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Optimal Design of A Radial Flow Membrane Reactor As A Nov 2013 International
Optimal Design of A Radial Flow Membrane Reactor As A Nov 2013 International
journalhomepage:www.elsevier.com/locate/he
a a a a
Davood Iranshahi , Mitra Jafari , Razieh Rafiei , Mohsen Karimi ,
a a,b,
Shahram Amiri , Mohammad Reza Rahimpour *
a Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz
71345, Iran
bDepartment of Chemical Engineering and Materials Science, University of California, Davis, 1 Shields Avenue, Davis, CA
95616, United States
Article history: The significance of the catalytic naphtha reforming process in the petroleum refining and petrochemical
Received 17 December 2012 industry generates continuous evolution of the technology. These im-provements would be observed in
Received in revised form 9 April presenting more efficient reactor setups in order to improve production yield and operating conditions, as well
2013 as elucidating better kinetic and deactivation models with higher predicting ability. Both of these items have
Accepted 12 April 2013 Available been considered in this work. An optimized radial-flow moving bed membrane reactor has been proposed as a
online 22 May 2013 novel configuration for naphtha reforming process. Optimization has been carried out by differential
evolution (DE) method considering 40 decision variables. A detailed kinetic model has also been presented.
Keywords: The proposed kinetic model consists of 32 lumped pseudo-components and 84 reactions. Deactivation rate of
Naphtha reforming catalyst has also been taken into account by considering coke deposition on both acidic and metallic sites.
Continuous catalyst regeneration Plant data have been used to validate the modeling results. In order to assess the performance of the proposed
Membrane reactor configuration, the obtained modeling results have been compared with those of conventional configuration,
Kinetic model which shows the superiority of the presented one.
Deactivation model
Differential evolution
Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author. Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz
71345, Iran. Tel.: þ98 711 2303071; fax: þ98 711 6287294.
E-mail addresses: mrahimpour@ucdavis.edu, rahimpor@shirazu.ac.ir (M.R. Rahimpour).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.04.059
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8385
produce aromatics (mostly benzene, toluene, and xylenes). Hydrogen, as a been made by Smith in 1959 [5]. His model consists of three basic
valuable component, and liquefied petroleum gas are also produced in components including paraffins, naphthenes, and aro-matics (PNA),
both cases. which undergo four reactions. Krane et al. [6] investigated the presence of
various hydrocarbons in the whole naphtha and presented a reaction
1.1. Continuous catalyst regeneration reformer (CCR) network of twenty different components, containing hydrocarbons from
C6 to C10. Padmavathi et al. [7] considered 26 lumps of hydrocarbons
Catalytic naphtha reforming units could be categorized ac-cording to the undergoing 48 reactions. Evolution in the considered number of lumped
catalyst regeneration procedure into three main classes, including semi- components and reactions in catalytic naphtha reforming kinetic is
regenerative catalytic reformer (SRR), cyclic catalytic reformer, and presented in Table 1.
continuous catalyst regenera-tion reformer (CCR).
SRR is the most commonly used type of the catalytic reforming units 1.3. Membrane reactor
[1]. In this process, reactors operate continu-ously and catalyst activity
decreases mainly due to the coke deposition. At the end of the cycle, Membrane reactors are widely used either as “extractor” in which certain
which occurs approxi-mately once each 6e24 months, all of the catalysts products remove from reaction zone or as “distributer” in which a certain
are re-generated in situ during routine catalyst regeneration shutdowns. To reactant distributes into the reactor [18]. This effective configuration has
maximize the length of time (cycle) between regenerations, SRR units are various advan-tages such as increasing reaction rate, reducing by product
operated at high pressures, about 1.380e2.070 MPa. formation, requiring lower energy, and operating under rela-tively safe
conditions. Several researchers have investigated the application of
membrane technology in chemical reaction processes. Dittmeyer et al.
In the cyclic catalytic reformer unit, an extra spare or swing reactor [19] studied pd-membrane reactors and discussed two different membrane
exists and each reactor can be removed from the process flow, reactor concepts which both rely on supported palladium, on the one hand
regenerated, and then put back into service without shutting down the unit as a permselective membrane material, and on the other hand as base
and losing production. It should be mentioned that application of the component of a membrane-type hydrogenation catalyst. Pereira et al. [20]
cyclic catalytic reformer unit for naphtha reforming process is not very studied ethyl lactate synthesis in a perva-poration membrane reactor.
common. The operational pressure of cyclic reforming re-actors is Parvasi et al. [21] analyzed PdeAg membrane methanol loop reactors and
approximately 1.5 MPa. applied differential evolution (DE) method as a powerful method for
optimization of the process.
The most modern type of the catalytic reformers is CCR, which
represents a step change in reforming technology compared to semi-
regenerative and cyclic processes. In this unit, the catalyst regenerates
continuously in a special regen-erator and then is sent to the operating
reactors. Due to the continuous regeneration of the catalyst, this process is 1.4. Objective
suited for higher severity operations relative to semi-regenerative fixed-
bed reformers [2,3]. The CCR process has enabled ultra-low pressure In this work the benefits of the membrane reactor and the continuous
operations at about 0.345 MPa. The advantages of CCR process against catalyst regeneration mode of operation has been combined to improve
traditional methods are [3,4]: the performance of the catalytic naphtha reforming unit. The flow pattern
in the reactor is considered to be radial-flow due to its advantageous over
Lower required recycle ratio and the lower operational pressure with naphtha reforming kinetic.
high yield of hydrogen Number of Number of Year Investigator Reference
lumped reactions
component
3 4 1959 Smith [5]
1.2. Kinetic model
31 78 1980 Jenkins et al. [8]
28 81 1987 Froment [9]
It is revealed that naphtha is a complex mixture of more than 300 35 36 1997 Taskar et al. [10]
components, mainly hydrocarbons. Considering all of these components 26 48 1997 Padmavathi et al. [7]
and their corresponding reactions in a ki-netic model is a complex 24 71 2000 Ancheyta- [11]
problem. In order to take into ac-count the main components and Juarez et al.
reactions, as well as avoiding the complexity of considering large number 17 17 2004 Hu et al. [12]
21 51 2004 Hu et al. [13]
of components and reactions, “lumped” models have been presented. In
20 31 2006 Weifeng et al. [14]
this kind of model, the large numbers of chemical components are
18 17 2006 Weifeng et al. [15]
classified to smaller set of kinetic lumps. The first significant attempt to 27 52 2010 Hongjun et al. [16]
model a reforming system by this approach has 38 86 2012 Wang et al. [17]
8386 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
axial-flow pattern such as lower pressure drop. A reaction network coated by a PdeAg membrane layer. Hydrogen permeates from reaction
containing 32 pseudo-component and 84 reactions has also been area to the gap through membrane, and is car-ried by the sweeping gas
presented. Then for modeling the conventional and membrane reactor, which flows radially. Catalyst moves axially and the feedstock flows
mass and energy balances, thermo-dynamic and kinetic equations, radially inward the reaction media. The operating conditions and specific
deactivation model, and auxiliary relations have been applied. The properties of the catalyst and reactor of this configuration are presented in
obtained conven-tional reactor model has been validated by comparing Table 3.
with industrial data. DE method has been used to optimize the membrane
reactor characteristics and operating conditions via optimization of 40
decision variables. Finally, the perfor-mance of the optimized membrane
reactor (OMR) has been compared with that of conventional reactor (CR) 3. Reaction model
to assess OMR superiority.
3.1. Kinetic model
Fig. 1 e (a) A simple process flow diagram for conventional catalytic naphtha reforming CCR unit, (b) A schematic diagram of conventional radial-flow
moving bed reactor.
8388 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
3.2. Catalyst deactivation model The basic structure of the model consists of heat and mass balance
equations, which are considered in two dimensions. These equations
Naphtha reforming catalyst is a bifunctional catalyst consists of a metal should be coupled with auxiliary relations such as the deactivation model,
function, mainly platinum, and an acid function, usually chloride alumina. thermodynamic and kinetic re-lations, and auxiliary correlations to be able
The metal function mainly cata-lyzes the hydrodealkylation and to predict physical properties as well as operating conditions and molar
dehydrogenation reactions and the acid function mostly promotes the flow rate of pseudo-components. In order to derive the equations, heat and
isomerization re-actions [22]. In addition, some of the reactions such as material balance equations are written upon a small element of the reactor.
hy-drocracking or dehydrocyclization occur on either or both of these The flow pattern of the feedstock in the membrane reactor is assumed to
functions. be radial, while catalysts move axially. The corresponding mass and
energy balance equations, the pres-sure drop correlation, hydrogen
The yield of catalytic naphtha reforming process depends strongly on permeation rate, and velocity distribution are presented in Table 5.
the catalyst properties. In order to improve the catalyst activity, stability,
and selectivity various metals such as Re, Ir, Rh, Ge, In, and Sn have been
added to the metal function. Among these secondary metals, tin prevents
coke deposition on the Pt metal particles and support, also enhances the
selectivity to aromatics and the stability of Pt/Al 2O3 [23]. PteSn catalysts 5. Optimization
are regenerated easily, thus they are used in the systems in which the
catalyst is regenerated continuously [24]. DE optimization technique has been widely used as an efficient and
simple method. In this research, DE algorithm is used to
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8389
optimize the characteristics as well as operating conditions of the The ratio of hydrogen/hydrocarbon affects the coke deac-tivation.
membrane reactor in CCR mode of operation in order to achieve higher Low H2/HC ratio causes catalyst deactivation due to the coke formation.
production of aromatics and hydrogen and saving in operation and Hydrogen is produced during naphtha reforming reaction and removed
fabrication costs. Employing DE, very little input is required from the from reaction media by the mean of membrane. The value of this
user. The main input variables chosen by the user are NP, number of parameter in the input of the reactor is equal to 2.193. If the value of
populations, F, scaling factor (step size) and CR, crossover constant, H2/HC ratio be-comes less than this amount, coke deposition increases
which their value depend on the conditions of the issue. In this work, the considerably. Thus, the amount of the passed hydrogen through membrane
value of NP is set to be equal to 360. DE step size, which generally should should be controlled in a way that in each reactor this ratio remains higher
be in the range of 0.5e1.0 [29], is chosen to be 0.8. The value of CR is than 2.193. Therefore, the following constrain is applied to control H 2/HC
chosen to be equal to 0.8. ratio:
The following objective function is considered to maximize the yield ðH2 =HCÞ 2:193 (2)
In situ
and production of aromatics and hydrogen:
DFAr DFH
OF ¼ YAr þ YH2 þ þ 2
(1) Due to the presence of membrane, H2/HC ratio in OMR is less than CR.
2500 2000
Decrease in the value of H2/HC contributes to an increase in the amount
where Y and DF denote yield and production, respectively. In order to give
equal weights to each term during the optimi-zation procedure, the above
terms are divided by appropriate numbers (2500 for aromatics production
and 2000 for hydrogen production) in a way to have the same order of
magnitude. This avoids maximizing one term while the other terms are not
at their optimum values. In fact, both yield and production can be
maximized simultaneously in this way.
of coke deposition. In order to avoid higher amount
of coke deposition in OMR respect to CR, the
amount of the deposited coke over catalyst in OMR
is adjusted to be less than conventional reactor,
which is 5%. In contin-uous catalyst regeneration
mode of operation, the amount of deposited coke
could be controlled by adjusting the rate of catalyst
circulation. The corresponding constrain is written
as:
8390 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
(17)
(15)
(11)
(6)
(13)
(4)
(14) (18)
CC %5
(12) Sum of the mass distribution of catalyst in the reactors, must be
equal to 1. The relative constrain in OMR is defined by:
(10)(16)
X
Wi ¼
(1)
(2) where i represents the number of the reactors, and Wi is the
mass distribution of the catalysts in each reactor.
(3) In order to avoid high pressure drop, the following constrain is
applied to keep the pressure drop in each reactor less than 25 kPa.
dp 1.8 mm
Pt 0.3 wt%
Sn 0.3 wt%
s 220 2 G4 ¼ maxf0; ððW1 þ W2 þ W3 þ W4Þ 0:99999Þg (12)
a m /g
r 680 3
B Kg/m 4
ε 0.36 e
X
X
i¼1
6.Numerical solution
(4) The obtained governing equations and auxiliary relations of the system
are partial differential equations (PDEs) which should be solved by
appropriate method. To solve this set of equations, forward finite
difference approximation is applied here. In this method, the reactor is
divided into a series of nodes and for each node; derivatives in differential
equations become difference equations that are functions of the
surrounding cells. Then, boundary conditions of the
(5)
In addition, the following constrains are applied to ensure that the yield
and production of aromatics and hydrogen in OMR remain higher than
CR.
process are used for initial nodes of the reactor and the
result of each node is used as boundary conditions for the
following nodes and this procedure is repeated for all
nodes in the reactor.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8391
r
69
r ACH9+
n-P9+
29 r A
r r39
19
9+
r
49
r99
i-P9+
r ACP9+
79
59
r r
18-4
118
r r r
68-1 68-2 18-2
2
r MX
n-P8 r ACH8 r r
X
O
18-1
28 102 OX 169-1
r r38 r106 r104
103
48
r 98
r r
r
r r
10
68-4
i-P8 58 ACP8 78-4
EB 105 PX
r
r r r 68-3
r
78-1 18-3 78-3 117
r
78-2
2T
r
67 r r
r
2
r 168-1 169-2
17
7
n-P7 ACH7 T
r r37
47
r 97
r
87
5
i-P7 7
ACP7 r
66
r
77
r B r
16
168-2 r
r 167
26
n-P6 ACH6
r r36 r
157
46
96
r
r
r
86
i-P6 56
ACP6
r
76
CP
r r r r r r r
55
i-P5 146 147 158 148 159 149
r95
45
r r r r r r
r
r r r r r r r r r r
r 122
5
P
1
Table 4 e Thermodynamic and kinetic comparison of the main reforming reactions [30].
Reaction Reaction Thermal effect Reach thermodynamic H
2
rate equilibrium
Cyclohexane Dehydrogenation Very rapid Very endothermic Yes Produces
Naphthene Isomerization Rapid Exothermic Yes None
Paraffin Isomerization Rapid Slightly exothermic Yes None
Paraffin Dehydrocyclization Slow Very endothermic Yes Produces
Hydrocracking Very slow Exothermic No Consumes
Hydrodealkylation Very slow Exothermic No Consumes
8392 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
Table 5 e Mass and energy balances and auxiliary relations for OMR in CCR system.
Mass balance (Reaction side)
ai nr
ij i
8
JH2 j ¼ H2 ; P H2PH ¼
i 1; 2; .; m
s 2
C m
NOS 0 jsH2 j 1; 2; .; n
vCj j Cj vur rb <
JH2 j H2; PH2
s (16)
vr ¼ r u r vr þ
ur i¼1 pr Rq ur > PH2 ¼
X
s r s 8 ;P P ¼
JH2 j ¼ H2 sH2 H2
vCjs Cjs Cj vu s
NOS s
< 0 jsH2 s
j 1; 2; .; n (17)
vr ¼ r ur vr þ
pr ð1 Rq ur JH2 j ¼ H2; PH2 > PH2
Energy balance (Reaction side) :
vT rb X
m NOS s
¼ ðDHi ai rÞ þ U ðT TÞ
vr urCTCP i¼1 i pr Rq ur CT CP
(18)
NOS JH2 HH2 HH2 PH2 PHs2
s
þ ( HH2 H
s
pr Rq ur CT CP J H2 þ H2 PH2 > PH2
Energy balance (Sweep gas side)
5 1 1
Q0 ¼ 1:65 10 mol$m $s $kPa 2
(22)
¼ þ
vr r CTs vr pr ð1 RqÞ CTs JH2 PH2 > PH2
Collector (Reaction side)
vFj 2pRi Rq j ¼ 1; 2; .; n
vz ¼NOS ureCje
vT 1 2pR T 2pR T vC
(2
i i P
ureRqCTe
vz ¼ FTCP NOS CTeureRqCpe ðTe TÞ FT NOS CP vz
Collector (Sweep gas side) 3)
s 2pR
vFj i s s RqÞ j ¼ 1; 2; .;
n
vz ¼ NOS ureCje ð1
vTs CTesures 2pRi ð1 RqÞ Cpe s s
2pRi
s s
Ts vCP
Ts
(24)
vz ¼ FTsCP NOS Te T F Ts NOS ure ð1 RqÞ CTe CP vz
Ergun equation (Pressure drop)
dP rþ 1:75r ð1 εÞ
150m ð1 εÞ2 u
u2r (25)
dr ¼ fs2dp2 ε3
f
sdp ε3
Additional relations
q1
Rq ¼
q1 þ q2 (2
6)
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8393
Table 6 e The optimized parameters for moving bed membrane reactor in CCR naphtha reforming process.
No. Decision variable Plant value Min. Max. Optimized value
1 Inlet temperature of the first reactor (K) 798 600 798 798
2 Inlet temperature of the second reactor (K) 798 600 798 798
3 Inlet temperature of the third reactor (K) 798 600 798 798
4 Inlet temperature of the fourth reactor (K) 798 600 798 798
5 Pressure of inlet feed to the 1st reactor (kPa) 595 300 595 594.137
6 Pressure of inlet feed to the 2nd reactor (kPa) 550 300 550 548.216
7 Pressure of inlet feed to the 3rd reactor (kPa) 505 300 505 504.810
8 Pressure of inlet feed to the 4th reactor (kPa) 460 300 460 458.840
9 Number of subsections (NOS) for the 1st reactor e 4 100 51.362
10 Number of subsections (NOS) for the 2nd reactor e 4 100 34.753
11 Number of subsections (NOS) for the 3rd reactor e 4 100 22.057
12 Number of subsections (NOS) for the 4th reactor e 4 100 13.993
13 Total fresh naphtha feed to the plant (kmol/h) 2196.37 2000 3000 2705.428
14 Hydrogen mole fraction in the recycle gas 0.8293 0.50 0.99 0.767
15 Catalyst circulation velocity (m/s) 7.660 10 5 7 10 5 50 10 5 20.25 10 5
16 Catalyst distribution for the 1st reactor (weight fraction) 0.1207 0.01 0.99 0.214
17 Catalyst distribution for the 2nd reactor (weight fraction) 0.1798 0.01 0.99 0.216
18 Catalyst distribution for the 3rd reactor (weight fraction) 0.2498 0.01 0.99 0.254
19 Catalyst distribution for the 4th reactor (weight fraction) 0.4497 0.01 0.99 0.316
20 Inner radius of collector for the 1st reactor (m) 0.625 0.20 1.00 0.663
21 Inner radius of collector for the 2nd reactor (m) 0.625 0.20 1.00 0.744
22 Inner radius of collector for the 3rd reactor (m) 0.650 0.20 1.00 0.712
23 Inner radius of collector for the 4th reactor (m) 0.650 0.20 1.00 0.588
24 LOD of first reactor 3.883 2 7 3.092
25 LODof second reactor 4.404 2 7 5.298
26 LOD of third reactor 4.778 2 7 5.898
27 LOD of fourth reactor 5.324 2 7 5.979
28 Membrane thickness of 1st reactor (mm) e 1 10 10
29 Membrane thickness of 2nd reactor (mm) e 1 10 10
30 Membrane thickness of 3rd reactor (mm) e 1 10 8
31 Membrane thickness of 4th reactor (mm) e 1 10 9
32 Hydrogen mole fraction in the sweep gas e 0.01 1.00 0.972
33 Sweep gas molar flow rate of 1st reactor (kmol/h) e 10.00 100.00 32.226
34 Sweep gas molar flow rate of 2nd reactor (kmol/h) e 10.00 100.00 56.402
35 Sweep gas molar flow rate of 3rd reactor (kmol/h) e 10.00 100.00 82.230
36 Sweep gas molar flow rate of 4th reactor (kmol/h) e 10.00 100.00 57.143
37 The ratio of Rq; for the 1st reactor e 0.70 0.99 0.928
38 The ratio of Rq; for the 2nd reactor e 0.70 0.99 0.903
39 The ratio of Rq for the 3rd reactor e 0.70 0.99 0.880
40 The ratio of Rq for the 4th reactor e 0.70 0.99 0.834
system, are presented. The modeling results of OMR are compared with considered reactions may occur in each of the reactors, the possibility of
those of CR in three different subsections. At first, variation of occurrence of fast reactions in the initial reactors is more than the terminal
temperature, as one of the most important parameters, is presented. Then ones. Dehydrogenation of naph-thenes, which is a highly endothermic
catalyst deactivation which is an important parameter in the rate of reaction, is the fastest of all the reforming reactions, and mainly occurs in
reactions is compared in CR and OMR. Finally, production and the first reactor. This reaction continues in the second reactor along with
consumption of pseudo-components of both configurations are presented the isomerization which is an exothermic and moder-ately fast reaction.
as an acceptable evidence for superiority of OMR configuration over CR Dehydrocyclization is an endothermic and comparatively slow reaction,
one. and mostly takes place in the third reactor. Dehydrogenation reaction will
occur after dehydrocyclization and produced naphthens will be con-verted
In the aforementioned figures, some of the parameters are elucidated to aromatics. Hydrocracking, which is an exothermic and slow reaction,
in 3-D figures in which the change of parameter is demonstrated in radial occurs in the third and fourth reactor. Hydrodealkylation is also
and axial direction, while the change of others is demonstrated in 2-D considered as the slowest reaction. This exothermic reaction mostly
figures, along axial or radial di-rection. In the latter case, the average occurs in the last reactor. Although hydrocracking and hydrodealkylation
value of the investigated parameter is taken into account for the absent occur in the third and fourth reactors, they are not the predominant re-
dimension. actions in these reactors.
Naphtha feedstock consists of many different hydrocarbons which While these reactions include both exothermic and endo-thermic ones,
undergo various reactions. Although each of the catalytic naphtha reforming is considered as an
8394 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
endothermic reaction. The endothermicity of this reaction is concluded variations along the radius of CR and OMR is depicted in Fig. 4(b).
from the positive value of total heat of reaction. Thus, temperature According to the considered reactions, endothermic re-actions, such as
reduction is expected as reaction proceeds. Temperature distribution along dehydrogenation and dehydrocyclization, mainly produce hydrogen and
CR as a function of dimen-sionless length and radius is depicted in Fig. exothermic reactions, such as hydrocracking and hydrodealkylation,
4(a). Temperature is reduced along the radius of all of the reactors which mainly consume hydrogen. As a result of hydrogen removal from reaction
in-dicates the predominance of the endothermic reactions. This decreasing medium, endothermic reactions shift to produce more hydrogen and more
trend reduces considerably from the first reactor to the forth one. This is heat consumes, while exothermic ones tend to consume less hydrogen and
mainly due to the degree of endo-thermiciy and exothermicity of the less heat generates. These effects contribute to more temperature
reactions that occur in these reactors. For instance, hydrocracking and reduction in OMR respect to CR.
hydro-dealkylation reactions, which are exothermic reactions, mostly
occur in the terminal reactors, thus the temperature reduction of these
reactors is less than the initial ones. It should be mentioned that the
temperature of the input stream of the three last reactors is increased to 8.2. Catalyst deactivation
that of the first one by the mean of intermediate heaters in order to
compensate the appeared temperature reduction. The observed increase in The yield of catalytic naphtha reforming process depends strongly on the
temperature through length of the reactors is due to the decrease in the catalyst properties. During operation, the catalyst undergoes
catalyst activity. Deposition of coke on the catalyst pellet contributes to physiochemical changes, which contribute to reduction in the activity for
reduction in the rate of reactions, therefore less heat consumes and aromatic production. In the catalytic naphtha reforming process, coke
temperature drop decreases along length of the reactor. formation is the most important cause of the catalyst deactivation. In this
section, the amount of deposited coke over catalyst and the catalyst
activity along radius and length of the reactors are discussed.
In order to assess the effect of hydrogen removal on the temperature Coke weight fraction along the length and radius of the CR is
profile of the reactors, the temperature demonstrated in Fig. 5(a). In this figure the generated
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8395
Fig. 4 e (a) Temperature distribution in CR as a function of dimensionless length and radius, (b) Temperature drop along radius of the OMR compared
with CR.
coke on metal and acid sites as well as total amount of generated coke are parameters, the membrane reactor is optimized in such a manner that the
depicted separately. Since metal and acid sites catalyze different reactions, weight percent of deposited coke becomes lower than that of conventional
different amount of coke deposits on these sites. ACP has been considered reactor (this issue is consid-ered as one of the optimization constrains).
as the most important hydrocarbon component involved in cata-lyst This aim is accompanied by adjusting H 2/HC ratio as well as catalyst
deactivation [26e28]. It could be concluded from equa-tions (31) and (32) movement velocity.
in Table B2 that reduction in ACP concentration contributes to reduction
in the rate of coke formation. Along the radius of the reactors, coke
formation decreases due to reduction in ACP concentration. In addi-tion, 8.3. Production and consumption of pseudo-components
temperature reduction contributes to decrease in the formation of coke.
The naphtha feedstock consists of a mixture of a several types of
paraffinic, naphthenic, and aromatic compounds under-going various
reactions. The goal of this section is the inves-tigation of the effect of
The amount of deposited coke over catalyst increases through length hydrogen removal from reaction medium along with optimization on
of the reactors due to the continuous coke deposition on the catalyst pellet pseudo-components molar flow rate. In order to reach this end, the
during its axial movement. It should be taken into consideration that production and consumption of different components through radius of
catalyst pellets move with a lift gas through one reactor to the other. In CR and OMR are compared.
this movement, catalyst pellets would be mixed, thus in the input of the
each reactor, the amount of the coke weight fraction is equal to an average Production of hydrogen, as a valuable by product of the naphtha
value of the coke weight fraction through radius in the outlet length of the reforming unit, has become increasingly desirable, since it is used in
previous reactor. hydro-processing units for removal of sulfur as well as for hydrocracking
reactions. As mentioned, although hydrogen is mainly produced in
With the aim of comparing the catalyst coke deposition and activity in naphtha reforming reaction, it consumes in a number of reactions. This
OMR and CR, total amount of the deposited coke in these reactors is produc-tion and consumption for main reforming reactions could be
shown in Fig. 5(b). Lower H2/HC ratio of OMR respect to CR contributes observed in Table 4. Hydrogen production through the radius of the CR
to higher coke deposition, while lower temperature and ACP and OMR is depicted in Fig. 6. During the process, hydrogen production
concentration result in lower coke formation in OMR respect to CR. rate increases along radius as hydrogen
Considering these
8396 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
180
a
OMR
140
120
100
80
60
40
20
300
(kmol/h)
250 OMR
consumption
200
Alkylcyclohexane
50
150
100
Fig. 5 e (a) coke weight fraction along the length and the radius of CR Fig. 7 e (a) ACP and (b) ACH consumption in OMR and CR along
(b) total amount of the deposited coke along dimensionless length of dimensionless radius.
OMR and CR configurations.
6000
The most abundant naphthenes in petroleum have a ring of either five
CR or six carbon atoms. In the presented model, naph-thene components are
5000
OMR considered as alkylcyclopentanes (ACP) and alkyl-cyclohexenes (ACH)
which undergo different re-actions. Consumption of these components in
Hydrogennproductio (kmol/h)
4000
a 40
CR
900
35
800 CR OMR
yield
OMR 30
I-paraffin consumption (kmol/h)
700
600
ofLight ends
25
500 20
400
ePercentag
10
15
300 5
200
100
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
Radius of reactor (Dimensionless) Radius of reactor (Dimensionless)
b 900
Fig. 10 e Percentage of light end yield across radius of the OMR and
800 CR
CR.
OMR
(kmol/h)
700
600
paraffin is lower than N-paraffin, because I-paraffin is produced in the
isomerization of N-paraffin.
N-paraffin consumption
500
400 The octane number of aromatics, which are the main products of
naphtha reforming process, is always above 100 (except for benzene). As
300 depicted in Fig. 9, aromatics are produced continuously through
200 dehydrogenation reaction. In the OMR configuration, removing hydrogen
100
form reaction media shifts the dehydrogenation reactions toward more ar-
omatics production. Thus, the production rate of aromatics in the OMR is
0
356 kmol/h more than CR. In addition to this issue, in this study the OMR
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 is optimized in order to maximize the aromatic production.
Radius of reactor (Dimensionless)
OMR
1400
1200
1000 9. Conclusion
800
Due to the importance of catalytic naphtha reforming process in
400
petrochemical and refinery industries, attempts are focused on revamping
600
200 this process. In this work, an optimized radial-flow membrane reactor
with continuous catalyst regeneration system has been proposed as a
novel configu-ration for catalytic naphtha reforming process. Optimum
0
values of 40 decision variables, such as inlet temperature, pressure,
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
number of subsections, hydrogen mole fraction, catalyst circulation
Radius of reactor (Dimensionless)
velocity, catalyst distribution, etc., have been obtained by applying DE
Fig. 9 e Aromatics production through the radius of CR and OMR. method. In addition, the
8398 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9
C concentration, kmol m 3
yi mole fraction of component (j)
C 3
ACP alkylcyclopentane concentration, kmol m Y yield
CCA coke weight fraction on acidic function of catalyst, W catalyst mass fraction
1
kg kgcat
CCM coke weight fraction on metallic function of catalyst, Greek letters
1
kg kgcat ε void fraction of catalyst bed
C 3
j0 inlet concentration of component j, kmol m m viscosity, kg m 1 s 1
specific heat capacity at constant pressure, v stoichiometric coefficient of component j in
Cp ij
1 1 reaction i
kJ kmol K
3
Cv specific heat capacity at constant volume, rb reactor bulk density, kg m
1 1 4 sphericity
kJ kmol K s
3 reaction side angle
CT total concentration, kmol m q1
dp particle diameter, m q2 sweep side angle
2 1 d membrane thickness, m
De effective diffusivity, m s H2
1 DH 1
Ec coke formation activation energy, J mol heat of reaction, kj mol
F molar flow rate, kmol h 1 Dz control volume length, m
1 3 1
Fj molar flow rate of component j, kmol h aA constant of deactivation, m kmol
1 a 3 1
FT total flow rate to the reactor, kmol h CA constant of deactivation, m kmol
J 2 1 a 3 1
H2 hydrogen permeation rate, kmol m h CM constant of deactivation, m kmol
H enthalpy, J mol 1 p pi number, 3.14156
1 3 1
Hj enthalpy of component j, J mol aM constant of deactivation, m kmol
k 1 1
thermal conductivity, W m K
kCA constant of deactivation equation for acidic Superscript
1 n 1.5 1.5 s sweep side
function, kg kg kPa 1 m kmol
kCM constant of deactivation equation for metallic
1 n 1.5 1.5 Subscript
function, kg kg kPa 1 m kmol
k 1 1 e exit condition
eff effective thermal conductivity, W m k
k i numerator for reactions
in reaction rate constant for reaction (in)
K j numerator for components
in
equilibrium constant for reaction (in)
t tube side
L length of reactor, m
mnumber of reactions Abbreviations
1
Mj molecular weight of component j, kg kmol A aromatic
1
M mean molecular weight in the flow, kg kmol ACH alkylcyclohexane
nnumber of components ACP alkyl- cyclopentane
n1 constant of deactivation equation CCR continuous catalyst regeneration reformer
n2 constant of deactivation equation CR conventional reactor
n acidic function activity power number DE differential evolution
A
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 8 3 8 4 e8 3 9 9 8399
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