Steady State.... 2013

Chemical Engineering Journal 229 (2013) 153–176
Contents lists available at SciVerse ScienceDirect
Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej
Applying new kinetic and deactivation models in simulation of a novel

thermally coupled reactor in continuous catalytic regenerative naphtha
process
Davood Iranshahi a, Razieh Rafiei a, Mitra Jafari a, Shahram Amiri a, Mohsen Karimi a,
Mohammad Reza Rahimpour a,b,⇑
a
Department 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
h i g h l i g h t s
A novel thermally coupled reactor in CCR naphtha reforming process is modeled.

A new kinetic model involving 32 pseudo-component and 84 reactions is proposed.
Modeling is carried out in two dimensions considering a new deactivation model.
Nitrobenzene hydrogenation is employed as the heat source.
The aromatics and hydrogen increase 92 and 190 kmol/h, respectively.
a r t i c l e i n f o a b s t r a c t
Article history: Naphtha reforming unit occupies a key position in refineries to obtain high octane gasoline and BTX
Received 6 January 2013 (benzene, toluene, and xylene) components which are the basic substances of petrochemical industries.
Received in revised form 8 May 2013 In this study, a novel thermally coupled reactor for continuous catalytic regenerative naphtha process has
Accepted 14 May 2013
been proposed to boost the aromatics and hydrogen productions and to produce aniline as a valuable
Available online 22 May 2013
product. In this configuration, the naphtha reforming (endothermic reaction) and nitrobenzene hydroge-
nation (exothermic reaction) reactions are carried out simultaneously. According to complex kinetic of
Keywords:
reforming process a new kinetic model including 32 pseudo components with 84 reactions is proposed.
Thermally coupled reactor
Naphtha reforming process
As well, a novel catalyst deactivation model considering acidic and metallic functions of catalyst is
Hydrogenation of nitrobenzene presented to predict the behavior of the reactions which subject to the catalyst deactivation. Mathemat-
Deactivation model ical modeling of coupled reactor is considered in two dimensions (radial and axial directions). In order to
Kinetic model assess the performance of the new configuration, the modeling results of thermally coupled reactor (TCR)
is compared with the obtained results of conventional reactor (CR). By employing coupled reactors, aro-
matics production rates is improved acceptably (about 92 kmol/h in comparison with conventional sys-
tem), and the amount of produced hydrogen is increased greatly (190 kmol/h compared to CR).
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction choice to reach this goal [1]. The significance of the catalytic
naphtha reforming process in the petroleum refinery and petro-
1.1. Naphtha reforming chemical industry contributes to continuous evolution of this tech-
nology. This progress is observed in elucidating better kinetic and
In order to fulfill environmental legislations, octane number of deactivation mechanisms with higher predictive ability, as well as
the produced gasoline should be increased to an acceptable level. presenting more efficient reactor setups for improving the produc-
Catalytic naphtha reforming process is considered as a proper tion yield and operating conditions.
Naphtha feedstock is a complex mixture of different hydrocar-
bons which undergo various reactions. Considering all of these
⇑ Corresponding author at: Department of Chemical Engineering, School of components and reactions in one kinetic model is a very complex
chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran. Tel.: +98 task. In order to solve this problem, ‘‘lumped’’ models have been
711 2303071; fax: +98 711 6287294.
presented in which the large number of chemical components is
E-mail addresses: rahimpor@shirazu.ac.ir, mrahimpour@ucdavis.edu
(M.R. Rahimpour).
classified to smaller set of kinetic lumps. The first significant
1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.05.052
154 D. Iranshahi et al. / Chemical Engineering Journal 229 (2013) 153–176
Nomenclature
ai catalyst activity in endothermic reaction side kdea2,H constant of deactivation equation in exothermic reac-
aA acidic function activity in endothermic reaction side tion side
aC A acidic function activity for coke formation in endother- kdea3,H constant of deactivation equation in exothermic reac-
mic reaction side tion side
aC M metallic function activity for coke formation in endo- kdea,Ca constant of deactivation equation in exothermic reac-
thermic reaction side tion side
aM metallic function activity in endothermic reaction side keff effective thermal conductivity (W m1 k1)
a0 catalyst activity in exothermic reaction side kin reaction rate constant for endothermic reaction (in)
Ar cross section area of reactor in radial direction (m2) Kin equilibrium constant for endothermic reaction (in)
Ap available side area for heat transfer (m2) k0 reaction rate constant for exothermic reaction
A0 frequency factor (mol kg1 s1)
C concentration in endothermic reaction side (kmol m3) KNB adsorption constant of nitrobenzene (Pa1)
CExo concentration in exothermic reaction side (kmol m3) K H2 adsorption constant of hydrogen (Pa0.5)
CACP alkyl-cyclopentane concentration (kmol m3) L length of reactor (m)
C CA coke weight fraction on acidic function of catalyst in m number of reactions in endothermic reaction side
endothermic reaction side (kg kgcat1) Mj molecular weight of component j (kg kmol1)
C CM coke weight fraction on metallic function of catalyst in M mean molecular weight in the flow (kg kmol1)
endothermic reaction side (kg kgcat1) n number of components in endothermic reaction side
C Exo
Ca coke weight fraction on active sites in exothermic reac- n1 constant of deactivation equation in endothermic reac-
tion side (kg kgcat1) tion side
Cp specific heat capacity at constant pressure in endother- n2 constant of deactivation equation in endothermic reac-
mic reaction side (kJ kmol1 K1) tion side
C Exo
P specific heat capacity at constant pressure in exother- nA acidic function activity power number in endothermic
mic reaction side (kJ kmol1 K1) reactionside
Cv specific heat capacity at constant volume in endother- nCA acidic function activity power number in endothermic
mic reaction side (kJ kmol1 K1) reaction side
C Exo
v specific heat capacity at constant volume in exothermic nM metallic function activity power number in endother-
reaction side (kJ kmol1 K1) mic reaction side
CT total concentration in endothermic reaction side nC M metallic function activity power number in endother-
(kmol m3) mic reaction side
C Exo
T total concentration in exothermic reaction side n0 number of components in exothermic reaction side
(kmol m3) Nj molar flux of component j (kmol m2 h1)
dp particle diameter (m) P total pressure (kPa)
dr control volume thickness in radial direction (m) P An partial pressure of n carbon aromatic (kPa)
dz control volume length (m) PACHn partial pressure of n carbon alkyl-cyclohexane (kPa)
De effective diffusivity (m2 s1) PACPn partial pressure of n carbon alkyl-cyclopentane (kPa)
Ec coke formation activation energy in endothermic reac- P H2 partial pressure of hydrogen in endothermic reaction
tion side (J mol1) side (kPa)
E0 activation energy of the hydrogenation of nitrobenzene PH2 partial pressure of hydrogen in exothermic reaction side
(kJ mol1) (Pa)
EA,Ca activation energy (kJ mol1) PIPn partial pressure of n carbon iso-paraffin (kPa)
Fj molar flow rate of component j in endothermic reaction PNB partial pressure of nitrobenzene (Pa)
side (kmol h1) PNPn partial pressure of n carbon normal-paraffin (kPa)
F Exo
j molar flow rate of component j in exothermic reaction r radius (m)
side (kmol h1) ri rate of ith reaction (kmol kgcat1 h1)
FT total molar flow rate in endothermic reaction side rin rate of inth reaction (kmol kgcat1 h1)
(kmol h1) r0 rate of hydrogenation of nitrobenzene reaction
F Exo
T total molar flow rate in exothermic reaction side (mol kgcat1 s1)
(kmol h1) r oC rate of coke formation on fresh catalyst in endothermic
Hj enthalpy of component j in endothermic reaction side reaction side (kg kgcat1 h1)
(J mol1) rCA rate of coke formation on acidic function of catalyst in
HExo
j enthalpy of component j in exothermic reaction side endothermic reaction side (kg kgcat1 h1)
(J mol1) rCM rate of coke formation on metallic function of catalyst in
k thermal conductivity (W m1 K1) endothermic reaction side (kg kgcat1 h1)
kC A constant of deactivation equation for acidic function in r 0Ca rate of coke formation on active sites in exothermic
endothermic
reaction
side reaction side (kg kgcat1 s1)
1 n 1:5
kg kgcat kPa1 m1:5 kmol R gas constant (J mol1 K1)
kC M constant of deactivation equation for metallic function Ri inner diameter (m)
in
endothermic reaction side Ro outer diameter (m)
1 n 1:5
kg kgcat kPa1 m1:5 kmol Sa specific surface (m2 g1)
kCa,0 constant of deactivation equation in exothermic reac- T temperature of endothermic reaction side (K)
ðm m Þ
tion side ðkPa 2 1 s1 Þ TExo temperature of exothermic reaction side (K)
kdea1,H constant of deactivation equation in exothermic reac- U overall heat transfer coefficient (W m2 K1)
tion side Uj internal energy of component j (J mol1)
ur radial velocity in endothermic reaction side (m s1)
D. Iranshahi et al. / Chemical Engineering Journal 229 (2013) 153–176 155
uExo
r radial velocity in exothermic reaction side (m s1) Superscript
uz catalyst axial velocity in endothermic reaction side Exo exothermic reaction side
(m s1)
uExo
z catalyst axial velocity in exothermic reaction side Subscripts
(m s1) e exit condition (in inner radius of reactor condition)
yj mole fraction of component j i numerator for reaction in endothermic reaction side
j numerator for component in endothermic and exother-
Greek symbols mic reaction sides
e void fraction of catalyst bed in endothermic reaction n number of carbon atom
side T total
l viscosity (kg m1 s1)
vij stoichiometric coefficient of component j in reaction i in Abbreviations
endothermic reaction side A acidic function of catalyst
vj stoichiometric coefficient of component j in exothermic ACH alkyl-cyclohexane
reaction side ACP alkyl-cyclopentane
qb reactor bulk density in endothermic reaction side CCR continuous catalyst regeneration reformer
(kg m3) CR conventional reactor
qExo
b reactor bulk density in exothermic reaction side FBP final boiling point
(kg m3) HC hydrocarbon
/s sphericity IBP initial boiling pint (°C)
h1 endothermic reaction side angle IP iso paraffin
h2 exothermic reaction side angle LOD length over diameter
DH heat of reaction in endothermic reaction side (kJ mol1) M metallic function of catalyst
DHExo heat of reaction in exothermic reaction side (kJ mol1) NOS number of subsections
aA constant of deactivation (m3 kmol1) NP normal paraffin
aC A constant of deactivation (m3 kmol1) Pt platinum
aC M constant of deactivation (m3 kmol1) Sn tin
p Pi number TCR thermally coupled reactor
aM constant of deactivation (m3 kmol1)
attempt to model the naphtha reforming process was made by tion function to the coke content by an exponential relation. Many
Smith in 1959 [2]. Smith’s model consists of three basic compo- investigators have been investigated the performance of various
nents including paraffins, naphthenes, and aromatics (PNA) which reactor configurations in this type of process. For instance,
take part in four reactions. In 1997, Taskar et al. [3] presented a Rahimpour et al. suggested various configurations such as,
model consists of 36 lumps of hydrocarbons with 35 reactions. In axial-flow fluidized bed membrane tubular reactor [17], and radial
the same year, Padmavathi et al. [4] considered 26 lumps of flow multi-stage spherical reactor [19]. Iranshahi et al. [16] and
hydrocarbons taking part in 48 reactions. Juarez et al. [5] Pourazadi et al. [18] presented radial-flow tubular reactor and
considered the reactions in terms of isomers of the same nature thermally coupled reactor, respectively. Liang et al. [20] studied
(paraffins, naphthenes, and aromatics) and developed a new the performance of naphtha catalytic reforming in a radial-flow
kinetic model consisting of 24 lumps of hydrocarbons and 71 reac- tubular reactor. Ancheyta-Juarez et al. [21], Taskar et al. [3], and
tions. In 2010, Hongjun et al. [6] suggested a lumped kinetic model Hu et al. [12] used three axial-flow fixed bed tubular reactors in
with 27 lumps and 52 reactions in order to predict aromatic com- series in SR mode of operation to assess the validation of their sug-
positions in more detail. Other similar work were performed by gested kinetic model for naphtha reforming process.
Jenkins et al. [7], Kan and Palmer [8], Marin et al. [9], Van Trimpont Cyclic units employ a swing reactor to substitute for one of the
et al. [10], Hu et al. [11], and Hu and Zhu [12]. on-line operating reactors while the catalysts of the replaced reac-
tor are regenerated in a separate regeneration system [13]. The
1.2. Process classification advantageous of this mode of operation over semi-regenerative
process are less variation of the overall catalyst activity, high per-
According to the catalyst regeneration procedure, catalytic reac- cent of conversion and increase in the products purity.
tion processes could mainly be categorized in three types, includ- The most modern type of catalyst regeneration system is CCR in
ing: semi-regenerative (SR), cyclic, and continuous catalyst which the catalyst is continuously removed from the last reactor,
regenerative (CCR). regenerated in a catalyst regenerator with two combustion beds,
In SR type, reactors operate continuously and at the end of cycle and then transferred back to the first reactor. The movement of
all of the catalysts are regenerated in situ. In order to regenerate the catalyst from the top of the first reactor to the bottom of the
the catalyst, the deposited coke is burned. The coke burning is last one usually lasts about 7 days. This unit usually operates at
accomplished in presence of nitrogen at 750–850 F [13].The regen- 700–800 K and 0.3–1 MPa [22]. Although this type of process has
eration procedure occurs approximately once each 6–24 months. some drawbacks such as difficulty in maintaining the flow of solids
Fukase et al. [14] developed a new process of light naphtha aroma- or attrition and break-up of catalyst pellets due to impact against
tization (LNA process). They were able to use a conventional fixed- reactor walls, CCR technology attracts manufacturer attention
bed reactor in a semi-regenerative process because they used a and in some of the petrochemical units such as reformers, most
new catalyst having long term stability. Li et al. modeled and opti- of the new units are manufactured based on this technology. This
mized a semi-regenerative catalytic naphtha reformer [15]. They is mainly due to significant advantageous of this technology such
modeled the deactivation of catalyst through relating the deactiva- as ease of catalyst regeneration, high conversion rate, and good
selectivity. Application of CCR process has been studied in different ence of supercritical carbon dioxide (scCO2) and ethanol. The selec-
chemical units. Stijepovic et al. [23] studied the continuous cata- tivity of aniline (AN) in scCO2 is greater than 80%, which is twice as
lytic regenerative reformer unit and present a new approach for high as that in ethanol, in which comparable amounts of AN and
simulation and optimization of the process. Moghimpour Bijani azobenzene (AB) are produced. In scCO2, the overall conversion
and Sahebdelfar [24] developed a mathematical model for the per- of NB increases with CO2 pressure, has a maximum at around
formance of a radial flow moving-bed reactor for dehydrogenation 10 MPa, and then decreases at 14 MPa. The product selectivity in
of light paraffins. Mu et al. [25] presented an optimum design of ra- scCO2 does not change much with the size of Pt particles while,
dial flow moving-bed reactors based on a mathematical hydrody- in the ethanol, the selectivity to aniline changes slightly with the
namic model. particle size. Prasad Reddy et al. [38] coupled dehydrogenation of
1, 4-butanediol to c-butyrolactone reaction with the hydrogena-
1.3. Coupling technique tion of nitrobenzene to aniline in the vapor phase by using a fixed
bed reactor in the presence of Cu/MgO catalysts. They studied the
Recently, one of the most significant trends in chemical engi- effect of H2presence in the adsorbed state in the coupling reaction.
neering and process technology is process intensification (PI) Diao et al. [39] studied gaseous hydrogenation of nitrobenzene
which assesses the reduction of environmental emissions, as well over a Cu/SiO2 catalyst in a two-stage and in a single-stage fluid-
as reducing the energy and materials consumption. Reactors, as ized bed reactor, at 513–553 K and atmospheric pressure. The
the heart of chemical process, are one of the main aims of this con- placement of the second perforated plate in the fluidized bed reac-
cept. In this regard, multi-functional auto-thermal reactors have tor inhibits the backmixing of gases and solids and consequently
been emerged as a novel concept and their application in coupling increases the local molar ratio of hydrogen to nitrobenzene in
of endothermic and exothermic reactions have been extended the second stage. Thus, the conversion of nitrobenzene and the
[26,27]. First appropriate study of the coupling process was carried selectivity of aniline production and the stable life of the catalyst
out by Towler et al. [28] in 1994. In their model, the promising are significantly increased in the two-stage fluidized bed reactor,
application of reaction coupling in improving the equilibrium of as compared with those in the single-stage one. Arab Aboosadi
high-temperature gas-phase dehydrogenation reactions by cou- et al. [40] utilized hydrogenations of nitrobenzene to aniline reac-
pling CO2 via the water–gas shift reaction was investigated. They tion in the shell side of a thermally coupled fixed-bed reactor in or-
studied the application of carbon dioxide as a coupling agent for der to provide the required heat for the steam reforming process.
recovery of sulfur from hydrogen sulfide, production of styrene
from ethylbenzene and production of olefins from light alkanes. 1.5. Objective
After their attempt, coupling of various reaction systems in differ-
ent reactor configurations have been studied widely and the num- In the present work, attempts have been made to present a no-
ber of published papers rises gradually. Abashar [29] used fixed vel configuration with higher performance and lower energy con-
bed catalytic reactor for simultaneous production of styrene and sumption for conventional catalytic naphtha reforming and
cyclohexane. He concluded that the fixed bed reactor (FBR) with hydrogenation of nitrobenzene to aniline processes. In order to
auxiliary reactions achieves substantial increase in ethylbenzene achieve this goal, the concept of continuous catalytic regeneration
conversion (100%) compared to the fixed bed reactor. Dehydroge- process is combined with thermally coupled reactor. A two-dimen-
nation of ethylbenzene to styrene, as the main reaction, was car- sional mathematical model is utilized to predict the parameters
ried out on iron-promoted catalysts and hydrogenation of variation along both radial and axial directions. This model is com-
benzeneto cyclohexane, as auxiliary reaction, was catalyzed by bined with a new reaction network containing 32 pseudo-compo-
nickel catalysts. The temperature and pressure of the reactor were nents with 84 reactions and a new deactivation model. In order to
873.0 K and 128.7 kPa, respectively. Rahimpour et al. [30] studied assess the performance of the presented configuration, the ob-
coupling the methanol synthesis on CuO/ZnO/Al2O3 catalyst with tained results of coupled reactor are compared conventional one.
the dehydrogenation of cyclohexane to benzene on Pt/Al2O3 cata-
lyst in a co-current flow and catalytic fixed-bed double-membrane
reactor configuration. The simulation results show 17.61% and 2. Process description
18.81% enhancement in the methanol productivity in thermally
coupled membrane reactor and thermally coupled double-mem- 2.1. Conventional system
brane reactor in comparison with the conventional one. Also,
15.76% and 10.81% enhancement in the hydrogen and benzene 2.1.1. Catalyst circulation
production rate relative to thermally coupled membrane reactor A schematic diagram for CCR process is shown in Fig. 1.The con-
are seen, respectively. Other studies employing couple technique ventional system employs a series of four separate radial-flow
were done by Tiemersma et al. [31], Ramaswamy et al. [32,33], reactors and a regeneration system. Regenerated catalysts enter
and van Sint Annaland [34]. the top of first reactor, move axially through the reactor by the
help of gravity flow and exit from the bottom of the reactor. The
1.4. Hydrogenation of nitrobenzene to aniline catalysts move from the bottom of first reactor to the top of the
next one and this procedure continues for all of reactors. After
The catalytic hydrogenation of nitrobenzene is an industrially leaving the last reactor, the catalysts enter to the regenerator and
important reaction for aniline production. This reaction is highly after regeneration they move in the first reactor again. Gas-lift
exothermic, and good temperature control is essential to avoid vio- method is applied for catalyst circulation between the reactors
lent decomposition of nitrobenzene or partially hydrogenated and the regenerator.
intermediates [35]. Aniline is mainly used for the synthesis of
methylene diphenyldiisocyanate (MDI), and as an additive for rub- 2.1.2. Feed passage
ber processing. It has also been used as a pesticide and herbicide. As shown in Fig. 2, the inlet feed enters the top of reactor and
About 85% of global aniline is produced by catalytic hydrogenation proceeds downward near the shell of reactor and then flows radi-
of nitrobenzene [36]. Various investigations are made on hydroge- ally into the catalyst bed (reaction media). After passing through
nations of nitrobenzene. For instance, Zhao et al. [37] investigated the catalyst bed, it enters an axial collector. As it can be observed
hydrogenation of nitrobenzene (NB) with Pt/C catalysts in the pres- in Fig. 1, the feed passes through all reactors and the obtained
Fig. 1. A schematic diagram of conventional naphtha reforming process in CCR mode of operation.
stream from the last reactor is sent to a separator, in which hydro-

gen rich gas separates from hydrocarbons. The obtained liquid
from the separator is sent to a stabilizer and the exit reformate
from the bottom of the stabilizer is sent to storage for gasoline
blending. Table 1 shows the specific properties and operating con-
ditions of the conventional configuration that are taken from an
industrial plant.
2.2. Thermally coupled configuration
A simple schematic diagram of CCR process including the ther-

mally coupled reactors is illustrated in Fig. 3a. Four individual ther-
mally coupled reactors and two regenerators are employed in this
configuration. The right side regenerator burns the deposited coke
on naphtha reforming catalysts and the other regenerator regener-
ates the nitrobenzene hydrogenation catalysts. As can be observed
in the schematic diagram of the thermally coupled reactor (Fig. 3b),
the cross section area is divided into some subsections. Each sub-
section consists of two parts. In one part, the naphtha reforming
reaction occurs and the other one is employed for nitrobenzene
hydrogenation reaction to provide the required heat for naphtha
reforming. The design of TCR is such that the naphtha and nitroben-
zene feeds flow radially through the beds and then enter two sepa-
rate axial collectors. Like the conventional process, the catalysts of
naphtha reforming reaction in TCR move axially through the reac-
tors and transfer from the bottom of one reactor to the top of the
next one. The nitrobenzene hydrogenation catalysts, after leaving
each reactor, are transported to the regenerator and after regener-
ation transported back to the reactor. Table 2 shows the specific
properties and operating conditions of this new configuration.
3. Reaction model
3.1. Endothermic side (naphtha reforming reactions)
Naphtha feedstock is a complex mixture of hydrocarbons with

several hundred components that generally are divided in three
categories of naphthenes, paraffins, and aromatics. Naphthenes
and paraffins constitute the major part of naphtha (typical
straight-run naphtha is made up of 40–70 wt% paraffins and 20–
50% naphthenes). Naphthenes (cycloalkanes) mostly consist of a
hydrocarbon ring with five or six carbon atoms. Paraffins (alkanes)
are the main components of virgin naphtha which are either
Fig. 2. A schematic diagram of conventional reactor (CR). straight-chain (n-paraffins) or branched structures (i-paraffins).
Table 1
Specific properties and operating conditions for the conventional configuration.
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 1.30, 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%
sa 220 m2/g
qB 680 Kg/m2
e 0.36 –
The most desirable components in the naphtha reforming pro- range from about 755–866 K and 5–50 psia [41]. Although, the rate
cess are aromatic components because these components have a of dehydrocyclization is comparatively slow, the conversion of par-
key role in increasing the octane number. In addition, unsaturated affins to aromatics causes a noticeable increase in aromatics con-
aromatics with 6–8 carbon atoms (BTX) are considered as impor- tent. Dehydrocyclization reaction is promoted by the metallic and
tant building blocks for petrochemical industry. Due to the com- acidic sites of catalyst. The isomerization of paraffins, naphthenes,
plexity of naphtha feedstock, which includes several hundred and C8 aromatics has been considered in the present model. Isom-
components undergoing various reactions, presenting a detailed ki- erization reactions are slightly exothermic, moderately rapid, and
netic-based model considering all components and reactions is catalyzed by acidic sites.
infeasible. A proper kinetic model is reported by Padmavathi et al. Alkylcyclopentanes undergo isomerization reaction to produce
[4] that consists of 26 pseudo-components and 46 reactions. The alkylcyclohexanes. This reaction involves a ring rearrangement
presented model in this article is an extension of padmavathi’s and is a desirable reaction due to dehydrogenation of the alkylcy-
model. The 8-carbon aromatics are subdivided in details, also some clohexane into aromatics in the subsequent stage. The naphtha
main relevant reactions of aromatics such as dehydrocyclization of feed consists of more percentage of normal paraffins (40–50%
paraffins to aromatics, isomerization and transalkylation of aro- vol.) compared to isoparaffins (2–5 vol.%) [22]. Since the octane
matics are considered. The added reactions to padmavathi’s model number of isoparaffins is higher than normal paraffins, the isomer-
are marked in the following reaction tables. In the proposed model, ization of normal paraffins to isoparaffins is desirable. For the 8-
the naphtha feedstock has been categorized to naphthenes (alkyl- carbon aromatics, the isomerization reactions between PX (para
cyclohexanes: ACH, alkylcyclopentanes: ACP), paraffins (normal xylene), MX (meta xylene), and OX (ortho xylene) occur rapidly,
paraffins: NP, isoparaffins: IP), and aromatics (A) lumps. In addition, while isomerization between EB (ethylbenzene) and xylene iso-
the considered pseudo-components take part in six reaction cate- mers occurs slowly. Transalkylation is a reaction in which one of
gories such as dehydrogenation, dehydrocyclization, isomerization, the alkyl groups is transferred from one alkyl aromatic molecule
transalkylation, hydrocracking, and hydrodealkylation (84 reac- to another one. It should be mentioned that transalkylation occurs
tions). Dehydrogenation reaction, in which naphthenes convert to mainly in very severe conditions of pressure. An especially desir-
aromatics, is one of the main reforming reactions. Due to its high able pressure range is from about 10 to about 40 atm [42]. The last
reaction rate, it occurs mostly in the first reactor. It is a highly endo- two types of the naphtha reactions (hydrocracking and hydro-
thermic reaction and causes a sharp temperature drop in the first dealkylation reactions) are much slower reactions respect to the
reactor (for more details refer to reference [4]). It is promoted by other ones and produce less valuable products. These reactions
the metallic function of catalysts and is favored at high temperature are exothermic and the reaction rates increase with temperature
and low pressure. Similar to dehydrogenation, dehydrocyclization and pressure increasing. Hydrocracking of naphthenes is less than
reaction is favored at high temperature and low pressure. Preferred that of paraffins, and the amount of aromatics cracking is not con-
temperature and pressure for dehydrocyclization reaction is in the siderable [4]. The cracking of naphthenes and paraffins, as well as
(a)
(b)
Fig. 3. (a) A schematic diagram of thermally coupled naphtha reforming process in CCR mode of operation and (b) a diagram of thermally coupled reactor (TCR).
hydrodealkylation reactions is irreversible. The reaction rates and 3.2. Exothermic side (hydrogenation of nitrobenzene to aniline)
constants are tabulated in Tables 3,4A,4B,4C,5A,5B,6,7A,7B,8. It
should be mentioned that an optimization procedure is utilized Aniline is one of the hundred most important building blocks in
to find the unknown constants of reaction rates. These constants chemistry. This component is utilized in more than 300 different
are determined via simultaneous minimization of the outlet tem- end products. Hydrogenation of nitrobenzene is the predominant
perature, molar flow rate, and coke concentration differences be- production method used by almost entire world producers. The
tween the modeling results and plant data. The proposed hydrogenation of nitrobenzene to aniline is a highly exothermic
network kinetic is presented in Fig. 4. reaction which can proceed along different reaction pathways
Table 2
Specific properties and operating conditions for the thermally coupled configuration.
Parameter 1st Reactor 2nd Reactor 3rd Reactor 4th Reactor

Inner and outer Diameter (m) 1.25, 2.63 1.25, 2.70 1.30, 2.79 1.30, 3.08
Length (m) 10.23 11.90 13.34 16.41
NOS (Number Of Subsection) 20 20 20 20
Rh = h1/(h1 + h2) 0.5 0.6 0.7 0.8
Specific properties and operating conditions for endothermic side
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 –
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
dp 1.8 mm
Pt 0.3 wt%
Sn 0.3 wt%
sa 220 m2/g
qB 680 Kg/m2
e 0.36 –
Specific properties and operating conditions for exothermic side

Composition Numerical value Unit
Nitrobenzene 0.0666 –
Hydrogen 0.2681 –
Aniline 0.0066 –
Steam 0.6587 –
Diameter of catalyst particle 4.7 mm
Catalyst density 1400 Kg/m3
Void fraction 0.46 –
Feed molar flow rate(mol/s) 1041.34 983.95 856.50 750.39
and involves several intermediates. The kinetic and rate expres- functions is shown in Table 10. In order to improve the catalyst
sions of this reaction are tabulated in Table 9 [43,44]. activity, stability, and selectivity, various metals such as Re, Ir,
Rh, Ge, In, and Sn have been added to the metallic function. Pt–
3.3. Catalyst deactivation model in naphtha reforming process Sn catalysts regenerate easily, thus, they are used in the systems
in which the catalyst is regenerated continuously such as continu-
The catalyst of naphtha reforming process is a bifunctional cat- ous catalytic regenerative naphtha reformers [46]. In the catalytic
alyst consists of a metallic function (mainly platinum) and an naphtha reforming process, coke formation is the most important
acidic function (chloride alumina). The metallic function generally reason for catalyst deactivation [47]. Prediction of coke formation
catalyzes the hydrodealkylation and dehydrogenation reactions is a very complex task because this phenomenon depends on var-
and the acidic function mainly promotes the isomerization reac- ious parameters such as temperature [48], pressure [49] and
tions [45]. The other reactions in naphtha reforming process such hydrogen over hydrocarbon ratio [50]. It is worth mentioning that
as hydrocracking or dehydrocyclization occur on either or both of in some investigations alkylcyclopentane concentration is consid-
functions. The occurrence of the considered reactions on catalyst ered as a factor affecting deactivation rate. Tailleur et al. [51] pro-
Table 3
Reaction rate, rate constants, and the heat of dehydrogenation reactions.
ACHn M An + 3H2 r 1n ¼ k1n ðP ACHn

PAn P3H2 (1)
K 1n Þ
Rate constant Unit Equilibrium constant Unit

E
k1n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 1n ¼ exp A TB (kPa)3
E
kJ
DH molH a R
A B
2
C6 68.73 18.75 19.50 59.90 24.80 103

C7 208.47 20.70 19.50 60.23 25.08 103
C8
for An = MXa 64.50 17.89 19.50 60.37 23.27 103
for An = OXa 65.10 19.15 19.50 60.32 23.49 103
for An = PXa 64.74 18.66 19.50 60.13 23.36 103
for An = EBa 68.70 18.71 19.50 60.40 24.78 103
Cþ
9
66.05 20.38 19.50 61.05 21.33 103
a
Added reactions into the Padmavathi et al. [4] model.
Table 4A
Reaction rate, rate constants, and the heat of paraffin dehydrocyclization to alkylcyclohexane reactions.

ACHn + H2 M NPn r 2n ¼ k2n P ACHn P H2 PKNPn (2)
2n

E
k2n ¼ exp a RT 1
kmol kgcat: h
1
kPa
2
E
kJ
DH molH a R
A B
2
C6 43.64 24.37 33.11 9.12 5.24 103

C7 32.85 29.10 33.11 8.95 3.95 103
C8 32.55 27.81 33.11 8.34 3.91 103
Cþ
9
28.00 29.76 33.11 8.12 3.37 103

ACHn + H2 M IPn r 3n ¼ k3n P ACHn P H2 PKIPn (3)
3n

E
k3n ¼ exp a RT 1
kmol kgcat: h
1 2
kPa K 3n ¼ exp A TB (kPa)1
E
kJ
DH molH a R
A B
2
C6 52.00 26.36 33.11 14.35 6.25 103

C7 39.30 25.75 33.11 13.65 4.73 103
C8 49.40 29.00 33.11 13.17 5.94 103
Cþ
9
49.00 29.76 33.11 12.39 5.89 103
⁄
Added reactions into the Padmavathi et al. [4] model.
Table 4B
Reaction rate, rate constants, and the heat of paraffin dehydrocyclization to alkylcyclopentane reactions.

NPn M ACPn + H2 r 4n ¼ k4n P NPn PACPn PH2 (4)
K 4n
E

k4n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 4n ¼ exp A BT kPa
E
kJ
DH molH a R
A B
2
C5a 69.73 30.75 33.11 14.39 8.38 103

C6 60.74 31.94 33.11 14.77 7.31 103
C7 60.75 33.43 33.11 14.63 7.31 103
C8 61.75 31.31 33.11 15.98 7.43 103
Cþ
9
59.00 32.96 33.11 15.21 7.09 103

IPn M ACPn + H2 r 5n ¼ k5n P IPn PACPn PH2 (5)
K 5n
E

k5n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 5n ¼ exp A BT kPa
E
kJ
DH molH a R
A B
2
C5a 76.67 29.83 33.11 16.18 9.22 103

C6 70.60 30.87 33.11 16.03 8.50 103
C7 67.20 32.95 33.11 15.47 8.08 103
C8 78.60 34.19 33.11 16.37 9.45 103
Cþ
9
80.00 32.96 33.11 16.02 9.62 103
a
Added reactions into the padmavathi et al. [4] model.
Table 4C
Reaction rate, rate constants, and the heat of paraffin dehydrocyclization to aromatic reactions.

NPn M An + 4H2 P P4
r 6n ¼ k6n P Npn AnK 6nH2 (6)

E
k6n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
E
kJ
DH molH a R
A B
2
C6a 66.50 16.87 18.86 35.73 7.99 103

C7a 63.20 17.17 18.86 35.21 7.60 103
C8a
for An = MX 56.51 17.32 18.86 34.13 6.79 103
for An = OX 56.95 17.89 18.86 34.21 6.85 103
for An = PX 56.70 17.01 18.86 34.16 6.81 103
for An = EB 59.66 16.96 18.86 34.63 7.17 103
Cþ
9
a 59.29 18.90 18.86 33.56 6.36 103

IPn M An + 4H2 P P4
r 7n ¼ k7n P Ipn AnK 7nH2 (7)

E
k7n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
E
kJ
DH molH a R
A B
2
C6a 68.18 16.44 18.86 36.01 8.20 103

C7a 64.83 16.90 18.86 35.47 7.79 103
C8a
for An = MX 60.73 16.27 18.86 34.81 7.30 103
for An = OX 61.17 16.78 18.86 34.87 7.35 103
for An = PX 60.90 16.04 18.86 34.83 7.32 103
for An = EB 63.88 15.93 18.86 35.23 7.68 103
Cþ
9
a 60.77 17.66 18.86 34.81 7.3 103
a
Table 5A
Reaction rate, rate constants, and the heat of isomerization of naphthene and paraffin reactions.

ACPn M ACHn r 8n ¼ k8n P ACPn PKACHn (8)
8n

E

k8n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 8n ¼ exp A BT –
E
kJ
DH mol a R
A B
C6 17.10 15.11 23.81 5.20 2.06 103

C7 27.90 24.73 23.81 6.63 3.36 103
C8 29.20 25.78 23.81 6.83 3.51 103
Cþ
9
31.00 26.13 23.81 7.16 3.73 103

NPn M IPn r 9n ¼ k9n P NPn PKIPn (9)
9n

E

k9n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 9n ¼ exp A BT –
E
kJ
DH mol a R
A B
C4a 9.23 25.08 26 0.80 1.11 103

C5a 6.94 24.89 26 1.17 0.83 103
C6 9.86 24.70 26 0.69 1.19 103
C7 6.45 24.15 26 1.27 0.76 103
C8 13.95 25.54 26 0.04 1.68 103
Cþ
9
21.00 24.48 26 1.09 2.53 103
a
posed deactivation model in which the rate of deactivation de- where roC is rate of coke formation on fresh catalyst, Ec is coke for-
pends on alkylcyclopentane concentration to the power of 0.5. mation activation energy, CACP is alkyl-cyclopentane concentration,
Based on the accomplished studies, the rate of coke formation and P is pressure of the reaction side.
could be considered as a function of most effective parameters as The obtained relations for deactivation of both metallic and
bellow: acidic functions are tabulated in Table 11, and detailed explanation
E of these relations is provided in Appendix A. Similar to the un-
exp RT c
0:5
r oC / C ACP ð19Þ known constants of kinetic reaction network, the unknown con-
n1 H2 n2
P HC stants of deactivation model are determined via simultaneous
Table 5B
Reaction rate, rate constants, and the heat of isomerization of aromatic reactions.

RMP for n ¼ 1; . . . ; 6 : r 10n ¼ k10n P R KP10n
P (10)

E

k10n ¼ exp a RT 1
kmol kgcat h
1
kPa
1
K 10n ¼ exp A TB –
E
R P kJ
DH mol a R
A B
n = 1a OX PX 10.50 25.21 21.24 12.13 1.26 103

n = 2a OX MX 17.60 24.50 21.24 11.00 2.11 103
n = 3a MX EB 12.60 24.53 21.24 15.81 1.50 103
n = 4a OX EB 10.84 25.17 21.24 15.54 1.30 103
n = 5a EB PX 11.89 25.84 21.24 11.91 1.43 103
n = 6a MX PX 0.71 24.47 21.24 13.7 0.085 103
a
Table 6
Reaction rate, rate constants, and the heat of transalkylation reactions.

2R M P + C for n ¼ 7; 8 : r 11n ¼ k11n P 2R PKP11n
PC (11)

E

k11n ¼ exp a RT 1
kmol kgcat h
1 2
kPa K 11n ¼ exp A TB –
E
R P C DH kJ a R
A B
mol
n = 7a T B PX 16.20 16.68 21.24 16.41 1.95 103

n = 8a OX T A9+ 09.16 15.48 21.24 15.28 1.10 103
a
Table 7A
Reaction rate, rate constants, and the heat of cracking of paraffin reactions.

for n = 2: P2 + H2 ? 2P1 r 12n ¼ k12n PNPn (12)
Pt
for n = 3: P3 + H2 ? P1 + P2
for n ¼ 4 : NP 4 þ H2 ! 23 ðP 3 þ P 2 þ P 1 Þ
for n ¼ 5 : NP 5 þ H2 ! 12 ðNP4 þ P 3 þ P 2 þ P 1 Þ Rate constant Unit
P5 E
1 1
for n ¼ 6 9 : NP n þ n3
3 H2 ! 15
n
i¼1 P i
k12n ¼ exp a RT kmol kgcat h
E
DH molH kJ a R
2
C2a 65.20 37.85 34.61

C3a 53.60 39.95 34.61
C4a 49.50 40.15 34.61
C5a 47.80 41.60 34.61
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 ¼ 4 : IP 4 þ 32 H2 ! 12 ð3P 1 þ P 2 þ P 3 Þ r 13n ¼ k13n PIPn (13)
Pt
for n ¼ 5 : IP 5 þ H2 ! 12 ðIP 4 þ P 3 þ P 2 þ P1 Þ Rate constant Unit

P5 E
1 1
for n ¼ 6 9 : IP n þ n3
3 H2 ! 15
n
i¼1 P i
E
DH kJ a R
molH2
C4a 40.30 36.15 34.61

C5a 45.30 41.57 34.61
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
a

minimization of the outlet temperature, molar flow rate, and coke EA;Ca Pm1
concentration differences between the modeling results and plant
r0Ca ¼ kCa;0 exp NB
m2
exp kdea;Ca C Exo
Ca ð35Þ
RT PH2
data.
Exo
0
a ¼ exp kdea1;H C Ca for C Exo
Ca 6 0:2% ð36Þ

3.4. Deactivation kinetic in hydrogenation of nitrobenzene to aniline a0 ¼ exp kdea2;H C Exo
Ca for 0:2% 6 C Exo
Ca 6 0:4% ð37Þ

Exo Exo
Deactivation kinetic in the hydrogenation of nitrobenzene to a0 ¼ exp kdea3;H C Ca for C Ca P 0:4% ð38Þ
aniline is adopted from Amon et al. [43]:
Table 7B
Reaction rate, rate constants, and the heat of cracking of naphthene reactions.
P5
ACHn þ 3n H2 ! 15
n PACHn (14)
i¼1 P i r 14n ¼ k14n Pt
Rate constant Unit
E
1 1
E
DH kJ a R
molH2
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

for n ¼ 5 : ACP 5 þ 2H2 ! 12 ðNP 4 þ P 3 þ P 2 þ P 1 Þ r 15n ¼ k15n PACPn (15)
Pt
Rate constant Unit
P5 E
1 1
for n ¼ 6 9 : ACP n þ 3n H2 ! 15
n
i¼1 P i
E
DH kJ a R
molH2
C5a 68.74 40.23 34.61

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
a
Table 8
Reaction rate, rate constants, and the heat of hydrodealkylation reactions.
An+1 + H2 ? Ak + CmH2m+2 r 16n ¼ k16n P Anþ1 P 0:5 (16)

H2
Rate constant Unit
E
1 1 1:5
k16n ¼ exp a RT kmol kgcat h kPa
E
m k DH kJ a R
molH2
C7 1 n 41.81 7.64 17.92

C8
for An+1 = PX 1 n 42.32 5.57 17.92
for An+1 = EBa 2 n1 20.02 5.55 17.92
Cþ
9
for Ak = OX 1 n 52.57 8.91 17.92
for Ak = Ta 2 n1 30.80 5.57 17.92
a
where C Exo 0
Ca is the coke weight fraction on active sites, a is the activ- Diffusion of mass and heat in both radial and axial directions of
ity of catalysts, and r 0Ca is the rate of coke formation on active sites. reactor is neglected.
The required constants for calculating the deactivation rate is tabu- Intra-pellet heat and mass diffusions in catalyst pellet are
lated in Table 12. ignored.
Homogeneous catalyst moving bed is considered.
4. Mathematical modeling
By applying these assumptions, the mathematical modeling of
To develop the mass and energy balance equations, a two– this process is summarized in Table 13. Also, more details of this
dimensional (radial and axial directions) model has been taken mathematical model are described in Appendix B.
into consideration. In the modeling procedure, the heat and mate-
rial balance equations are made over an element of the reactor
with the length of Dz and the thickness of Dr (see Fig. 5). Then 5. Numerical solution
these equations are combined with the deactivation model, Erguan
equation, thermodynamic and kinetic relations, which are defined As the obtained governing equations and auxiliary relations in
as the auxiliary correlations, to predict the behavior of reforming the modeling procedure are partial differential equations (PDEs),
process. The following assumptions are taken into account: an appropriate method should be employed in order to solve this
PDEs system. In this study, forward finite difference approximation
Steady state condition is considered. is applied due to its accurate and ease of implementation. In this
Ideal gas law is applicable (Due to high temperature). method, the reactor is divided into a series of nodes in which deriv-
Heat loss is negligible. atives in differential equations become difference equations for
Peripheral gradient (gradient along the perimeter) is neglected. each node. The boundary conditions of process are utilized for ini-
Cross flow pattern (catalyst moves axially downward and the tial node of the reactor and its result is used as boundary condi-
gas stream moves radially) is considered in the both sides of tions for the following one. This procedure is repeated for the all
reactors. nodes of reactor to obtain the final solution.
r69
r29 r19
n-P9+ ACH9+ A9+
r49 r 39
r99
r89
i-P9+ r59
ACP9+
r79
r18-4 r118
r68-1 r68-2
2OX
r18-2
r28 r18-1 r102 r169-1
n-P8 ACH8 MX OX
r48 r 38 r106 r 104
r103
r98
r101
r88
r58 r78-4 r68-4 r105
i-P8 ACP8 EB PX
r68-3
r78-1
r78-3
r78-2 r18-3
r117
2T
r67
r27 r17 r168-1 r169-2

n-P7 ACH7 T
r47 r 37
r97
r87
i-P7 r57
ACP7 r77
r66
r16 r168-2 r167
B
r26
n-P6 ACH6
r46 r 36
r86
r96
i-P6 r56
ACP6
r76
r55 i-P5
CP
r 95
r45
r129 r139 r128 r138 r127 r137 r126 r136 r156 r146 r157 r147 r158 r148 r159 r149
n-P5
r94 r135
i-P4
r129 r139 r128 r138 r127 r137 r126 r136 r155 r125 r156 r146 r157 r147 r158 r148 r159 r149
n-P4
r129 r139 r128 r138 r127 r137 r126 r136 r155 r125 r124 r134 r135 r156 r146 r157 r147 r158 r148 r159 r149
P3
r123
r129 r139 r128 r138 r127 r137 r126 r136 r155 r125 r124 r134 r135 r156 r146 r157 r147 r158 r148 r159 r149 r168-2 r169-2
P2
r122
r129 r139 r128 r138 r127 r137 r126 r136 r155 r125 r124 r134 r135 r156 r146 r157 r147 r158 r148 r159 r149 r176 r168-1 r169-1
P1
Fig. 4. Proposed reactions network for catalytic reforming of naphtha.
Table 9
Reaction rate, rate constants, and the heat of hydrogenation of nitrobenzene to aniline reaction [43].
C6H5NO2 + 3H2 ? C6H5NH2 + 2H2O (17) k0 K NB K H2 PNB P H2

0:5
(18)
r0 ¼ 0:5 2
ð1þK NB PNB þK H2 P H2 Þ
DH = 443 kJ/mol
Rate constant Unit Equilibrium constants Unit

0 E0
k ¼ A0 exp RT 0 mol kgcat s1
1 KNB = 1.510 105 Pa1
A0 = 0.186 E0 = 10 (kJ mol1) K H2 ¼ 4:427 103 Pa0.5
Table 10
Catalyst functions on the main reactions in the proposed kinetic model (metallic (M) & acidic (A) functions).
Reaction no. Reactions Agent Reaction no. Reactions Agent

r1n ACHn M An + 3H2 M r9n NPn M IPn A
r2n ACHn + H2 M NPn M+A r10n RMP A
r3n ACHn + H2 M IPn M+A r11n 2R M P + C M
r4n NPn M ACPn + H2 M+A r12n P5 M or A
NPn þ ðn3 Þ
3 H2 ! 15
n
i¼1 P i
r5n IPn M ACPn + H2 M+A r13n ðn3Þ n
P5 M or A
IP n þ 3 H2 ! 15 i¼1 P i
P5
r6n NPn M An + 4H2 M+A r14n ACHn þ 3n H2 ! 15n M or A
i¼1 P i
P 5
r7n IPn M An + 4H2 M+A r15n ACP n þ 3n H2 ! 15
n M or A
i¼1 P i
r8n ACPn M ACHn A r16n An+1 + H2 ? Ak + CmH2m+2 M
Table 11
Catalyst deactivations model for endothermic reaction side.
(20)
8
> Reaction occurs on acid function ai ¼ aA
>
>
< Reaction occurs on metal function ai ¼ aM
r i ¼ ai r oi
>
> Reaction occurs on acid or metal function ai ¼ meanðaA ; aM Þ
>
:
Reaction occurs on acid as well as metal functions ai ¼ meanðaA ; aM Þ
Reaction occurs on metal function Reaction occurs on acid function

ri ¼ aM r oi (21) r i ¼ aA r oi (22)
daM
dC C
¼ aM anMM (23) daA
dC C
¼ aA anAA (24)
8 M 8 A
< nM ¼ 1 aM ¼ expðaM C C M Þ
> (25) < nA ¼ 1 aA ¼ expðaA C C A Þ
> (26)
nM –1 aM ¼ 1 nA –1 aA ¼ 1
>
: 1
n 1
>
: 1
n 1
ð1þðn 1Þa C Þ M M M CM ð1þðn 1Þa C Þ A
A A CA
rC M ¼ aC M r oC M (27) r C A ¼ aC A r oC A (28)
daC nC (29) daC nC (30)
dC CM ¼ aC M aC MM dC CA ¼ aC A aC AA
8 M 8 A
< nC M ¼ 1 aC M ¼ expðaC M 1 C C M Þ
> (31) < nC A ¼ 1 aC A ¼ expðaC A 1 C C A Þ
> (32)
nC M –1 aC M ¼ nC A –1 aC A ¼
>
: n
1
1
>
: n
1
1
ð1þðn 1Þa C Þ C M
CM CM CM ð1þðn 1Þa C Þ C A
CA CA CA
kC M exp ðERTc Þ (33) Ec

kC A exp ðRT Þ (34)
roC M ¼ H n2 C 0:5
ACP r oC A ¼ H n2 0:5
C ACP
P n1 2
HC Pn1 2
HC
the experimental and the predicted data from the model for CR. As
Table 12 can be observed, the model performed satisfactorily well under the
Required constants for calculating catalyst deactivation rate and activity in exother-
case of industrial conditions and the predicted results do not devi-
mic reaction side.
ate from the experimental results significantly. Thus, it could be
Parameter Value Unit concluded that the mathematical model is able to predict the re-
kdea1,H 461 – sults appropriately.
kdea2,H 327 –
kdea3,H 574 –
kdea,Ca 4325 – 7. Result and discussion
kCa,0 242.5 kPa
ðm2 m1 Þ
s
EA,Ca 37.1 kJ
mol
In this section, the results of the mathematical modeling of
m1 1.42 – thermally coupled configuration are illustrated in the following
m2 0.45 – plots. The variation of components molar flow rate, operating con-
ditions, and physical properties along the radial and axial direc-
tions of moving bed reactors are investigated. In the 2D plots, the
d
variation of parameters along one of the radial or axial directions
fee is shown by considering an average value of the parameters along
htha
ap the other direction. For some parameters, 3D plots are employed in
ln
dia
Ra order to show their variations along the axial and radial coordi-
Endothermic nates simultaneously. This section is divided into two subsections.
side Catalyst One discusses the variation of parameters in the endothermic side
particle
r of coupled reactors (naphtha reforming process) and another is
ed
e fe about the parameters variation in the exothermic side (nitroben-
zen
t roben zene hydrogenation).
ia l ni
Rad
Exothermic side 7.1. Endothermic side of coupled reactor
Catalyst particle
Since the operating pressure and the temperature have a signif-

icant role in the activity of catalyst, the yield and quality of refor-
z
mate, they are investigated first. The temperature profiles of the

conventional and thermally coupled reactors are depicted in
Fig. 6a, simultaneously. In the first reactor of both conventional
and coupled configurations, temperature decreases sharply due
to presence of the fast endothermic reactions (dehydrogenation
of naphthenes to aromatics). In the coupled reactor, lower temper-
ature drop (12.8 K) can be seen because of heat transfer from the
Fig. 5. A differential element for mass and energy balances. exothermic side to the endothermic side. In the second reactors
of both configurations, a lower temperature drop is seen in com-
6. Model validation parison with the first ones. Since the amount of naphthenes de-
creases as the feedstock passes through the reactors (229.8 kmol/
The obtained data from conventional model is compared to h reduction for CR and 251.1 kmol/h reduction for TCR), the rate
plant data in order to check the validity of model. Table 14 presents of dehydrogenation (an endothermic reaction) in the second reac-
Table 13
Mass and energy balances and auxiliary relations for the thermally coupled configuration.
Mass balance (Endothermic Reaction side)

(39)
@C j C j C j @ur qb X m
j ¼ 1; 2; . . . ; n
¼ þ ai mij ri
@r r ur @r ur i¼1 i ¼ 1; 2; . . . ; m
Mass balance (Exothermic Reaction side)

(40)
@C Exo
j C Exo
j C Exo
j @uExo
r qExo
¼ Exo b
þ Exo ða0 mj r0 Þ j ¼ 1; 2; . . . ; n0
@r r ur @r ur
Energy balance (Endothermic Reaction side)

(41)
@T qb X
m
NOS
¼ ðDHi ai r i Þ þ U ðT Exo TÞ
@r ur C T C P i¼1
pr Rh ur C T C P
Energy balance (Exothermic Reaction side)

(42)
Exo Exo
@T q NOS
¼ b
Exo Exo
ðDHExo a0 r 0 Þ þ U ðT T Exo Þ
@r uExo
r CT CP pr ð1 Rh Þ uExo
r C Exo Exo
T CP
Velocity distribution (Endothermic Reaction side)

(43)
@ur ur ur @C T qb X n X m
¼ þ ai mij r i
@r r CT @r C T j¼1 i¼1
Velocity distribution (Exothermic Reaction side)

(44)
n0
Exo X
@uExo
r uExo
r uExo
r @C Exo
T q b
¼ þ ða0 mj r0 Þ
@r r C Exo
T
@r Exo
C T j¼1
Mass and energy balance for Collector (Endothermic Reaction side)

(45)
@F j p Ri
@z
¼ 2NOS ure C je Rh j ¼ 1; 2; . . . ; n

1 2pRi 2pRi @C P
@T
@z
¼ F T CP
NOS
C Te ure Rh C pe ðT e TÞ FTT NOS
ure Rh C Te CTP @z
Mass and energy balance for Collector (Exothermic Reaction side)

(46)
@F Exo pRi Exo

j
@z
¼ 2NOS uExo
re C je ð1 Rh Þ j ¼ 1; 2; . . . ; n0
Exo Exo

Exo C Te ure 2pRi Exo Exo Exo T Exo 2pRi Exo Exo Exo @C Exo
@T
@z
¼ F Exo C Exo NOS ð1 Rh Þ C Pe T e T F Exo NOS
u re ð1 R h ÞC Te CT Exo @z
P
T P T P
Ergun equation (Pressure drop)

(47)
2
dP 150l ð1 eÞ 1:75q ð1 eÞ 2
¼ 2 2 ur þ ur
dr /s dp e3 /s dp e3
Additional relation
(48)
h1
Rh ¼
h1 þ h2
Table 14
Comparison between predicted molar flow rate in conventional configuration and plant data (steady-state model validation).
Pseudo components Molecular weight Input plant (mole fraction) Output plant (kmole/h) Output model (kmole/h) Deviation (kmole/h)
n-P6(C6H14) 86.178 0.0229 71.84 70.98 0.86
n-P7 (C7H16) 100.205 0.0292 46.65 46 0.65
n-P8(C8H18) 114.232 0.0239 8.1 7.63 0.47
n-P9(C9H20) 128.259 0.0156 1.15 1.25 0.1
i-P6(C6H14) 86.178 0.0232 216.06 216.06 0
i-P7 (C7H16) 100.25 0.0314 110.18 109.69 0.49
i-P8(C8H18) 114.232 0.0338 22.75 22.67 0.08
i-P9(C9H20) 128.259 0.0244 1.79 1.95 0.16
ACH6 (C6H12) 84.162 0.0077 0.51 0.92 0.41
ACH7 (C7H14) 98.189 0.0084 0.92 1.43 0.51
ACH8 (C8H16) 112.216 0.0115 2.33 2.34 0.01
ACH9 (C9H18) 126.243 0.0018 0.04 0.05 0.01
ACP5 (C5H10) 70.135 0.0001 2.14 2.11 0.03
ACP6 (C6H12) 84.162 0.003 26 26.02 0.02
ACP7 (C7H14) 98.189 0.0065 2.33 3.12 0.79
ACP8 (C8H16) 112.216 0.0084 0.6 0.6 0
ACP9 (C9H18) 126.243 0.0012 0.01 0.02 0.01
A6 (C6H6) 78.114 0.0086 205.84 206.39 0.55
A7 (C7H8) 92.141 0.0109 453.93 454.33 0.4
A8 (C8H10) 106.168 0.0021 163.02 163.47 0.45
A9 (C9H12) 120.195 0.0026 323.66 324.46 0.8
A8 (C8H10) 106.168 0.0015 113.62 113.4 0.22
A8 (C8H10) 106.168 0.0016 120.84 121.55 0.71
A8 (C8H10) 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 (C2H6) 30.07 0.0231 399.16 397.72 1.44
P3 (C3H8) 44.097 0.0202 352.36 351.69 0.67
P4 (C4H10) 58.124 0.0106 189.21 189.93 0.72
P5 (C5H12) 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
1800
Aromatic molar flow rate (kmol/h)
(a) 1600 CR
TCR
Endothermic side temperature (K)
790
1400
780
1200
770
760 1000
750 800
740
600
730
400
720
CR
710 TCR 200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
700 Radius of reactor (Dimensionless)
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. 7. Aromatic molar flow rates vs. the radius of conventional and thermally
coupled reactors.
(b) 600
11000
Endothermic side pressure (kPa)
580 CR
Hydrogen molar flow rate (kmol/h)
TCR CR
560 10000 TCR
540 9000
520
8000
500
480 7000
460 6000
440
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 5000
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. 6. (a) Temperature and (b) pressure profile of endothermic side for the TCR and
CR. Fig. 8. Hydrogen molar flow rate of CR and TCR.
35
(a)
450 CR
Naphthene molar flow rate (kmol/h)
Molecular weight (kg/kmol)

TCR
400 CR
TCR
350 30
300
38
250
36
200 34 25
150 32
30
100 0.96 0.98 1
50 20
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
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. 10. A comparison between mean molecular weight of components along the
(b) 2000 radius of TCR and conventional reactors.
Paraffin molar flow rate (kmol/h)
CR
1800 both CR and TCR endothermic sides. The pressure drop in TCR is
TCR
higher than CR mainly owing to the design of coupled reactor in
1600
which the radius of coupled reactors is longer than that of conven-
1400 tional ones, so the feed has to pass longer distance and higher pres-
1200 sure drop appears. The sudden pressure drops during the passage
of stream through the reactors are due to piping and utilizing inter-
1000 mediate instruments such as furnaces.
800 The aromatic molar flow rate vs. the dimensionless radius of CR
and TCR is depicted in Fig. 7. The value of aromatic molar flow rate
600
increases as the stream passes through the radius of reactors which
400 is due to aromatic producing reactions such as dehydrogenation
and dehydrocyclization of paraffins to aromatics. As shown in the
200
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 plot, higher aromatic production can be obtained in TCR configura-
Radius of reactor (Dimensionless) tion (92 kmol/h) and consequently, high octane gasoline can be
produced in this configuration. In the first two reactors, the rate
(c) 2000 of aromatics production is higher than that of the last two ones
owing to the dehydrogenation of naphthenes to aromatics. When
Light end molar flow rate (kmol/h)
CR
TCR
the heat is transferred from the exothermic side to the endother-
1800
mic side, the yield of naphthenes dehydrogenation reaction in-
creases; therefore, more aromatics can be obtained in
1600
comparison with the conventional system.
As previously discussed hydrogen is a main by-product in the
1400
naphtha reforming process which its molar flow rate increases
along the radius of reactors. One of the other main benefits in
1200
the application of TCR is upgrade of hydrogen production in the
process. According to Fig. 8a, the hydrogen production in TCR is
1000
190 kmol/h more than the one in CR. In TCR, more heat is available
for endothermic reactions such as dehydrogenation and dehydro-
800 cyclization that produce hydrogen; therefore, these reactions yield
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
increases compared to conventional configuration and more
hydrogen can be obtained.
Fig. 9. (a) Naphthene, (b) paraffin, and (c) light end molar flow rates vs. the radius The naphthenes, paraffins, and light ends molar flow rates are
of conventional and thermally coupled reactors. illustrated in Fig. 9a-c. Naphthenes and paraffins constitute the
main part of naphtha. Since dehydrogenation of naphthene is the
tors is lower than the first ones. This causes a lower temperature major source of aromatic production and octane number enhance-
drop in the second reactors. Owing to heat transfer, the lower tem- ment, naphthenes play a very important role in naphtha reforming
perature drop in TCR is reasonable. In the last two reactors, dehy- process.
drocyclization of paraffins to naphthenes and dehydrogenation of Fig. 9a presents the molar flow rate of naphthenes along the ra-
naphthenes to aromatics, which are endothermic reactions, decline dius of conventional and thermally coupled reactor. Since naphth-
the reactors temperature but by increasing the degree of hydro- enes are consumed in the naphtha reforming process, their molar
cracking and hydrodealkylation as the exothermic and slow reac- flow rates decline along radius of reactors. By coupling nitroben-
tions which take place mostly in the last two reactors, this zene hydrogenation with naphtha reforming reaction, more heat
temperature drop is moderated. In the last two coupled reactors is available for the dehydrogenation of naphthens which is endo-
the temperature increases due to the heat transfer from exother- thermic and its yield increases by consuming more heat. As well,
mic side to the endothermic side. Therefore, the temperature drop hydrocracking as another naphthene consumer reaction is favored
in TCR is lower than that of CR (18.6 K for the third reactor and at high temperature; therefore, the highest conversion of naph-
27.2 K for the fourth one). Fig. 6b shows the pressure profile of thene is observed in TCR which operates at higher temperature.
5
(a) Total
H2 / HC molar ratio (kmol/kmol)

CR
/kg cat )
4.5 TCR
0.06
coke
0.05 4
Coke weight fraction ( kg
0.04
0.03 3.5
0.02
3
0.01
0 2.5
1
0.8 1
0.8
Metallic function 0.6 0.6 2
0.4 0.4 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Acidic function
0.2 0.2
0 0
Length of reactor (Dimensionless) Radius of reactor (Dimensionless)
Fig. 12. H2/HC molar ratio vs. the radial coordinates of both CR and TCR.
(b) 180
Alkylcyclopentane molar flow rate
160 CR 900
TCR
Exothermic side temperature (K)

140 880
33 860
120
(kmol/h)
32 840
100 31
30 820
80
29 800
60 28
0.96 0.98 1 780
40 760
20 740
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
720
Radius of reactor (Dimensionless) 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
(c)
Fig. 13. Temperature profile for exothermic side of TCR.
Metallic function
1
yield of hydrocracking reaction is higher in TCR due to higher oper-
Catalyst activity
0.9 ating temperature.

0.8 Fig. 10 shows a comparison between the mean molecular
weight of components along the radius of reactors in the both con-
0.7
figurations, as an important physical property in the reforming
0.6 process. Because of production of light components such as hydro-
0.5
gen and light ends during the process, mean molecular weight of
1 components in TCR and CR plots show a decreasing trend. As can
0.8
0.6
1 be observed, mean molecular weight in TCR is lower than CR, be-
0.8
Acidic function 0.4 0.6 cause in this configuration the reactions progress further and con-
0.2 0.4
0 0
0.2 sequently, the production of hydrogen and light components
Length of reactor (Dimensionless) Radius of reactor (Dimensionless) increase greatly.
One of the main parameters in catalytic reforming is the coke
Fig. 11. (a) Coke weight fractions along the length and radius of the thermally
formation over the catalyst during the process. The coke weight
coupled reactor for both acidic and metal functions, (b) ACP concentration vs. the
radius of CR and TCR, and (c) activity of catalysts for TCR. fraction along the length and radius of the coupled reactors for
acidic and metallic functions, as well as the total coke weight frac-
tion are demonstrated in Fig. 11a. As can be seen, during the pro-
Fig. 9b depicts and compares the molar flow rate of paraffins along cess the trend of coke deposition is ascendant in the axial
the radius of reactors. As seen, the paraffins molar flow rate de- direction. Along the radius of reactors, unlike the axial direction,
clines continuously (1324.8 kmol/h for CR and 1489.8 kmol/h for coke deposition declines. As previously discussed, temperature,
TCR) along the radius of reactors due to dehydrocyclization and alkylcyclopentane concentration, the ratio of hydrogen over hydro-
hydrocracking reactions. In TCR, more heat is accessible which carbon and pressure determine the behavior of coke formation. In
drives the dehydrocyclization toward consuming more paraffins. the radial direction, temperature and alkylcyclopentane concentra-
On the other hand, hydrocracking is favored at high temperature tion decrements (see Fig. 6a and Fig. 11b) and the ratio of H2/HC
and it can progress further in TCR which has a higher operating increment lead to reduction of coke formation rate. Although pres-
temperature. Thus, its plot has a lower position in comparison with sure decreasing tries to compensate some amount of this decline,
CR. Fig. 9c illustrates the light ends variation along the radius of the reducer factors are more effective. Along the length of the reac-
reactors. The value of light ends production increases as the stream tors, coke deposition increases because when the catalyst pellets
passes through the radius of reactors due to light ends producing moves axially, they are coked continuously owing to reactions pro-
reactions such as hydrocracking of naphthenes and paraffins. The gress. It is worth mentioning that the amount of coke deposition in
the inlet of one reactor is different from the outlet of the previous
one. This difference is due to the fact that the catalyst pellets is
transported by gas lift. At the end of reactors, the catalyst pellets
have different coke content depending on their distance from the
Production (mol/s)
collector. When these pellets with different coke deposition are
mixed together, the use of an average amount of coke weight frac-
tion in the inlet of the next reactor is reasonable. Fig. 11c shows the
activity of catalysts during the process. Due to inverse relation be-
tween the coke deposition and catalyst activity, an inverse trend
for activity of the catalysts can be seen.
One of the other determinant parameter in the naphtha reform-
ing process is the hydrogen over hydrocarbon molar ratio. The vari-
ations of H2/HC molar ratio vs. the radial coordinate of both CR and First reactor Second reactor Third reactor Fourth reactor
TCR is depicted in Fig. 12. H2/HC is a controlling parameter in
naphtha reforming process. The low value of this ratio causes more Fig. 15. Aniline and steam total production in the coupled reactors.
coke deposition on the surface of catalyst. As seen, the H2/HC molar
ratio increases by reaction proceeding due to increasing the hydro-
gen production. In TCR, owing to higher production of hydrogen, spot appears in lower temperature. The reason of this issue is
H2/HC ratio is higher than CR. due to the difference between the inlet feed of exothermic side.
The inlet feed decreases from reactor to reactor. In the first reactor
higher amount of feed enters; thus, more heat is generated and the
7.2. Exothermic side of coupled reactor reactor temperature increases extremely. As can be observed in the
plot, owing to higher progress of naphtha reactions in first reactor
Fig. 13 illustrates the temperature profile of exothermic side of its temperature profile compared to the others decreases more.
coupled configuration. As seen, all of the plots have an increasing As previously discussed, one of the main goals of coupling
trend before decreasing one. At first, the heat is generated, but it naphtha reforming process and nitrobenzene hydrogenation is ani-
does not have a sufficient time to be transferred; therefore, the line production. Fig. 14a and b shows the variations of aniline and
temperature increases firstly. Then, a peak of temperature profile steam molar flow rates vs. radius of coupled reactors. At the first
(hot spot) appears where the transfer heat is equal to the generated part of reactor, the production rates of aniline and steam are high-
heat. After that, by increasing the heat transfer the reactor temper- est due to high rate of reaction. As the reaction proceeds, owing to
ature decreases. From the first reactor to the fourth one, the hot the decrease in reactants, their rate decreases and consequently,
lower quantity of aniline and steam are produced. From one reac-
(a) 70 tor to the next one, their contents declines owing to the difference
between the inlet amounts of exothermic side feed.
Aniline molar flow rate (mol/s)
60 The production quantity of exothermic side products is illus-

trated in Fig. 15. As mentioned in the previous part, the highest
50 amount of aniline and steam is obtained in the first reactor due
to presence of higher reactants content.
40
30 8. Conclusion
20 In this study, a new configuration for CCR technology in the

naphtha reforming process is proposed via utilizing couple tech-
10
nique to boost aromatics and hydrogen productions. Increasing
0
aromatics content can improve the efficiency of reformers. In the
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 thermally coupled reactors, naphtha reforming is coupled with
Radius of reactor (Dimensionless) nitrobenzene hydrogenation. To simulate the thermally coupled
reactor, a two dimensional mathematical model in the radial and
(b) 800 axial directions is accomplished and a new reaction network is pro-
posed. In the modeling procedure, deactivation of catalysts in the
750 both exothermic and endothermic sides is taken into account. As
Steam molar flow rate (mol/s)
the naphtha catalyst is a bifunctional catalyst, both acidic and

700 metallic functions are considered. The modeling results show
about 92 and 190 kmol/h increase in the aromatics and hydrogen
650 molar flow rates, respectively. Due to aromatics increment and
lower heat load of the furnace, as well as aniline production utiliz-
600 ing thermally coupled reactor is given priority.
550 Appendix A
500
A.1. Developing of catalyst deactivation model for endothermic
reaction side
450
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Rate of reaction i in the endothermic reaction side based on
activity of catalyst and the endothermic reaction rate on the fresh
Fig. 14. Aniline and steam molar flow rates in TCR exothermic side. catalyst can be presented as follows:
r i ¼ ai r oi ðA:1Þ Thus, the coke weight fraction on the metallic function (C CM Þ de-
pends on the rate of coke formation on the metallic function of
where ai is define as:
8
spent catalyst (rC M Þ and catalyst velocity (uz). r C M is defined as:
> Reaction occurs on acidic function ai ¼ aA
>
> rC M ¼ aC M r oC M ðA:12Þ
< Reaction occurs on metallic function ai ¼ aM
>
>
> Reaction occurs on acidic or metallic function ai ¼ meanðaA ; aM Þ where r oC M
is rate of coke formation on metallic function of fresh cat-
:
Reaction occurs on acidic as well as metallic functions ai ¼ meanðaA ; aM Þ alyst which is defined by:
E
kCM exp RTc
Thus, the reaction rate that is catalyzed by metallic function could roC M ¼
n1 H2 n2
C 0:5
ACP ðA:13Þ
be written as: P HC
r i ¼ aM r oi ðA:2Þ In addition, aC M could be calculated by:
Metallic function activity is a function of weight fraction of depos- daCM nC

¼ aC M aCMM ðA:14Þ
ited coke on metallic function of the catalyst. Thus aM is defined as dC C M
follows:
nCM and aC M , like unknown constants in Eq. (A.3), is determined via
daM minimization of plant data and modeling output. With integration
¼ aM anMM ðA:3Þ
dC CM from Eq. (A.14), we have:
8
where aM is a constant and nM is a power number of metallic func- < If nCM ¼ 1 aC M ¼ expðaC M C C M Þ
>
tion activity. aM and nM is determined via minimization of plant If nCM –1 aC M ¼ 1 ðA:15Þ
data and modeling output. Then with integration of recent equa- >
: 1
nC 1
ð1þðnC 1ÞaC C C Þ M
tion, we have: M M M
8 By substituting Eqs. (A.15) and (A.13) in Eq. (A.12) the rate of coke
< If nM ¼ 1 aM ¼ expðaM C CM Þ
>
formation on the metallic function is calculated. Then by substitut-
If nM – 1 aM ¼ 1 ðA:4Þ
> ing coke formation rate in Eq. (A.11), coke weight fraction on the
: 1
nM 1
ð1þðnM 1ÞaM C C Þ
M metallic function (C C M Þ could be calculated. With same procedure,
reaction rates that are catalyzed by acidic site could be achieved.
In order to calculate C CM the mass balance for coke on metallic func-
The results are shown in Table 11. In addition,required constants
tion should be written. In order to achieve this end, following trend
to calculate catalyst deactivation rate and activity are presented
is applied:
in Table A.1.
Coke balance on the metallic function for one part of endother-
mic reaction side is considered as:
Appendix B
2pr
F C M jz F CM jzþdz þ rC M qb Rh dr dz
NOS B.1. Developing of governing equations
¼0 ðA:5Þ
Here the derivations of mass and energy balances, and velocity
In the above equation Rh is defined as: distribution are presented.
h1
Rh ¼ B.1.1. Mass balance in the endothermic reaction side
h1 þ h2
The mass balance for a control volume with length of dz and
By considering the Taylor’s extension, the above equation becomes: cross section area of below formula is:

@F C M 2pr 2pr
¼ rC M qb Rh dr ðA:6Þ Cross section area : dr Rh
@z NOS NOS
where F C M and r C M , are the mass flow rate of coke and the rate of
coke formation on the metallic function of catalyst. In addition,
Table A.1
F C M can be defined as:
Required constants for calculating catalyst deactivation rate and activity in endo-
_ Cat:
F CM ¼ CCM m ðA:7Þ thermic reaction side.
Parameter Value Unit

Mass flow rate of catalyst is defined by:
nM 1 –
2pr aM 26 kgcat:
_ Cat: ¼ qb
m Rh dr uz ðA:8Þ kgcoke
NOS nC M 1 –
By substituting the above equation in Eq. (A.7): aCM 12.34 kgcat:
kgcoke
nA 1 –
2pr aA
F C M ¼ C C M qb Rh dr uz ðA:9Þ 14.5 kgcat:
kgcoke
NOS nC A 1 –
Then, the Eq. (A.9) is replaced in the Eq. (A.6): aCA 10.18 kgcat:
kgcoke
kC M 0.384 kgcoke ðkPaÞn1 m1:5
@C C M kgcat: ðkmolÞ0:5 h
uz ¼ rCM ðA:10Þ kC A 1.386 kgcoke ðkPaÞn1 m1:5
@z kgcat: ðkmolÞ0:5 h
Ec 4055 J
By rearranging above equation, we have: mol
n1 0.94 –
@C C M r C M n2 1.33 –
¼ ðA:11Þ
@z uz
Input—Output þ Production—Consumption ¼ Accumulation ðB:1Þ The first term can be written as:
Xm
@nj j ¼ 1;2;...;n 1 @ ur C j @Ar @C j @ur
ðNj Ar Þjr ðNj Ar Þjrþdr þ qb ai v ij ri Ar dr ¼ ðAr ur C j Þ ¼ ur Cj
@t i ¼ 1; 2;...; m Ar @r Ar @r @r @r
i¼1
ðB:2Þ
ur C j @C j @ur
¼ ur Cj ðB:15Þ
r @r @r
In the mentioned equation, j and i refer to number of component
By substitution of the new style of first term,
and reaction, respectively. Also nj is the mole of component j in
ur C j @C j @ur Xm
j ¼ 1; 2; . . . ; n
the control volume. ur Cj þ qb ai mij ri ¼ 0
By writing the Taylor’s extension of second term in the left hand r @r @r i¼1
i ¼ 1; 2; . . . ; m
of equation, the mass balance becomes: ðB:16Þ
@ðNj Ar Þ Xm
@nj
dr þ qb ai v ij r i Ar dr ¼ ðB:3Þ And finally the mass balance becomes as follows:
@r @t
i¼1 @C j C j C j @ur qb X m
j ¼ 1; 2; . . . ; n
¼ þ ai mij r i ðB:17Þ
Now the mass balance equation is divided by the Ar dr. @r r ur @r ur i¼1 i ¼ 1; 2; . . . ; m
1 @ðNj Ar Þ Xm
1 @nj
þ qb ai v ij r i ¼ ðB:4Þ
Ar @r A r dr @t B.1.2. Energy balance in the endothermicreaction side
i¼1
By considering the endothermic reaction side as the system and
Concentration of component j in control volume is equal to the in the absence of shaft work the energy balance is:
mole of component j in volume of fluid. The volume of fluid is e
@T @T X
n Xn
times of the volume of control volume element:

K eff Ar þ K eff Ar þ N j Ar H j N j Ar H j
@r r @r rþdr j¼1 j¼1

nj r rþdr
Cj ¼ ðB:5Þ
ðAr dr eÞ þ 2 Ap U ðT Exo TÞ
P
n
or @ j¼1 nj U j
¼ ðB:18Þ
nj ¼ C j ðAr dr eÞ ðB:6Þ @t
Cross section area is obtained as follows: The available side area for heat transfer is as follows:
Ap ¼ dr dz ðB:19Þ
2pr dz h1
Ar ¼ ðB:7Þ
NOS h1 þ h2 By considering the Taylor’s extension and dividing the energy bal-
ance by Ar dr, we have:
and P
n
1 @ @T 1 @ j¼1 N j Ar H j 2 Ap
Rh ¼
h1
ðB:8Þ K eff Ar þ U ðT Exo TÞ
h1 þ h2 Ar @r @r Ar @r Ar dr
1 X n
@U j 1 X n
@nj
Subtitling the Eq. (B.8) into (B.7), the cross section area is define as: ¼ nj þ Uj ðB:20Þ
Ar dr j¼1 @t Ar dr j¼1 @t
2pr dz
Ar ¼ Rh ðB:9Þ
NOS Substituting (B.9) and (B.19) in the above equation, the energy bal-
ance becomes:
Applying the above equations, the mass balance equation can ob-
tain as: 1 @ @T 1X n
@ðNj Ar Þ X n
@Hj NOS
K eff Ar Hj Nj þ
Ar @r @r Ar j¼1 @r @r pr Rh
1 @ðNj Ar Þ Xm
@C j
j¼1
þ qb ai v ij r i ¼ e ðB:10Þ U ðT Exo TÞ
Ar @r i¼1
@t
Xn
@U j Xn
@C j
Inwhich Nj is molar flux of component j. The molarflux comprises ¼ e Cj þ e Uj ðB:21Þ
two terms, ones due to the bulk motion and the other one for diffu- j¼1
@t j¼1
@t
sion of component j is as follows:
@ðN j Ar Þ
The term is not known and is replaced from Eq. (B.10):

@r
X !
@C j 1 @ @T n Xm
@C j
Nj ¼ Dej þ C j ur ðB:11Þ K eff Ar þ Hj qb ai v ij r i þ e
@r Ar @r @r @t
j¼1 i¼1
or
Xn
@Hj NOS
@C j Nj þ U ðT Exo TÞ
Nj Ar ¼ Ar Dej þ Ar C j ur ðB:12Þ j¼1
@r pr Rh
@r
Xn
@U j Xn
@C j
Substitution in governing mass balance equation gives: ¼ e Cj þ e Uj ðB:22Þ
j¼1
@t j¼1
@t
1 @ @C j 1 @ Xm
@C j j ¼ 1;2;.. .;n
Dej Ar ðAr ur C j Þ þ qb ai mij ri ¼ e
Ar @r @r Ar @r @t i ¼ 1;2;...;m hence:
i¼1
X !
ðB:13Þ 1 @ @T n Xm Xn
@C j
K eff Ar Hj qb ai v ij r i þ Hj e
Ar @r @r j¼1 i¼1 j¼1
@t
As the CCR process is steady state, and diffusion in comparison to
bulk motion is negligible, the first term in the above equation is Xn
@Hj NOS
removed. Then we have: Nj þ U ðT Exo TÞ
j¼1
@r p r Rh
1 @ Xm
j ¼ 1; 2; . . . ; n Xn Xn
ðAr ur C j Þ þ qb ai mij r i ¼ 0 ðB:14Þ @U j @C j
Ar @r i ¼ 1; 2; . . . ; m ¼ e Cj þ e Uj ðB:23Þ
i¼1
j¼1
@t j¼1
@t
Now we have: By neglecting conductive heat transfer in comparison to convective

! heat transfer and heat of reaction,
1 @ @T Xm X n Xn
K eff Ar qb ðHj v ij Þ ai r i Nj @T Xm
NOS
Ar @r @r ur C T C P qb ðDHi ai r i Þ þ U ðT Exo TÞ ¼ 0
i¼1 j¼1 j¼1 @r i¼1
pr Rh
@Hj NOS
þ U ðT Exo TÞ ðB:38Þ
@r pr Rh
X n Xn and finally,
@U j @C j
¼ e Cj þ e ðU j Hj Þ ðB:24Þ @T qb X m
NOS
j¼1
@t j¼1
@t ¼ ðDHi ai r i Þ þ
@r ur C T C P i¼1 pr Rh ur C T C P
The following definitions are used to simplify the recent equation:
U ðT Exo TÞ ðB:39Þ
X
n
DH i ¼ ðv ij Hj Þ ðB:25Þ
j¼1 B.2. Velocity distribution in the endothermicreaction side
@Hj @Hj @T @T To obtain velocity distribution equation, the mass balance equa-
¼ ¼ C Pj ðB:26Þ
@r @T @r @r tion is used.
n @C j C j C j @ur qb X m
j ¼ 1; 2; . . . ; n
Xn
@Hj X @T ¼ þ ai mij r i ðB:40Þ
Nj ¼ ðJ j þ C j ur Þ C Pj @r r ur @r ur i¼1 i ¼ 1; 2; . . . ; m
j¼1
@r j¼1
@r
! Then, by integrating the above equation:
@T Xn Xn
@T X X
¼ ððJ j þ C j ur Þ C Pj Þ ’ ur C j C Pj ðB:27Þ
n
@C j n
C j 1 @ur X
n
q X n X m
@r j¼1 @r ¼ Cj þ b ai mij ri ðB:41Þ
j¼1
j¼1
@r j¼1
r ur @r j¼1 ur j¼1 i¼1
! ! Pn
X
n n
X X
n By considering
Cj j¼1 C j ¼ C T the velocity equation becomes:
C j C Pj ¼ CT C Pj ¼ CT yj C P j ¼ C T C P ðB:28Þ
CT @C T C T C T @ur qb X n X m
j¼1 j¼1 j¼1 ¼ þ ai mij r i ðB:42Þ
@r r ur @r ur j¼1 i¼1
ðU j Hj Þ ¼ Pv j ¼ RT ðB:29Þ ur
The above equation is multiplied by CT
,
X
n
@C j X
n
@C j @C T ur @C T ur @ur qb Xn X m
ðU j Hj Þ ¼ RT ¼ RT ðB:30Þ ¼ þ ai mij r i ðB:43Þ

@t @t @t CT @r r @r C T j¼1 i¼1
j¼1 j¼1
Eventually, the velocity distribution equation is:

@U j @U j @T @T
¼ ¼ CVj ðB:31Þ @ur ur ur @C T qb X n X m
@t @T @t @t ¼ þ ai mij r i ðB:44Þ
@r r CT @r C T j¼1 i¼1
C V j ¼ C Pj R ðB:32Þ
@C T
To find @r
in this equation, we use ideal gas law:
CV ¼ CP R ðB:33Þ P
CT ¼ ðB:45Þ
RT
Additionally:
! Then by doing the following algebraic operations on the above rela-
Xn
@U j X n
@T @T X n X n
@T tions, we have:
Cj ¼ Cj CV j ¼ Cj CV j ¼ CjCVj ðB:34Þ
j¼1
@t j¼1
@t @t j¼1 j¼1
@t @C T 1 @P P @T
! ! ¼ ðB:46Þ
X n X n X n @r RT @r RT 2 @r
Cj
CjCV j ¼ CT CVj ¼ CT yj C V j ¼ C T C V ðB:35Þ
j¼1 j¼1
CT j¼1
B.3. Mass and energy balances and velocity distribution in the
where CV and CP are the average heat capacities of mixture at con- exothermic reaction side
stant volume and pressure respectively. Accordingly, based on the
above definition: With same procedure, for exothermic reactionside we have:
!
1 @ @T Xm
@T
K eff Ar qb DHi ai r i ur C T C P B.3.1. Mass balance
Ar @r @r i¼1
@r
þ
NOS
U ðT Exo TÞ @C Exo
j C Exo
j C Exo
j @uExo
r qExo
b
pr Rh ¼ Exo þ Exo ða0 mj r 0 Þ j ¼ 1; 2; . . . ; n0 ðB:47Þ
@r r ur @r ur
@T @C T
¼ eC T C V eRT ðB:36Þ where n0 is the number of component in the exothermic reaction
@t @t
side.
and then,
!
1 @ @T Xm
@T B.3.2. Energy balance
K eff Ar qb DHi ai r i ur C T C P
Ar @r @r i¼1
@r
@T Exo qExo
þ
NOS
U ðT Exo TÞ þ eRT
@C T ¼ b
Exo Exo
ðDHExo a0 r 0 Þ
pr Rh @t @r uExo
r CT CP
NOS
¼ eC T C V
@T
ðB:37Þ þ Exo Exo
U ðT T Exo Þ ðB:48Þ
@t pr ð1 Rh Þ uExo
r CT CP
B.3.3. Velocity distribution Then,

@ðF T C P TÞ 2pRi
0 ¼ C Te ure Rh C pe ðT e TÞ ðB:61Þ
@uExo uExo uExo @C Exo qExo X
n @z NOS
r
¼ r rExo T þ Exob
ða0 mj r0 Þ ðB:49Þ @F T @T @C P 2pRi
@r r CT @r C T j¼1 CP T þ F T CP þ FT T ¼ C Te ure Rh C pe ðT e TÞ ðB:62Þ
@z @z @z NOS
Now the above equation is divided by the FT CP T.
B.4. Collector mass and energy balance for endothermic reaction side
1 @T 1 @C P 1 @F T 1 2pRi
þ þ ¼ C Te ure Rh C pe ðT e TÞ
The mass balance for one part of endothermic reaction collector T @z C P @z F T @z F T C P T NOS
can be written as: ðB:63Þ
F j jz F j jzþdz þ F je ¼ 0 j ¼ 1; 2; . . . ; n ðB:50Þ
@T 1 2pRi
¼ C Te ure Rh C pe ðT e TÞ
where Fj, is the molar flow rate of component j in z direction and Fje @z F T C P NOS
is the output molar flow rate of component j from endothermic
T 2pRi T @C P
reaction side that enters to the collector. ure Rh C Te ðB:64Þ
F T NOS C P @z
2pRi
F je ¼ C je ure Are ¼ C je ure dz Rh j ¼ 1; 2; . . . ; n ðB:51Þ With same procedure for one part of exothermic reaction collector,
NOS
the mass and energy balances are defined as follows:
where Cje and ure are concentration of component j and radial veloc-
ity in inner radius of reactor. @F Exo
j 2pRi Exo
¼ uExo
re C je ð1 Rh Þ j ¼ 1; 2; . . . ; n0 ðB:65Þ
By considering the Taylor’s extension, the mass balance equa- @z NOS
tion is changed to:
@T Exo C Exo Exo
2pRi
@F j 2pRi Te ure
¼ Exo ð1 Rh Þ C Exo T Exo T Exo
¼ ure C je Rh j ¼ 1; 2; . . . ; n ðB:52Þ @z FT CP Exo NOS Pe e
@z NOS
Exo
Then, to calculate total molar flow rate FT, the summation of recent T 2pRi Exo T Exo @C Exo
Exo uExo
re ð1 R h ÞC Te Exo P
ðB:66Þ
equation for all pseudo-components in endothermic reaction side is FT NOS CP @z
considered:
X
n Xn
@F j 2pRi References
¼ ure C je Rh ðB:53Þ
j¼1
@z j¼1
NOS
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Chemical Engineering Journal 229 (2013) 153–176

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

Applying new kinetic and deactivation models in simulation of a novel

A novel thermally coupled reactor in CCR naphtha reforming process is modeled.

stream from the last reactor is sent to a separator, in which hydro-

2.2. Thermally coupled conﬁguration

A simple schematic diagram of CCR process including the ther-

3.1. Endothermic side (naphtha reforming reactions)

Naphtha feedstock is a complex mixture of hydrocarbons with

Parameter Numerical value Unit

Parameter 1st Reactor 2nd Reactor 3rd Reactor 4th Reactor

Speciﬁc properties and operating conditions for exothermic side

ACHn M An + 3H2 r 1n ¼ k1n ðP ACHn

C6 68.73 18.75 19.50 59.90 24.80  103

Rate constant Unit Equilibrium constant Unit

C6 43.64 24.37 33.11 9.12 5.24  103

Rate constant Unit Equilibrium constant Unit

C6 52.00 26.36 33.11 14.35 6.25  103

C5a 69.73 30.75 33.11 14.39 8.38  103

C5a 76.67 29.83 33.11 16.18 9.22  103

Rate constant Unit Equilibrium constant Unit

C6a 66.50 16.87 18.86 35.73 7.99  103

Rate constant Unit Equilibrium constant Unit

C6a 68.18 16.44 18.86 36.01 8.20  103

Rate constant Unit Equilibrium constant Unit

C6 17.10 15.11 23.81 5.20 2.06  103

Rate constant Unit Equilibrium constant Unit

C4a 9.23 25.08 26 0.80 1.11  103

Rate constant Unit Equilibrium constant Unit

n = 1a OX PX 10.50 25.21 21.24 12.13 1.26  103

Rate constant Unit Equilibrium constant Unit

n = 7a T B PX 16.20 16.68 21.24 16.41 1.95  103

C2a 65.20 37.85 34.61

for n ¼ 5 : IP 5 þ H2 ! 12 ðIP 4 þ P 3 þ P 2 þ P1 Þ Rate constant Unit

C4a 40.30 36.15 34.61

C6 45.45 42.15 34.61

C5a 68.74 40.23 34.61

An+1 + H2 ? Ak + CmH2m+2 r 16n ¼ k16n P Anþ1 P 0:5 (16)

C7 1 n 41.81 7.64 17.92

r27 r17 r168-1 r169-2

Fig. 4. Proposed reactions network for catalytic reforming of naphtha.

C6H5NO2 + 3H2 ? C6H5NH2 + 2H2O (17) k0 K NB K H2 PNB P H2

A0 = 0.186 E0 = 10 (kJ mol1) K H2 ¼ 4:427  103 Pa0.5

Reaction no. Reactions Agent Reaction no. Reactions Agent

Reaction occurs on metal function Reaction occurs on acid function

kC M exp ðERTc Þ (33) Ec

Since the operating pressure and the temperature have a signif-

mate, they are investigated ﬁrst. The temperature proﬁles of the

Mass balance (Endothermic Reaction side)

Mass balance (Exothermic Reaction side)

Energy balance (Endothermic Reaction side)

Energy balance (Exothermic Reaction side)

Velocity distribution (Endothermic Reaction side)

Velocity distribution (Exothermic Reaction side)

Mass and energy balance for Collector (Endothermic Reaction side)

Mass and energy balance for Collector (Exothermic Reaction side)

@F Exo pRi Exo

Ergun equation (Pressure drop)

Molecular weight (kg/kmol)

H2 / HC molar ratio (kmol/kmol)

Exothermic side temperature (K)

0.9 ating temperature.

C6 68.73 18.75 19.50 59.90 24.80 103

C6 43.64 24.37 33.11 9.12 5.24 103

C6 52.00 26.36 33.11 14.35 6.25 103

C5a 69.73 30.75 33.11 14.39 8.38 103

C5a 76.67 29.83 33.11 16.18 9.22 103

C6a 66.50 16.87 18.86 35.73 7.99 103

C6a 68.18 16.44 18.86 36.01 8.20 103

C6 17.10 15.11 23.81 5.20 2.06 103

C4a 9.23 25.08 26 0.80 1.11 103

n = 1a OX PX 10.50 25.21 21.24 12.13 1.26 103

n = 7a T B PX 16.20 16.68 21.24 16.41 1.95 103

A0 = 0.186 E0 = 10 (kJ mol1) K H2 ¼ 4:427 103 Pa0.5

kC M exp ðERTc Þ (33) Ec

ðU j Hj Þ ¼ RT ¼ RT ðB:30Þ ¼ þ ai mij r i ðB:43Þ