-zene, toluene, and xylene) by As shown in Fig. 1, 60% of total capacity of reforming pro-cess is the
conversion of paraffins and naphthenes to aromatics-rich products which semi regenerative scheme, while the continuous regeneration and the
are the basic substances of the petrochemical processes. Hydrogen is also cyclic have 28% and 12% of total capac-ity of reforming, respectively
considered as a main by-product and in the most refineries is used in (Antos and Aitani, 1995). Today, due to many benefits of continuous
hydrocracking, hydrotreating, and other hydrogen consuming reactions regeneration, all new units are designed based on this technology and old
(Aitani, 2005a,b; Antos and Aitani, 1995; Hongjun et al., 2010). Full- units are revamped to the continuous regeneration process or are combined
range naphtha is the fraction of the crude oil with a boiling temperature with this process. There are some advantages of CCR process against
◦
between 30 and 200 C, and constitutes typically 15–30 wt% of the crude traditional methods, such as producing higher octane reformate even
oil (Antos and Aitani, 1995). Based on the mode of catalyst regeneration, working with a low feed quality, long time working of the process due to
the reforming process is generally classified into three types: lack of shut down, operating in the lower pressure by the low pressure
drop,
∗
Corresponding author at: Dept. of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran. Tel.: +98 711
2303071; fax: +98 711 6287294.
E-mail addresses: rahimpor@shirazu.ac.ir, mrahimpour@ucdavis.edu (M.R. Rahimpour). Received 26 April
2013; Received in revised form 11 September 2013; Accepted 14 December 2013
0263-8762/$ – see front matter © 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2013.12.012
CHEMICAL ENGINEERING RESEARCH AND DESIGN 9 2 ( 2 0 1 4 ) 1704–1727 1705
Notation r rate of inth reaction, kmol kg cat

−1 −1
h
in
o
ai catalyst activity r rate of coke formation on fresh catalyst,
C −1 −1
aA acidic function activity kg kg cat h
r
CA rate of coke formation on acidic function of cat-
aCA acidic function activity for coke formation
−1 −1
alyst, kg kg cat h
aCM metallic function activity for coke formation r
CM rate of coke formation on metallic function of
aM metallic function activity −1 −1
catalyst, kg kg cat h
Ar cross-section area of reactor in radial direction, R
gas constant, J mol K−1
−1
m2 Ri inner diameter, m
C
concentration, kmol m−3 Ro outer diameter, m
C −3 2 −1
ACP alkyl-cyclopentane concentration, kmol m Sa specific surface, m g
C
CA coke weight fraction on acidic function of cata- T temperature, K
−1 U
lyst, kg kg overall heat transfer coefficient, W m−2 K−1
C
CM coke weight fraction on metallic function of cat- Uj internal energy of component j
−1 −1
alyst, kg kg ur radial velocity, m s
C −3
j0 inlet concentration of component j, kmol m yj mole fraction of component (j)
Cp specific heat capacity at constant pressure,
−1 −1
kJ kmol K Greek letters
Cv specific heat capacity at constant volume, ε void fraction of catalyst bed
−1 −1 −1 −1
kJ kmol K viscosity, kg m s
C −3 v
T total concentration, kmol m ij stoichiometric coefficient of component j in
dp particle diameter, m reaction i
2 −1 b −3
De effective diffusivity, m s reactor bulk density, kg m
−1
Ec coke formation activation energy, J mol s sphericity,
F H −1
molar flow rate, kmol h−1 heat of reaction, kJ mol
−1
Fj molar flow rate of component j, kmol h z control volume length, m
Ft −1 r control volume thickness in radial direction, m
total molar flow rate to the reactor, kmol h
H 3 −1
enthalpy, J mol −1
˛A constant of deactivation, m kmol
−1 ˛ 3 −1
Hj enthalpy of component j, J mol CA constant of deactivation, m kmol
k thermal conductivity, W m K
−1 −1 ˛ 3 −1
CM constant of deactivation, m kmol
k
CA constant of deactivation equation for acidic
−1 n 1.5 −1.5
function, kg kg kPa1 m kmol ˛M
k
CM constant of deactivation equation for metallic Subscript
−1 n 1.5 −1.5
function, kg kg kPa1 m kmol
k −1 −1 Pi number, 3.14156
eff effective thermal conductivity, W m k 3 −1
k constant of deactivation, m kmol
in reaction rate constant for reaction
K equilibrium constant for reaction
in
L length of reactor, m e exit condition
mnumber of reactions
−1 i numerator for reaction
Mj molecular weight of component j, kg kmol
j numerator for component
M −1
mean molecular weight in the flow, kg kmol nnumber of carbon atom
nnumber of components
Ttotal
n constant of deactivation equation
1
n2 constant of deactivation equation Abbreviations
nA acidic function activity power number A aromatics
n acidic function activity power number
CA ACH alkyl-cyclohexane
n metallic function activity power number
M ACP alkyl-cyclopentane
n
CM metallic function activity power number CCR continuous catalyst regeneration reformer
−2 −1
Nj molar flux of component j, kmol m h F scaling factor
P total pressure, kPa HChydrocarbon
P partial pressure of aromatic with n carbon, kPa
An ◦
P IBP initial boiling pint, C
ACHn partial pressure of alkyl-cyclohexane with n
IP iso-paraffin
carbon, kPa NP normal-paraffin
P partial pressure of alkyl-cyclopentane with n
ACPn RON research octane number
carbon, kPa Pt platinum
P partial pressure of hydrogen, kPa
H2 Sn tin
P partial pressure of iso-paraffin with n carbon,
IPn
kPa
P partial pressure of normal-paraffin with n car-
NPn
bon, kPa using catalyst with less stability but higher selectivity and yield, requiring
r radius, m lower recycle ratio, economic design, produc-ing more reformate with
−1 −1 higher aromatic content and steady production of hydrogen with constant
ri rate of ith reaction, kmol kg cat h
purity (93% compared to 80% in the semi regenerative process) (Aitani,
2005a,b; Antos and Aitani, 1995; Hongjun et al., 2010; Edgar, 1983;
Lee et al., 1997). In addition, the deposited coke in the semi
regenerative
1706 CHEMICAL ENGINEERING RESEARCH AND DESIGN 9 2 ( 2 0 1 4 ) 1704–1727
by considering catalyst deactivation. Recently, Iranshahi et al. (2010a,b,c)

and Rahimpour et al. (2011) proposed new con-figurations including axial
flow spherical reactor, axial flow spherical membrane reactor, radial flow
spherical reactor, and thermally coupled fixed bed reactors for naphtha
reforming process to boost hydrogen and aromatic production in refiner-
ies. As discussed in this literature survey, various studies have been done
on the naphtha reforming process, but few studies have been carried out
on the continuous catalyst regenera-tion system. Hongjun et al. (2010),
Weifeng et al. (2007), and Mahdavian et al. (2010) introduced modeling
Fig. 1 – Capacity of different types reforming process in the world. and simulations approaches for CCR process.
reformer can be varied from a few weight percent on the first reactor to 20
wt% coke in the last reactor. In the cyclic regen-erative reformers, catalyst
regeneration is usually based on economics performance for one or more
of the reactors in the reforming process loop. While in the CCR process 2. Kinetic model
that operates with a platinum/tin catalyst, the deposited coke on the cata-
lyst is usually restricted to less than 7 wt% in the last reactor (Antos and An effective kinetic model of naphtha reforming must repre-sent all the
Aitani, 1995). Thus, according to these advantages of CCR process the major types of reactions in the reforming process. A kinetic model
capacity of the CCR reforming units has increased quickly in the recent inherently satisfies both heat and material balances; because it takes into
years. Generally, the naphtha reforming unit consists of four reactors, account the stoichiometry of the reactions. As discussed, the naphtha
catalyst regeneration unit, distillation column which separates products feedstock consists of several hundred components and each of them takes
into light hydrocarbons and reformates, and due to endothermic reac-tions part in various reactions. Thus, presenting a detailed kinetics-based model
in the reforming process, inlet stream to each reactor is preheated via a considering all components and reactions is infeasi-ble. In past decades,
furnace. many attempts have been made (Marin et al., 1983; Froment, 1987;
Ramage et al., 1987; Jorge and Eduardo, 2000; Hu et al., 2003; Weifeng et
al., 2006) to propose a perfect kinetic model for naphtha reforming
Accomplished researches regard naphtha reforming pro-cess could be process by con-sidering most kinetic lumps and reactions. Padmavathi and
classified in three categories. The first category consists of the Chaudhuri (1997) proposed appropriate model for naphtha reforming
accomplished studies on kinetic models of cat-alytic naphtha reforming. kinetic, but in their model, some of the main lumps and reactions have
To reduce the complexity of the reaction system, similar chemical been ignored. Whiles in the reforming pro-cess, aromatics are the main
components are lumped together and represented as a pseudo component, products, 8-carbon aromatics were not subdivided in details. In addition,
and the reactions among the pseudo components are considered (Hongjun some of the main reactions such as dehydrocyclization of paraffins to
et al., 2010). Primary studies about lumped kinetic have been done by aromat-ics, isomerization and transalkylation of aromatics have been
Smith (1959), Krane et al. (1959) Kmak (1972), Ramage et al. (1980), ignored. In the proposed model, 8-carbon aromatics are subdi-vided to
Wolff and Kramarz (1979) and Jenkins and Stephens (1980). To satisfy four lumps (ethylbenzene, para-xylene, meta-xylene and ortho-xylene) and
various demands on the reforming process, different pseudo components the variations of each of them are inves-tigated. Also ignored reactions in
have been considered in the proposed network kinetic models. Marin et al. Padmavathi and Chaudhuri (1997) study, are characterized in Tables 1–9.
(1983) and Froment (1987) published the reac-tion network for the whole
range of naphtha reforming. In addition, by considering this fact that the
reaction pathways derived for each carbon number fraction are almost
identi-cal to each other, Ramage et al. (1987) used the same reaction
network within each carbon number group. Jorge and Eduardo (2000) Proper kinetic modeling of reforming reactions is the key to effective
proposed a 24 lumps model in order to model the kinetic of catalytic representation of the process over a wide operating range. The first effect
naphtha reforming reactions. Hu et al. (2003) pro-posed kinetic model of the kinetics of the reactions on the product properties is the effect of
with 17-lumpes while Weifeng et al. (2006) proposed kinetic model with operating variables on the octane number (Taskar and Riggs, 1997).
18-lumpes. The second class of studies have been focused on improving Therefore, by consid-ering important kinetics in the reforming process and
the operation and selectivity of the catalyst and reduce the probability of all of the accomplished studies, in this study, a new reaction network is
coke formation on the catalyst surface by adding some metals such as Sn, proposed.
In, and Ge to the catalyst. The literature sur-vey about these concepts is
discussed extensively in previous work (Iranshahi et al., 2012). The third Paraffins, naphthenes and aromatics are the different hydrocarbon
category consists of the performed studies on presenting and modeling groups in the reforming feedstock. In the pre-sented model, the naphtha
novel config-urations with better performance. Some studies in this field feedstock has been subdivided to naphthenes (alkylcyclohexanes: ACH,
were carried out by Taskar and Riggs (1997), Juarez et al. (2001), and alkylcyclopentanes: ACP), paraffins (normal paraffins: NP, isoparaffins:
Weifeng et al. (2007). Rahimpour (2009), proposed a novel fluidized-bed IP), and aro-matics (A) lumps with carbon numbers ranging from C 6 to C9
membrane reactor for naphtha reforming in the presence of catalyst +
, this kinetic model consists of 32 pseudo components with 84 reactions.
deactivation to enhance hydrogen pro-duction. Also Mostafazadeh and
As shown in Fig. 2, in this model, all of the main reactions are included,
Rahimpour (2009) assessed the membrane insertion in naphtha reforming
and the defined pseudo components are related by major reforming
catalytic bed reactions. In addition, rate con-stants in the proposed model are obtained
by optimization, so that deviation between output results of model and
com-mercial data is minimized. In the following, main reactions in the
reforming process are discussed, and the reactions, rate
Table 1 – Rate constants and heat of reactions in dehydrogenation reactions.

P P 3 −1 − 1 B 3
An H k1n = exp a − E 1
h kPa
P −
2
K RT − ) T (kPa)
(1)ACHn ↔ An + 3H2 r1n = k1n ACHn 1n (kmol kgcat K1n = exp A −
−1 ) a E A B
C6 H (kJ (mol H2 ) R
68.73 18.75 19.50 59.90 3
C7 24.80 × 10
208.47 20.70 19.50 60.23 3
C8 25.08 × 10
a 64.50 17.89 19.50 60.37 3
for An = MX 23.27 × 10
a 65.10 19.15 19.50 60.32 3
for An = OX 23.49 × 10
a 64.74 18.66 19.50 60.13 3
for An = PX 23.36 × 10
a 68.70 18.71 19.50 60.40 3
for An = EB 24.78 × 10
+ 66.05 20.38 19.50 61.05 3
C9 21.33 × 10
a Ignored reactions in Padmavathi and Chaudhuri (1997) study.
constants, characteristics and the calculated heat of reactions are listed. catalyst (Antos and Aitani, 1995; Taskar and Riggs, 1997). The reaction is
endothermic and produces a sharp drop in tem-perature. The needed
reaction constants for calculating the reaction rate constants (k1n ) and
2.1. Dehydrogenation equilibrium constants (K1n ) are presented in Table 1.
Dehydrogenation reaction, due to produce high octane num-ber aromatics,

is a principal reaction in the reforming process (Matar and Hatch, 2000). 2.2. Dehydrocyclization
Octane number is gained at a loss of volume, when a naphthene is
converted to an aromatic (Taskar and Riggs, 1997). This reaction is the Dehydrocyclization of paraffins to naphthenes and aromatics is a desirable
fastest amongst all the reforming reactions, thus reaches equilibrium very reaction in the reforming process because it induces the most considerable
quickly and is catalyzed by the metallic function of the increase in octane number among the naphtha reforming reactions. But
unfortunately,
Table 2 – Rate constants and heat of reaction in paraffin dehydrocyclization to naphthene.

H (kJ mol−1 ) a − E A B
−1 −1 −2 −1
(2)ACH H NP r k k a− A
P
↔ =
P P
H K
NP
=
exp E
(kmol kg h kPa ) K
=
exp −
B
(kPa)
n+ 2
n 2n 2n ACHn 2 2n 2n RT cat 2n T
R
−43.64 24.37 33.11 −9.12 3
C6 −5.24 × 10
−32.85 29.10 33.11 −8.95 3
C7 −3.95 × 10
−32.55 27.81 33.11 −8.34 3
C8 −3.91 × 10
+ −28.00 29.76 33.11 −8.12 3
C9 −3.37 × 10
P
−1 −1 −2 −1
H (kJ mol−1 )
=
a −
E A B
(3)ACH H IP r k P P IPn
k exp a E (kmol kg h kPa ) K exp A B (kPa)
n+ ↔ n = 3n H K = − cat 3n −
2 3n ACHn 2 3n 3n RT T
R
C6 −52.00 26.36 33.11 −14.35 3
−6.25 × 10
−39.30 25.75 33.11 −13.65 3
C7 −4.73 × 10
C8 −49.40 29.00 33.11 −13.17 3
−5.94 × 10
+ −49.00 29.76 33.11 −12.39 3
C9 −5.89 × 10
P P −1 −1
H (kJ mol− ) a
R A B
−1
(4)NP ACP H r k P ACPn
K
H2
k exp a− E (kmol kg h kPa ) K exp A B (kPa)
n↔ n+ 2 4n = 4n NPn − 4n 4n = RT cat 4n = −T
1 E
a 69.73 30.75 33.11 14.39 3

C5 8.38 × 10
C6 60.74 31.94 33.11 14.77 3
7.31 × 10
C7 60.75 33.43 33.11 14.63 3
7.31 × 10
61.75 31.31 33.11 15.98 3
C8 7.43 × 10
+ 59.00 32.96 33.11 15.21 3
C9 7.09 × 10
r kn P P P
kn a E −1 −1 −1 A B
(5)IPn ACPn H n ACPn H2 exp (kmol kg h kPa ) K exp (kPa)
↔ + 2 5 = 5 K 5 = − cat 5n =
IPn − 5n RT −T
1 E
−
H (kJ mol ) a R A B
a 76.67 29.83 33.11 16.18 3
C5 9.22 × 10
70.60 30.87 33.11 16.03 3
C6 8.50 × 10
C7 67.20 32.95 33.11 15.47 3
8.08 × 10
78.60 34.19 33.11 16.37 3
C8 9.45 × 10
+ 80.00 32.96 33.11 16.02 3
C9 9.62 × 10
Table 3 – Rate constants and heat of reactions in paraffin dehydrocyclization to aromatic.

4 E −1 −1 −1 B 4
PAn P (kmol kg h kPa ) (kPa)
(6)NP A 4H r k (P ) k exp a K exp A
H
2
−
= =
H(kJ (mol H2 )−1 ) a E A B
n ↔ n +2 6n
=
6n NPn
−
K6n 6n RT cat 6n −T
R
a 66.50 16.87 18.86 35.73 3
C6 7.99 × 10
a 63.20 17.17 18.86 35.21 3
C7 7.60 × 10
a 3
C8 6.79 × 10
for An = MX 56.51 17.32 18.86 34.13
56.95 17.89 18.86 34.21 3
for An = OX 6.85 × 10
56.70 17.01 18.86 34.16 3
for An = PX 6.81 × 10
59.66 16.96 18.86 34.63 3
for An = EB 7.17 × 10
+a 59.29 18.90 18.86 33.56 3
C9 6.36 × 10
(7)IP ↔ A + 4H r k (P P P 4 ) k exp a E −1 −1 −1 K exp A B 4
An H 2 (kmol kg h kPa ) (kPa)
n n
H(kJ (mol H2 )−1 ) a − E A B
2 7n = 7n IPn − K
7n 7n = RT cat 7n = −T
R
a 68.18 16.44 18.86 36.01 3
C6 8.20 × 10
a 64.83 16.90 18.86 35.47 3
C7 7.79 × 10
a 3
C8 7.30 × 10
for An = MX 60.73 16.27 18.86 34.81
61.17 16.78 18.86 34.87 3
for An = OX 7.35 × 10
60.90 16.04 18.86 34.83 3
for An = PX 7.32 × 10
63.88 15.93 18.86 35.23 3
for An = EB 7.68 × 10
+a 60.77 17.66 18.86 34.81 3
C9 7.3 × 10
Table 4 – Rate constants and heat of reactions in isomerization of naphthenes and paraffins. (8)ACP n ↔ ACHn
r =k
8n 8n
B
A− (−)
T
−1 a E A B
H (kJ mol ) R
−17.10 15.11 23.81 −5.20 3
C6 −2.06 × 10
−27.90 24.73 23.81 −6.63 3
C7 −3.36 × 10
−29.20 25.78 23.81 −6.83 3
C8 −3.51 × 10
+ −31.00 26.13 23.81 −7.16 3
C9 −3.73 × 10
(9)NP IP r k (P P ) k exp a E −1 −1 −1 K exp A B
( )
IPn (kmol kg h kPa )
K a − =
n↔ n − −
H (kJ mol−1 ) E A B
9n
=
9n NPn 9n 9n
=
RT cat 9n −T
R
a −9.23 25.08 26 0.80 3
C4 −1.11 × 10
a −6.94 24.89 26 1.17 3
C5 −0.83 × 10
−9.86 24.70 26 0.69 3
C6 −1.19 × 10
C7 −6.45 24.15 26 1.27 3
−0.76 × 10
−13.95 25.54 26 0.04 3
C8 −1.68 × 10
+ −21.00 24.48 26 −1.09 3
C9 −2.53 × 10
Table 5 – Rate constants and heat of reactions in isomerization of aromatics.

B
(10)R P for n 1, ..., 6 r k P PP k exp a E (kmol kg−1 h−1 kPa−1 ) K exp A ( )
R
= a − A
↔ = = −
R P (kJ
cat
B
10n 10n −
K10n 10n
=
RT 10n −T
H mol
−1
)
E
R
a OX PX −10.50 25.21 21.24 12.13 3
n=1 −1.26 × 10
a OX MX −17.60 24.50 21.24 11.00 3
n=2 −2.11 × 10
a MX EB 12.60 24.53 21.24 15.81 3
n=3 1.50 × 10
a OX EB 10.84 25.17 21.24 15.54 3
n=4 1.30 × 10
a EB PX −11.89 25.84 21.24 11.91 3
n=5 −1.43 × 10
a MX PX 0.71 24.47 21.24 13.7 3
n=6 −0.085 × 10
Table 6 – Rate constants and heat of reactions in Transalkylation.

P P
(11)2R P C for n 7, 8 r k P
2 P C k exp a E
(kmol kg
−1
h
−1
kPa
−2
) K exp A B ( )
− −
↔ + 11n = −
R P C H (kJ mol ) a A B
= 11n = 11n R K11n 11n = RT cat −T

−1 E
R
a T B PX 16.20 16.68 21.24 16.41 3
n=7 1.95 × 10
a OX T A9+ 09.16 15.48 21.24 15.28 3
n=8 1.10 × 10
these reactions are the most difficult reaction to promote (Matar and the number of carbon atoms (Matar and Hatch, 2000). The reactions are
Hatch, 2000). The most reactions of dehydrocy-clization are unaffected by pressure, whiles from a kinetic viewpoint, the equilibrium
depends mainly on the temper-ature. It should be mentioned that
endothermic and promoted by high temperature, low
isomerization reactions are promoted by the acidic function (Antos and
pressure and by both metallic and acidic functions of the Aitani, 1995). The isomerization of alkylcyclopentanes into alkylcy-
catalyst. The needed reaction constants for calculating clohexanes involves a ring rearrangement. In the subsequent stage, the
the reaction rate constants k k k k k and k7n) produced alkylcyclohexanes undergo dehydrogena-tion reaction and
( 2n, 3n, 4n, 5n, 6n
and equilibrium constants K K K K K and K produce aromatics. Thus, isomerization of naphthenes is considered as a
( 2n, 3n, 4n, 5n, 6n 7n )
of dehydrocyclizationreactionsarepresented in desirable reaction. Aro-matics with 8-carbon atoms also undergo the
Tables 2 and 3. isomerization reactions, the isomerization between P-xylene, M-xylene
and O-xylene occur rapidly, while isomerization between ethylbenzene
and xylene isomer occurs slowly (Weifeng et al., 2006). Calculated
2.3. Isomerization
constants for isomerization reac-tions of naphthenes, paraffins and
aromatics are shown in Tables 4 and 5.
Three types of isomerization reactions are investigated in the reforming
process, including isomerization of paraffins, naph-thenes and aromatics.
Paraffins isomerization rearranges the molecule with essentially no
change in the volume. These reactions are fast, slightly exothermic and do
not affect
Table 7 – Rate constants and heat of reactions in Cracking of Paraffins.

for n = 2 for n = 3
P2 + H2 → 2P1 P3 + H2 → P1 + P2
for n = 4 for n = 5 1
2
NP + H → P
(12) 4 2 3( 3 + P2 + P1 ) NP5 + H2 → 2 (NP4 + P3 + P2 + P1 )
for n = 6 − 9 : Pi k exp a −1 −1
(kmol kg h )
n−3
5 r =k P
NPn
NPn + H2 → n 12n 12n Pt

= − E
3 15 cat
i=1 12n RT
−1 ) a E
H(kJ (mol H2 ) R
a −65.20 37.85 34.61
C2
a −53.60 39.95 34.61
C3
a −49.50 40.15 34.61
C4
a −47.80 41.60 34.61
C5
C6 −47.26 42.08 34.61
C7 −46.69 42.48 34.61
C8 −46.61 40.53 34.61
C9+ −46.15 43.85 34.61
for n = 4 IP4 + 3 1 + P3 ) for n = 6 − 9 :
2 H2 → 2 (3P1+ P2 5
n 1 P P P n−3 n P
P
+ + E 1 1
(13) for = 5 IPn
IP H
5+ 2→2 (IP4 + 3 2 1 ) IPn + 3 H2 → 15 i
i=1
− −
r13n = k13n k13n = exp a − (kmol kgcat h )
Pt RT
−1 E
H(kJ (mol H2 ) ) a
R
a −40.30 36.15 34.61
C4
a −45.30 41.57 34.61
C5
C6 −37.40 40.53 34.61
C7 −41.85 41.57 34.61
C8 −36.00 41.51 34.61
C9+ −35.65 42.93 34.61

Table 8 – Rate constants and heat of reactions in cracking of naphthenes.

5
P
−1
(14)ACH n
H n P r k ACHn
k exp a E
(kmol kg h−1 )
n+3 2 → 15 i=1 i 14n = 14n 14n = − cat
Pt RT
H(kJ (mol H2 )
−1
) a E
R
C6 −45.45 42.15 34.61
C7 −40.76 44.70 34.61

C8 −41.00 43.90 34.61
C9+ −40.10 44.15 34.61
= k15n
r
for n=5: 1 15n Pt E 1 1
P
ACPn
+ 6 9:2 RT −
(15) for n h )
−
ACP 2H (NP P P P ) k exp a (kmol kg
5 2 → 4 + 3 + 2 + 1 15n = − cat
= − 5
n n
ACPn +3 H2 → 15 Pi
i=1
−1 ) a E
H(kJ (mol H2 ) R
a −68.74 40.23 34.61
C5
C6 −54.00 41.55 34.61
C7 −52.71 43.75 34.61
C8 −51.95 43.65 34.61
C9+ −50.40 44.15 34.61

2.4. Transalkylation 2.5. Hydrocracking
Transalkylation is the reaction between two similar or dis-similar Breaking of carbon bonds in the reforming is called hydroc-racking.
molecules involving transfer of an alkyl group. In the alkyl-transfer Bond’s breaking can occur at any position along the hydrocarbon chain.
reactions, shift of alkyl groups from one ring to the other, depends on the This reaction by removing the low octane number paraffins and
number of alkyl groups on the aromatic ring/s, the type of alkyl naphthenes from reformate and pro-ducing lighter hydrocarbons, such as
substituent/s and the chain length (Roldán et al., 2004). In the proposed methane, ethane and propane, helps to improve the octane in the products
model, transalkylation between aromatics is considered. Two toluene rings (Matar and Hatch, 2000). Hydrocracking is an irreversible reaction and is
can disproportionate to produce one benzene ring and one Para xylene favored at high temperature and high pressure, also is cat-alyzed by the
ring, in addition, two Ortho-xylene rings disproportionate to produce one acidic or metallic function of the catalyst (Antos and Aitani, 1995; Matar
+
toluene and higher aro-matics (A9 ). These reactions are promoted by and Hatch, 2000). Reaction constants for hydrocracking of paraffins and
the catalyst metallic function, and with increase in the reaction tempera- naphthenes are shown in Tables 7 and 8, respectively.
ture, the conversion increases. It should be mentioned that transalkylation
occurs mainly in very severe conditions of pressure (Roldán et al., 2004).
Calculated constants for reac-tion rate in the transalkylation reactions are
presented in Table 6. 2.6. Hydrodealkylation
Hydrodealkylation is the breakage (or cleavage) of the branched radical of

aromatics ring in presence of
Table 9 – Rate constants and heat of reactions in hydrodealkylations.

(16)A +H → A C H r =k P k exp a E
(kmol kg
−1 −1
h kPa
−1.5
)
m
0.5
k
A
P a E
n+1 2 2m+2 16n
H(kJ (mol H2 )−1 )
= −
k+ m 16n n+1 H2 16n RT cat
R
C7 1 n −41.81 7.64 17.92
C8 −42.32
for An+1 = PX 1 n 5.57 17.92
for An+1 = EBa 2 n−1 −20.02 5.55 17.92
+ −52.57
C9
for Ak = OX 1 n 8.91 17.92
for Ak = T
a 2 n−1 −30.80 5.57 17.92

Fig. 2 – Reaction network scheme for naphtha reforming process.
hydrogen. Like hydrocracking, this reaction is favored by high recycle hydrogen gas and, after heating to the desired reac-tion
temperature and high pressure also it is an irreversible reaction, and temperature (798 K), it is sent to a series of reactors. The specification of
promoted by the metallic function of the cat-alyst. hydrodealkylation is conventional process such as reactors, feed, product and catalyst are
the slowest of all the reforming reactions. This reaction is desirable shown in Table 10.
because it changes the relative equilibrium distribution of the aromatics in In the CCR process, spherical catalysts are used in the reac-tors to
favor of benzene and octane number (Taskar and Riggs, 1997; Matar and facilitate catalyst circulation by gravity. Coked catalyst is withdrawn from
Hatch, 2000). The needed hydrodealkylation constants to calculate the
the last reactor and sent to the regenera-tion unit, then, regeneration of the
reaction rate constants (k16n ) is presented in Table 9. catalyst is performed as the catalyst moves down in the regeneration unit
on a con-tinuous basis. Regenerated catalyst is added to the top of the first
reactor to keep the efficiency of process at the certain level, and catalyst
regeneration leads to reduction in operat-ing cost, whiles, poor catalyst
will lead to low product yields and increase in operating expense. As
3. Process description shown in Fig. 4, cata-lyst flows vertically in the reactor; and the feed
flows radially through the catalyst bed (reaction side) of the reactor, thus
The Continuous Catalyst Regeneration (CCR) process is a part of process cross flow pattern exist in the reactors.
used in the petroleum and petrochemical indus-tries. With the advent of
the continuous catalytic regeneration process, significant progress was
observed. Also, catalytic reformers and in particular, continuous catalyst
regeneration, have indispensable role in the refiners’ plans due to current
environment regulations for reducing air pollutants induced by sulfur of 4. Catalyst deactivation model
gasoline (Aitani, 2005a,b).
Coke deposition on the catalyst is an undesirable by-product in the
The CCR process consists of regeneration unit and adia-batic cross- reforming process, and the amount of deposited coke depends on feed
flow reactors that are arranged in a conventional side-by-side pattern. As quality, catalyst state and transit time of catalyst from the reactors (Taskar
shown in Fig. 3, the first reactor is always smaller than the other reactors and Riggs, 1997). Catalyst deactivation is primarily a function of coke
and the last reactor is always the largest. In this process, each catalyst deposition on the catalyst. Controlling coke deposition is equivalent to
particle moves continuously from the first reactor toward the last reac-tor. control-ling catalyst deactivation. In the CCR process, the catalyst
Then, catalyst particles are sent to the regeneration unit to restore. Also, circulation rate can be adjusted to maintain a specified weight percent
hydrotreated naphtha is combined with the carbon on the catalyst (Antos and Aitani, 1995).
Fig. 3 – Process flow scheme for CCR reforming process.
The main characteristics of a catalyst are: activity, selec-tivity and functions directly affect the selectivity of reactions (Lieske et al., 1987).
stability (Barbier, 1986). The activity expresses the catalyst ability to Catalysts used in this processes are bimetallic Pt-Sn and support is high
increase the rate of the reactions. The selec-tivity expresses the catalyst purity alumina (acidic function). The metal site is provided by platinum
ability to favor desirable reactions rather than others. The stability and metal promoter is tin. The reaction in this process starts on the metal
characterizes the change of the catalyst performance with time (i.e. sites and continues on the acid sites (Carter et al., 1982; Lieske et al.,
activity and selec-tivity) while operating conditions and feed are stable. 1987).
The catalyst affects reaction rates through its two different func-tions:
metallic and acidic, which promote different type of reactions (Carter et The metallic function is mainly responsible for dehydro-genation,
al., 1982). Coking on the metallic and acidic transalkylation and hydrodealkylation activity and these reactions are
practically unaffected by the presence or
Table 10 – Specifications of reactors, feed, product and catalyst of plant for fresh catalyst.
Parameter Numerical value Unit
Naphtha feed stock 233637.01 kg/h
Reformate 216488.63 kg/h
H2 /HC mole ratio 2.193 −
Mole percent of hydrogen in recycle 0.83 −
1st reactor 2nd reactor 3rd reactor 4th reactor
Inlet temperature (K) 798 798 798 798
Inlet pressure (kPa) 595 550 505 460
Inner and outer Diameter (m) 1.25, 2.19 1.25, 2.35 1.30, 2.53 1.3, 2.89
Length (m) 8.50 10.35 12.1 15.39
Catalyst distribution (wt %) 12 18 25 45
Distillation fraction of naphtha feed
ASTM D86 ◦
Naphtha feed ( C)
IBP 81
5% 91.2
10% 93.2
20% 96.9
30% 101.1
40% 105.7
50% 111.4
60% 117.6
70% 124.5
80% 132.7
90% 143.1
95% 150.5
FBP 159
Typical properties of catalyst
dp 1.8 mm
Pt 0.3 wt%
Sn 0.3 wt%
220 2
sa m /g
680 3
B kg/m
ε 0.36 −
Table 11 – Catalyst functions on the main reactions in the proposed kinetic model (metallic (M) and acidic (A) functions).
Reactions Agent Reactions Agent
ACHn ↔ An + 3H2 M r9n NPn ↔ IPn A
r1n
r2n ACHn + H2 ↔ NPn M +A r10n R↔P A
r3n ACHn + H2 ↔ IPn M +A r11n 2R ↔ P + C M
5
(n−3) 5=
r4n NPn ↔ ACPn + H2 M +A r12n NPn + H2 →

n P M or A
3 15 i
i 1
IPn ↔ ACPn + H2 IPn + 3 H2 → 15
r5n M +A r13n i=51 Pi M or A
(n−3) n
r6n M +A r14n n n M or A
NPn → An + 4H2 ACHn + 3 H2 → i5=1P
i
15
r7n M +A r15n n n i=1 M or A

IPn ↔ An + 4H2 ACPn + 3 H2 → Pi
15
r8n ACPn ↔ ACHn A r16n An+1 + H2 → Ak + Cm H2m+2 M
absence of acid sites, while the acidic support provides activity for the and published literatures. According to previous studies (Figoli et al.,
isomerization reactions. Two of the naphtha reform-ing reactions 1983a,b; Mieville, 1991; Bishara et al., 1984), the rate of deactivation
(hydrocracking and dehydrocyclization) can also be catalyzed by the depends on operating conditions such as: temperature, pressure and
metallic and acidic function (Antos and Aitani, 1995; Barbier, 1986; hydrogen over hydrocarbon mole ratio, also according to models proposed
Lieske et al., 1987). Table 11 shows the catalyst functions on the main by Liu et al. (1997, 2002) and Tailleur and Davila (2008) the rate of
reactions in the proposed kinetic model. deactivation depends on alkylcyclopentane concentrations. Thus, the rate
of coke formation on the fresh catalyst could be written as follows:
This section proposes a model for catalyst deactiva-tion rate that is
developed on the basis of pilot-plant data
exp(−Ec /RT) ×
o (17)
r ∝
C0.5
C n n2 ACP
P 1 (H2 /HC)
o
where rC , Ec , CACP , P and (H2 /HC)are the rate of coke formation on
the fresh catalyst, coke formation activation energy, alkyl-cyclopentane
concentration, pressure and hydrogen over hydrocarbon mole ratio,
respectively. In addition, the rate of reaction over a spent catalyst is
calculated by multiplying the catalyst activity on the dominant function
and rate of reaction over fresh catalyst.
o (18)
ri = a i × ri
where ri represents the ith reaction. The catalyst activity (ai ) is a function
of deposited coke weight fraction, which could be written as:
˛ ai i ni = 1 1
i
− = × n If
dCCi If n i =/ 1
ai = exp(−˛i × CCi )
ai =
(1/(ni 1))
dai
(1 +(ni − 1)˛i × CC ) −
i (19)
In the recent equation, ˛i is a constant and ni is a power number of

dominant function activity. Also, CCi . is the coke weight fraction on the
dominant function, that, to calculate CCi , coke formation rate must be
considered, as:
r =a ×r o , (20)
Ci Ci C i
0
where rCi and rC i are coke formation rate of spent catalyst on dominant
function and rate of coke formation on domi-nant function of fresh
catalyst, respectively. Similar to catalyst activity in the reaction rate,
Fig. 4 – Structure of reforming reactor in CCR process. catalyst activity in coke formation
rate also is a function of deposited coke weight fraction, which could be

defined as:
− = ˛Ci × aCCii If nCi = 1 aCi = exp(−˛Ci × CC i ) (1/(nCi −1))

dCCi If nC i =/ 1 ai = 1
daCi n
(1 + (nCi − 1)˛Ci × CCi )

(21)
In the recent equation, aCi is activity of dominant function for coke

formation, nCi is activity power number, and ˛Ci is a constant. As
previously discussed, reaction rate is affected by catalyst functions
(metallic and acidic). If the reaction occurs on the metallic site of catalyst,
metallic function activity must be considered i.e. ai = aM . In other case,
when reaction occurs on catalyst acidic site, acidic function activity must
be con-sidered i.e. ai = aA . Finally, if one of the catalyst functions is
needed (acidic or metallic), or both functions of the cata-lyst are required,
the mean activities must be considered. The obtained relations for
calculating catalyst deactivation rate based on catalyst functions in the
reforming reaction are pre-sented in Table 12. The auxiliary correlations
are described in Appendix A.
5. Mathematical modeling Fig. 5 – (a) Control volume for modeling with the lngth of dz (b) top view
of control volume.
To develop a model for CCR process, heat and material balance equations
6. Numerical solution
are made over a small element of the reactor with the length of z and the
thickness of r. Then these equations are combined with the deactivation
The obtained mathematical model in the previous section is a set of partial
model, Ergun equation, also thermodynamic and kinetic relations as
differential equations (PDEs). These equations are integrated through each
auxiliary corre-lations for predicting the behavior of reforming process. In
reactor to describe the molar flow rate of reformate and physical
the previous studies, that have been done for modeling of CCR process
properties along the length and radius of the reactors. By considering these
(Hongjun et al., 2010; Weifeng et al., 2007; Mahdavian et al., 2010),
complex equa-tions, a numerical method must be employed. In this study,
variations of parameters are assumed in one dimension. While, in this
finite difference method with explicit solution of all the dif-ferential
study, the mathematical modeling of the reactor is done in two dimensions
equations in the mathematical model is employed. In this method, the
(radial and axial), and its results had better compliance with the actual
reactor is divided into a series of nodes and for each node derivatives in
data. A differ-ential volume element of the reactor on which the energy
differential equations become difference equations that are functions of the
and mass balance equations has been applied, is shown in Fig. 5a, also top
surrounding cells (Nauman, 2001). Then, boundary conditions of the pro-
view of this control volume is shown in Fig. 5b. The obtained results of
cess are used for initial nodes of the reactor and the result of each node is
the mathematical model are described in Table 13. Also, details of the
mathematical modeling for this process are described in Appendixes B– used as boundary conditions for the follow-ing nodes and this procedure is
D.Basic assumptions repeated for all nodes in the reactor (Nauman, 2001).
To develop mathematical modeling based on mass and energy

balances and other auxiliary correlations, the following assumptions are
applied: 7. Model validation
In order to validate the model estimations, the results of kinetic and

• Steady state condition is considered. operation conditions of plant data are compared with the model prediction
• Diffusion of mass and heat in both radial and axial direc-tions of results. Molar flow rate of compo-nents at the output of the process are
reactor is neglected. shown in Table 14. As can be seen, model results have an acceptable
• Homogeneous catalyst moving bed is considered. agreement with the commercial data. Also, Table 15 presents the plant
• Ideal gas law is applicable. (Due to high temperature) data and the model predicted temperatures and pressure in the output of
• Adiabatic conditions exist. (insulated outlet wall) each reactor and molecular weight in the output of the process. It can be
• Cross flow pattern is considered in the reactors. (Gas stream moves observed in Tables 14 and 15 that only minor deviations exist between
radially and catalyst moves axially downward) commercial data and calcu-lated results. These minor deviations are due to
• Peripheral gradient (gradient along the perimeter) is neglected. the two facts. First, the kinetic model used for reaction system of process
underestimates the true reaction rate; second, some simplify-ing
• Physical properties are assumed to be variable during the process. assumptions in the mathematical modeling of process are applied.
• Intra-pellet heat and mass diffusion in catalyst pellet are ignored.

Table 12 – Catalyst deactivations model.

(22)ri = ai × ri Reaction occurs on acid function =
ai = aA
o Reaction occurs on metal function a ia M
Reaction occurs on acid or metal function ai = mean(aA , aM )
React ion occurs on metal function
Reaction occurs on acid as well as metal functions ai = mean(aA , aM )
Reaction occurs on acid function
o
o (24)ri = aA × ri
(23)ri = aM × ri
(26)− n
(25)− n daA
daM
dC
CM = ˛M × aM
M
dC
CA
= ˛A × aA
A
(27)n /1 a = − × 1 (28)n /1 a = − × 1
nM = 1 aM exp( ˛M CC M ) nA = 1 aA exp( ˛A C CA )
M= A=
M = A =
(1/(n −1)) (1/(n −1))

(1 + (nM − 1)˛M × CCM ) M (1 + (nA − 1)˛A × CCA ) A
(29)rCM = aCM × rCoM (30)rCA = aCA × rCoA
da n da n
(31) CM ˛ a CM (32) CA ˛ a C
− = CM × CM − × − = CA × CA
A − ×
dCCM dCCA
(33)n C /1 aC = 1 (34)n C /1 aC = 1
nCM = 1 aC M exp( ˛CM CCM ) nCA = 1 aCA exp( ˛CA CCA )

M = = A = =
M A
(35) (1/(nC −1)) (36) (1/(nC −1))

r CM =
o k
P n1(H 2 /HC) n2 ×
ACP
(1 + (nCM − 1)˛CM × CCM )
C
0.5
M
r CA =
o k
P n1 (H2 / HC) n 2 ACP
(1 + (nCA − 1)˛CA × CCA )
C
0.5
×
A
CM ×exp(−Ec /RT) CA ×exp(−Ec /RT)
8. Results and discussion Results of modeling involve the following main issues in the process:
The process of continuous catalyst regeneration is charac-terized by high

catalyst activity, high quality reformate, and high hydrogen purity. The • Variations of operating conditions.
results of the mathematical mod-eling for the CCR process are illustrated • Variations of coke concentration and activity of catalyst.
in the following. The variations of parameters have been investigated in • Variations of molar flow rate of pseudo-components.
the dimen-sionless radial and axial coordinates for 3-D plots, also the • Variations of physical properties.
variations of some parameters have been investigated in 2-D plots.
As can be seen in the results (Tables 14 and 15), satis-factory

agreement can be observed between the simulated
Table 13 – Mass and energy balances and auxiliary relations for CCR process.
Mass balance
1 ∂ 1 m j = 1, 2, ..., n
(37)D (A ∂Cj ) ∂ (A u C ) a r ε ∂Cj
ej r b i=1 ij
= ∂t i = 1, 2, ..., m
j
Ar ∂r ∂r − rm r + ×
Ar ∂r i i
(38) ∂Cj Cj C ∂ur i=1 a r j = 1, 2, ..., n

b
j
∂r ∂r i × ij i i = 1, 2, ..., m
− +
=−r ur ur
Energy balance
1 m n n n n j = 1, 2, ..., n
(39) ∂ (K A ∂T ) i=1 j=1 (H v )
a r N ∂Hj ε C ∂Uj ε (U H ) ∂Cj
∂r r b ij i j j ∂t + j ∂t
j
eff
× j=1 j=1
Ar − i × − j=1 ∂r = j−
i = 1, 2, ..., m
∂rm
=− ( H × a × r )
(40) ∂r ur CT CP i i i i = 1, 2, ..., m
∂T b
i=1
Velocity distribution
n m j = 1, 2, ..., n
(41) ∂ur ur ur ∂CT b a r
∂r − × ∂r + j=1 i=1 × ij i i = 1, 2, ..., m
=−r CT Ct i
Collector (mass balance)
(42)Fj |z − Fj |z+dz + Fje = 0 j = 1, 2, ..., n
∂F
j
(43) ∂z = 2 Ri ure Cje j = 1, 2, ..., n
Collector (energy balance)
| n
∂T T ∂CP T j=1 1
z − FT CP T|z+dz +
(44)FT CP T Fje Cpje (Te − T) = 0
(45) = − − (2 Ri × ure × CTe ) + × 2 Ri × ure × CTe × Cpe × (Te − T)
∂z CP ∂z
FT FT CP
Ergun equation (pressure drop)

(1−ε)2 (1−ε)
(46) dP = 150 ur + 1.75 u2
dr 2 2 3 d 3r
s d p ε s p ε
Table 14 – Comparison between predicted production rate and plant data.

Pseudo components Molecular Input plant Output Output model Deviation
weight (mole fraction) plant (kmol/h) (kmol/h)
(kmol/h)
n-P6 (C6 H14 ) 86.178 0.0229 71.84 70.98 0.86

n-P7 (C7 H16 ) 100.205 0.0292 46.65 46 0.65
n-P8 (C8 H18 ) 114.232 0.0239 8.1 7.63 0.47
n-P9 (C9 H20 ) 128.259 0.0156 1.15 1.25 −0.1
i-P6 (C6 H14 ) 86.178 0.0232 216.06 216.06 0
i-P7 (C7 H16 ) 100.25 0.0314 110.18 109.69 0.49
i-P8 (C8 H18 ) 114.232 0.0338 22.75 22.67 0.08
i-P9 (C9 H20 ) 128.259 0.0244 1.79 1.95 −0.16
ACH6 (C6 H12 ) 84.162 0.0077 0.51 0.92 −0.41
ACH7 (C7 H14 ) 98.189 0.0084 0.92 1.43 −0.51
ACH8 (C8 H16 ) 112.216 0.0115 2.33 2.34 −0.01
ACH9 (C9 H18 ) 126.243 0.0018 0.04 0.05 −0.01
ACP5 (C5 H10 ) 70.135 0.0001 2.14 2.11 0.03
ACP6 (C6 H12 ) 84.162 0.003 26 26.02 −0.02
ACP7 (C7 H14 ) 98.189 0.0065 2.33 3.12 −0.79
ACP8 (C8 H16 ) 112.216 0.0084 0.6 0.6 0
ACP9 (C9 H18 ) 126.243 0.0012 0.01 0.02 −0.01
A6 (C6 H6 ) 78.114 0.0086 205.84 206.39 −0.55
A7 (C7 H8 ) 92.141 0.0109 453.93 454.33 −0.4
A8 (C8 H10 ) 106.168 0.0021 163.02 163.47 −0.45
A9 (C9 H12 ) 120.195 0.0026 323.66 324.46 −0.8
A8 (C8 H10 ) 106.168 0.0015 113.62 113.4 0.22
A8 (C8 H10 ) 106.168 0.0016 120.84 121.55 −0.71
A8 (C8 H10 ) 106.168 0.0036 276.56 276.8 −0.24
H2 2.016 0.6226 10071.31 10090.82 −19.51
P1 (CH4 ) 16.043 0.0211 398.53 396.64 1.89
P2 (C2 H6 ) 30.07 0.0231 399.16 397.72 1.44
P3 (C3 H8 ) 44.097 0.0202 352.36 351.69 0.67
P4 (C4 H10 ) 58.124 0.0106 189.21 189.93 −0.72
P5 (C5 H12 ) 72.151 0.0035 71.06 71.69 −0.63
i-P4 58.124 0.0073 140.75 139.38 1.37
i-P5 72.151 0.0076 149.21 149.49 −0.28
results and commercial values. Thus, the proposed model predicts the observed during the passage of a stream through one reactor to another
reactor and catalyst performance and quality of reformate very well. Some due to piping and instruments such as a furnace.
variables such as feedstock properties, temperature and pressure of In order to consider the variation of temperature in cat-alytic naphtha
reaction, space veloc-ity, and hydrogen over hydrocarbon molar ratio, reforming, the temperature profile of the plant is depicted in Fig. 6b. In
affect the enhancement of main products yield and reactor performance this 3-D plot, temperature vs. dimen-sionless radial and axial coordinates
(Pisyorius, 1985). Since the operating conditions (pressure and of reactor is illustrated. Since the major reforming reactions are highly
temperature) of process side play a significant role in the per-formance of endothermic, temperature decreases by proceeding of the reactions, and
the catalyst as well as the yield and quality of reformate, these variables then production rate of reactions decrease. Consequently, to maintain the
have been investigated firstly. reaction temperature at suitable level, commer-cial catalytic reformers are
designed with multiple reactors and intermediate furnaces. In the first
reactor, naphthenes concentration are high and dominant reaction in this
8.1. Investigation of operating conditions during the process reac-tor (dehydrogenation) is very fast and endothermic, thus, it causes a
very sharp temperature drop in the radial direction in the first reactor,
which is demonstrated in Fig. 6b. Due to the remarkable decrease in the
In this section, variation of operating conditions (pressure and temperature of first reac-tor, the outlet stream of the first reactor is
temperature) in CCR process is investigated. One of the advan-tages of preheated via a furnace to the same entrance temperature of the first reac-
the CCR process is the negligible pressure drop in the reactors, which tor and then is sent to the second reactor. In the second
allows the use of smaller catalyst particles with higher efficiency. As
shown in Fig. 6a, the variations of pressure inside the reactors are slight,
and sudden drops are
Table 15 – Comparison between predicted temperature, pressure and molecular weight with plant data.
Reactor number Outlet temperature Outlet pressure Outlet molecular weight
Plant Model Plant Model Plant Model

1 707 710.7 581 585.1 – –
2 725 726.4 535 540.3 – –
3 743 743.2 490 495.7 – –
4 761 758.9 446 451.4 21.9 21.87
reaction rates through its two different functions: metallic and acidic
(Carter et al., 1982), which coke can be formed on the both of them. This
coke causes a decrease in the activity of the catalyst.
Fig. 7 depicts coke weight fraction distribution in the metal-lic and

acidic functions and total amount (sum of both) in the axial and radial
directions for the CCR process. Coke distri-bution is plotted as a function
of dimensionless radial and axial coordinates. Fig. 7a illustrates coke
weight fraction dis-tribution in the metallic function along the four
reactors in this process. As can be seen, the variations in the coke con-tent
are in the radial and axial directions in all of the reactors. In the radial
direction the largest coke content occurs at the entrance of each reaction
side (R = Rinput ), because high tem-perature, relatively high
alkylcyclopentane concentration and the low ratio of H 2 /HC exist in the
entrance of reaction side. In addition, due to reduction of temperature and
alkylcy-clopentane concentration as well as increase of H 2 /HC ratio, and
according to the coke formation rate (Eq. (17)), coke for-mation decreases
in this direction. In the axial direction of reactors, catalyst moves
downward in the reaction side with gravity and due to the occurrence of
reactions in each site, coke deposits on the catalyst surface and
deactivation of cat-alyst take place. After passing from this site and
transferring to the next site, the new coke is deposited to the catalyst. Con-
sequently, this trend continues to bottom of reactor. The same trend is
observed for coke weight fraction distribution in the acidic function in
Fig. 7b. Total coke content in the process is equal the sum of coke content
in the metallic and acidic func-tions, as shown in Fig. 7c. In addition, total
coke content vs. radius of reactors in various lengths of each reactor is
depicted in a two-dimensional plot in Fig. 7d. According to the commer-
cial data, coke weight fraction in the output of fourth reactor is .05. As can
be seen in Fig. 7c and d, acceptable agreement can be observed between
Fig. 6 – Changes of (a) temperature and (b) pressure during the process.
simulated and commercial values.
reactor, remaining naphthenes take part in the dehydrogena-tion reaction.

But, due to the decrease in the amount of naphthenes in this reactor, the
lower dehydrogenation reac-tion occurs, thus temperature drop decreases. The catalyst activity in the CCR process is illustrated in Fig. 8. The
In order to compensate temperature reduction, the effluent stream of the variations of catalyst activity are inversely related to the coke weight
second reactor is preheated again and then is sent to the third reactor. fraction distribution in the process. Thus, by enhancement of coke
Reduction in the temperature drop also can be observed in the third deposition, catalyst activity decreases. In order to investigate the catalyst
reactor. In this reactor, dehydrocy-clization of paraffins (endothermic activity, metallic and acidic functions activities are plotted as a function of
reaction) decreases the temperature, but hydrocracking of naphthenes and dimensionless radius in the various lengths of the reactors in Fig. 8a and
paraffins (exothermic reactions) increase temperature. Thus moderate b, respectively. As previously discussed, in the radial direction of reactors,
temperature drop is achieved in the third reactor. The low-est temperature reduction of coke deposition can be seen, also in the axial direction, coke
reduction is observed in the last reactor. In this reactor dehydrocyclization formation increases. Consequently, according to the inverse relation of
of paraffins to naphthenes and dehydrogenation of naphthenes to coke formation and cat-alyst activity, enhancement of catalyst activity in
aromatics which are endothermic reactions, cause temperature drop, while the radial direction and reduction in the axial direction can be observed.
exothermic reactions in this reactor (hydrodealkylation and hydrocracking
reactions) have more effect than the previ-ous reactors. Consequently, the
average temperature in the last reactor is higher than the first ones. As can
be seen in Fig. 6b, temperature increases very slightly in the axial
direction (length) of the reactors. These increases are due to deactivation 8.3. Effects and changes of H2 /HC molar ratio
of catalyst in this direction, and consequently, reactions rate decrease and
temperature increases. Hydrogen over hydrocarbon molar ratio is one of the key parameters in
the naphtha reforming process. As previously mentioned, coke deposition
on the catalyst surface has a major role in the catalyst deactivation. A
proper H2 /HC molar ratio enhances the catalyst life time and keeps the
catalyst safe from the coke formation and deactivation; so it has effect on
the appropriate production of hydrogen and aromatics. In Fig. 9, the 3-D
plot of H2 /HC molar ratio vs. the radial and axial coordinates of reactor is
8.2. Catalyst investigation
illustrated. As can be seen, the H 2 /HC molar ratio increases continuously
In the CCR operation, the amount of deposited coke on the catalyst must in the radial direction, and ascending trend is observed for the H 2 /HC
be kept at a low level to maintain reason-able activity, proper regenerator molar ratio in the process due to continuous production of hydrogen.
performance and high-purity products. As previously mentioned, the
catalyst affects the
Fig. 7 – Coke concentration distribution in (a) metallic function, (b) acidic function and (c) total coke. (d) comparison coke content in various length
of reactors.
8.4. Pseudo-components the process depend on the isomerization, hydrocracking and

dehydrocyclization reactions. As shown in Fig. 10b, in the radial direction
As previously discussed, the proposed kinetic model is based on 32 the amount of ACP decreases as a result of isomerization and
pseudo-components, and naphtha feed has been characterized by hydrocracking reactions, but in the last two reactors, due to the production
naphthenes (alkyl-cyclohexenes: ACH, alkyl-cyclopentanes: ACP), of ACP in the dehydrocycliza-tion reaction, consumption rate decreases.
paraffins (normal paraffins: NP, iso paraffins: IP), and aromatics (A) Variations of molar flow rate of naphthenes (ACH and ACP) along the
lumps. One of the main aims in the naphtha reforming process is the length of annulus are shown by solid lines in Fig. 10a and b. Unreacted
production of aromatic components such as benzene, toluene and xylene naphthenes accumulate along the length of annulus, and then at the bottom
(BTX), by consuming paraffins and naphthenes. In this sec-tion, the of reactor are sent to the next reactor to take part in the new reactions,
variations of molar flow rate of pseudo-components have been thus, molar flow rate decreases during the process.
investigated along the dimensionless radial and axial coordinates. In this
coordinates, in the radial direction, for any radius, mean variations of
molar flow rate in the axis is considered. Also, the variations of molar Paraffins have a similar behavior to the naphthenes in the reforming
flow rate of pseudo-components along the length of collector (annulus) process. Paraffins, as one of the main reactants in the naphtha reforming
are illustrated by solid lines. process, lead to higher aromatics pro-duction rate. The variations of n-
paraffins and iso-parrafins in the process are shown in Fig. 11. As can be
seen in Fig. 11a, molar flow rate of n-paraffins, due to being of the
Naphthene has a main role in the reforming process because high dehydrocy-clization, hydrocraking and isomerization reactions decrease
octane number of reformate can be obtained by transformation of along the radius of reactors (dotted curve). As shown in Fig. 11b, iso-
naphthenes to aromatics. In this study, naphthene has been considered in paraffins have a similar trend to n-paraffins, but consumption of NPs due
two categories, including alkyl-cyclohexane (ACH) and alkyl- to isomerization reactions are more than the IPs. The variations of
cyclopentane (ACP). The variations of alky-cyclohexane during the paraffins (normal and iso) along the length of annulus have a similar
process are depicted in Fig. 10a. Molar flow rate of ACH in the radial pattern to the naphthenes variations in the CCR process that are illustrated
direction decreases, because it takes part in the dehydrogenation and in Fig. 11a and b by solid lines.
hydrocracking reactions. In the second reactor, reduction of ACH is lower
than the first one, because the occurrence of iso-merization reactions
(moderately fast reactions), that produce ACH, in this reactor is more than In the naphtha reforming process, aromatics are the main products.
the first one. In addition, in the last two reactors, dehydrocyclization The considered aromatics in the proposed kinetic model are: benzene,
reactions produce more ACH than the first two ones, thus, consumption ). One
toluene, xylene (BTX), ethylbenzene and heavy aromatics (A9 +
rate of ACH is lower in these reactors. The variations of ACP in

of the main byproduct in this pro-cess is hydrogen. In the
following, the variations of these pseudo-components are
investigated. Aromatics with eight
a1 a
Z=0 300
Molar flow rate along inner annulus of reactor
Z=L/4
molar flowrate(kmol/h)
250 Mean molar flow rate along radius of reactor
0.95
catalyst
Mean
Z=3/4*L 200
ofthe
Z=L
0.9
activity
0.85 150
Metallicfunction
0.8
Alkylcyclohexane
100
0.75 50
0.7 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Radius of reactor (Dimensionless) Annulus Length(Radius) of reactor (Dimensionless)
b
b1 180
0.95 Z=0 160 Molar flow rate along inner annulus of reactor
Z=L/4 Mean molar flow rate along radius of reactor
rate(kmol/h)
catalyst
0.85 Mean 120

Z=L
0.9 Z=3/4*L 140
flow
100
of the
0.8
Acidic functionactivity
0.75
molar
80
0.7
eAlkylcyclopentan
60
0.65
40
0.6
20
0.55
0.5 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Radius of reactor (Dimensionless) Annulus Length(Radius) of reactor (Dimensionless)
Fig. 8 – Catalyst activity in (a) metallic function and (b) Fig. 10 – Variations of molar flow rate of (a) alkyl-cyclohexane
acidic function. and (b) alkyl-cyclopentane in the process.
carbon atoms such as ethylbenzene, and ortho-, meta-, and para-xylene are reactions, such as r1691-1 and r169-2 ), molar flow rate decreases.
depicted in Fig. 12a, and aromatics with six and seven carbon atoms, also
Aromatics molar flow rate along the length of collector is shown by solid
+
heavy aromatics (A9 ) are shown in Fig. 12b. Aromatics molar flow rate lines in Fig. 12a and b. Produced aromatics in the reactor collect in the
+
except heavy aromat-ics (A9 ), during the process have a similar pattern. annulus, and then, are sent to the next reactor. In the next reactor,
As can be seen in Fig. 12a and b, aromatics are produced along the radius aromatics production contin-ues. Thus, as shown in Fig. 12a and b by
of reactor, but production rate in the first two reactors is more than the last solid lines, molar flow rate of aromatics increases during the process.
two reactors, because dehydrogenation as a fast reaction occurs mostly in
the first two reactors that pro-duces aromatic components. Also, heavy Hydrogen, as a main byproduct in the reforming pro-cess, has a dual
+
aromatics (A9 ) have similar conditions, but in the last reactor due to role in the naphtha reforming as a product and reactant. It acts as a
consumption of heavy aromatics in the slow reactions (hydrodealkylation product in the dehydrogena-tion and dehydrocyclization reactions and as a
reactant in the hydrodealkylation and hydrocracking reactions. But total
hydrogen during the process increases because its production rate is more
than the consumption rate. As shown in Fig. 13, hydrogen molar flow rate
increases during the process but production rate decreases, because, as
previously discussed, hydrodealkylation and hydrocracking reactions, as
slow reac-tions, take place in the last two reactors. Other products in the
naphtha reforming process are light ends that have a main role in the
refineries. Light ends are produced in the hydroc-racking reactions that
occur in all reactors. But, owing to these reactions take place mostly in the
last two reactors, produc-tion rate of light ends increases in these reactors,
as shown in Fig. 14.
8.5. Physical properties
In this study, physical properties such as heat capacity, viscosity and

Fig. 9 – The H2/HC molar ratio in the CCR process. molecular weight are considered as variable
a a
900 300
(kmol/h)
Molar flow rate along inner annulus of reactor Molar flow rate along inner annulus of reactor
800 Mean molar flow rate along radius of reactor M-xylene

Mean molar flow rate along radius of reactor
250
flowrate)(kmol/h
700
rate
O-xylene
500
200
carbon aromatics molar flow

600
P-xylene
molar
400
150
100
Normal paraffin
300
200
100 50
Eight
Ethylbenzene
0
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Annulus Length(Radius) of reactor (Dimensionless) Annulus Length(Radius) of reactor (Dimensionless)
b b
500
1000 Molar flow rate along inner annulus of reactor
900 Molar flow rate along inner annulus of reactor 450 Mean molar flow rate along radius of reactor
Mean molar flow rate along radius of reactor
molar flow rate (kmol/h)

400 Toluene A
9+
flow rate(kmol/h)
800
600
350
700 300
500
250 Benzene
200
molar
400
Aromatic
150
Iso-paraffin
200
300 100
100
50
0
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Annulus Length(Radius) of reactor (Dimensionless)
Fig. 11 – Variations of mloar flow rate of (a) normal-paraffin and (b) iso- Fig. 12 – Molar flow rate of (a) aromatics with eight carbon atoms and
paraffin in the process. (b) Toluene, Benzene and heavy aromatics with A9+.
parameters. In this section, variations of these physical prop-erties are

8.6. Superficial velocity
illustrated in radial coordinates. Heat capacity variations, is depicted in
Fig. 15a. As previously mentioned, the major reforming reactions are
The superficial gas velocity is one of the key parameters in design and
highly endothermic, thus, temperature decreases in radial direction and
operation of various moving bed reactors, from an engineering viewpoint.
due to direct relationship between heat capacity and temperature, heat
As the gas volumetric flow rate is divided by the cross-sectional area, it
capacity decreases in the reactors. As can be seen in Fig. 15a, at the
defined according to Eq.
entrance of reactors heat capacity is high due to high temperature, but
(47):
endothermic reactions in the reactors cause temperature drop.
Consequently, reduction of heat capacity can be observed in each reactor. Rm• T (47)
The outlet stream of reac-tors is preheated via a furnace that causes
sudden jumps in the heat capacity plot. During the process, increase of Ur = PMA
12000
tem-perature has a positive effect on the heat capacity, but due to
production of hydrogen, which has a very low heat capacity in Molar flow rate along inner annulus of reactor
comparison of other components, downward trend occurs. Mean molar flow rate along radius of reactor
10000
(kmol/h)
8000
In the viscosity behavior, dominant agent is temperature of

molar flow rate
6000
components. Thus, during the process, the trend of viscosity obeys
temperature conditions. As shown in Fig. 15b, viscos-ity decreases along
the radius of reactors due to temperature reduction, and an ascendant trend
can be observed during the process, because the outlet stream of reactors
Hydrogen
4000
is heated by the furnace. One of the other significant physical properties in 2000
the naphtha reforming process is molecular weight, which is affected by

proceeding of the reactions. In Fig. 15c, molecu-lar weight is depicted vs. 0
radius of reactors. Molecular weight decreases in the radial direction due
to proceeding of reactions and produce light products such as hydrogen 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
and light ends.
Fig. 13 – Molar flow rate of hydrogen in the CCR process.

1800
Molar flow rate along inner annulus of reactor
1600 Mean molar flow rate along radius of reactor
(kmol/h)
1400
1200
Light end molar flow rate
1000
800
600
400
200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Fig. 14 – Molar flow rate of light end.

Fig. 16 – Superficial velocity in the reforming process.
a 140
capacity(KJ/Kmol.K)
130
120
110 Superficial velocity can be varied with the changes of tem-perature

(T), pressure (P), molecular weight (M) or cross section area (A) at
various radial positions. But superficial gas velocity almost is unchanged
Heat
100
at various axial locations because in the axial direction the temperature

and pressure gradient are very small, cross section area is constant, and
90
molecular weight is almost unchanged in this direction. Consequently,
80 superfi-cial velocity along the various lengths of reaction side in each
radius is nearly constant. As shown in 3-D plot in Fig. 16, in the radial
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 direction, superficial velocity increases, because in this direction pressure,
Radius of reactor (Dimensionless) temperature, molecular weight and cross section area decrease. Although
b -5
x 10 diminution in temper-ature causes reduction of superficial velocity, but the
1.8
effect of decrease in molecular weight, cross section area and pressure are
Viscosity(Kg/m.s)
1.75
more. Consequently, according to Eq. 47, superficial veloc-ity increases in

the radial direction. Auxiliary correlations of velocity distribution are
1.7
presented in Appendix D.
1.65
1.6
9. Conclusions
Catalytic reforming is one of the key processes in the refinery to produce

high-octane gasoline, aromatics and hydrogen as a clean fuel. In this
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 study, mathematical modeling of continuous catalytic regeneration in the
Radius of reactor (Dimensionless)
naphtha reforming unit has been developed. This model includes a new
c
35 kinetic model for the catalytic naphtha reforming with 32 pseudo
components and 84 reactions. In addition, a new model for the catalyst
deacti-vation rate, by considering cross flow pattern in the reactors, is
presented. Some variables such as reaction temperature and pressure,
weight(kg/kmol)
30
superficial velocity, and hydrogen to hydrocarbon molar ratio (Antos and
Molecular
25
Aitani, 1995) have effect on the per-formance of the catalytic naphtha
reforming process. In this work, variations of these parameters along the
radial and axial directions of reactors, also the variations of proposed
pseudo components in the reforming process have been investigated.
Acceptable agreement has been obtained between commer-cial values and
simulated results of the molar flow rate of pseudo components, coke
content of catalysts, operating con-ditions and physical properties which
20 indicate the acceptable prediction ability of the proposed kinetic model.
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Radius of reactor (Dimensionless)
Fig. 15 – Physical properties in the process (a) heat capacity (b) viscosity
(c) molecular weight.
Appendix A. Catalyst deactivation model Then, Eq. (A9) is replaced in Eq. (A6):
uz ∂CC =r
CM
(A10)
M
Reaction rate of pseudo-components based on activity of cat-alyst and
∂z
reaction rate on the fresh catalyst can be obtained by:
By rearranging above equation, we have:
∂C = r (A11)
CM CM
o (A1)
ri = a i × ri
∂z uz
Then, by considering catalyst function for each reaction,
Reaction occurs on acidic function ai aA

=
=
Reaction occurs on metallic function =

ai aM
Reaction occurs on acidic or metallic function ai mean(aA , aM )
Reaction occurs on acidic as well as metallic functions ai = mean(aA , aM )
Thus, the rate of reaction that is catalyzed by metallic function could be Thus, the coke weight fraction on the metallic function (CCM ),
written as: depends on the rate of coke formation on the metal-lic function of spent
catalyst (rCM ) and catalyst velocity (uz ). Therefore to solve Eq. (A11),
o (A2)
ri = aM × ri the rate of coke formation must be calculated:
Also, metallic function activity (aM ) is a function of deposited coke

weight fraction on the metallic function of catalyst, which could be r =a ×r o (A12)
CM CM C M
calculated by:
o
nM rC M is rate of coke formation on the metallic function of fresh catalyst,
daM = ˛M × aM (A3)
which is defined by:
−
dCCM o 0.5 (A13)
kCM × exp(−Ec /RT)
r = n n2 ×C
where ˛M is a constant and nM is a power number of metallic function CM P 1 (H2 /HC) ACP
activity. ˛M and nM must be determined via minimiza-tion of difference
In addition, aCM could be calculated by:
between plant data and modeling output. Then With integration of recent
da n (A14)
equation, we have:
CM
If n /1 a × 1 (A4) − dC =˛ ×a
C ) C M
If nM = 1 aM = exp(−˛M CM CM CM C M
M= M=
nCM and ˛CM similar to unknown constants of Eq. (A3), must be
(1 + (nM − 1)˛M × CC M )(1/(nM −1)) determined via minimization of difference between plant data and
modeling output. With integration from Eq. (A14), we have:
In the above equation CCM is coke weight fraction on the metallic

If n /1 a = − × 1 (A15)
function that the following coke balance on the metallic function along the n
If CM = 1 aCM exp( ˛CM C
CM
)
Z direction is applied for its cal-culation:
= CM =
CM
(1 + (nC M − 1)˛C M
× CC M )(1/(nCM −1))
FCM |z − FCM |z+dz + rCM × ( B × 2 × × r × r × dz) = 0 (A5)
To calculate the rate of coke formation on the metallic func-tion Eqs.
By considering the Taylor’s extension, the above equation becomes: (A15) and (A13) must be replaced in Eq. (A12), then by substituting coke
formation rate in Eq. (A11), coke weight frac-tion on the metallic function
∂F (A6) (CCM ) could be calculated. With same procedure, the rate of reactions that
= rCM × ( B × 2 × × r × r)
CM are catalyzed by acidic site could be achieved, the results shown in Table
∂z 12. In addition, required constants to calculate catalyst deactivation rate
and activity are presented in Table A.1.
where FCM and rCM , are mass flow rate of coke and rate of coke
formation on the metallic function of catalyst. In addition, FCM can be
defined as: Appendix B. Developing of governing
. (A7) equations
F =C ×m
CM CM Cat.
B.1. Mass balance
Also, mass flow rate of catalyst is defined by:
. To develop the mathematical model the derivation of govern-ing equations

× × r × r × uz (A8)
mCat. = b × 2 (mass and energy balances) have been discussed here. The mass balance
for a control volume with length of dz and cross section area of A is:
By substituting the above equation in Eq. (A7):
(A9)
FCM = CCM × ( b × 2 × × r × r × uz ) Input − Output + Consumption = Accumulation (B1
)
Cross section area is obtained as follows:

Table A.1 – Require constants to calculate catalyst
Ar = 2 r × dz (B7)
deactivation rate.
Parameter Value Dimension
nM 1 – By applying the above equations one can obtain:

26 kg
˛M cat
m
1 ∂(Nj × Ar ) ∂Cj
kg
coke
1 – − + b (B8)
nC M ai × vij ri = ε ∂t
Ar ∂r i=1
12.34 kg
˛CM cat
kg coke
The molar flux comprises two terms, ones due to the bulk motion and
nA 1 –
the other one for diffusion of component j as fol-lows:
˛A 14.5 kg
cat
kg ∂Cj (B9)
coke
nC A 1 – Nj = −Dej ∂r + Cj ur
10.18 kg or
˛CA cat
kg coke Nj Ar = −Ar Dej ∂C + A C u (B10)

n 1.5
j r j r
kCM 0.384 kgcoke ×(kPa) 1 m
0.5 ∂r
kgcat (kmol)
1.386 n 1.5
kCA kgcoke ×(kPa) 1 m
0.5 By substituting the above equation in Eq. (B8), we have:
kgcat (kmol)
J
Ec 4055
1 ∂ ∂Cj 1 ∂ m
mol
n1 0.94 – D (Ar )−
ej Ar ∂r ∂r Ar ∂r (Ar ur Cj ) + bai
i=1
n2 1.33 –
× ij ri = ε∂C j = 1, 2, ..., n (B11)
j
∂t i = 1, 2, ..., m
The CCR process is steady state, and diffusion in comparison to bulk

motion is negligible, thus:
m
(Nj × Ar )|r − (Nj × Ar )|r+dr + b
1 ∂ m j = 1, 2, ..., n
ai × vij ri × Ar
− i = 1, 2, ..., m (B12)
Ar ∂r (Ar ur Cj ) + b 1 ai × ij ri = 0
i=1
i
× dr = ∂n j = 1, 2, ..., n (B2) =
j
∂t i = 1, 2, ..., m
To simplify this equation, the following relation is used:
where nj is mole of component j in control volume and Nj is molar flux of − 1 ∂ (A u C ) = −ur Cj ∂A ∂Cj ∂ur
r r j r
component j, by writing the Taylor’s exten-sion of second term in left
Ar ∂r Ar ∂r − ur ∂r − Cj ∂r
hand of mass balance equation, is obtained:
ur Cj ∂Cj ∂ur (B13)
= − r − u ∂r − C ∂r
m r j
∂(Nj × Ar ) ∂nj
− (B3)
· dr + b ai × vij ri × Ar × dr =
∂r i=1 ∂t
By substituting recent equation in Eq. (B12):
ur Cj ∂Cj
m j = 1, 2, ..., n
Then, by dividing the above equation over the volume of the ∂ur
differential element: −
r − ur ∂r − Cj ∂r + b 1ai × ij ri = 0
i i = 1, 2, ..., m
m =
1 ∂(Nj × Ar ) 1 ∂nj (B14)
− (B4)
+ b ai × vij ri =
Ar ∂r i=1
Ar × dr ∂t
Consequently, final equation of mass balance in the CCR pro-cess obtains:
m j = 1, 2, ..., n
To simplify the above equation, by considering concentra-tion of ∂Cj Cj Cj ∂ur b
component j in control volume: =− − + i (B15)

∂r r ur ∂r ur 1 ai × ij ri i = 1, 2, ..., m
(B5) =
Cj = nj
(Ar × dr × ε) B.2. Energy balance
Or
nj = Cj × (Ar × dr × ε) (B6) Energy balance in the CCR process is obtained by applying

the first law of thermodynamic:
Rate of Rate of Rate of Hence:
of energy to the system the system 1 ∂ (K Ar

∂T
) n H m a vr n H ε
∂C
j
accumulation energy added energy leaving j i
= + eff − b × ij + ×
within the by conduction by conduction Ar ∂r ∂r n i j ∂t
n ∂Hj n ∂Uj ∂Cj
system heat transfer heat transfer j=1 i=1 j=1
Rate of Rate of energy − N =ε C +ε U (B21)

work done added to the j=1 j ∂r j ∂t j ∂t
j=1 j=1
+ by the system by mass
m n
system on the + flow into the Now we have:

surroundings system (K
Ar ∂r ) − b (Hj vij ) × ai × ri
leaving flow of heat
Ar ∂r eff
Rate of energy Rate of 1 ∂ ∂T

+ flow out of + from the n
∂H
n
n ∂U j=1 ∂C
system by massto the system i=1
the system surroundings j j j
− N = ε C + ε (U − H ) (B22)
(B16) j=1 j ∂r j=1 j ∂t j=1 j j ∂t
By using the following definitions, the last equation can be

In the absence of shaft work the energy balance is (Fogler, simplified:
1992):
n
−Keff Ar ∂r r + K A dr + n j=1
eff r ∂r r Nj Ar Hj = j=1
Hi (vij Hj )
∂T ∂T + j 1
= r
n
∂Hj = ∂Hj × ∂T = CP × ∂T
∂( j
∂r ∂T ∂r ∂r
N AH = (B17)
− n j r j = i 1, 2, ..., m n n ∂T
nj U j ) ∂Hj
j = 1, 2, ..., n
∂t
=1
j
j 1
+
= N )
r dr
j =((Jj + Cj ur ) × CPj ×
j=1 ∂r ∂r
j=1
Uj is internal energy component j in the system and Hj is enthalpy of n n
∂T ∂T
component j, by considering the Taylor’s exten-sion, we have: =
CC )
∂r j=1 ((Jj + Cj ur ) × CPj ) ur ( j Pj ∂r
j=1
(K A )− n ∂r
∂r Ar n n n
Ar ∂r eff r
Cj
∂( N j A r Hj )
1 ∂ ∂T 1 j=1
n n ( CC ) C ( ( )C ) C yC C C
1 ∂Uj 1 ∂nj j Pj = T j=1 CT Pj = T j Pj = T P
j=1 j=1
= n + U (B18)
Ar × dr j ∂t Ar × dr j=1 j ∂t (Uj − Hj ) = −Pvj = −RT
j=1
n n
∂Cj ∂Cj ∂CT
Substituting Eq. (B5) in the above equation obtains:
j=1 (Uj − Hj ) ∂t = −RT ∂t = −RT ∂t
1 ∂ ∂T 1 n n j=1
∂(Nj Ar ) ∂Hj
(Keff Ar )− ∂Uj ∂Uj ∂T ∂T
Ar ∂r ∂r Ar Hj ∂r −Nj ∂r
∂T × ∂t = CVj × ∂t
=
j=1 j=1
∂t
n n
∂Uj ∂Cj C C R
(B19) Vj = Pj −
= εCj ∂t + εUj ∂t
j=1 j=1
CV = CP − R
The term ∂(Nj Ar ) is replaced from Eq. (B8):
Also:
∂r
(K A ) Hj − b j n n ∂T ∂T n n ∂T
∂r + n ai × vij ri + ε ∂t
Ar ∂r eff r ∂Uj
1 ∂ ∂T m ∂C
C C = CC ( CC )
n j=1 i=1
Cj = j Vj × j Vj = j Vj
j=1 ∂t ∂t ∂t j=1 ∂t
j=1 j=1
n ∂Hj n (B20)
− Nj ∂r
j=1
∂Uj ∂Cj
=ε +ε n n n
Cj ∂t Uj ∂t Cj
j=1 j=1 (C C ) C ( ( )C ) C yC C C
j Vj = T j=1 CT Vj = T j Vj = T V
(B23)
(B24)
(B25)
(B26)
(B27)
(B28)
(B29)
(B30)
(B31)
(B32)
(B33)
n n
In the above equations, CV and CP are the average heat capacities of ∂Fj
mixture at constant volume and pressure, respec-tively. Thus, by applying (C5)
j=1 ∂z = 2 Ri ure(Cje )
these auxiliary equations, we have: j=1
∂FT = 2 Ri × ure × CTe (C6)
1 ∂ ∂T m
∂z
(Keff Ar
Ar ∂r ∂r ) − b ( Hi × ai × ri )
i=1 Also, energy balance in the Z coordinates for a control volume is:
∂T ∂T ∂CT (B34)
− ur CT CP ∂r = εCT CV ∂t − εRT ∂t
n
And then,
FT CP T|z − FT CP T|z+dz + Fje Cpje (Te − T) = 0 (C7)
j=1
1 ∂ ∂T m
Then, following definitions are used to simply the recent equa-tion:

(Keff Ar
Ar ∂r ∂r ) − b ( Hi × ai × ri )
i=1
∂T ∂T ∂CT (B35) n
− ur CT CP ∂r + εRT ∂t = εCT CV ∂t FT = Fj (C8)

j=1
M n (C9)
Due to steady state conditions and low amount of conduc-tive heat
transfer in comparison with convective heat transfer, therefore, heat
M j Fj
transfer simplify to: j=1
=
F
∂T
m T
n
−ur CT CP ∂r − b( Hi × ai × ri ) = 0 (B36)
Fj Cpj
i=1
j=1
Cp = (C10)
Consequently, final equation for energy balance in the CCR process FT
obtains: n n C n
je
∂T m
b
=− ( Hi × ai × ri ) (B37) (C C ) C (( )C ) C (y C ) C C
∂r ur CT CP je Pje = Te C
Te Pje = Te je Pje = Te Pe
i=1 j=1 j=1 j=1
(C11)
Appendix C. Collector equations
To represent the governing equations in the collector, mass and energy By substituting the above equation in governing energy bal-ance:
balances have been applied for a control volume with length of dz and
2
cross section area of Ri , thus, the mass balance for control element in Z
n
direction is:
FT CP T|z − FT CP T|z+dz +Cje ure 2 Ri × dz × Cpje (Te − T) = 0 j=1
Fj |z − Fj |z+dz + Fje = 0 (C1) (C12)
where Fj , is molar flow rate of component j in Z direction and Fje is

output molar flow rate of component j from reaction side that enters to the By writing the first and second terms of Taylor’s extension in left hand
collector: of equation, ones can obtain:
Fje = Cje ure Are = Cje ure 2 Ri × dz (C2) ∂(FT CP T) = 2 Ri × ure × CTe × Cpe × (Te − T) (C13)
∂z
where Cje and ure are concentration of component j and radial velocity in
inner radius of reactor. By substituting recent equa-tion in Eq. (C1), final Now, by applying algebraic definitions Eq. (C13) simplifies:
equation for mass balance in the collector obtains:
CP T ∂(FT ) + FT CP ∂(T) + FT T ∂(CP ) = 2 Ri

∂Fj = 2 Ri ure Cje (C3)
∂z ∂z ∂z
∂z × ure × CTe × Cpe × (Te − T) (C14)
Then, to calculate total molar flow rate FT, the summa-tion of recent 1 ∂T + 1 ∂C + 1 ∂F = 1 ×2 R
P T i
equation for all pseudo-components must be considered:
n n T ∂z
∂Fj CP ∂z FT ∂z F T CP T
= (2 Ri ure Cje ) (C4) × ure × CTe × Cpe × (Te − T) (C15)
j=1 ∂z
j=1
And by rearranging Eq. (C15) we have: deactivation and on product yield and quality during naphtha catalytic
reforming. Appl. Catal. 13, 113–125.
∂T = − T ∂C T ∂FT 1 Carter, J.L., Mcvinker, G.B., Weissman, W., Kmak, M.S., Sinfelt, J.H., 1982.
P
∂z C ∂z − F ∂z +
FT C P
Bimetallic catalysis; application in catalytic reforming. Appl. Catal. 3, 327–
P T 346.
× 2 Ri × ure × CTe × Cpe × (Te − T) (C16) Edgar, M.D., 1983. Catalytic reforming of naphtha in petroleum refineries.
In: Applied Industrial Catalysis. Academic Press, New York, pp. 1–123.
Then by substituting Eq. (C6) in the recent equation we have: Figoli, N.S., Beltramini, J.N., Barra, A.F., Martinelli, E.E., Sad, M.R., Parera,
J.M., 1983a. Influence of total pressure and hydrogen: hydrocarbon ratio
∂T T ∂CP T 1 on coke formation over naphtha-reforming catalyst. In: Coke Formation on
∂z = − C ∂z − (2 Ri × ure × CTe ) + × 2 Ri Metal Surfaces ACS Symp. Ser., vol. 202, pp. 239–252.
P FT FT C P
× ure × CTe × Cpe × (Te − T) (C17) Figoli, N.S., Beltramini, J.N., Marinelli, E.E., Sad, M.R., Parera, J.M., 1983b.
Operational conditions and coke formation on Pt-Al2 O3 reforming
catalyst. Appl. Catal. 5, 19–32.
Appendix D. Velocity distribution Fogler, H.S., 1992. Elements of Chemical Reaction Engineering, 2nd ed.
Prentice-Hall, Englewood Cliffs, NJ.
Froment, G.B., 1987. The kinetic of complex catalytic reactions.
For velocity distribution by using mass balance in the CCR process
Chem. Eng. Sci. 42, 1073–1087.
Hongjun, Z., Mingliang, S., Huixin, N., Zeji, L., Hongbo, J., 2010. Modeling
∂Cj C C ∂ur b m j = 1, 2, ..., n and simulation of moving bed reactor for catalytic naphtha reforming.
j j
Petrol. Sci. Technol. 28, 667–676.
=− − + i a× r i = 1, 2, ..., m (D1)
∂r r Hu, Y.Y., Su, H.Y., Chu, J., 2003. Modeling and simulation of
ur ∂r ur
= 1 i ij i
commercial catalytic reformers. Chin. J. Chem. Eng. 17, 418–424.
Then the summation of recent equation for all pseudo-components must Iranshahi, D., Bahmanpour, A.M., Pourazadi, E., Rahimpour, M.R., 2010a.
be calculated Mathematical modeling of a multi-stage naphtha reforming process using
novel thermally coupled recuperative reactors to enhance aromatic
n n n n m
∂Cj Cj 1 ∂ur b production. Int. J. Hydrogen Energy 35, 10984–10993.
= − − Cj + ur ai × ij ri(D2)
j=1 ∂r j=1 r ur ∂r Iranshahi, D., Pourazadi, E., Paymooni, K., Bahmanpour, A.M., Rahimpour,
j=1 j=1 i=1
M.R., Shariati, A., 2010b. Modeling of an axial flow, spherical packed bed
n m
∂CT CT CT ∂ur reactor for naphtha reforming process in the presence of the catalyst
deactivation. Int. J. Hydrogen Energy 35, 12784–12799.
b
=− − + a× r (D3)
∂r r ur ∂r ur i ij i
j=1 i=1 Iranshahi, D., Pourazadi, E., Paymooni, K., Rahimpour, M.R., 2012. A novel
ur n m dynamic membrane reactor concept with radial-flow pattern for reacting
∂CT ur ∂ur b
material and axial-flow pattern for sweeping gas in catalytic naphtha
× =− (D4)
− + C
ai × ij ri reformers. AICHE J. 58, 1230–1247.
CT ∂r r ∂r T j=1
i=1
Iranshahi, D., Rahimpour, M.R., Asgari, A., 2010c. A novel dynamic radial
By rearranging Eq. (D4) velocity distribution equation can be obtained: flow, spherical-bed reactor concept for naphtha reforming in the
presence of catalyst deactivation. Int. J. Hydrogen Energy 35, 6261–
6275.
n m
∂ur ur ur ∂CT b
Jenkins, J.H., Stephens, T.W., 1980. Kinetics of catalytic reforming.
(D7) Hydrocarb. Process. 11, 163–167.
=− − × + ai × ij ri
∂r r CT ∂r Ct Jorge, A.J., Eduardo, V.M., 2000. Kinetic modeling of naphtha catalytic
j=1 i=1
reforming reactions. Energy Fuels 14, 1032–1037.
To find ∂CT in the recent equation, we can use ideal gas low:
Juarez, J.A., Macias, E.V., Garcia, L.D., Arredondo, E.G., 2001. Modeling
∂r
P (D8) and simulation of four catalytic reactors in series for naphtha
CT = reforming. Energy Fuels 15, 887–893.
RT Kmak, W.S., 1972. A Kinetic simulation model of the
powerformmg process. AIChE Meeting, Houston, TX.
Then by doing algebraic operations on the above relations, we have: Krane, H.G., Groh, A.B., Schuhnan, B.L., Sinfeh, J.H., 1959. Reactions in
catalytic reforming of naphthas. In: 5th World Petroleum Congress,
New York, May 30–June 5.
∂CT = 1 ∂P − P ∂T (D9) Lee, J.W., Ko, Y.C., Jung, Y.K., Lee, K.S., Yoon, E.S., 1997. A Modeling and
∂r RT ∂r simulation study on a naphtha reforming unit with a catalyst circulation and
RT ∂r
2
regeneration system. Comput. Chem. Eng. 21, 1105–1110.
References
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Antos, G.A., Aitani, A.M., 1995. Catalytic naphtha reforming, 2nd ed. Marcel over Pt-Re/Al2 O3 : reaction network, kinetics, and apparent selective
Dekker, New York. catalyst deactivation. J. Catal. 206, 188–201.
Barbier, J., 1986. Deactivation of reforming catalysts by coking—a review. Mahdavian, M., Shohreh, F., Fazeliz, A., 2010. Modeling and
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Bishara, A., Stanislaus, A., Hussain, S., 1984. Effect of feed
composition and operating conditions on catalyst
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J. Chem. React. Eng. 8. 1987. A review of mobil’s industrial process modeling philosophy. Adv.
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Chem. Eng. 2, 1–7. Transformation of mixtures of benzene and xylenes into toluene by
Matar, S., Hatch, L.F., 2000. Chemistry of Petrochemical Processes, 2nd ed. transalkylation on zeolites. Appl. Catal. A 266, 203–210.
Gulf Publishing Company, Texas.
Mieville, R.L., 1991. Coking kinetics of reforming. Stud. Surf. Sci. Smith, R.B., 1959. Kinetic analysis of naphtha reforming with platinum
Catal. 68, 151–159. catalyst. Chem. Eng. Prog. 55, 76–80.
Mostafazadeh, A.K., Rahimpour, M.R., 2009. A membrane catalytic bed Tailleur, R.G., Davila, Y., 2008. Optimal hydrogen production through
concept for naphtha reforming in the presence of catalyst deactivation. revamping a naphtha-reforming unit: catalyst deactivation. Energy
Chem. Eng. Process. 48, Fuels 22, 2892–2901.
683–694. Taskar, U., Riggs, J.B., 1997. Modeling and optimization of a
Nauman, E.B., 2001. Chemical Reactor Design, Optimization, and Scaleup. semiregenerative catalytic naphtha reformer. AIChE J. 43, 740–753.
McGraw-Hill, New York.
Padmavathi, G., Chaudhuri, K.K., 1997. Modeling and simulation of Weifeng, H., Hongye, S., Yongyou, H., Jian, C., 2006. Modeling, simulation
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Rahimpour, M.R., Iranshahi, D., Pourazadi, E., Paymooni, K., Bahmanpour,
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Further reading
bed membrane naphtha reformers in the presence of catalyst deactivation.
AIChE J. 57, 3182–3198.
Perry, R.H., Green, D.W., Maloney, J.O., 1999. Perry’s Chemical
Ramage, M.P., Graziani, K.P., Krambeck, F.J., 1980. Development of mobil’s Engineers’ Handbook, 7th ed. McGraw-Hill, New York.
kinetic reforming model. Chem. Eng. Sci. 35,
41–48.

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CHEMICAL ENGINEERING RESEARCH AND DESIGN 9 2 ( 2 0 1 4 ) 1704–1727

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

Modeling of naphtha reforming unit applying detailed

1. Introduction 1. Semi regenerative.

Notation r rate of inth reaction, kmol kg cat

by considering catalyst deactivation. Recently, Iranshahi et al. (2010a,b,c)

Table 1 – Rate constants and heat of reactions in dehydrogenation reactions.

2.1. Dehydrogenation equilibrium constants (K1n ) are presented in Table 1.

Dehydrogenation reaction, due to produce high octane num-ber aromatics,

Table 2 – Rate constants and heat of reaction in paraffin dehydrocyclization to naphthene.

a 69.73 30.75 33.11 14.39 3

Table 3 – Rate constants and heat of reactions in paraffin dehydrocyclization to aromatic.

Table 5 – Rate constants and heat of reactions in isomerization of aromatics.

Table 6 – Rate constants and heat of reactions in Transalkylation.

= 11n = 11n R K11n 11n = RT cat −T

Table 7 – Rate constants and heat of reactions in Cracking of Paraffins.

NPn + H2 → n 12n 12n Pt

a Ignored reactions in Padmavathi and Chaudhuri (1997) study.

Table 8 – Rate constants and heat of reactions in cracking of naphthenes.

C7 −40.76 44.70 34.61

a Ignored reactions in Padmavathi and Chaudhuri (1997) study.

Hydrodealkylation is the breakage (or cleavage) of the branched radical of

Table 9 – Rate constants and heat of reactions in hydrodealkylations.

a Ignored reactions in Padmavathi and Chaudhuri (1997) study.

Fig. 2 – Reaction network scheme for naphtha reforming process.

Fig. 3 – Process flow scheme for CCR reforming process.

Distillation fraction of naphtha feed

r4n NPn ↔ ACPn + H2 M +A r12n NPn + H2 →

r7n M +A r15n n n i=1 M or A

r8n ACPn ↔ ACHn A r16n An+1 + H2 → Ak + Cm H2m+2 M

In the recent equation, ˛i is a constant and ni is a power number of

rate also is a function of deposited coke weight fraction, which could be

− = ˛Ci × aCCii If nCi = 1 aCi = exp(−˛Ci × CC i ) (1/(nCi −1))

(1 + (nCi − 1)˛Ci × CCi )

In the recent equation, aCi is activity of dominant function for coke

To develop mathematical modeling based on mass and energy

In order to validate the model estimations, the results of kinetic and

• Intra-pellet heat and mass diffusion in catalyst pellet are ignored.

Table 12 – Catalyst deactivations model.

Reaction occurs on acid function

(1/(n −1)) (1/(n −1))

nCM = 1 aC M exp( ˛CM CCM ) nCA = 1 aCA exp( ˛CA CCA )

(35) (1/(nC −1)) (36) (1/(nC −1))

CM ×exp(−Ec /RT) CA ×exp(−Ec /RT)

The process of continuous catalyst regeneration is charac-terized by high

As can be seen in the results (Tables 14 and 15), satis-factory

(38) ∂Cj Cj C ∂ur i=1 a r j = 1, 2, ..., n

Ergun equation (pressure drop)

Table 14 – Comparison between predicted production rate and plant data.

n-P6 (C6 H14 ) 86.178 0.0229 71.84 70.98 0.86

Plant Model Plant Model Plant Model

Fig. 7 depicts coke weight fraction distribution in the metal-lic and

reactor, remaining naphthenes take part in the dehydrogena-tion reaction.

8.4. Pseudo-components the process depend on the isomerization, hydrocracking and

rate of ACH is lower in these reactors. The variations of ACP in

Z=L/4 Mean molar flow rate along radius of reactor

0.85 Mean 120

0.9 Z=3/4*L 140

8.5. Physical properties

In this study, physical properties such as heat capacity, viscosity and

800 Mean molar flow rate along radius of reactor M-xylene

carbon aromatics molar flow

molar flow rate (kmol/h)