Fuel 90 (2011) 34923508

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Fuel
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Detailed description of kinetic and reactor modeling for naphtha catalytic reforming
Miguel A. Rodrguez, Jorge Ancheyta
Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas Norte 152, Col. San Bartolo Atepehuacan, Mexico City 07730, Mexico

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

Article history: Kinetic and reactor modeling of catalytic reforming of naphtha is described in the present work. The
Available online 22 June 2011 development of a kinetic reforming model is reported with detail. The validation of the developed kinetic
model with bench-scale isothermal reactor experiments is also carried out. The kinetic and reactor mod-
Keywords: els are applied for the simulation of commercial semi-regenerative reforming unit. The effect of benzene
Catalytic reforming precursors in the feed in both laboratory and commercial reactors is also simulated, and the use of the
Reactor modeling reactor model to predict other process parameters is highlighted.
Kinetic modeling
2011 Published by Elsevier Ltd.

1. Introduction
Catalytic reforming is a chemical process used to convert petro-
leum naphtha, particularly low-octane number straight-run naph-
tha into high-octane gasoline called reformate. In addition to
producing reformate catalytic reforming is also a primary source
of aromatics used in the petrochemical industry (BTX: benzene,
toluene, and xylenes).
The typical feed to catalytic reforming is a mixture of straight-
run naphthas: 3090 C light naphtha (C5 and C6), 90150 C med-
ium naphtha (C7 and C9), and 150200 C heavy naphtha (C9 and
C12).
In commercial practice, the most-preferred feed to catalytic
reforming is naphtha with boiling range of 85165 C, since the
light fraction (85 C) is not good feedstock due to its composition
(low molecular weight parafns tending to crack to C4 and to be
benzene precursor formation, which is undesirable because of
environmental regulations) and the heavy fraction (180 C+)
hydrocracks to excessive carbon lay-down on the reformer
catalyst.
Prior to catalytic reforming, the naphtha feed needs to be
hydrotreated to reduce the impurities content (sulfur, nitrogen,
and oxygen compounds) to acceptable levels, which if not removed
will poison the reforming catalysts. This pretreatment is manda-
tory since the catalyst is gradually poisoned leading to excessive
coking and rapid deactivation.
To convert the low-quality naphthas, the catalytic reforming
process re-arranges the hydrocarbon molecules to form more com-
plex molecular shape hydrocarbons with improved octane values.
Although certain degree of cracking occurs the conversion is done
Corresponding author.
E-mail address: jancheyt@imp.mx (J. Ancheyta).
without changing the boiling point range of the feed. During this
transformation catalytic reforming produces signicant amounts
of hydrogen, which is used in other processes such as hydrotreat-
ing and hydrocracking, as well as small amounts of methane, eth-
ane, propane and butanes.
Catalytic reforming processes are commonly classied accord-
ing to the frequency and mode of catalyst regeneration, into (1)
semi-regenerative, (2) cyclic regeneration, and (3) continuous
regeneration. The main difference among the three types of pro-
cesses is the need of unit shut-down for catalyst regeneration in
the case of semi-regenerative process, the use of an additional
swing or spare reactor for catalyst regeneration for the cyclic pro-
cess, and the catalyst replacement during normal operation for the
continuous regeneration type. The most-used process worldwide is
the semi-regenerative type followed by the continuous regenera-
tion and by the less common cyclic regeneration. Currently, cata-
lytic reformers are mostly designed with continuous regeneration
and the former semi-regenerative plants are being revamped to
operate as continuous regeneration.
A large number of reactions occur in catalytic reforming over
bifunctional catalysts, such as dehydrogenation and dehydroiso-
merization of naphthenes to aromatics, dehydrogenation of paraf-
ns to olens, dehydrocyclization of parafns and olens to
aromatics, isomerization or hydroisomerization to isoparafns,
isomerization of alkylcyclopentanes and substituted aromatics
and hydrocracking of parafns and naphthenes to lower hydrocar-
bons. All reactions are desirable except hydrocracking, which oc-
curs to a greater extent at high temperature and converts
valuable C 5 + molecules (reformate) into light gases.
Various kinetic models for catalytic reforming reactions have
been reported in the literature [128], which have been subject
of several reviews. The level of sophistication of these models var-
ies from a few lumps to detailed kinetic models, and is related to
the development of high-speed hardware and large-capacity

0016-2361/$ - see front matter 2011 Published by Elsevier Ltd.

doi:10.1016/j.fuel.2011.05.022
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3493

Nomenclature

a, b, c parameters of the hydrogen reaction rate equation N10 naphthenes with 10 atoms of carbon
A aromatics N 10 naphthenes with 10 + 11 atoms of carbon
A, B, C, D constant for calculating Cp N11 naphthenes with 11 atoms of carbon
A10 aromatis with 10 atoms of carbon pi partial pressure of component i
A10 aromatis with 10 + 11 atoms of carbon P reaction pressure; parafns
A11 aromatis with 11 atoms of carbon Po base reaction pressure
Cp molar specic heat P10 parafns with 10 atoms of carbon
C10 hydrocarbons with 10 atoms of carbon P10 parafns with 10 + 11 atoms of carbon
C10 hydrocarbons with 10 + 11 atoms of carbon P11 parafns with 11 atoms of carbon
C11 hydrocarbons with 11 atoms of carbon ri rate of reaction of component i
dp particle diameter R ratio of hydrocarbon compositions
EA activation energy Rg universal constant of gases
F molar ow Rep Reynolds number based on particle diameter
gc force to mass conversion factor, 9.8066 (kgm m)/(kgf s2) S cross sectional area
G supercial mass velocity SV space-velocity
DGo reaction standard Gibbs energy T reaction temperature
DH heat of reaction To base reaction temperature
ki kinetic constant at T x conversion
o
ki kinetic constant at To WABT weighted average bed temperature
k10 kinetic constant for hydrocarbons with 10 atoms of car- WAIT weighted average inlet temperature
bon Wci weight fraction of catalyst in each reactor bed respect to

k10 kinetic constant for hydrocarbons with 10 + 11 atoms of the total
carbon WHSV weight hourly space velocity
k11 kinetic constant for hydrocarbons with 11 atoms of car- yi molar composition of component i
bon z reactor length
K ratio of kinetic constants
Ke equilibrium constant Greek letters
LHSV liquid hourly space velocity e void fraction of the catalyst bed
MW molecular weight q density of the gas mixture
n reaction order qc density of the catalyst
N number of reactors; naphthenes l viscosity of the gas mixture
NC number of components

computers. A chronological evolution of the catalytic reforming ki-
netic modeling is presented in Fig. 1.
Fig. 2 shows the reaction schemes used in the development of
some kinetic models. The rate equations, values of kinetic param-
eters, properties of catalyst and feedstock used during experiments
and other details can be found in the respective references.
Most of the published kinetic models based on the lumping
approach report the rate constants to be dependent on feed
and catalyst properties. Some models are neither capable to pre-
dict the composition of alkylcyclopentanes nor the composition
of n-parafns and i-parafns, nor the detailed composition of
hydrocracking reaction products, not the whole range of hydro-
carbons present in naphtha composition. The level of sophistica-
tion varies from just a few lumps to a very detailed kinetic
model. On the other hand, sophisticated models based on funda-
mental approaches, e.g., single event kinetic model, although
overcoming some drawbacks of the lumping models, still have
to be validated under conditions, e.g., other feedstocks, different
from those they were derived, and provide a more convincing
comparison with industrial reality. Also, lumping models involve
reduced number of kinetic parameters and require relatively
small amount of experimental data for their estimation. While
fundamental detailed models are quite complicated, with large
number of parameters, and frequently need larger number of
experiments. Therefore a kinetic modeler faces to a big dilemma,
either one uses a lumped-kinetic model or a more fundamental
approach. The decision is not easy to make. However, there are
some important points that affect this decision. Most of the
times, the model is needed to simulate a commercial unit and
anticipate the effect of minor changes of process parameters
on product yields and quality. If a model with only few lumps
is chosen, the predictive capability surely is not sufcient to rep-
resent the desired situation. But, if a detailed mechanistic model
is selected, it may be too complex to implement, not because of
the solution of the model which with the modern computers and
algorithms has become a relatively easy task, but due to the cost
and amount of experimental information needed to determine
the model parameters. Thus, why not use an intermediate ap-
proach that maintains the simplicity of the lumping approach
and is detailed enough to correctly predict the behavior of com-
mercial catalytic reforming plant? By intermediate approach one
must understand that the number of lumps is such that the
composition of the product is predicted with all the desired
components. The answer to this question is the reason why
lumped kinetic models are still commonly used to characterize
reactive groups and describe the reaction kinetics of complex
processes in a tractable manner. It is the general conclusion of
all the published scientic papers that the lumping approach is
sufciently reliable for describing the relationships between pro-
cess variables and reaction rates. The comparisons of simulated
results by using lumping kinetic models with data obtained at
different scales included those at commercial scale support this
conclusion.
The aim of this work is to propose a kinetic model for naphtha
catalytic reforming and to describe in detail how it was developed
and used together with the reactor model to validate experimental
information obtained in a bench-scale isothermal reactor and to
simulate commercial catalytic reformers.
3494 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

Stijepovic et al. (2009)

Wei et al. (2008)
Sotelo and Froment (2008)
Shanyingu and Zhu (2004)
Rahimpour et al. (2003) Hou et al.
Hu et al. (2003) (2006, 2007)
Taskar and Riggs (1997)
Kinetic Model Padmavathi and Chaudhuri (1997) Joshi et al. (1999)
Coppens and Froment (1996) Szczygiel (1999)
Taskar (1996)
Van Trimpont et al. (1988) Turpin (1992)

Marin and Froment (1982) Ramage et al. (1987)

Kmak and Stuckey (1973) Ramage et al. (1980)

Jenkins and Stepehns (1980)
Kmak (1972)
Zhorov et al. (1970)
Krane et al. (1959) Henningsen and Bundgarrd-Nielson (1970)
Smith (1959)
Burnett et al. (1965)
Zhorov et al. (1965)

1955 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010
Year

Fig. 1. Evolution of kinetic modeling for catalytic reforming.

C8+ Lumps: C5- P N5 N6 A C5 -

Naphthene + H 2 Aromatics + 3H 2
C7 Lumps: C5- P N5 N6 A C5 -

n
Gas Paraffin
3
C6 Lumps: C5- P N5 N6 A C5 -

Smith (1959) Ramage et al. (1980)

P9 +
N9 + A9+
PX MX OX
P8 N8
EB
P7 N7 A7
Alkyl- Alkyl-
n-Paraffins
ciclohexanes Benzene P6 N6 A6
(NP)
(ACH) (ACH)
Cracked P5
Products
(0) P4
Alkyl- P3
i-Paraffins
ciclopentanes
(IP)
(ACP) P2

P1
Henningsen and Bundgaard-Nielson (1970) Hou et al. (2007)

Fig. 2. Examples of some reaction schemes used to develop catalytic reforming kinetic models.

2. Development of the kinetic model
The kinetic model used for simulation of the catalytic reforming
reactors is an extension of that reported in [1], which utilizes lum-
ped mathematical representation of the reactions that take place.
These representations are written in terms of isomers of the same
nature (parafns, naphthenes or aromatics). These groups range
from 1 to 10 carbon atoms for parafns, and from 6 to 10 carbon
atoms for naphthenes and aromatics. The original reported model
[1] includes 53 chemical reactions, which are summarized in Table 1.
To account for more reactions and have better naphtha compo-
sition predictability, the following modications to the original
model were done.
2.1. Kinetic parameters for hydrocarbons with 11 atoms of carbon
Typical naphthas used as feed to catalytic reforming include
hydrocarbons with up to 11 atoms of carbon as can be seen in
Table 2. The original model [1] considers reactions only for hydro-
carbons with 10 atoms of carbon. To maintain the original values of
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3495

kinetic parameters it was assumed that the reported hydrocarbons and 11 atoms of carbon: C
10 = C10 + C11. In such a way, the different
with 10 atoms of carbon are in fact a lump of hydrocarbons with 10 hydrocarbon species can be de-lumped as:
P10 P10 P11 1
Table 1
Chemical reactions considered in the original kinetic model reported by Krane et al.
N10 N10 N11 2
[1], activation energies and factors for pressure effect for each reforming reaction. A10 A10 A11 3
Reaction Number of reactions EAj (kcal/mol)
The originally reported reaction rate equation for each hydro-
Parafns carbon can be then expressed as:
Pn ? Nn 5 45
Pn ? Pni + Pi 21 55 dC 10
k10 C 10 k10 C 10 C 11 4
Subtotal 26 d1=SV
Naphthenes
This equation can also be written as function of C10 and C11 and
N n ? An 5 30
Nn ? Nni + Pi 6 55 their individual kinetic parameters (k10 and k11) as follow:
Nn ? Pn 5 45
Subtotal 16 dC 10
k10 C 10 k11 C 11 5
Aromatics
d1=SV
An ? Ani + Pi 6 40 By combining Eqs. (4) and (5) the following relationship can be
An ? P n 4 45 derived:
An ? N n 1 30
Subtotal 11 k10 R 1
k10 6
R K
Reaction ak
where
Isomerization 0.370
Dehydrocyclization 0.700 C 10
R 7
Hydrocracking 0.433 C 11
Hydrodealkylation 0.500
Dehydrogenation 0.000 k11
K 8
n: number of atoms of carbon (1 6 i 6 5). k10

Table 2
Typical compositions of various feeds to catalytic reforming process.

Naphthas Average value

1 2 3 4 5 6
n-Parafns
C4 0 1.568 0 0 0 0 0.261
C5 1.818 11.368 9.818 10.362 1.983 1.392 6.124
C6 9.633 8.034 8.356 8.412 9.467 9.477 8.897
C7 8.116 6.778 7.114 7.148 8.386 8.402 7.657
C8 6.464 5.326 5.602 5.616 6.640 6.683 6.055
C9 4.454 3.514 3.858 3.809 4.625 4.68 4.157
C10 1.640 1.403 1.707 1.635 1.948 2.066 1.733
C11 0.297 0.266 0.321 0.292 0.318 0.370 0.311
Subtotal 32.422 38.257 36.776 37.274 33.367 33.07 35.194
i-Parafns
C4 0 0.076 0 0 0 0 0.013
C5 0.565 6.459 3.191 3.771 0.794 0.453 2.539
C6 8.868 7.289 7.548 7.495 5.373 5.413 6.998
C7 6.779 5.676 5.973 5.965 6.943 6.963 6.383
C8 7.070 5.897 6.310 6.187 7.289 7.344 6.683
C9 6.241 5.066 5.499 5.311 6.448 6.509 5.846
C10 3.526 2.84 3.384 3.221 3.899 4.402 3.545
C11 0.212 0.203 0.281 0.254 0.289 0.374 0.269
Subtotal 33.261 33.506 32.186 32.204 31.035 31.458 32.275
Naphthenes
C5 0.897 0.977 0.973 0.978 0.333 0.286 0.741
C6 5.069 4.345 4.435 4.434 5.226 5.166 4.779
C7 6.934 6.038 6.071 6.065 7.179 7.157 6.574
C8 5.112 4.307 4.593 4.565 5.320 5.461 4.893
C9 1.842 1.535 1.655 1.578 1.938 1.970 1.753
C10 0.495 0.398 0.558 0.492 0.561 0.641 0.524
C11 0.096 0.085 0.106 0.099 0.105 0.125 0.103
Subtotal 20.445 17.685 18.391 18.211 20.662 20.806 19.367
Aromatics
C6 1.393 1.074 1.200 1.199 1.380 1.351 1.266
C7 3.506 2.676 3.024 3.038 3.634 3.576 3.242
C8 5.326 4.015 4.529 4.542 5.507 5.428 4.891
C9 2.908 2.186 2.956 2.671 3.488 3.218 2.905
C10 0.707 0.569 0.903 0.830 0.891 1.056 0.826
C11 0.032 0.032 0.035 0.031 0.036 0.037 0.034
Subtotal 13.872 10.552 12.647 12.311 14.936 14.666 13.164
3496 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

Eqs. (6)(8) can be used for calculating the values of the individ- procedure in a graphic way for two reactions of hydrocracking of
ual kinetic parameters for hydrocarbons with 10 and 11 atoms of parafns to parafns with less number of carbon atoms. The nal
carbon, k10 and k11 respectively. For this calculation, the relation- set of individual kinetic parameters for the reactions of hydrocar-
ships dened by Eqs. (7) and (8) are needed. bons with 10 and 11 atoms of carbon are detailed in Table 3.
To determine the value of the constant R for each hydrocarbon
type (Eq. (7)), typical feed of a commercial catalytic reforming unit 2.2. Reactions for the formation of benzene
was analyzed in different periods of time, whose compositions are
reported in Table 2. From this table, the corresponding values of R The original model does not take into account neither the for-
for this specic feed are: mation of cyclohexane (N6) via methylcyclopentane (MCP) isomer-
ization (MCP M N6) nor the production of MCP from P6 (P6 M MCP).
P10
RP 9:109 9 The Krane model (1) only considers the following path reaction:
P11
P6 M N6 M A6.
Due to the importance for accurate prediction of benzene con-
N10
RN 5:106 10 tent in reformate, it is necessary to add those reactions in which
N11
benzene is taking part. Thus, the reaction network shown in
Fig. 4, and the corresponding contribution to the reaction rate
A10
RA 24:414 11 equations were added to the kinetic model. Also, it was assumed
A11 that all the benzene is produced via cyclohexane dehydrogenation.
For calculation of RP, the total amount of parafns was used,
that is the sum of n-parafns plus i-parafns. 2.3. Isomerization of parafns
The values of K (Eq. (8)) were obtained for each reaction by
extrapolation of the relationships calculated with the original re- The reactions of isomerization of n-parafns to i-parafns are
ported kinetic parameters [1] as function of the number of atoms highly desired during catalytic reforming of naphtha, since the pro-
of carbon (e.g., k7/k6, k8/k7, k9/k8 and k10/k9). Fig. 3 illustrates this duced i-parafns contribute to the increase of octane number of

1.8
1.6678 P11 P9 +P2
1.7 k11/k10
1.6 k10/k9
1.6499 P11 P10+P11
k9 /k8
1.5

1.4
Constant K

k8 /k7
1.3
k6 /k5
1.2

1.1

1.0
k7 /k6
0.9

0.8
6 7 8 9 10 11 12 13
Number of atoms of carbon

Fig. 3. Example of the extrapolation procedure to calculate the constant K.

Table 3
Individual kinetic constants for hydrocarbons with 10 and 11 atoms of carbon.

Reaction C6/C5 C7/C6 C8/C7 C9/C8 C10/C9 C11/C10a

k10 b k10c k11c

P?N 2.2931 1.3609 1.4033 1.4645 0.0254 0.0243 0.0356

Pn ? Pn1 + P1 1.1667 1.0000 1.3571 1.5789 1.6333 1.6678 0.0049 0.0046 0.0077
Pn ? Pn2 + P2 1.2000 1.0000 1.3888 1.5600 1.6154 1.6499 0.0063 0.0059 0.0097
Pn ? Pn3 + P3 1.1852 1.3438 1.5814 1.6029 1.6170 0.0109 0.0103 0.0166
Pn ? Pn4 + P4 1.5714 1.6182 1.6212 0.0089 0.0084 0.0135
Pn ? Pn5 + P5 0.0124 0.0117 0.0191
N?P 0.1351 2.3500 1.1489 1.0000 1.0000 0.0054 0.0054 0.0054
N?A 2.2587 2.3678 1.1395 1.0000 1.0000 0.2450 0.2450 0.2450
Nn ? Nn1 + P1 14.111 1.0551 1.0000 0.0134 0.0134 0.0134
Nn ? Nn2 + P2 1.0551 1.0000 0.0134 0.0134 0.0134
Nn ? Nn3 + P3 1.0000 0.0080 0.0080 0.0080
An ? An1 + P1 5.0000 1.2000 1.0000 0.0006 0.0006 0.0006
An ? An2 + P2 1.2000 1.0000 0.0006 0.0006 0.0008
A?P 1.0000 1.0000 1.0000 1.0000 0.0016 0.0016 0.0016
a
Extrapolated values.
b
Original kinetic parameters reported by Krane et al. [1].
c
Calculated values of kinetic parameters.
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3497

the reformate. Isomerization is a fast reaction catalyzed by acid The effect of temperature on equilibrium constant is given by
sites and it reaches the equilibrium at catalytic reforming condi- [29]:
tions. Hence, parafns distribution can be estimated by thermody-
DGoi
namic equilibrium calculation. lnK ei  14
Rg T
For the following general isomerization reaction:
nPi $ iPi 12 where DGo is the reaction standard Gibbs energy. DGo can be deter-
mined with
the equilibrium constant (Ke) is
Z Z
yipi yipi DGo DGo0  DHo0 DHo0 1 T
DCp T
DCp dT
K ei 13 dT  15
ynp 1  yipi Rg T Rg T 0 Rg T T T0 Rg T0 Rg T
To calculate DGo with Eq. (15), the following dependence of
P6 MCP heat capacity on temperature can be used:
(C6 Paraffins) (Methyl Cyclopentane)
Cpi Ai Bi T C i T 2 Di T 3 16
By sustituting Eq. (16) in Eq. (15), the integrals can evaluated
with the following nal forms:
Z T
DB 2 DC 3
N6 A6 DCpdT DAs  1T 0 s  1T 20 s  1T 30
(Benzene) T0 2 3
(Cyclohexane)
DD 4
Fig. 4. Reaction network for benzene formation.
s  1T 40 17
4

Table 4
Thermodynamic data of various parafns [30].

Name A B C D Ho Go
n-Butane 2.266 7.91E02 2.65E05 6.74E10 30.15 4.10
i-Butane 0.332 9.19E02 4.41E05 6.92E09 32.15 4.99
n-Pentane 0.866 1.16E01 6.16E05 1.27E08 35.00 2.00
2 Methyl butane 2.275 1.21E01 6.52E05 1.37E08 36.92 3.54
2,2 Dimethyl propane 3.963 1.33E01 7.90E05 1.82E08 39.67 3.64
n-Hexane 1.054 1.39E01 7.45E05 1.55E08 39.96 0.06
2 Methyl pentane 2.524 1.48E01 8.53E05 1.93E08 41.66 1.20
3 Methyl pentane 0.570 1.36E01 6.85E05 1.20E08 41.02 0.51
2,2 Dimethyl butane 3.973 1.50E01 8.31E05 1.64E08 44.35 2.30
2,3 Dimethyl butane 3.489 1.47E01 8.06E05 1.63E08 42.49 0.98
n-Heptane 1.229 1.62E01 8.72E05 1.83E08 44.88 1.91
2 Methyl hexane 9.408 2.06E01 1.50E04 4.39E08 46.59 0.77
3 Methyl hexane 1.683 1.63E01 8.92E05 1.87E08 45.96 1.10
2,2 Dimethyl pentane 11.966 2.14E01 1.52E04 4.15E08 49.27 0.02
2,3 Dimethyl pentane 1.683 1.63E01 8.92E05 1.87E08 47.62 0.16
2,4 Dimethyl pentane 1.683 1.63E01 8.92E05 1.87E08 48.28 0.74
3,3 Dimethyl pentane 1.683 1.63E01 8.92E05 1.87E08 48.17 0.63
3 Ethyl pentane 1.683 1.63E01 8.92E05 1.87E08 45.33 2.63
n-Octane 1.456 1.84E01 1.00E04 2.12E08 49.82 3.92
2 Methyl heptane 21.435 2.97E01 2.81E04 1.10E07 51.50 3.05
3 Methyl heptane 2.201 1.88E01 1.05E04 2.32E08 50.82 3.28
4 Methyl heptane 2.201 1.88E01 1.05E04 2.32E08 50.69 4.00
2,2 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 53.71 2.56
2,3 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 51.13 4.23
2,4 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 52.44 2.80
2,5 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 53.21 2.50
3,3 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 52.61 3.17
3,4 Dimethyl hexane 2.201 1.88E01 1.05E04 2.32E08 50.91 4.14
3 Ethyl hexane 2.201 1.88E01 1.05E04 2.32E08 50.40 3.95
2,2,3 Trimethyl pentane 2.201 1.88E01 1.05E04 2.32E08 52.61 4.09
2,2,4 Trimethyl pentane 1.782 1.86E01 1.02E04 2.19E08 53.57 3.27
2,3,3 Trimethyl pentane 2.201 1.88E01 1.05E04 2.32E08 51.73 4.52
2,3,4 Trimethyl pentane 2.201 1.88E01 1.05E04 2.32E08 51.97 4.52
2 Methyl 3 ethyl pentane 2.201 1.88E01 1.05E04 2.32E08 50.48 5.08
3 Methyl 3 ethyl pentane 2.201 1.88E01 1.05E04 2.32E08 51.38 4.76
n-Nonane 0.751 1.62E01 4.61E05 7.12E09 54.74 5.93
2,2,3 Trimethyl hexane 10.899 2.52E01 1.71E04 4.75E08 57.65 5.86
2,2,4 Trimethyl hexane 14.405 2.64E01 1.84E04 5.23E08 58.13 5.38
2,2,5 Trimethyl hexane 12.923 2.62E01 1.85E04 5.39E08 60.71 3.21
3,3 Diethyl pentane 16.067 2.69E01 1.91E04 5.51E08 55.44 8.38
2,2,3,3 Tetramethyl pentane 13.037 2.60E01 1.81E04 5.12E08 56.70 8.20
2,2,3,4 Tetramethyl pentane 13.037 2.60E01 1.81E04 5.12E08 56.64 7.80
2,2,4,4 Tetramethyl pentane 16.099 2.79E01 2.06E04 6.15E08 57.83 8.13
2,3,3,4 Tetramethyl pentane 13.117 2.61E01 1.82E04 5.15E08 56.46 8.15
n-Decane 1.890 2.30E01 1.26E04 2.70E08 59.67 7.94
3,3,5 Trimethyl heptane 16.808 2.94E01 2.07E04 5.86E08 61.80 8.02
2,2,3,3 Tetramethyl hexane 14.052 2.94E01 2.11E04 6.17E08 61.66 11.28
2,2,5,5 Tetramethyl hexane 14.890 2.97E01 2.14E04 6.25E08 68.32 4.66
3498 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

Table 5
Example of calculation of Ke for the isomerization of n-hexane (T = 400 K).

DA DB DC DD DHo0 DGo0 DGo

RT
Ke

n-Hexane M 2 methyl pentane

1.47 0.0087 1.1E05 3.8E09 1.7 1.14 1.200 3.32
n-Hexane M 3 methyl pentane
0.484 0.0031 5.95E06 3.5E09 1.06 0.45 0.303 1.35
n-Hexane M 2,2 dimethyl butane
2.919 0.0113 8.6E06 8.5E10 4.39 2.24 1.890 6.62
n-Hexane M 2,3 dimethyl butane
2.435 0.0079 6.1E06 7.8E10 2.53 0.92 0.455 1.58

Z T
DCp DC 2 7 parafns lumps. That is, 41 new parafns lumps are incorporated
dT DA lns DBs  1T 0 s  1T 20
T0 T 2 to the model.
DD 3
s  1T 30 18 2.4. Effects of pressure and temperature on kinetic parameters
3
where The model reported by [1] does not include the inuence of
temperature and pressure on the kinetic parameters. To overcome
T these limitations, an Arrhenius-type variation of the rate constants
s 19
T0 with activation energy values for each type of reaction, and a factor
To apply the above described procedure for equilibrium calcula- that accounts for the pressure effect can be used. The equation for
tion of the parafns isomerization reactions that occur in catalytic the combined effect of temperature and pressure on kinetic param-
reforming, some thermodynamic data are required, which are de- eters can be expressed as follows:
picted in Table 4. For example, for the isomerization of n-hexane,    ak
0 EAj 1 1 P
four isomers are obtained: 2 Methyl pentane, 3 Methyl pentane, ki ki  21
Rg T 0 T P0
2,2 Dimethyl butane, and 2,3 Dimethyl butane. Each isomerization
reaction needs to be considered separately. The calculated values The values of activation energies (EAj) for each reaction j, and
of all parameters required to evaluate DGo are reported in Table 5. pressure effect factors (ak) are given in Table 1. Krane et al. [1] re-
o
With DGo, Ke is then computed with Eq. (14). Once the values of all ported values of kinetic parameters ki at temperatures ranging
Ke have been determined, the formulae to calculate the composi- from 471 to 515 C and Po = 300 psig, H2-to-oil ratio of 28 mol/
tion (yi) of all isomers is deduced from Eq. (13), which is mol, and WHSV of 0.75.0 h1. Because for each reaction, only
one value of the corresponding kinetic parameter for each reaction
K ei rate was reported in this range of temperatures, the base temper-
yi Pnisomers 20
1 i1 K ei ature was considered to be the average of both values (To = 493 C).
The values of Ke and equilibrium composition calculated by
2.5. The extended proposed kinetic model
using this procedure for the isomers of parafns ranging from 6
to 11 atoms of carbon at different temperatures are summarized
Based on all the previous considerations, a kinetic model with
in Table 6.
33 lumps plus 41 parafns isomers was developed. The proposed
Splitting the total parafns lumps, as reported by (1), into n-
reaction scheme is shown in Fig. 5. All reactions are assumed to
parafns and i-parafns, allows then for extending the model to
be pseudo-rst order with respect to the hydrocarbon. The reaction
consider 48 parafns plus i-parafns lumps instead of the original
rate of each lump is given by the following equations, which com-
prise the kinetic model. Each rate reaction equation is function of
Table 6 the kinetic constants (ki) and the concentration of each pseudo-
Equilibrium constants and molar composition for hexane isomerization. component (Pi, Ni, Ai). The values of all rate constants are reported
Reaction Equilibrium constants in Table 7.
Parafns:
n-Hexane M 300 K 400 K 500 K 600 K 700 K 800 K
2 Methyl pentane 6.73 3.32 2.20 1.69 1.41 1.24 dP11
k34 N11 k58 A11  k1 k2 k3 k4 k5 k6 P11 22
3 Methyl pentane 2.11 1.35 1.04 0.87 0.76 0.69 d1=SV
2,2 Dimethyl 41.83 6.62 2.20 1.07 0.65 0.45
butane
dP 10
2,3 Dimethyl 4.60 1.58 0.82 0.54 0.39 0.32 k2 P11 k39 N10 k61 A10
butane d1=SV
Equilibrium molar composition  k7 k8 k9 k10 k11 k12 P10 23
Isomers 300 K 400 K 500 K 600 K 700 K 800 K
dP9
2 Methyl pentane 11.96 23.94 30.30 32.76 33.51 33.59 k3 P11 k8 P10 k44 N9 k65 A9
3 Methyl pentane 3.76 9.76 14.26 16.78 18.09 18.76 d1=SV
2,2 Dimethyl 74.33 47.73 30.34 20.73 15.33 12.08  k13 k14 k15 k16 k17 P9 24
butane
2,3 Dimethyl 8.17 11.36 11.34 10.37 9.36 8.52
butane dP8
k4 P11 k9 P10 k14 P9 k48 N8 k68 A8
n-Hexane 1.78 7.21 13.76 19.36 23.71 27.05 d1=SV
Total 100.00 100.00 100.00 100.00 100.00 100.00  k18 k19 k20 k21 k22 P8 25
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3499

A11

(nP11 iP11) N11

A10
(nP10 iP10) N10
A9
(nP9 iP9) N9
A8
(nP8 iP8) N8
A7
(nP7 iP7) N7
MCP

(nP6 iP6) N6 A6

(nP5 iP5)

(nP4 iP4)

P3

P2

P1

Fig. 5. Proposed reaction scheme for catalytic reforming of naphtha.

Table 7
Kinetic parameters of the proposed model (T = 490 C).

Reaction step k (h1) Reaction step k (h1) Reaction step k (h1)

P11 ? N11 + H2 0.0356 k1 P7 + H2 ? P5 + P2 0.0018 k25 N8?A8 + 3H2 0.2150 k49
P11 + H2 ? P10 + P1 0.0075 k2 P7 + H2 ? P4 + P3 0.0043 k26 N 8 + H2 ? N 7 + P 1 0.0007 k50
P11 + H2 ? P9 + P2 0.0100 k3 P6 ? N6 + H2 0.0000 k27 N 7 + H2 ? P 7 0.0019 k51
P11 + H2 ? P8 + P3 0.0135 k4 P6 ? MCP + H2 0.0042 k28 N7 ? A7 + 3H2 0.0788 k52
P11 + H2 ? P7 + P4 0.0135 k5 P6 + H2 ? P5 + P1 0.0018 k29 N 6 + H2 ? P 6 0.0204 k53
P11 + H2 ? P6 + P5 0.0191 k6 P6 + H2 ? P4 + P2 0.0016 k30 N6 ? A6 + 3H2 0.1368 k54
Pl0 ? Nl0 + H2 0.0243 k7 P6 + H2 ? 2P3 0.0025 k31 N6 ? MCP 0.0040 k55
Pl0 + H2 ? P9 + P1 0.0015 k8 P5 + H2 ? P4 + P1 0.0018 k32 MCP + H2 ? P6 0.0008 k56
Pl0 + H2 ? P8 + P2 0.0054 k9 P5 + H2 ? P3 + P2 0.0022 k33 MCP ? N6 0.0238 k57
Pl0 + H2 ? P7 + P3 0.0160 k10 N11 + H2 ? P11 0.0050 k34 A11 + 4H2 ? P11 0.0016 k58
Pl0 + H2 ? P6 + P4 0.0095 k11 N11 ? A11 + 3H2 0.6738 k35 A11 + H2 ? A10 + P1 0.0006 k59
Pl0 + H2 ? 2P5 0.0095 k12 N11 + H2 ? N10 + P1 0.0134 k36 A11 + H2 ? A9 + P2 0.0006 k60
P 9 ? N 9 + H2 0.0500 k13 N11 + H2 ? N9 + P2 0.0134 k37 A10 + 4H2 ? P10 0.0016 k61
P9 + H2 ? P8 + P1 0.0030 k14 N11 + H2 ? N8 + P3 0.0080 k38 A10 + H2 ? A9 + P1 0.0006 k62
P9 + H2 ? P7 + P2 0.0039 k15 N10 + H2 ? P10 0.0054 k39 A10 + H2 ? A8 + P2 0.0006 k63
P9 + H2 ? P6 + P3 0.0068 k16 N10 ? A10 + 3H2 0.3198 k40 A10 + H2 ? A7 + P3 0.0000 k64
P9 + H2 ? P5 + P4 0.0058 k17 N10 + H2 ? N9 + P1 0.0134 k41 A9 + 4H2 ? P9 0.0016 k65
P 8 ? N 8 + H2 0.0266 k18 N10 + H2 ? N8 + P2 0.0134 k42 A9 + H2 ? A8 + P1 0.0005 k66
P8 + H2 ? P7 + P1 0.0019 k19 N10 + H2 ? N7 + P3 0.0080 k43 A9 + H2 ? A7 + P2 0.0005 k67
P8 + H2 ? P6 + P2 0.0056 k20 N9 + H2 ? P9 0.0054 k44 A8 + 4H2 ? P8 0.0011 k68
P8 + H2 ? P5 + P3 0.0034 k21 N9 ? A9 + 3H2 0.2205 k45 A8 + H2 ? A7 + P1 0.0001 k69
P8 + H2 ? 2P4 0.0070 k22 N9 + H2 ? N8 + P1 0.0127 k46 A7 + 4H2 ? P7 0.0016 k70
P 7 ? N 7 + H2 0.0076 k23 N9 + H2 ? N7 + P2 0.0127 k47 A6 + 3H2 ? N6 0.0015 k71
P7 + H2 ? P6 + P1 0.0027 k24 N8 + H2 ? P8 0.0025 k48

dP7 dP5
k5 P11 k10 P10 k15 P9 k19 P8 k51 N7 k70 A7 k6 P11 2k12 P10 k17 P 9 k21 P8 k25 P7 k29 P6
d1=SV d1=SV
 k23 k24 k25 k26 P7 26  k32 k33 P 5 28

dP6 dP4
k6 P11 k11 P10 k16 P9 k20 P8 k24 P7 k53 N6 k5 P11 k11 P10 k17 P9 2k22 P8 k26 P7 k30 P6 k32 P5
d1=SV d1=SV
k56 MCP  k27 k28 k29 k30 k31 P6 27 29
3500 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

dP3 dA7
k4 P11 k10 P10 k16 P9 k21 P8 k26 P7 2k31 P6 k52 N7 k64 A10 k67 A9 k69 A8  k70 A7 44
d1=SV d1=SV
k33 P5 k38 N11 k43 N10 k64 A10 30
dA6
k54 N6  k71 A6 45
dP2 d1=SV
k3 P11 k9 P10 k15 P9 k20 P8 k25 P 7 k30 P6
d1=SV The hydrogen balance can be derived from the stoichometry of
k33 P5 k37 N11 k42 N10 k47 N9 k60 A11 the reactions in which it is involved, either those that consume
hydrogen or those that produce hydrogen. The resulting reaction
k63 A10 k67 A9 31
rate for hydrogen is then:
dP1 dH2 X7 X6 X6
k2 P11 k8 P10 k14 P9 k19 P8 k24 P 7 k29 P6 aP
i1 i 12i
bN
i1 i 12i
 cA
i1 i 12i
 k56 MCP
d1=SV d1=SV
k32 P5 k36 N11 k41 N10 k46 N9 k50 N8 46
k59 A11 k62 A10 k66 A9 k69 A8 32 The values of ai, bi, and ci, are reported in Table 8.

Naphthenes:
3. Results and discussions
dN11
k1 P11  k34 k35 k36 k37 k38 N11 33
d1=SV 3.1. Validation of the kinetic model with bench-scale reactor
experiments
dN10
k7 P10 k36 N11  k39 k40 k41 k42 k43 N10 34
d1=SV 3.1.1. Experiments in an isothermal bench-scale reactor
To validate the modied kinetic model various experiments
dN9 were conducted with a hydrodesulfurized straight-run naphtha
k13 P9 k37 N11 k41 N10  k44 k45 k46 k47 N9
d1=SV recovered from a commercial naphtha HDS unit (82168 C distil-
35 lation range, 0.74 g/mL density at 20 C, and <0.5 wppm sulfur).
The detailed composition of this feed for catalytic reforming exper-
dN8 iments determined by GC analysis is presented in the rst column
k18 P8 k38 N11 k42 N10 k46 N9  k48 k49 k50 N8 of Table 9.
d1=SV
36
Table 9
dN7 Molar composition of the feed for bench-scale reactor and of different reformates
k23 P7 k43 N10 k47 N9 k50 N8  k51 k52 N7 37 obtained at 10.5 kg/cm2 pressure, 6.5 H2/oil molar ratio, and 3.54 h1 WHSV.
d1=SV
Reaction temperature
dN6 Feed 490 C 500 C 510 C
k27 P6 k57 MCP k71 A6  k53 k54 k55 N6 38
d1=SV
n-Parafns
P11 2.20 0.01 0.01 0
dMCP P10 2.97 0.09 0.00 0
k28 P6 k55 N6  k56 k57 MCP 39 P9 5.09 0.40 0.28 0.18
d1=SV
P8 6.36 1.22 0.91 0.63
Aromatics: P7 3.20 2.92 2.45 1.97
P6 4.40 5.51 5.22 4.40
dA11 P5 3.80 5.26 4.97 4.85
k35 N11  k58 k59 k60 A11 40 Total 28.02 15.41 13.84 12.03
d1=SV
i-Parafns
dA10 iP10 6.22 0.28 0.17 0.85
k40 N10 k59 A11  k61 k62 k63 k64 A10 41 iP9 8.31 1.50 1.24 0.67
d1=SV iP8 6.51 3.76 2.75 2.01
iP7 6.20 8.01 7.29 6.07
dA9 iP6 6.70 9.41 9.50 9.83
k45 N9 k60 A11 k62 A10  k65 k66 k67 A9 42 iP5 3.40 6.40 6.19 5.53
d1=SV
Total 37.34 29.36 27.14 24.96

dA8 Naphthenes
k49 N8 k63 A10 k66 A9  k68 k69 A8 43 N11 0.40 0.00 0.00 0
d1=SV N10 0.60 0.00 0.00 0
N9 3.56 0.01 0.02 0.01
N8 4.71 0.63 0.66 0.38
N7 5.80 0.33 0.31 0.27
Table 8 N6 3.21 0.01 0.01 0.01
Coefcients of the balance equation of hydrogen. MCP 0.42 1.35 1.23 1.15
Total 18.70 2.33 2.23 1.82
i ai bi ci
Aromatics
1 k1  (k2 + k3 + k4 + k5 + k6) 3k35  (k34 + k36 + k37 + k38) 4k58 + k59 + k60 A11 0.30 0.97 1.10 1.25
2 k7  (k8 + k9 + k10 + k11 + k12) 3k40  (k39 + k41 + k42 + k43) 4k61 + k62 + k63 + k64 A10 2.70 5.61 5.76 5.99
3 k13  (k14 + k15 + k16 + k17) 3k45  (k44 + k46 + k47) 4k65 + k66 + k67 A9 4.21 12.53 13.20 14.17
4 k18  (k19 + k20 + k21 + k22) 3k49  (k48 + k50) 4k68 + k69 A8 4.71 15.66 16.90 18.2
5 k23  (k24 + k25 + k26) 3k52  k51 4k70 A7 3.22 12.82 13.91 15.02
6 k27 + k28  (k29 + k30 + k31) 3k54  k53 3k71 A6 0.80 5.30 5.91 6.56
7 (k32 + k33) Total 15.94 52.90 56.78 61.19
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508
Reactor
TI
TI
PI
TI
Feedstock
Feedstock Feed H2
vessel dryer dryer
Fig. 6. Experimental bench-scale unit for catalytic reforming experiments.
The tests were carried out in a xed-bed bench-scale stainless-
steel reactor (2.5 cm internal diameter and 25 cm length) with
hydrogen recycle. The reactor is operated in isothermal mode by
independent temperature control of a three-zone electric furnace.
A general diagram of the experimental setup is depicted in Fig. 6.
All the experiments were done at pressure of 10.5 kg/cm2, H2/oil
molar ratio of 6.5 and temperatures of 490, 500 and 510 C. To sim-
ulate a series of three reforming reactors, the bench-scale reactor
was loaded with different amounts of catalyst, i.e. 6, 15 and
30 mL, keeping the same naphtha owrate at constant value of
102 mL/h in order to have different space-velocities (WHSV):
17.72, 7.09 and 3.54 h1, respectively. These amounts of catalyst
and WHSV were selected in order to have 20% of the total mass
of catalyst in the rst reactor, 30 % in the second reactor and 50%
in the third reactor, which are typical percentages of catalyst load-
ing in commercial catalytic reforming reactors.
The catalyst used in all experiments was a commercial available
Pt-Re reforming sample (0.29 wt.% Pt, 0.29 wt.% Re), having specic
surface area of 221 m2/g, pore volume of 0.36 mL/g and particle
diameter of 1.6 mm. The catalyst beds were diluted with an inert
material both with the same particle size in order to have a better
distribution of heat losses over the reactor, so that uniformity of
the temperature can take place more easily. The degree of dilution
was varied depending on the amount of catalyst loaded to the reac-
tor. The highest dilution was used for experiments with 20% of the
total mass of catalyst. The temperature drop, measured with an ax-
ial thermocouple, was less than 5 C thus the operation can be as-
sumed as isothermal.
Reformate samples were collected in a high pressure product
receiver. The remaining C4  (butane and lighters) cracking prod-
ucts were removed by distillation afterwards (stabilization). The
stabilized reformate was analyzed on parafns, i-parafns, naphth-
enes and aromatics by gas chromatography.
3.1.2. Results of the simulation
3.1.2.1. Reforming experiments. Table 9 shows the detailed molar
composition of the reformate as function of reaction temperature.
From this table, the following observations can be made:
 The total amount of aromatics increases from 15.94 mol% to
52.90, 56.78 and 61.19 mol% at 490, 500 and 510 C, respec-
3501
PIC
PI
Separator
On-line
gas
chromatography
PI
Separator
Reformate
Compressor
tively. The most important increase is observed for lighter aro-
matics, particularly A6, A7 and A8.
 Naphthenes react relatively easily and are highly selective to
aromatics compounds via dehydrogenation. This reaction pro-
ceeds essentially to completion. For instance N6, N9, N10 and
N11 disappear completely and the conversions of N7 and N8
are higher than 87%. It is also conrmed that naphthenes dehy-
drogenation is favored by high reaction temperature as they
were almost completely converted at temperatures higher than
490 C (>87% conversion of total amount of naphthenes). This is
the main reason why naphthenes are the most desirable com-
ponents in reforming feedstocks.
 Parafns isomerization reaction is important because naphtha
contains high percentage of n-parafns, which after isomeriza-
tion, yield products with higher octane number. The naphtha
used in the present experiments has high parafn content:
28.02 mol% n-parafns and 37.34 mol% i-parafns. This reaction
occurs rapidly at commercial operating temperatures and is
limited by the thermodynamic equilibrium. The temperature
has little inuence on it because the heat of reaction is low.
 The most difcult reaction to promote is the dehydrocyclization
of parafns, which consists of molecular arrangements of paraf-
ns to naphthenes. Heavy parafns (P9, P10 and P11) have con-
versions higher than 92% and lighter parafns showed lower
values. This is because the increase in the probability of ring for-
mation is high as the molecular weight of the parafn increases.
Similarly to naphthenes dehydrogenation reaction, parafns
dehydrocyclization is favored at high reaction temperatures.
3.1.2.2. Validation of the kinetic model. The kinetic model described
previously was incorporated into an isothermal pseudo-homoge-
neous one-dimensional reactor model. The use of diluent and prop-
er particle size of the catalytic bed ensures that the data were
collected under kinetic regime and transport effects can be ne-
glected. To evaluate the product composition as function of the
reactor length, the mass balance equations were solved with a
Runge Kutta Method.
Fig. 7 presents a comparison of the experimental and predicted
molar reformate composition for some selected hydrocarbons: nP5,
iP5, nP6, nP7, MCP, N6, N7 and A6) at 510 C as function of catalyst
3502 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

8 catalyst, i.e., catalytic reforming is conducted as a gassolid reac-

tion. Radial and axial dispersion effects can also be neglected since
7 the reactor diameter and length are much larger than the diameter
of the catalyst particle. In addition, at steady-state conditions the
6 catalyst activity can be assumed to be constant. Thus, the commer-
cial semi-regenerative reforming reactors can be represented with
5 A6 the one-dimensional pseudo-homogeneous adiabatic model. The
mol %

following ordinary differential equations constitute the reactor

4
model, which are integrated through each reactor bed to describe
the reformate composition, temperature and pressure proles
3
N7 along the length of the reactors. The Ergun equation was used to
2
predict the total pressure drop of the reactors.
N6
dyi MW i
1  ri 47
dz zWHSV
MCP
0 PNR
dT S i1 r i DH Ri
PNC 48
7 dz i1 F i Cpi

6 i-P5 dP 1  e G2 1  e2 Gl
 1:75  105 1:5  103
5 n-P5 dz e qdP g c
3 e3 qd2P g c
P6 49
mol %

4
3 P7
2 equation, heats of reaction (DHRi) are necessary which are deter-
1 X
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Fractional catalyst weigth
Fig. 7. Experimental (d) and predicted () composition of the reformate obtained
at 510 C in the bench-scale reactor.
bed length. The following conclusions can be pointed out from this
comparison:
 The predicted product molar composition agrees very well with
experimental data. The average deviation between experimen-
tal and predicted values is less than 3%.
 As the naphtha passes through the catalyst bed, A6 concentra-
tion increases. The same behavior is found for all aromatics
compounds.
 The concentrations of N6 and N7 and heavy parafns (P7P11,
only P7 is shown in the gure) decrease as they undergo conver-
sion. High rate of conversion of naphthenes is found in the rst
30 % of the catalyst bed. After 60 % catalyst bed, naphthenes
concentration approaches a very low steady-state value.
 The relative reaction rates of naphthenes and parafns are dif-
ferent in the rst 2030 % of the catalyst bed. While N6 and
N7 are almost totally converted in this section, MCP and paraf-
ns have low conversion. This means that MCP is much less
reactive than N6 and N7.
 The calculated A6 (benzene) composition matches very well
with experimental data with a maximum deviation of 2%, which
is the result of proper description of benzene reaction
mechanism.
Eqs. (47)(49) are solved simultaneously with the kinetic model
rate equation for each component (ri) described previously using a
fourth-order RungeKutta method. To solve the energy balance
mined with the following equations:
X
DH R mp Hfp  mr Hfr 50
0.8 0.9 1 Z T
Hfi H0fi CpdT 51
298K
Cp A BT CT 2 DT 3 52
The values of heats of formation H0f ,
and constants (a, b, c, and
d) for calculating the specic heat (Cpi) are reported in Table 10.
3.2.2. Reaction conditions of the commercial reformer
The commercial semi-regenerative reforming unit has four
reactors with interstage heaters, and operates at the following
reaction conditions: 495 C inlet temperature, 10.5 kg/cm2 reactor
pressure, 6.3 mol/mol hydrogen-to-oil ratio, and feedstock ow
rate of 30,000 BPD. The hydrodesulfurized straight-run naphtha
used as feedstock has the following main properties: 0.7406 spe-
cic gravity 60/60 F, 104.8 g/mol molecular weight, 88180 C
distillation range, 59.11 mol% total parafns, 20.01 mol% total
naphthenes, and 20.88 mol% total aromatics. The catalyst used in
the commercial reforming unit is the same than that employed
in the bench-scale experiments described previously.
The main characteristics of each of the four reactors of the semi-
regenerative reforming unit are detailed in Table 11. The inverse of
weight hourly space velocity (100/WHSV) is reported in this table
since this parameter is more common to indicate the increased
reaction severity and reactants reactor positions. As can be seen
the rst reactor is always smaller than the other reactors and the
last reactor is the largest. This difference in reactor sizes is because
some of the reactions occurring in the rst reactors are very fast,
and those taking place in the last reactors are slow.

3.2. Simulation of commercial semi-regenerative reforming reactors
3.2.1. The reactor model
At the typical catalytic reforming conditions the feed (naphtha)
enters the reactor in gas phase, and is put in contact with the solid
3.2.3. Results of the simulation
3.2.3.1. Composition of the reformate. Fig. 8 presents the results of
simulated reformate molar composition and the commercial re-
ported values at the exit of the fourth reactor for different hydro-
carbons. From this table, the following observations can be drawn:
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3503

Table 10
Properties of pure compounds contained in reforming feed and products.

PM sg Tb (K) PVR (bar) RON MON A B C D Hof (J/mol)

2 3
Gases Cp = A + BT + CT + DT
Hydrogen 2.016 9.0E5 20.3 2.714E+1 9.274E3 1.381E5 7.645E9 0.0
Methane 16.043 0.3000 111.6 1.925E+1 5.213E2 1.197E5 1.132E8 7.490E+4
Ethane 30.070 0.3564 184.6 5.409E+0 1.781E1 6.938E5 8.713E9 8.474E+4
Propane 44.094 0.5077 231.1 13.100 98.90 97.10 4.224E+0 3.063E1 1.586E4 3.215E8 1.039E+5
Butane 58.124 0.5844 272.7 3.558 93.80 89.60 9.487E+0 3.313E1 1.108E4 2.822E9 1.262E+5
n-Parafns
Pentane 72.151 0.6310 309.2 1.073 61.70 62.60 3.626E+0 4.873E1 2.580E4 5.305E8 1.465E+5
Hexane 86.178 0.6640 341.9 0.342 24.80 26.00 4.413E+0 5.820E1 3.119E4 6.494E8 1.673E+5
Heptane 100.205 0.6882 371.6 0.112 0.00 0.00 5.146E+0 6.762E1 3.651E4 7.658E8 1.879E+5
Octane 114.232 0.7068 398.8 0.037 19.00 15.00 6.096E+0 7.712E1 4.195E4 8.855E8 2.086E+5
Nonane 128.259 0.7217 424.0 0.012 17.00 20.00 8.374E+0 8.729E1 4.823E4 1.031E7 2.292E+5
Decane 142.286 0.7342 447.3 0.004 16.01 21.10 7.913E+0 9.609E1 5.288E4 1.131E7 2.498E+5
Undecane 156.313 0.7439 469.1 0.001 14.10 23.00 8.395E+0 1.054E+0 5.799E4 1.237E4 2.705E+5
i-Parafns
Isobutane 58.124 0.5631 261.4 4.978 93.00 92.09 1.390E+0 3.847E1 1.846E4 2.895E8 1.346E+5
2 Methylbutane 72.151 0.6247 301.0 1.409 92.30 90.30 9.525E+0 5.066E1 2.729E4 5.723E8 1.546E+5
2,2 Dimethylbutane 86.178 0.6540 322.8 0.679 95.60 93.40 1.663E+1 6.293E1 3.481E4 6.850E8 1.857E+5
2,2 Dimethylpentane 100.205 0.6782 352.4 0.241 92.80 95.60 5.010E+1 8.956E1 6.360E4 1.736E7 2.063E+5
2,2,4 Trimethylpentane 114.232 0.6962 372.4 0.118 100.00 100.00 7.461E+0 7.779E1 4.287E4 9.173E8 2.243E+5
2,2 Dimethylheptane 128.242 0.7146 405.9 0.029 101.10 100.30 2.089E+1 9.668E1 6.120E4 1.570E7 2.470E+5
3,3,5 Trimethylheptane 142.286 0.7469 428.9 0.012 94.20 90.55 7.037E+1 1.232E+0 8.646E4 2.455E7 2.587E+5
Naphthenes
Methylcyclopentane 84.162 0.7536 345.0 0.310 91.3 80.0 5.011E+1 6.381E1 3.642E4 8.014E8 1.068E+5
Cyclohexane 84.162 0.7834 353.8 0.225 83.0 77.2 5.454E+1 6.113E1 2.523E4 1.321E8 1.232E+5
Methylcyclohexane 98.189 0.7740 374.1 0.111 74.8 71.1 6.192E+1 7.842E1 4.438E4 9.366E8 1.549E+5
Ethylcyclohexane 112.216 0.7922 404.9 0.033 45.6 40.8 6.389E+1 8.893E1 5.108E4 1.103E7 1.719E+5
Propylcyclohexane 126.243 0.7977 429.9 0.012 17.8 14.0 6.252E+1 9.889E1 5.795E4 1.291E7 1.934E+5
Butylcyclohexane 140.260 0.8031 454.1 0.004 70.31 68.50 6.296E+1 1.081E+0 6.305E4 1.400E7 2.133E+5
Hexylcyclopentane 154.297 0.8006 476.3 0.001 70.00 68.00 5.832E+1 1.128E+0 6.536E4 1.473E7 2.096E+5
Aromatics
Benzene 78.114 0.8844 353.2 0.222 108.00 98.00 3.392E+1 4.739E1 3.017E4 7.130E8 8.298E+4
Toluene 92.141 0.8718 383.8 0.071 120.10 105.00 2.435E+1 5.125E1 2.765E4 4.911E8 5.003E+4
Ethylbenzene 106.168 0.8718 409.3 0.025 107.90 97.90 4.310E+1 7.072E1 4.811E4 1.301E7 2.981E+4
Propylbenzene 120.195 0.8665 432.4 0.010 101.50 98.70 3.129E+1 7.486E1 4.601E4 1.081E7 7.830E+3
Butylbenzene 134.222 0.8646 456.5 0.003 100.40 95.50 2.299E+1 7.934E1 4.396E4 8.570E8 1.382E+4
Pentylbenzene 148.250 0.8624 478.6 0.000 110.00 92.00 4.218E+1 9.772E1 6.242E4 1.570E7 3.380E+4

Table 11
Main characteristics of the commercial catalytic reforming reactors.

Reactor 1 2 3 4 Total
Length, m 4.902 5.410 6.452 8.208 24.972
% of reactor length 19.6 21.7 25.8 32.9 100.0
Accumulated % of reactor length 19.6 41.3 67.1 100.0
Diameter, m 2.438 2.819 2.971 3.505
Catalyst weight, ton 9.13 13.82 22.82 42.58 88.35
wt.% of catalyst bed 10.3 15.7 25.8 48.2 100
Accumulated wt.% of catalyst bed 10.3 26.0 51.8 100
WHSV, h1 16.0 10.6 6.4 3.4 36.4
Accumulated WHSV, h1 16.0 26.6 33 36.4
100/WHSV 6.25 9.43 15.63 29.41 60.72
Accumulated 100/WHSV 6.25 15.68 31.31 60.72

 Good agreement is obtained between simulated and reported
commercial values. The content of hydrocarbons with ten and
eleven atoms of carbon and those involved in benzene forma-
tion (MCP, A6, P6 and N6) as well as iso-parafns are well calcu-
lated. Thus the reactor and kinetic models predict with good
accuracy the reformate composition.
 As the feedstock passes through the reactor in series the content
of all aromatic hydrocarbons increases. The most important
change is observed for A6, A7, A8 and A9, while for A10 the
increase is low and A11 remains essentially unchanged.
 Naphthenes with six and more atoms of carbon react relatively
easy and their reactions proceed essentially to completion. Sim-
ilar behavior is found for heavy parafns, i.e. P10 and P11. P8 and
P9 also exhibited high conversions, while the content of some
light parafns is increased because they are produced by hydro-
cracking or hydrogenolysis.
 The contents of N6N10 and heavy parafns (P8P11) decrease as
they undergo conversion. High conversion of naphthenes is
found in the rst and second reactors. After the third reactor,
naphthenes content approaches a very low steady-state value.
The relative rates of these naphthenes and parafns conversions
are very different in the rst two reactors. While N6 and N7 are
almost totally converted in this section, parafns have a very
low conversion.
 There is an insignicant change in iso-parafns content in the
rst and second reactors, and in the last two reactors the change
is higher. Similar behavior is found with light parafns. This
means that the increase in aromatics content in the third and
3504 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

60 6 5
A

50 5
4

40 4
3
mol %

30 3
i-P
2
20 2
n-P MCP
1
10 1 N8
N7 N9
N N6 N10
0 0 0
6 12 20
A8
nP6 10
5 iP6
16
A7
iP7
4 8 A9
12
mol %

3 nP5 6
nP7 8
2 4 iP8
A6
nP8 A10
iP5 4
1 2 iP9
nP9
A11
nP10
0 nP11 0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
100/WHSV 100/WHSV 100/WHSV

Fig. 8. Proles of predicted () and commercial (s) molar composition of the reformate.

fourth reactors appears to be solely because of the disappear-
ance of parafns.
3.2.3.2. Delta-T of reactors. Fig. 9 shows the temperature proles in
the four reactors in series. In the rst reactor, the major reactions
are endothermic and fast (e.g., dehydrogenation of naphthenes to
aromatics), causing a very sharp temperature drop from 495 to
443 C. This remarkable decrease in temperature (DT1 = 52 C) al-
most quenches all reactions and more catalyst in the rst reactor
would not provide additional conversion.
The outlet stream of the rst reactor is reheated to the same
temperature as that of the inlet of the rst reactor (495 C) and
fed to the second reactor. Here, mostly the isomerization reaction
500
R-1 R-2 R-3
takes place, the remaining naphthenes are dehydrogenated and a
moderate temperature drop is observed (DT2 = 30 C). From the
second reactor the efuent is again reheated to 495 C before
entering the third reactor, and nally, the same sequence is fol-
lowed in the fourth reactor. The temperature drops across the third
and fourth reactors are lower (17 and 14 C, respectively), which
are due to the exothermic hydrocracking of parafns reaction.
Dehydrogenation and cracking reactions take place in the last
two reactors. The average temperature and the amount of catalyst
in the last reactors are higher that those of the rst ones. This al-
lows the transformation of parafns into aromatics by dehydrocyc-
lization and into light parafns by hydrocracking.
The comparison of simulated and actual temperature drops
indicates that the reactor model predictions match well with the
information reported in the commercial reforming unit. The accu-
mulated absolute difference between predicted and actual reactor
R-4 delta-T is smaller than 3 C.
To =495C

490 3.3. Simulation of the effect of benzene precursors in the feed

Reactor temperature, C

3.3.1. Preparation of the feed

480
The feed used in this case is slightly different from that em-
ployed in previous sections. The new feed (Feed A) has the follow-
470 ing main properties: 0.730 specic gravity 60/60 F, 110 g/mol
molecular weight, and 60190 C distillation range. Having an ini-
tial boiling point (IBP) of 60 C indicates that the precursors of ben-
460 zene formation are present in this feed, since the hydrocarbons
involved in the benzene formation network have the following
normal boiling points: 80.1 C benzene, 68.7 C hexane, 71.8 C
450 methyl cyclopentane, and 80.7 C cyclohexane.
To evaluate the effect of benzene formation precursors Feed A
was fractionated to adjust its initial boiling point to 88 C in order
440
0 10 20 30 40 50 60 70 to prepare a free-benzene precursors feed. This other feed (Feed B)
resulted with the following main properties: 0.734 specic gravity
100/WHSV
60/60 F, 112 g/mol molecular weight, and 88190 C distillation
Fig. 9. Proles of predicted reactor temperature () and commercial value (s). range.
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3505

The compositions of Feed A and Feed B determined by gas chro- 8

matography are presented in Table 12. It is clearly observed that
Feed A possesses certain amount of the precursors of benzene for- 7
mation and benzene itself (1.12 mol% A6, 7.69 mol% P6, 0.64 mol%
MCP, and 4.23 mol% N6), while in Feed B their contents are substan- 6
tially reduced (0.26 mol% A6, 0.44 mol% P6, 0 mol% MCP, and
3.45 mol% N6). 5 N7
Because of separation of light compounds, Feed B became a A6

mol %
little bit heavier than Feed A, which is observed as an increase 4
in specic gravity and molecular weight. i-P5, i-P6 and MCP were
totally removed by adjusting IBP of Feed A, and n-P5 and n-P6 N6
3
were reduced considerably (>94%). Cyclohexane (N6) exhibited
a reduction of 18.4%, while reduction in benzene (A6) was of
2
68.3%.
The main benzene formation precursors are N6 and MCP, and
1
in less importance n-P6. By adjusting the IBP of Feed A from 60
to 88 C, MCP and n-P6 are almost totally eliminated, but N6 is MCP
still present in high amount in Feed B. It is expected that at 0
0 10 20 30 40 50 60 70 80 90 100
the beginning of the reaction N6 will not be produced via MCP
Fractional catalyst weight
isomerization, since Feed B does not have MCP in its composi-
tion. Therefore, benzene will be obtained only by dehydrogena- Fig. 10. Comparison of experimental (d) and predicted () molar composition of
tion of the N6 originally present in Feed B. As the reaction the reformate obtained at 510 C in the bench-scale reactor.
proceeds, MCP will be formed from P6, and N6 and hence A6 pro-
duction will increase. 3.3.2.1. Isothermal model predictions versus experimental data. Fig. 10
shows a comparison of experimental and predicted reformate mo-
3.3.2. Results of the simulations lar composition of some selected hydrocarbon types (MCP, N6, N7
For this case, the simulations were carried out rst in isother- and A6) as function of the position in the catalyst bed. It is observed
mal mode of operation to compare the predicted reformate compo- that the calculated compositions agree well with experimental
sition with experimental values obtained in the bench-scale bench-scale reactor information with average deviation less than
reactor, and then in adiabatic mode to predict the behavior of a 3%. Particularly, the calculated A6 (benzene) composition matches
commercial reforming unit. with high accuracy the experimental data with maximum devia-
tion of 2%.
It is worthy to mention that rate constants of lumped kinetic
Table 12 models usually depend on feedstock and catalyst properties, and
Molar composition of feeds with and without benzene formation precursors. it may be inappropriate to use them for simulating reforming reac-
Feed A Feed B tors for feed conditions different to those from which the parame-
n-Parafns ters were determined. However, if the kinetic model is sufciently
nP11 0.77 0.79 detailed, rate constants can be considered to be independent of ini-
nP10 2.72 3.55 tial feedstock composition, and thus be used to simulate the reac-
nP9 4.05 5.82 tor for other feed conditions. A problem when using more detailed
nP8 5.52 7.88
models is that the simplicity of kinetic representations used in
nP7 6.77 9.75
nP6 7.69 0.44 models with small number of lumps is partially lost, since the
nP5 6.80 0.09 use of kinetic models with large number of lumps, where the num-
Total 34.32 28.32 ber of parameters is signicantly increased, means that greater
i-Parafns amounts of experimental data are also required. Despite this, the
iP10 4.10 5.53 results shown in Fig. 10 clearly indicate that the developed kinetic
iP9 4.52 5.20
model is sufciently detailed to consider the kinetic parameters to
iP8 6.50 8.39
iP7 5.64 6.68 be independent of feed composition.
iP6 6.72
iP5 2.46 3.3.2.2. Predictions with the adiabatic model. Fig. 11 presents the ef-
Total 29.94 25.80 fect of feed composition on benzene and its formation precursors
Naphthenes hydrocarbon as well as total aromatics content in the reformate
N11 and commercial reactor delta-T, as function of the inverse of
N10 0.87 1.15
space-velocity (100/WHSV) and temperature. The following effects
N9 3.56 4.72
N8 4.04 7.00 are observed:
N7 5.95 8.43
N6 4.23 3.45  Feed B produces less benzene in the reformate than Feed A (3.4
MCP 0.64
versus 6.1 mol% at the exit of the fourth reactor).
Total 19.29 24.75
 The benzene production rate in the rst two reactors using Feed
Aromatics
A is higher than that of Feed B. In these two reactors, benzene is
A11 0.96 0.90
A10 1.34 1.25 mainly produced by N6 dehydrogenation. After reactor 2 there is
A9 4.24 5.75 no considerable increase in benzene content when Feed B is
A8 5.77 8.45 used (from 2.95 mol% at the exit of the second reactor to
A7 3.02 4.52 3.41 mol% at the exit of fourth reactor), while this increase
A6 1.12 0.26
was indeed higher with Feed A (from 4.5 to 6.1 mol% at the exit
Total 16.45 21.13
of the same reactors).
3506 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508

7 150
R-1 R-2 R-3 R- 4
6
140
Benzene, mol % .

4 130

Total delta-T, C
3
120
2
110
1
T=490C
0 100
0 10 20 30 40 50 60
100/WHSV
8 90
A6
80

Total aromatics, mol %

nP6
6
70
mol % .

A6
4
nP6 60

2
MCP 50
MCP
N6 40
0
470 480 490 500 510 520 470 480 490 500 510 520
Temperature,C Temperature,C

Fig. 11. Simulation of the operation of commercial reforming reactors with feeds with benzene formation precursors (, Feed A) and without benzene formation precursor
(- - -, Feed B).

 The complete separation of MCP as in Feed B aids to reduce model can be used to analyze other aspects of the catalytic reform-
cyclohexane formation, and thus benzene production. ing process. Turpin [14] proposed a procedure to validate the per-
 N6 conversion is almost 100% at all reaction temperatures for formance of a catalytic reforming unit. This procedure considers
the two feeds. As the reaction temperature is increased MCP the calculation of the global and hydrogen material balances, com-
content in reformate obtained from both feeds also increases parison of experimental and calculated feed and product densities,
with respect to feed initial values, which is produced mainly analysis of the gas composition (calculation of some quotients, iso-
from P6. The increase in MCP contributes to N6 formation, and butene to n-butane molar ratio), probability plots of feed and refor-
hence, benzene content in reformate is also increased. mate components, and ring balance. All this information and more
 The effect of temperature on benzene formation is lesser in Feed can be generated with the developed kinetic and reactor models.
A compared with Feed B. A6 increases from 1.12 mol% to 8 mol% As examples, Tables 13 and 14 show the global and hydrogen
at 510 C for Feed A, while this increase for Feed B is from mass balances for a case of study simulated at the following condi-
0.26 mol% to 4 mol%. This indicates that the separation of ben- tions: bench-scale isothermal reactor, 750 C inlet temperature,
zene formation precursors from the reforming feed also helps 10.5 kg/cm2 reactor pressure, and 6.3 mol/mol hydrogen-to-oil
to decrease A6 formation as the reaction temperature is ratio.
increased. From the data of these tables, the balance errors are calculated
 Reactor delta-T is less when Feed B is used, which means that with:
this feed has lower content of those reacting compounds that  
Feed mass flowrate  Product mass flowrate
contribute in higher extent to reaction exothermality than Feed Mass balance error
Feed mass flowrate
A.
 Another reason for the differences of reactor delta-T with both  100
feeds is the different heats of reforming reaction, and the place 53
and extent where they take place. For instance, in the rst reac-
 
tor the major reactions are endothermic and very fast, such as H2 mass flowrate  H2 mass flowrate
H2 balance error  100
dehydrogenation of naphthenes to aromatics, in the second H2 mass flowrate
reactor, mostly the isomerization takes place and the remaining 54
naphthenes are dehydrogenated, in the third and fourth reac-
Table 13
tors exothermic hydrocracking of parafns and dehydrogena-
Global mass and molar balances.
tion reactions occur.
 Feed B produces more aromatics than Feed A, which is due to Stream Inlet (g/h) Outlet (g/h)

the higher initial contents of aromatics and naphthenes in Feed Naphtha (C5C12) 119.9916 110.4971
B (21.12 and 24.75 mol% respectively) compared with Feed A Hydrogen 19.6989 20.8477
Gases (C1C4) 0.0000 8.3458
(16.45 and 19.29 mol% respectively).
Total 139.6905 139.6905
Inlet (mol/h) Outlet (mol/h)

3.4. Use of the model to predict other process parameters Naphtha (C5C12) 1.0857 1.0653
Hydrogen 9.7713 10.3411
Gases (C1C4) 0.0000 0.2064
Apart from calculating the reformate composition, temperature
Total 10.8570 11.6125
and pressure proles along the reactors system, the developed
 M.A. Rodrguez, J. Ancheyta / Fuel 90 (2011) 34923508 3507

Table 14 rules, such as density and molecular weight. Other properties,

Hydrogen balance. e.g. RON, MON, RVP, depend non-linearly on the mixture composi-
Hydrogen content in hydrocarbons Inlet (g/h) Outlet (g/h) tion thus requiring non-linear mixing rules or other approaches,
n-Parafns e.g. structural group contribution.
nP11 0.0000 0.0000
nP10 2.4727 0.7595
4. Concluding remarks
nP9 2.5915 1.5639
nP8 2.9667 2.2383
nP7 2.2658 2.3005 The complexity of the various kinetic models reported in the lit-
nP6 1.8799 2.2477 erature varies from a few lumps to detailed reaction schemes. Sim-
nP5 0.4216 1.1713 ple old-fashion models, based on only a few lumps, should not be
nP4 0.0000 0.6009
nP3 0.0000 0.5552
used for rigorous simulation of catalytic reforming reactors. The
nP2 0.0000 0.2581 most detailed kinetic models, although their authors claim that
nP1 0.0000 0.1411 they represent the catalytic reforming process in a rigorous man-
Sub-total 12.5981 11.8365 ner, have still to be validated under conditions different from those
Naphthenes from which they were derived, e.g. comparisons of the predicted
N11 0.0000 0.0000 reactor behavior against commercial data of catalytic reforming
N10 0.0000 0.0412
units are mandatory for such complex models in order to provide
N9 1.2115 0.0615
N8 0.7757 0.0827 a more convincing applicability. The kinetic model proposed in this
N7 0.8411 0.1792 work combines the simplicity of the lumping-based models with
N6 0.4163 0.1305 the complexity of the most advanced model, since it can predict
MCP 0.0000 0.0000 the detailed composition of the reformate and takes into consider-
Sub-total 3.2446 0.4951
ation the most important process variables that affect the behavior
Aromatics of the reacting system. The validation and application of the model
A11 0.0000 0.0000
A10 0.3309 0.5416
are indeed carried out with real data obtained from controlled iso-
A9 0.6146 1.4930 thermal bench-scale reactor experiments and with data recovered
A8 0.5921 1.2787 from commercial plants.
A7 0.1996 0.6850
A6 0.0420 0.1432
Sub-total 1.7793 4.1416
Acknowledgments
Total H2 in hydrocarbons 17.6220 16.4732
Hydrogen gas 19.7003 20.8491
The authors thank Instituto Mexicano del Petrleo for its nan-
Total 37.2323 37.2323 cial support. M.A. Rodrguez also thanks CONACyT for nancial
support (PDF).

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