Applied Energy 109 (2013) 79–93

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Progress in catalytic naphtha reforming process: A review

Mohammad Reza Rahimpour a,b,⇑, Mitra Jafari a, Davood Iranshahi a
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

a r t i c l e i n f o a b s t r a c t

Article history: Catalytic naphtha reforming process is a vital process for refineries due to the production of high-octane
Received 12 July 2012 components, which is intensely demanded in our modern life. The significance of this industrial process
Received in revised form 12 March 2013 induced researchers to investigate different aspects of catalytic naphtha reforming process intensively.
Accepted 28 March 2013
Some of the investigators try to improve this process by representing more effective catalysts, while oth-
Available online 25 April 2013
ers try to elucidate its kinetic and deactivation mechanisms and design more efficient reactor setups. The
amount of these established papers is so much that may confuse some of the researchers who want to
Keywords:
find collective information about catalytic naphtha reforming process. In the present paper, the published
Catalytic naphtha reforming
Catalyst
studies from 1949 until now are categorized into three main groups including finding suitable catalyst,
Kinetic model revealing appropriate kinetic and deactivation model, and suggesting efficient reactor configuration
Deactivation model and mode of operation. These studies are reviewed separately, and a suitable reference is provided for
Reactor configuration those who want to have access to generalized information about catalytic naphtha reforming process.
Finally, various suggestions for revamping the catalytic naphtha reforming process have been proposed
as a guideline for further investigations.
Ó 2013 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2. Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.1. Bimetallic catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.2. Trimetallic catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3. Reaction model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.1. Kinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.2. Catalyst deactivation model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4. Reactor configurations and process classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.1. Suggested reactor configuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.1.1. Axial-flow tubular reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
4.1.2. Radial-flow tubular reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.1.3. Radial-flow spherical reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.1.4. Axial-flow spherical reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2. Process classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
4.2.1. Semi-regenerative catalytic reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.2.2. Cyclic catalytic reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4.2.3. Continuous catalyst regeneration reformer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
5. Suggestions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

⇑ Corresponding author at: Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran. Tel.: +98 711
2303071; fax: +98 711 6287294.
E-mail addresses: rahimpor@shirazu.ac.ir, mrahimpour@ucdavis.edu (M.R. Rahimpour).

0306-2619/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.03.080
80 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93
1. Introduction
Although burning any fossil fuel contributes to environmental
problems due to carbon dioxide and other gas emissions, they are
the main energy source in our world [1–5]. In order to protect envi-
ronment, various legislations are passed including increase in oc-
tane number. One of the key processes in the petroleum refining
and petrochemical industries is catalytic naphtha reforming, which
is used extensively to convert low-octane hydrocarbons of naphtha
to more valuable high-octane gasoline components without chang-
ing the boiling point range [6,7]. Naphtha is a fraction of petroleum,
typically constitutes 15–30% of crude oil, by weight, and boils be-
tween 30 °C and 200 °C. This complex mixture consists of hydrocar-
bon molecules with 5–12 carbon atoms, mainly including paraffins,
olefins, naphthenes, and aromatics. Other components such as sul-
fur, nitrogen, oxygen, water, salt, and a number of metal containing
constituents such as vanadium, nickel, and sodium are also exist [8].
In addition, the produced reformate in catalytic naphtha
reforming process includes valuable aromatics such as benzene,
toluene, and xylenes (BTX) that are very important petrochemical
materials. Hydrogen is a valuable byproduct of catalytic naphtha
reforming process, which in most refineries is used for hydrocrack-
ing, hydrotreating, and other hydrogen-consuming processes. It
also should be mentioned that according to the problems induced
by the energy crisis and global warming, hydrogen has the poten-
tial to revolutionize transportation and, possibly, our entire energy
system [9,10].
Many researchers have investigated different aspect of the cat-
alytic naphtha reforming process. These studies mainly focused on
three important issues:
1. Inventing and investigating new catalysts with better selec-
tivity, stability, and performance, as well as lower
deactivation.
2. Studying the nature of the catalytic naphtha reforming reac-
tion and revealing suitable kinetic and deactivation models.
3. Suggesting reactor configurations and mode of operations
with higher yield and better operational conditions.
The moiety of these categories in accomplished studies from
1949 until now is shown in Fig. 1.
In addition, the total number of existing literature and the per-
centage of the aforementioned classes in different years are shown
in Fig. 2a and b, respectively, in order to show the distribution of
the publications thorough time.
2. Catalyst
Naphtha reforming catalyst is a bifunctional catalyst consists of
a metal function, mainly platinum, and an acid function, usually
chloride alumina. The metal function catalyzes the hydrogenation
reactor configuration
24%
catalyst
49%
kinetic and
deactivation
modeling
27%
Fig. 1. The percentage of the accomplished studies of different categories from 1949 until now.
and dehydrogenation reactions and the acid function promote
the isomerization and cyclization reactions [11–13]. In order to
achieve an optimum performance of the naphtha reforming cata-
lyst, adequate balance between these functions is needed [14].
Improving the stability and selectivity of the catalyst as well as
reducing catalyst deactivation is a vital issue for enhancing the effi-
ciency and yield of the process. This practice could be achieved by
modification of both acid and metal function.
Addition of components to the acid function, such as chloride,
changes the strength and amount of support acid sites. Higher acid
strengths increase the acid-catalyzed coking and cracking rates
[15]. Although an excessive amount of chlorine would increase
the hydrocracking reactions, carbon deposits would also increase
[14].
Modification of metal function could be achieved by adding sec-
ondary or ternary metal component to Pt, which is summarized
here.
2.1. Bimetallic catalysts
The first formulation of the naphtha reforming catalyst, which
was introduced in 1949 by UOP, consisted of monometallic plati-
num supported over chloride alumina (Pt/Al2O3–Cl) [16,17]. In or-
der to slow down the coking of this kind of catalyst, high hydrogen
pressures were used, which are thermodynamically not favorable.
The development of bimetallic catalysts permitted this hydrogen
excess to decrease considerably and improved the catalyst effi-
ciency of metal [18–22]. Some of the added metals have catalytic
properties on their own (Ir, Rh, Re), while others, such as Sn, Ge
are catalytically inactive. The addition of second metal to Pt was
started in 1968 by adding Re to the metal function [23], which con-
tributed to reduction in the catalyst deactivation rate and improve-
ment in catalytic properties such as hydrogen uptake and
enhancement in aromatic yields [24,25]. In 1969, the effect of addi-
tion of Sn to the metal function was examined [26]. Addition of tin
prevents coke deposition on the Pt metal particles and support, and
also enhances the selectivity to aromatics and the stability of Pt/
Al2O3 [27–31]. Pt–Sn catalysts are regenerate easily, thus they
are used in the systems in which the catalyst is regenerated contin-
uously [32,33]. Addition of germanium to monometallic platinum-
supported catalysts was studied in 1971 [34]. This practice contrib-
utes to improvement in the catalyst selectivity and stability, as
well as enhancement of the thioresistance of platinum at reaction
conditions [18]. In 1976, addition of Ir and In were considered
[35,36]. Pt–Ir catalysts had a strong hydrogenolytic capacity and
sulfiding pretreatments had to be incorporated in the industrial
practice to prevent the dangerous exothermal runaway produced
by massive C–C bond cleavage of the feedstock in the early stages
of the reaction [37]. Indium improves the resistance to deactiva-
tion by coke formation and enhance the aromatization/cracking
catalyst
kinetic and deactivation modeling
reactor configuration
 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93 81

(a)

number of published papers

year

(b) 70.00%
60.00%

50.00%
percentage

40.00%

30.00%

20.00%

10.00%

0.00%

year

Fig. 2. (a) Total number of the published papers in different years, (b) the difference between accomplished studies of different classes through time.

ratio of the reforming reaction and increases the production of gas-
oline [38,39].
Secondary metals have different properties. For example, rhe-
nium and iridium are active metals for hydrogenolysis reactions,
thus Pt–Re/Al2O3 and Pt–Ir/Al2O3 catalysts are usually presulfided
in situ during commercial practice to passivate their initial hyper-
activity for exothermic demethylation reactions. In contrast, Pt–
Ge/Al2O3 and Pt–Sn/Al2O3 catalysts are not presulfided because
germanium and tin are inactive metals for naphtha reforming reac-
tions. Therefore, Pt–Ge and Pt–Sn catalysts are good candidates for
use in novel low pressure naphtha reforming processes employing
continuous catalyst regeneration because these catalysts do not re-
quire complex activation procedures [40].
The addition of alternative component to the metal function re-
sults in different effects such as:
 modifying the electronic state of the metal,
 changing the geometry of adjacent Pt atom clusters,
 changing the final Pt particle size.
These items affect the hydrogenation and dehydrogenation
reaction kinetics and regulate effective size of Pt clusters, which
contribute to better selectivity, stability, and activity of the catalyst
[41–44].
2.2. Trimetallic catalysts
In order to improve the function of catalysts, the third metal has
been added to the bimetallic catalyst. According to our knowledge,
the first attempt in preparation of three metallic catalysts for naph-
tha reforming process was in 1982, in which Ge was added to Pt–
Re/Al2O3 catalyst [45].
Ge addition modified the properties of the metal and acid func-
tions of the bimetallic catalysts. The modification of the acidity is
due to the deposition of a part of Ge on the support. Ge was also
added to Pt–Ir/Al2O3 catalyst. Studies showed that Ge deposits pro-
duce a greater modification of the metal function of Pt–Ir–Ge cat-
alysts, as compared to Pt–Re–Ge [13]. In both cases a strong
inhibition of the dehydrogenating and hydrogenolytic activity
upon Ge addition is seen. Ge also modifies the acidity of the parent
Pt–Re and Pt–Ir catalysts.
The addition of tin to the bimetallic Pt–Ir increases the stability
of the catalysts and also the selectivity toward toluene. Studies
showed that the same toluene yield is obtained with Pt–Sn/Al2O3
and Pt–Ir–Sn/Al2O3 catalysts after 65 h of reaction, but less tin is
needed in the case of the trimetallic catalyst [46].
In the case of the trimetallic Pt–Re–Sn catalyst, Sn addition to
Pt–Re decreases the hydrogenolytic activity and increases both
the isomerization activity and the stability [47]. The best catalyst
82 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93

is the one with 0.1% Sn. The addition of Sn to Pt–Re catalysts also significant attempt to model a reforming system has been made
decreases the benzene/i-C7 ratio of reformate, which is an impor- by Smith in 1959 [61]. His model consists of three basic compo-
tant issue from an environmental point of view. In addition, using nents including paraffins, naphthenes, and aromatics (PNA), which
Pt–Re–Sn catalyst in naphtha reforming process would contribute undergo four reactions. In this model, which is probably the sim-
to elimination of complicated sulfiding pretreatments [48]. plest model, each hydrocarbon class is considered as a single com-
The application of other trimetallic catalysts such as Pt–Re–Ir/ ponent with average properties of that class. After his model, other
Al2O3 and Pt–Sn-In/Al2O3 in catalytic naphtha reforming process researchers presented more complicate models with more compo-
was also patented, which could be found in respective Refs. [49– nents and reactions. Evolution in number of lumped components
51]. and number of reactions considered in catalytic naphtha reforming
Evolution of two and three metallic catalyst for naphtha reform- kinetic is presented in Table 2.
ing process is presented in Table 1. In 1959, Krane et al. [74] investigated the presence of various
The addition of zeolite to the reforming catalyst is also a poten- hydrocarbons in the whole naphtha. This model consists of a reac-
tial way to improve the catalyst activity and stability and improv- tion network of twenty different components, containing hydro-
ing reformer performance [53–55]. carbons from C6 to C10. He also recognized the difference
between paraffins, naphthenes, and aromatics within each carbon
3. Reaction model number group. Henningsen and Bundgaard-Nielson [75] refined
Krane’s model in 1970. He also reported the frequency factors
3.1. Kinetic model and activation energy values of different reforming reactions of
C8 naphtha, and revealed that a linear relation exist between cata-
Naphtha is a very complex mixture of hydrocarbons. An analy- lyst activity and reactor inlet temperature. In 1972, Kmak [76] used
Langmuir–Hinshelwood kinetics to describe the catalytic naphtha
sis of a typical naphtha feed revealed that more than 300 compo-
nents are present in this hydrocarbon mixture [56]. Different reactions for the first time. He also studied reforming over a wide
range of operating conditions using pure components, mixtures
reactions occur between these components, including dehydroge-
nation and dehydroisomerization of naphthenes to aromatics, and naphtha feed and developed a detailed model in 1973 [77].
In 1980, Zhorov et al. [78] considered C5, C6 lumps of naphtha
dehydrogenation of paraffins to olefins, dehydrocyclization of par-
affins and olefins to aromatics, isomerization or hydroisomeriza- and direct formation of aromatics from paraffins. Marin et al.
[79] modified Kmak’s model in 1983. They used Hougen-Watson-
tion to isoparaffins, isomerization of alkylcyclopentanes and
substituted aromatics and hydrocracking of paraffins and naphth- type rate equations and suggested a kinetic model containing
hydrocarbons with C5 to C10 carbon numbers. Ramage et al.
enes to lower hydrocarbons [57,58]. Considering all of these com-
ponents and their corresponding reactions in a kinetic model is a [80,81] studied the nature of catalytic naphtha reforming reaction
and presented detailed complete model considering C6–C8 lumps
complex problem [59,60]. Thus, ‘‘lumped’’ models have been pre-
sented, in which the large number of chemical components are of naphthenes, paraffins and aromatics in 1980 and 1987. They de-
scribed different reactive particular raw materials in his model and
classified to smaller set of kinetic lumps. In this regard, the first
considered the deactivation of the catalysts due to the coke forma-
tion, which modified the process kinetics. Although, they published
Table 1 a detailed kinetic model based on extensive studies of an industrial
Evolution of two and three metallic catalyst of catalytic naphtha reforming process. pilot-plant reactor, only short range of hydrocarbons of C6–C8 were
Catalyst Year Investigator Reference considered in their model. In 1989 Bommanna and Saraf [82] re-
ported the approximate values of activation energies according to
Pt/Al2O3–Cl 1949 Haensel [16,17]
Pt–Re/Al2O3–Cl 1968 Kluksdahl [23] the plant data. Ancheyta-Juarez and Villafuerte-Macias [58] con-
Pt–Sn/Al2O3 1969 Raffinage [26] sidered the reactions in terms of isomers of the same nature (par-
Pt–Ge/Al2O3 1971 McCallister et al. [34] affins, naphthenes and aromatics) and developed a new kinetic
Pt–Ir/Al2O3 1976 Sinfelt [35]
model in 2000. In 2003, Rahimpour et al. [72] considered C6–C9
Pt–In/Al2O3 1976 Antos [36]
Pt–Re–Ge/Al2O3 1982 Antos [45]
hydrocarbons to simulate catalytic naphtha reformer. Klein et al.
Pt–Re–Ir/Al2O3 1985 Kresge et al. [49] [83,84] built and customized reforming reaction network using
Pt–Ir–Sn/Al2O3 1993 Baird et al. [52] the Kinetic Model Editor (KME) software in 2008. They also en-
Pt–Sn–In/Al2O3 2000 Bogdan [50] hanced the Kinetic Modeler’s Toolbox (KMT) and developed the

Table 2
Evolution in number of lumped components and number of reactions considered in catalytic naphtha reforming kinetic.

Number of Lumped component Number of reactions Year Investigator Reference

3 4 1959 Smith [61]
31 78 1980 Jenkins et al. [62]
28 81 1987 Froment [63]
22 40 1994 Saxena et al. [70]
35 36 1997 Taskar et al. [64]
26 15 1997 Vathi et al. [69]
26 48 1997 Padmavathi et al. [73]
24 71 2000 Ancheyta et al. [58]
17 17 2004 Hu et al. [65]
21 51 2004 Hu et al. [168]
20 31 2006 Weifeng et al. [67]
18 17 2006 Weifeng et al. [66]
17 15 2009 Arani et al. [68]
27 52 2010 Hongjun et al. [71]
38 86 2012 Wang et al. [166]
 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93 83

Kinetic Model Editor (KME) which presents an end-to-end solution

to the kinetic modeling process, including automated feedstock
modeling, reaction network construction, kinetic rate estimation,
model programming, process system configurations, model cust-
omizations, compilations, model execution and results analysis. Smith (1959) [61]
In 2009, Boyas and Froment considered the equilibriums of hydro-
genation and dehydrogenations in their model [85]. Stijepovic et al.
[56] recommended a semi-empirical kinetic model for catalytic
reforming and considered the most important reactions of the cat-
alytic reforming process in their kinetic model in 2009. In 2010,
Hongjun et al. [71] suggested a lumped kinetic model with 27
lumps in order to predict aromatic compositions in more detail.
In 2011, Rodríguez and Ancheyta [57] modified Krane’s model,
and proposed a model in which the simplicity of the lumping-
based models is combined with the complexity of the most ad-
vanced model. The presented reaction networks of some of these
studies are illustrated in Fig. 3.
Many other attempts are also done in this field that can be
found in the respective references. Hu et al. (2004) [65]
It should be noticed that a simple model with few lumps may
not be able to represent the desired situation, nevertheless, choos-
ing a complex model is not profitable because huge amount of
experimental information is needed to determine the model
parameters, which is a time- and money-consuming task. Thus, a
suitable model is that one which despite simplicity is able to pre-
dict the situation properly.

3.2. Catalyst deactivation model

The yield of catalytic naphtha reforming process depends

strongly on the catalyst properties. During operation, the catalyst
undergoes physiochemical changes, which contribute to decrease
in the activity for aromatic production.
The causes of the catalyst deactivation can be categorized into
four main groups [86,87]: Hongjun et al. (2010) [71]

 Poisoning due to chemisorption of some impurity (such as
heavy metals).
 Erosion and breakage.
 Hydrothermal aging, that is, loss of surface area (metallic area
and support area).
 Coke deposition.
The first three reasons are irreversible while the fourth is
reversible and the coke deposit could be removed from the
catalyst.
In the catalytic naphtha reforming process, coke formation is
the most important cause of the catalyst deactivation [88].
Although coke is formed in both acid and metal sites, it has been
demonstrated that the main fraction of the coke is deposited over
acid sites [89,90]. Prediction of coke formation is a very complex
task because this phenomenon depends on various parameters
such as operating conditions, oil feed composition, and catalyst
properties [91].
Operating conditions strongly affect the coke formation. This
parameter mainly includes the partial pressure of hydrogen
and hydrocarbon, time on stream, gas–oil feed flow, and the
reaction temperature. The influence of these factors on coke for-
mation in the commercial process has been described by several
authors.
Bishara et al. [92] investigated the effect of operating conditions
on catalyst deactivation as well as the yield and quality of refor-
mate for naphtha reforming over an industrial bimetallic reforming
catalyst. In their study, the aromatics yield showed a maximum in
the pressure range 7–10 bar, while the carbon deposition de-
creased with increasing pressure. Increase in temperature led to
Fig. 3. Examples of some reaction networks presented for catalytic naphtha
reforming reaction.
an increase in the yield of aromatics at the expense of reformates.
Hydrogen: hydrocarbon ratios (H2/HC) in the range 7–12.7 did not
show any pronounced effect on reformate or aromatics yield, how-
ever, lower H2/HC ratios (e.g.: 3.6) gave decreased aromatics and
increased carbon.
Figoli et al. [93] studied the influence of total pressure and
hydrogen: hydrocarbon ratio on coke formation over naphtha-
reforming catalyst. According to the obtained results, they con-
cluded that the decreasing of the total pressure and of the hydro-
gen to naphtha ratio produces the increment of the coke
formation over Pt/Al2O3. Critical values below which there is a
great increment of the amount of coke and its degree of polymer-
ization exist.
Barbier [94] reported that decrease in pressure induces an in-
crease in toxicity for the metallic activity, measured by the ben-
zene hydrogenation reaction, due to the increase in metal coking.
The increase in operating pressure contributes to less coke deposi-
tion on the metal function and higher stability, which is similar to
the effect of addition of Re or Ir to Pt. This is why the bimetallic cat-
alysts can be operated at lower pressure than the monometallic to
have the same rate of deactivation. He also showed that the change
of the coking temperature does not alter the nature and location of
coke on a Pt/A12O3 catalyst. The small influence of temperature is
reflected in low activation energy of coking, which is typical of a
reaction controlled by diffusion and migration of the coke precur-
sors from the metal to the support. The time of operation at severe
conditions produces an increase in the amount of coke on the
84 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93

Table 3
Some of the presented catalyst deactivation models in catalytic naphtha reforming reaction.

Deactivation model Researcher Reference

6 8955/T 0.94 1.28 1.33
%C = 4.99  10 e P WHSV (H2:naphtha) Figoli et al. [104]
rc ðtÞ ¼ dCK ¼ kc  expðEc =WAIT=RÞ  Aar  P bh  ðT FEL =T 0 Þc  v  expða  CKÞ Hu et al. [106]
dt
  
da
¼ K d exp  ERd 1T  T1R a7 Rahimpour [102]
dt

rcoke ¼ A:P 1  P 0:75

1
 coke  expð37; 000=RTÞ Mieville [100]
H2 feed
0.7
%C = k  P Barbier [94]
%C ¼ 12:67  0:248BP þ 0:001244BP 2 Figoli et al. [95]
cC = k  t1/n Barbier [96]
Carbon on catalyst, Wt% = 104.7 (H/HCmol ratio)1.68 Bishara et al. [92]
dC=dt ¼ ðkp pp þ kA pA ÞpnH12 C n2 aC Schroder et al. [99]
%C = 7.71P0.96 Figoli et al. [93]

dC=dt ¼ rc expðaCÞ Vathi et al. [69]
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
E Hovd et al. [103]
C cat ¼ kC CtCn exp RTcf1
rc

Coke ¼ gðZ 1 ; . . . ; Z n ÞðC=OÞn ðWHSVÞn1 eDEC =RT rx Sadeghbeigi [101]

%C ¼ 0:30P 1:54 þ 0:01P 1:86 þ 0:85P 2:84 þ 0:97  1016 BP 7:56 Figoli et al. [95]
P N A
ra ¼ da a
¼ 5:0  106 e32;000=RT aa C 0:5 Tailleur et al. [105]
dt ACP
a C 0:5
rm ¼ dadtm ¼ 1:2  104 e25;000=RT 1þ0:000809P
m ACP
H2

dC
PJ Pauw et al. [160]
r c ðzi ; tj Þ ¼ dt ¼ k¼1 ajk Cðzi ; tk Þ
h  a Cðzp ;sÞ  i
1 D;C
Cðzi ; tÞ ¼ aD;C ln 1 þ e s
1
t

 da
k b C2 aaS
¼ 1þbADC AAþbA E C E 1a Ostrovskii [165]
dt S
P
AeE=RT ACP
P2
Liu et al. [169,170]
dC H2
dw
¼ us expðaCÞ

support similar to the increase produced by a decrease in the space
velocity and the hydrogen-to-naphtha ratio at constant pressure.
In naphtha reforming, as in other hydrocarbon processes, the
characteristics of the feedstock strongly influence the catalyst
performance. Heavier cuts are cheaper but produce more coke,
making selection of the optimum cut points a compromise. Oil
feed composition, especially the relative quantities and structure
of alkanes, alkenes, naphthenes, aromatics, heterocycles, etc., as
well as the presence of impurities (metals, especially Ni) should
be considered in the deactivation model of the naphtha reforming
catalysts.
Figoli et al. [95] investigated the influence of mean boiling point
BP and composition of the feedstock on naphtha reforming catalyst
activity and stability. They found that cuts of very low or very high
BP produced higher coke depositions and catalyst deactivations.
When cuts of very high BP were used, only a very low increase in
the octane number occurred during reforming. Such cuts had a
high content of aromatics of high molecular weight, and the main
reforming reaction was the aromatics dealkylation to products of
lower octane number.
Bishara et al. [92] studied the effect of feed composition on cat-
alyst deactivation by using several naphtha blends having a wide
variation in the paraffin, naphthene and aromatics content. They
concluded that at any reforming severity, yields of reformate and
aromatics are higher and coke deposition is lower for a naph-
thene-rich naphtha.
The coke rate also depends widely on the catalyst properties
including the number, type and accessibility of the catalyst active
centers, which depend in turn on other more elementary variables,
such as composition, preparation, as well as internal structure and
pore size.
Barbier [96] reported that the deposited coke on the metal is
less dehydrogenated than the deposited coke on the support.
According to his results, for platinum catalysts small metallic par-
ticles are less sensitive to coke formation than larger particles. In
addition, the amount of coke deposited on the metallic function
of a bifunctional catalyst always corresponds to a small fraction
of the amount of coke accumulated on the whole of the catalyst.
Mazzieri et al. [97] studied the deactivation by coke deposition
and sintering and the regeneration of the metal function of Pt–Re–
Sn/Al2O3–Cl and Pt–Re-Ge/Al2O3–Cl catalysts. They found that the
Pt–Re–Sn catalysts were more stable than the Pt–Re-Ge ones. This
was due to the lower amount of coke deposited on the surface of
Pt–Re–Sn.
Macleod et al. [98] compared the deactivation of a number of
bi- and multi-metallic reforming catalysts including Pt–Re, Pt–Ir,
Pt–Sn, Pt–Ge and Pt–Ir–Ge. Addition of Ge (or Sn) to Pt, Ir or Pt–
Ir catalysts dilutes the active metal surface. This geometric effect
improves the selectivity of the catalyst and increased its resistance
to deactivation. The formation of bulk Pt–Ge, Pt–Sn and Pt–Ir–Ge
alloys contribute to the overall rate of deactivation of these sys-
tems. Both Pt–Ir and Pt–Re are highly resistant to deactivation.
Metallic Ir and Re provided sites for the hydrogenation/hydrogen-
olysis of coke fragments and therefore reduced the rate of deacti-
vation of these catalysts.
Quantitative correlations are developed for these observations
by different researchers. Some of these relations are summarized
in Table 3.
4. Reactor configurations and process classification
Naphtha reforming unit is one of the main units of petroleum
refining that is used extensively to convert paraffins and naphth-
enes to aromatics. Because of the industrial importance of this pro-
cess, researchers have studied the design aspect widely to find
appropriate configurations to enhance the production of the de-
sired products. Various types of reactor and different mode of oper-
ation have been suggested which are summarized here.
4.1. Suggested reactor configuration
Various reactor configurations with different advantageous and
disadvantageous have been proposed. These configurations could
be categorized according to the shape of the reactor and the en-
trance flow pattern of the feedstock as follow:

Fresh naphtha feed
F ee d to th e firs t r eac tor
Table 4
Estimated volume percent of different components in the feedstock and the product
of the catalytic naphtha reforming unit.
Component
Normal paraffins
Iso-paraffins
Olefins
Naphthenes
Aromatics
Hydrogen
 Axial-flow tubular reactor.
 Radial-flow tubular reactor.
 Axial-flow spherical reactor.
 Radial-flow spherical reactor.
Numerous research efforts have been focused on improving the
efficiency and operating conditions of these reactor configurations.
These efforts mainly include using membrane to remove hydrogen
from reaction media, suggesting reactors with lower pressure drop,
and using coupled reactor to reduce the capital and operational
cost.
Membrane reactor is a combination of chemical reactor and
membrane and is used in reaction systems in which removing
reaction products from reaction media or adding of reactants along
the reactor is beneficial [107–109]. This effective configuration has
various advantages such as increasing reaction rate, reducing by
product formation, requiring lower energy, and relatively safe
operating [110,111]. According to thermodynamic equilibrium, if
the reactants were removed from the product gases, chemical reac-
tants would shift to products. Considering this fact, researchers de-
signed Pd based membrane reactors in catalytic naphtha reforming
to remove hydrogen from reacting gases.
Presenting configurations with lower pressure drop also at-
tracts much attention because it has significant effects on the yield
and the operational conditions of the process. This parameter plays
an important role in the gas-phase reactions, because the concen-
tration of reactants and consequently the reaction rates and con-
versions are affected by change in the total pressure.
M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93 85
Hydrogen
Recycled hydrogen
T=775K
T=777K R-3
T=777K R-2 Off gas
Condenser
R-1
Reflux drum
P-30
LPG
Stabilizer
Flash drum
Vapor
Valve
Reboiler
Reformate
Furnace
Fig. 4. Schematic diagram of axial-flow tubular fixed-bed reactor.
Making exothermic and endothermic reactions proceeding
simultaneously in one reactor is an interesting idea to use the ther-
mal energy of the exothermic reaction as the heat source of the
Feed (vol%) Product (vol%) endothermic reaction [112,113]. The efficient coupling of exother-
40–50 20–35 mic and endothermic reactions contributes to saving energy and
2–5 10–15 consequently reducing the capital and operational cost that is
0–2 0 highly demanded in our recent world [114–116].
30–40 5–10
The aforementioned issues could be considered in the design of
5–10 45–60
0 2 the reactor of naphtha reforming process in different manners.
4.1.1. Axial-flow tubular reactor
A schematic process diagram of axial-flow tubular fixed-bed
reactor setup for catalytic naphtha reforming reaction is shown
in Fig. 4 [117,118]. The core of this process is consists of three or
four fixed-bed adiabatically operated reactors in series.
The naphtha feedstock is combined with a recycle gas stream
containing 60–90 mol% hydrogen. This mixture is heated, at first
by exchange with effluent from the last reactor and then by heat
exchanger. The inlet temperature of the beds is mostly adjusted
between 750 and 790 K, and operating pressure is about 3.5 MPa.
Naphtha reforming is an endothermic reaction and contributes
to temperature drop in the reactors. Thus, catalytic naphtha
reformers are designed with multiple reactors and with heaters be-
tween the reactors to maintain reactor temperature at desired lev-
els. The effluent from the last reactor is cooled and entered the
separator, in which hydrogen and some of the light hydrocarbons
separate from each other. The flashed vapor is passed to a com-
pressor and then combined with the naphtha charge with H2/HC
ratio in the range of 4–6. The obtained liquid from separator
mostly comprised of desired reformate product but light gases
are also exist. Therefore, this liquid is sent to a stabilizer. Refor-
mate of the bottom of the stabilizer is sent to storage for gasoline
blending. The estimated volume percent of different components
in the feedstock and the product of the catalytic naphtha reforming
unit are presented in Table 4.
Membrane concept can be assisted in the axial-flow tubular
reactors for selective separation of hydrogen that results in better
performance and higher yield [119]. The fixed-bed membrane
reactor is made up of two concentric pipes. The inner pipe is filled
86 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93

Products Naphtha
feed

carrier
hydrogen gas

carrier H2
hydrogen gas

Naphtha
Feedstock
Products
Fig. 5. Schematic diagram of fluidized bed membrane reactor.
Fig. 7. Schematic diagram of radial-flow tubular packed-bed reactor.

Naphtha Nitrobenzene Axial Flow of Permeated

Feed Feed Sweep Gas Hydrogen

Pd-Ag
Catalyst of Inlet Naphtha
Membrane
Feed
Endothermic Side
Catalyst
Perforated
Particle
Screen

Catalyst of
Exothermic Side

Fig. 6. Schematic diagram of coupled reactor in co-current mode of operation.

with catalyst in which catalytic reaction occurred, and hydrogen

flows through the shell side. The inner tube supports a dense film Catalyst particle
Radial naphtha
of Pd–Ag and the outer one is the non-permeable shell. Hydrogen feed
permeates along the reactor in order to control amount of hydro-
gen for better operation and efficiency.
The disadvantages of fixed-bed reactors are poor heat transfer
and low catalyst particle effectiveness factors. Catalyst particles
have severe diffusional limitations due to their size and smaller
Axial sweep
particle sizes are infeasible in fixed-bed systems because of pres-
gas
sure drop considerations [120].
Using a fluidized bed reactor is a promising way to overcome
the catalyst particle size limitations of fixed-bed reactor. Fluidized
bed membrane reactor is a multifunctional reactor that combines Center pipe
Membrane layer
the advantages of a membrane and a fluidized bed reactor. This
configuration has main advantages such as isothermal operation,
Fig. 8. Schematic diagram of radial-flow tubular membrane packed-bed reactor
arrangement of the membrane package and flexibility in mem- with axial-flow of sweeping gas.
brane and heat transfer surface, and negligible pressure drop [121].
The benefits of this concept over conventional fixed bed config- mode with the carrier hydrogen gas in shell. A schematic diagram
uration are the absence of radial and axial temperature gradients of this configuration is shown in Fig. 5 [124].
due to the excellent heat transfer characteristics of fluidization In a novel thermally coupled reactor, the naphtha reforming,
[122,123]. In this configuration, the mass and heat transfer occur which is an endothermic reaction, was coupled with hydrogena-
simultaneously between both sides and product yield improves be- tion of nitrobenzene to aniline to use its generated heat as a heat
cause of hydrogen permeation that is due to hydrogen partial pres- source [125,126]. Co-current mode of operation for coupled reac-
sure gradient. In order to fluidize the catalyst bed, the reacting gas tors is presented in Fig. 6. In this setup, the first two reactors in
is entered into the bottom of the fluidized-bed in a co-current flow the packed-bed configuration have been substituted with the
 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93
highly efficient recuperative reactors. Catalytic reforming takes
place in the shell side whereas the exothermic hydrogenation of
nitrobenzene to aniline, which provides the heat for reforming pro-
cess, occurs in the tube side.
Catalytic naphtha reforming has also been coupled with hydro-
dealkylation of toluene in a fixed bed reactor [127].
As mentioned, fluidized bed reactors have been used widely in
the chemical and petroleum industries because of their numerous
advantages. Coupling of the naphtha reforming and hydrogenation
reaction of nitrobenzene to aniline is also investigated in a fluid-
ized bed reactor [128].
4.1.2. Radial-flow tubular reactor
Radial-flow reactors have been used widely for different reac-
tion systems due to various advantages such lower pressure drop
and higher yield [129–131]. Radial-flow pattern has also been used
in a tubular fixed bed reactor for naphtha reforming process [132].
As shown in Fig. 7 this reactor consists of three concentric tubes.
The reaction takes place in the middle tube, which is packed by
catalyst. The outer annulus is filled by the naphtha feed, which is
distributed uniformly over the packed bed, while the inner annulus
is used as a collector to collect the products. It should be noticed
that the flow in the outer and inner annulus is in axial direction,
but the flow pattern in the bed of catalytic particle is radial.
Membrane concept can also be assisted in the radial-flow tubu-
lar reactors to improve the performance of the catalytic naphtha
reforming process. In this reactor configuration, the naphtha feed
flows radially while the sweeping gas could flow in radial or axial
direction [117,133,134]. Fig. 8 shows the radial-flow tubular mem-
brane reactor in which the naphtha feed flows radially through the
packed bed, whereas the sweeping gas flows axially in the gaps
(shell side).
4.1.3. Radial-flow spherical reactor
Spherical reactor configuration has been investigated widely as
a suitable alternative to conventional tubular reactors [135–138].
This reactor setup has various advantageous respects to packed
bed reactor such as lower pressure drop, smaller catalytic pellets
with higher effectiveness factor, and lower required material thick-
ness [139]. This reactor configuration has been used in naphtha
reforming process in both axial-flow and radial-flow mode.
A schematic diagram of the radial-flow spherical packed-bed
reactor is shown in Fig. 9 [140,141]. This configuration consists
Fig. 9. Schematic diagram of radial-flow spherical packed-bed reactor.
87
Fig. 10. Schematic diagram of axial-flow spherical packed-bed reactor.
of two concentric sphere. The catalyst is charged in the space be-
tween these spheres. The feed gas enters the reactor and flows
from the outside through the catalyst bed into the inner sphere.
The radial-flow in the spherical reactor offers a larger mean
cross-sectional area and reduced distance of travel for flow com-
pared to traditional vertical columns.
4.1.4. Axial-flow spherical reactor
Radial-flow spherical reactor encounter challenges such as dif-
ficulty in applying membrane concept and problems in feed distri-
bution [142]. These drawbacks are revamped in axial-flow
spherical packed bed reactor.
In the Axial-flow spherical packed-bed reactor, catalysts are
placed between two perforated screens. As depicted in Fig. 10
[143], the naphtha feed enters the top of the reactor and flows
steadily to the bottom of the reactor. Achieving a uniform flow dis-
tribution through the catalytic bed is important because the flow is
mainly occurring in an axial direction. Two screens are placed in
upper and lower parts of the reactor to hold the catalyst and act
as a mechanical support.
Membrane technology can be easily used in axial-flow spherical
reactor. The main difference between this setup and the previous
one is that the inner sphere is coated by a hydrogen perm–selective
membrane layer. Hydrogen permeates through the Pd–Ag mem-
brane layer to the shell side and the sweeping gas carries the per-
meated hydrogen. Thus, According to the Le Chatelier’s Principle,
the reaction shiftes toward the product side, and higher product
yields are achieved [144,145].
4.2. Process classification
Catalytic naphtha reforming units are usually categorized
according to the catalyst regeneration procedure. These procedures
could be categorized in three main groups:
1. Semi-regenerative catalytic reformer (SRR).
2. Cyclic catalytic reformer.
3. Continuous catalyst regeneration reformer (CCR).
Worldwide, the semi-regenerative scheme dominates reform-
ing capacity at about 60% of total capacity followed by continuous
regenerative at 28% and cyclic at 12% [146].
88 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93
4.2.1. Semi-regenerative catalytic reformer
The most commonly used type of the catalytic reforming unit is
SRR. This process is characterized by continuous operation over
long periods, with decreasing catalyst activity due to coke deposi-
tion. By decreasing the activity of the catalyst, the yield of aromat-
ics and the purity of the byproduct hydrogen decrease. In order to
maintain the conversion nearly constant, the reactor temperature
is raised as catalyst activity decline. When the reactors reach
end-of-cycle levels, the reformer is shut down to regenerate the
catalyst in situ. Different criteria may be used to determine the
end-of-cycle levels such as the reactor metallurgy temperature
limit, prescribed weighted average inlet temperature (WAIT) in-
crease, specified amount of C5+ yield decline, specified amount of
hydrogen decline, and refinery and reformer economics. To maxi-
mize the length of time (cycle) between regenerations, these early
units were operated at high pressures because high reactor pres-
sure minimizes deactivation by coking. The shutdown of this unit
occurs approximately once each 6–24 months. Research octane
number (RON) that can be achieved in this process is usually in
the range of 85–100, depending on an optimization between feed-
stock quality, gasoline qualities, and quantities required as well as
the operating conditions required to achieve a certain planned cy-
cle length.
The Pt–Re catalyst is usually used in SRR units because it toler-
ates high coke levels and regenerates easily. These catalysts enable
a lower pressure and higher severity operation.
Semi-regenerative reformers are generally built with three to
four catalyst beds in series. The fourth reactor could be added to
allow an increase in either severity or throughput while maintain-
ing the same cycle length. A schematic diagram of SRR unit is
shown in Fig. 4, and all of the aforementioned reactor configura-
tions have been proposed for this process.
4.2.2. Cyclic catalytic reformer
In the cyclic catalytic reformer unit, an extra spare or swing
reactor is exist, which, as well as other reactors, can be individually
isolated. Thus, each reactor can be undergoing in situ regeneration
Fig. 11. Schematic process diagram of continuous catalyst regeneration reformer (CCR) (in which reactors are placed separately behind each other).
while the other reactors are in operation. In this way, only one
reactor at a time has to be taken out of operation for regeneration,
while the reforming process continues in operation. In this process,
low operational pressure, wide boiling range feed, and low hydro-
gen-to-feed ratio may be used, which contributes to high deactiva-
tion rate of the catalyst. Thus, catalyst in individual reactors could
become exhausted in time intervals of from less than a week to a
month. The research octane number in this process is in the range
of 100–104.
Low operational pressure and less variation of the overall
catalyst activity, conversion, and hydrogen purity with time re-
spect to the semi-regenerative process are the main advanta-
geous of the cyclic process. A drawback of this process is that
all reactors alternate frequently between a reducing atmosphere
during normal operation and an oxidizing atmosphere during
regeneration. This switching policy needs a complex process
layout with high safety precautions and requires that all the
reactors be of the same maximal size to make switches be-
tween them possible.
However, the cyclic catalytic reformer units are not very com-
mon, and rarely are used for naphtha reforming process.
4.2.3. Continuous catalyst regeneration reformer
CCR is the most modern type of the catalytic reformers. The
continuous process represents a step change in reforming technol-
ogy compared to semi-regenerative and cyclic processes. In this
unit the catalyst regenerates continuously in a special regenerator
and adds to the operating reactors. The advantages of CCR process
against traditional methods are [147–150]:
– Production of higher octane reformate even working with a
low feed quality.
– Long time working of the process for hydrogen demand.
– Using catalyst with less stability but higher selectivity and
yield.
– Lower required recycle ratio and the lower operational pres-
sure with high yield of hydrogen.
 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93 89

Naphtha feed

Hydrogen Rich
Gas

Off Gas

Combined Feed Exchanger

CCR Regenerator

Separator

stabilizer
Reformate to
Regenerated storage
Catalyst

Spent Catalyst

Fig. 12. Schematic process diagram of continuous catalyst regeneration reformer (CCR) (in which reactors are stacked on top of one other).

Products Fresh Fresh

catalyst catalyst

Catalyst in
product product

Catalyst out

Naphtha Feed
Spent Spent
Fig. 13. Schematic diagram of axial-flow tubular rector in CCR process. catalyst catalyst
Naphtha
feedstock

This process could be designed in different manners. Reactors
may be placed separately behind each other or stacked on top of
one other, as shown in Figs. 11 and 12, respectively.
The catalyst moves from the bottom of one reactor to the top of
the next reactor. The regenerated catalyst is added to the first reac-
tor and the spent catalyst is withdrawn from the last reactor and
transported back to the regenerator. The design reformate octane
number in this process is in the 95–108 range.
The used catalyst in CCR process is mainly of the platinum/tin
alumina type because addition of tin enhances the selectivity to
aromatics, stability, and regeneration ability of Pt/Al2O3 [32–36].
It should mentioned that in CCR unit, catalyst regenerates contin-
uously, thus, selectivity to aromatics of the catalyst is more
Fig. 14. Schematic diagram of radial-flow tubular rector in CCR process.
important than its resistance to deactivation, while in SRR unit, de-
spite the ability to increase the yield of the process, catalyst should
be able to tolerates high coke levels.
It should be mentioned that only axial- and radial-flow tubular
rector have been suggested for this type of reforming unit which
are presented in Figs. 13 and 14, respectively [151,152].
Finally, some of the published modeling of the catalytic naphtha
reforming unit is presented in Table 5. The possibility of comparing
the operational conditions such as temperature and pressure in
different mode of operations as well as the catalyst, the reactor
configuration, and the kinetic model is prepared via this table.
90 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93

Table 5
Some of the published modeling of the catalytic naphtha reforming units.

Mode of Reactor configuration Number of Reaction Catalyst Temperature Pressure Author Reference
operation reactors model
SRR Radial-flow tubular reactor 4 Smith Pt–Re/Al2O3 468–521 °C 1.408– Liang et al. [153]
1.730 MPa
SRR Axial-flow thermally coupled membrane 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Pourazadi et al. [154]
tubular reactor
SRR Axial-flow fluidized bed membrane tubular 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Rahimpour [124]
reactor
SRR Axial-flow tubular reactor 1 – Pt/Si–Al2O3 847–904 K 200–600 psig Barker et al. [173]
SRR Axial-flow tubular reactor 4 – Pt–Re/g/ 480–510 °C 1.5–3 MPa Muktar et al. [174]
Al2O3
SRR Axial-flow fixed bed tubular reactor 3 Padmavathi Pt–Re/Al2O3 773 K 3.7 MPa Behin et al. [155]
SRR Axial-flow thermally coupled fluidized-bed 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Pourazadi et al. [171]
tubular reactor
SRR Axial-flow tubular reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Fathi et al. [172]
SRR Axial-flow tubular reactor 1 Schroder Pt–Re/cAl2O3 753–773 K 1.0–1.5 MPa Schroder et al. [99]
SRR Axial-flow fixed bed tubular reactor 3 Ancheyta Pt–Re 510 K 10.5 kg/cm2 Ancheyta et al. [156]
SRR Radial-flow tubular reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Rahimpour et.al [142]
SRR Axial-flow fixed bed tubular reactor 3 Tailleur PtReCl/Al2O3 740–780 K 3.8 MPa Tailleur et al. [105]
SRR Axial-flow thermally coupled reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Meidanshahi [127]
et al.
SRR Axial-flow tubular reactor 4 – Pt–Re/Al2O3 479 °C 13 kg/cm2 Otal et al. [157]
SRR Axial-flow fixed bed tubular reactor 3 Taskar – 750–790 K 2–3 MPa Taskar et al. [64]
SRR Radial-flow membrane tubular reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Iranshahi et.al [117]
SRR Axial-flow tubular reactor 3 – Pt/Al2O3–Cl 485–520 °C 30 kg/cm2 Sad et al. [176]
SRR Axial-flow membrane tubular reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Khosravanipour [119]
et.al
SRR Radial-flow tubular fixed bed reactor 3 Mohaddecy Pt–Re/Al2O3 497–515 °C 0.31 MPa Mohaddecy [158]
SRR Axial-flow tubular reactor 3 Arani Pt–Re/Al2O3 931 K 2.6–2.9 Mpa Arani et al. [68]
SRR Axial-flow fixed bed tubular reactor 1 – Pt–Re/Al2O3 540 °C 6–10 bar Ren et al. [88]
SRR Combination of spherical and membrane 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Rahimpour et al. [159]
tubular reactors
SRR Axial-flow tubular reactor 3 Hu Pt–Re/Al2O3 766 K 206 psia Hu et al. [168]
SRR Axial-flow tubular reactor 3 – Pt–Re/Al2O3 511.0– 29 bar Adžamić et al. [175]
515.2 °C
SRR Radial-flow spherical packed bed reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Iranshahi et.al [141]
SRR Axial-flow tubular reactor 1 – Pt/c-Al2O3 388–436 °C 1.54– Pauw et al. [160]
2.76 atm abs.
SRR Axial-flow spherical membrane reactor 3 Smith Pt–Re/Al2O3 775–777 K 3.4–3.7 MPa Iranshahi et.al [161]
SRR Axial-flow tubular packed bed reactor 1 – Pt–Sn/Al2O3 515 °C 8 bar Margitfalvi et al. [162]
CCR Fully thermally coupled distillation column 2 – Pt–Sn/Al2O3 84–170 °C 0.17 MPa Lee et al. [163]
CCR Radial-flow tubular reactor 4 Hu Pt–Sn/Al2O3 520 °C 0.35 MPa Hu et al. [106]
CCR Stacked radial-flow reactor 4 Hongjun Pt–Sn/A12O3 412–505 °C 1 Mpa Hongjun et al. [71]
CCR Radial-flow tubular reactor 3 Stijepovic Pt–Sn/A12O3 733 K 0.35 Mpa Stijepovic et al. [151]
CCR Stacked axial-flow reactor 4 Weifeng Pt–Sn/A12O3 515–528 °C 0.5 MPa Weifeng et al. [66]
CCR Stacked radial-flow reactor 4 Gyngazova Pt–Sn/Al2O3 520 °C 0.7 Mpa Gyngazova et al. [152]
CCR Axial-flow tubular reactor 4 Smith Pt–Sn/Al2O3 790 K 10.3 bar Lid et al. [164]
CCR Axial-flow tubular reactor 3 Padmavathi Pt–Sn/Al2O3 519 °C 0.54 MPa Mahdavian et al. [148]
CCR Axial-flow tubular reactor 4 Smith Pt–Sn/Al2O3 503 °C 23.5–28.5 bar Askari et al. [167]
CCR Axial-flow tubular reactor 1 – Pt–Sn/Al2O3 515 °C 8 bar Margitfalvi et al. [162]
CCR Circulating fluidized bed membrane 1 – Pt–Re/Al2O3 823 K 1013 kPa Chen et al. [86]
reformer
CCR Axial-flow tubular reactor 4 Wang Pt–Sn/Al2O3 516 °C 0.5 MPa Wang et al. [166]

5. Suggestions 2. More experimental efforts are needed to assess the pro-

Although many investigators have been studied different as-
pects of catalytic naphtha reforming process and huge amount of
papers have been published about this issue, more researches are
needed to characterize the nature of the reaction and revamping
the yield of this process. As a guideline for further investigations,
various suggestions have been proposed here.
1. Various kinetic models with different number of lumped
components and reactions have been proposed for catalytic
naphtha reforming reaction. Although considering simple
models may reduce the accuracy of the modeling, consid-
ering a very complex model may have no considerable
effect on the final results. Thus a comparative study is
needed to find out the proper and optimize number of
the lumped components and reactions.
posed kinetic model and the results of the reactor modeling.
3. In most of the studies, the reactors are modeled in one-
dimensional direction (only axial direction has been consid-
ered) while considering other directions (such as radial
direction) may have considerable effect on the obtained
results. It is suggested to compare the differences between
one-dimensional and two-dimensional modeling in order
to specify the proper assumptions of the modeling.
4. Most of the presented reactor models are homogeneous
models, while catalytic naphtha reforming reaction is a het-
erogeneous process inherently. It is better to study this pro-
cess as a heterogeneous reaction in future studies and
investigate the differences between these two models.
5. Fewer studies are accomplished on modeling of CCR unit
compared to SRR. Due to the superior features of this unit,
more studies are needed to assess this mode of operation.
 M.R. Rahimpour et al. / Applied Energy 109 (2013) 79–93
Investigating the application of various reactor configura-
tions such as membrane reactors and thermally coupled
reactors in CCR unit is a novel idea.
6. Conclusion
Catalytic naphtha reforming is one of the backbone processes in
refining industries. This process is used widely for production of
high-octane gasoline and aromatic components. Various investiga-
tors have been studied different aspects of the naphtha reforming
process due to the importance of this industrial process.
Finding a suitable catalyst with higher selectivity and stability
and lower coking and deactivation comprise an extensive part of
these studies. To achieve this purpose, various components have
been added to the metal and acid function of the catalyst.
Presenting a proper kinetic model with appropriate amount of
components and reactions, and deactivation model involving the
affecting parameters attracts much attention too. Another signifi-
cant field study is finding an efficient reactor configuration. The
suggested reactors are tubular or spherical reactors and the
feedstock may flow in axial or radial direction. Different modes
of operations are presented for a catalytic naphtha reforming unit
including semi-regenerative catalytic reformer (SRR), cyclic cata-
lytic reformer, and continuous catalyst regeneration reformer.
SRR is the most commonly used type of the catalytic reforming
unit, but due to the better performance of CCR, all new units are
designed based on this technology and old units are revamped to
the continuous process or combination of both.
Aforementioned topics have been investigated widely and
many articles have been published concerning them. Searching
among these huge papers may be a confusing and time confusing
task for those who want to have collective information about
naphtha reforming process. In this paper, the established papers
on catalytic naphtha reforming process were reviewed, and the ob-
tained results of the impressive studies in this field were presented
in tables. In addition, suggestions are presented as a guideline for
further investigations.
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