ANÁLISIS DE SENSIBILIDAD EN UN REACTOR DE CRAQUEO CATALÍTI

-
CO DE METANO PARA LA PRODUCCIÓN DE HIDRÓGENO
J. Pulgarín-León
1
, J. Saavedra-Rueda
2
, A. Molina
1,*

1
Bioprocesos y Flujos Reactivos, Facultad de Minas, Universidad Nacional de Colombia, Sede Medellín
2
Instituto Colombiano del Petróleo, Ecopetrol, Bucaramanga


Resumen: Se desarrolló un modelo de un reactor de craqueo catalítico de metano
para la producción de hidrógeno utilizando un mecanismo que simplifica las
múltiples reacciones heterogéneas que suceden en el reformado catalítico con tres
reacciones que incluyen la adsorción en sitios activos y el equilibrio químico. El
modelo considera al reactor como un lecho empacado y simplifica la transferencia
de masa en el catalizador considerando las reacciones como pseudohomogéneas.
Para el desarrollo del modelo se utilizó el software comercial ASPEN Plus y se es-
cribió un módulo de usuario que utiliza una rutina en FORTRAN escrita específi-
camente para representar la cinética química. Las predicciones del modelo son si-
milares a las tendencias reportadas en la literatura y en un reformador industrial. El
artículo concluye utilizando el modelo para entender el efecto de la variación de la
temperatura, relación vapor/carbono y tiempo de residencia sobre la conversión y
el rendimiento fraccional global para el hidrógeno.
Palabras Clave: Reformado de metano, Gas natural, Hidrógeno, ASPEN PLUS.


SENSITIVITY ANALYSIS OF A METHANE STEAM REFORMER
J. Pulgarín-León
1
, J. Saavedra-Rueda
2
, A. Molina
1,*

1
Bioprocesos y Flujos Reactivos, Facultad de Minas, Universidad Nacional de Colombia, Sede Medellín
2
Instituto Colombiano del Petróleo, Ecopetrol, Bucaramanga

Abstract: A model that predicts the conversion in a methane steam reformer for
hydrogen production was developed. The model makes use of a three-reaction
mechanism that simplifies the multiple heterogeneous reactions involved in re-
forming that include adsorption on catalyst active sites and chemical equilibrium.
The model considers the reformer as a packed bed and simplifies mass transfer in
the catalyst by considering reactions as pseudohomogeneous. The model was de-
veloped using a FORTRAN subroutine specially written for the former that was
linked to the commercial software ASPEN Plus. Model predictions are similar to
those found in the literature and with results from an industrial reformer. The pa-
per ends with a sensitivity analysis that uses the model to understand the effect that
the variation of temperature, steam to carbon ratio and residence time have on me-
thane conversion and on fractional conversion of hydrogen.
Keywords: Methane steam reforming, Natural Gas, Hydrogen, ASPEN PLUS.

*
Corresponding author: amolinao@unalmed.edu.co
1. Introduction
Despite the recent interest in different
technologies for hydrogen production,
such as biomass and coal gasification,
fluidized bed membrane reactors, fermen-
tative routes and water electrolysis; me-
thane steam reforming remains the major
production route of hydrogen. Although
this interest is mainly motivated by the
role that hydrogen can play as an energy
resource, hydrogen production for the
petrochemical, chemical and food industry
will remain a major activity of chemical
engineers.
In methane steam reforming, hydrogen is
produced in a furnace in which a mixture
of methane and water reacts in tubes iso-
lated from the combustion gases. With the
help of a catalyst (typically with Ni as
major component) a highly endothermic

Pulgarín et al., Innovaquímica, 2009
2
reaction converts methane and water into
a mixture of hydrogen and other com-
pounds, with carbon monoxide as major
component.
There is a vast literature on modeling
steam reformers. [1-22]. Most studies
date to the late 80s. In the 90s and early
21
st
century the number of papers in the
open literature on modeling methane
steam reformers decreased, probably be-
cause of licensing agreements between
production companies and research insti-
tutions as well as an increased interest in
alternative technologies for reforming
such as Fluidized Bed Membrane Reac-
tors [10, 13, 16-19], optimized control
strategies [12, 14, 15] and novel catalysts
formulations [11, 21].
One of the most refereed studies on me-
thane reformers was the work by Xu and
Froment [5, 7] that describes a model for
these reactors and carefully compares
experimental data with predictions. In
Colombia, as early as in 1981, Ríos de-
veloped a model that predicted hydrogen
production and methane conversion in an
industrial methane steam reformer [1].
More recently Acuña [14], in order to
improve the controllability of steam re-
formers, developed a detailed model of
the methane steam reforming process.
This paper presents preliminary results on
a model that predicts the conversion of
steam and methane in a reformer. Model
details, such as kinetic expressions and
input parameters are defined. The results
from the model are validated against pre-
vious literature results, and data from an
industrial reformer. The paper ends with a
sensitivity analysis that allows an addi-
tional test to the model and further under-
standing of the methane steam reforming
reaction. The results show that the model
can correctly predict most of the trends
observed in an industrial reformer.
2. Model
To simulate the conversion of methane to
hydrogen in a catalytic reactor it is neces-
sary to consider three elements: (1) the
kinetic expressions that describe the rate
of methane and water reaction on the cata-
lyst surface to produce hydrogen and other
byproducts, (2) the mathematical expres-
sions that address the mole, momentum
and energy balances in the reactor and (3)
the process parameters (both operational
and geometrical) that characterize the
reactor.
2.1 Kinetic data
As mentioned in the introduction, both
Ríos [1] and Acuña [14] modeled methane
steam reformers. While Ríos fitted expe-
rimental data to obtain the kinetic parame-
ters for his model, Acuña [14] used the
kinetic expressions described by Haldor
[23], as quoted by Acuña [14], that date
from 1965. The present research aimed at
making use of more contemporary kinetic
data.
A review of previous literature showed
that the model proposed by Xu and Fro-
ment [7] in 1989 is the one more quoted in
the literature. Although it is an old model,
it was recently successfully used by Za-
maniyan et al. [20] and Alberton et al.
[22] in the simulation of industrial me-
thane reformers.
Table 1 shows the reactions considered by
Xu and Fromment [7].
These authors came to the conclusion that
reactions R 6 to R 11 are not important
because the ratios of forward to reverse
reaction rates are always higher than 1 at
typical steam reforming conditions. Reac-
tions R 4 to R 5 are also considered of
minor importance because they, although
thermodynamically favored at typical
reforming conditions, describe trends
(lower CO
2
concentration as the length in
the reactor increases) that do not agree
with normal reactor performance. Al-

Pulgarín et al., Innovaquímica, 2009
3
though these are rather weak assumptions
as local conditions inside the reformer
may have concentrations that will thermo-
dynamically favor forward reactions, as a
first approximation in this paper, we
adopted Xu and Fromment [7] recom-
mendations and simply considered R 1 to
R 3 as the most important reactions in the
process.

Table 1. Reactions involved in methane steam reforming as reported
by Xu and Fromment [7]
Reaction ÷ΔH
298
(kJ/mol)
R 1
2 2 4
H 3 CO O H CH + = + ÷206.1
R 2
2 2 2
H CO O H CO + = +
41.15
R 3
2 2 4
H 4 CO O H 2 CH + = + ÷165.0
R 4
2 2 4
H 2 CO 2 CO CH + = + ÷247.3
R 5
O H 2 CO 4 CO 3 CH
2 2 4
+ = + ÷330.0
R 6
2 4
H 2 C CH + = ÷74.82
R 7
2
CO C CO 2 + =
173.3
R 8
O H C H CO
2 2
+ = +
131.3
R 9
O H 2 C H 2 CO
2 2 2
+ = +
90.13
R 10
O H 2 C 3 CO 2 CH
2 4
+ = +
187.6
R 11
O H 2 C 2 CO CH
2 2 4
+ = +
15.3

Xu and Fromment [7] carried out a bal-
ance of active sites on the catalysts for a
heterogeneous mechanisms they devel-
oped to simulate R 1 to R 3. From this
balance these authors derived three rate
expressions shown in E 1 to E 3 that con-
sider the partial pressure of hydrogen,
methane, water and carbon monoxide, (P
i
)
as well as kinetic (k
i
), equilibrium (K
i
) and
adsorption constants (K
j
, with j represents
CO, H
2
, CH
4
, H
2
O). E 5 to E 7 present the
mathematical expressions used to
represent the variation of the constant with
temperature. Table 2 to Table 4 show the
kinetic constants finally used in the model.
Equilibrium constants were calculated
using the free-domain code for gaseous
equilibrium Gas-Eq [24].
2
1
CO
3
O H CH 5 . 2
2 H
1
1
DEN
K
p p
p p
p
k
3
r
2
H
2 4
|
|
.
|

\
|
÷ ×
=
E 1

2
2
CO H
O H CO
2 H
2
2
DEN
K
p p
p p
p
k
r
2 2
2 |
|
.
|

\
|
÷ ×
=
E 2

2
3
CO
4
4
4 CH 5 . 3
2 H
3
3
DEN
K
p p
p p
p
k
4
r
2
2
H
O
2
H
|
|
.
|

\
|
÷ ×
=
E 3

(
(
(
¸
(

¸

+ +
+ +
=
2
2
2 4 4
2 2
H
O H
O H CH CH
H H CO CO
p
p
K p K
p K p K 1
DEN
E 4

i
r
T , i i
T
1
T
1
R
Ea
exp k k
(
¸
(

¸

|
|
.
|

\
|
÷ ÷ =

E 5

i
r
j
T , i i
T
1
T
1
R
H
exp K K
(
¸
(

¸

|
|
.
|

\
|
÷
A
÷ =

E 6

i
i bi
i i , eq
T
Ea
exp T A K |
.
|

\
|
÷ × × =

E 7


Pulgarín et al., Innovaquímica, 2009
4
Table 2. Kinetic constants used in the model
(adapted from [7])
k
i, 648K
Ea
i

(kmol × bar
1/2
/ kg cat × h) (kJ/mol)
k
1
1.84 × 10
-4
240.1
k
2
7.558 67.13
k
3
2.19 × 10
-5
243.9

Table 3. Adsorption constants used in the model
(adapted from [7])
K
j
T
r

ΔH
(bar
-1
) (K) (kJ/mol)
CH
4
0.1791 823 -38.28
H
2
O 0.4152* 823 88.68
CO 40.91 648 -70.65
H
2
0.02960 648 -82.90
*Dimensionless
Table 4. Equilibrium constants used in the mod-
el (calculated from[24])
A
i
(bar
2
) b
i
Ea
i
(K
-1
)
K
eq1
4.94×10
6
1.89 -25216
K
eq2
1.20×10
-6
* 1.24 5425
K
eq3
5.93 3.13 -19791
*Dimensionless
2.2 Balance equations in the reactor
As one of the objectives of the paper was
to perform a sensitivity analysis of the
methane steam reformer and given the
extended use of the commercial software
ASPEN in the Chemical Engineering in-
dustry, this research employed ASPEN
PLUS V 7.0, as simulation tool. Unfortu-
nately, as it happens with most commer-
cial software, the presence of non-
conventional kinetic expressions, (e.g. E 1
to E 3), impose the use of user-defined
models in ASPEN.
There are typically two possibilities when
modeling non-conventional rate expres-
sions in ASPEN. The first one, as illu-
strated by Barrera et al. [25], consists in
linking ASPEN to Excel and developing
the kinetic expressions through Excel by a
spreadsheet. The second one, adopted in
this research, consist on defining FOR-
TRAN-based subroutines. We consider the
second approach more suited for our re-
search needs as FORTRAN allows more
complex calculations that Excel.
As this was the first time that FORTRAN
was linked with ASPEN in our research
group, we developed our own code to
model a PFR reactor using MATLAB to
validate the ASPEN/FORTRAN approach.
Both programs (MATLAB and AS-
PEN/FORTRAN) yielded identical results.
Although the methane steam reformer
simulations by Ríos [1] and Acuña [14]
considered energy and momentum bal-
ances inside the reactor, this research used
predefined pressure and temperature pro-
files as inputs to the model. This was done
because emphasis was placed in the kinet-
ic approach and, as a first step; it was con-
sidered more important to address the
chemistry. Current work conducted in our
research group, is incorporating energy
and momentum expressions to the model.
In the treatment of the reactor in ASPEN
we adopted a PFR formulation and consi-
dered did not consider heterogeneous limi-
tations (pseudo-homogeneous approach).
This is clearly an oversimplification, al-
though frequently adopted in the literature
(e.g. [1, 14]). Future developments of the
FORTRAN subroutine will include mass
transfer to the particle with approaches
similar to those described by Xu and
Fromment [5], Zamaniyan et al. [20] and
Alberton et al. [22]
2.3 Process and reactor parameters
Although, as explained above, the AS-
PEN/FORTRAN reactor model was vali-
dated with an independent program de-
signed by our research group, additional
validation of the kinetic expressions was
mandatory before simulation of an indus-
trial furnace could be undertaken. This
kinetic validation was carried out using the
data presented by Zamaniyan et al. [20]. A

Pulgarín et al., Innovaquímica, 2009
5
comparison of our results with those of
Zamaniyan et al. [20] is presented in the
Results section.
In the simulations used to validate our
model against that of Zamaniyan et al.
[20], we employed the same input parame-
ters (temperature and pressure profile,
geometry, input stream gas composition,
temperature and pressure profiles) that
Zamaniyan describe in their paper [20].
For the simulation of the industrial me-
thane steam reformer a 15-m length, 12.6-
cm internal diameter reactor was consi-
dered. Table 5 shows the input-stream
composition as supplied by the reformer
operator. O
2
and N
2
were considered as
inert gases, given their low concentrations.
The concentrations of ethane, propane and
butane were added to that of methane fol-
lowing the equal-carbon concept described
by Zamaniyan et al. [20].
Table 5. Input-stream composition
Species CH
4
H
2
O O
2
N
2

Molar
fraction
0.1384 0.8424 0.0003 0.0017
Species C
2
H
6
C
3
H
8
C
4
H
10

Molar
fraction
0.0143 0.0027 0.0002

As only input and output data were availa-
ble for temperature and pressure, the tem-
perature and pressure profiles reported for
an industrial methane steam reformer in
the literature [20] were adjusted to obtain
the same input and output values as those
reported by the reformer operator. Figure
1 compares the temperature and pressure
profiles used in this paper for the industri-
al reformer with those of Zaminiyan et al.
[20]. It is evident that the use of these
profiles is a rather crude simplification.
Nevertheless, as it will be shown below, it
turned out to be an acceptable approxima-
tion.
Because, mass-transfer limitations were
not modeled, no data on the catalyst is
given different from the fact that it was a
Ni/Al
2
O
3
catalyst and the density was as-
sumed to be 2355.5 kg m
-3,
as reported in
[20].
3.Results and discussion
3.1 Model validation
Figure 2 compares the profiles of major
species (CH
4
, H
2
O, H
2
and CO) along the
reactor predicted by Zamaniyan et al. [20]
with those obtained using our model. Al-
though there are some clear differences in
trends, exit concentrations are very similar
for all species. Particularly the two more
important species, H
2
and CH
4
, show simi-
lar concentrations at the reactor exit. This
gives confidence on the model ability to
correctly predict the final result for the
reactor.
600
800
1000
1200
0 2 4 6 8 10 12 14
distance along reactor (m)
T

(
K
)
Zamaniyan et al.
this paper
a.
11
12
13
14
15
16
17
0 2 4 6 8 10 12 14
distance along reactor (m)
P

(
b
a
r
)
Zamaniyan et al.
this paper
b.

Figure 1. Comparison of (a) temperature and
(b) pressure profiles along the reactor. Data
from Zamaniyan et al. [20] and this paper
Contrary to the relative success in predict-
ing the final concentrations, Figure 2 a. to
d. show that our model tends to overesti-
mate methane conversion. This is evident
in Figure 2 because the predictions by
Zamaniyan et al. [20], show that methane
concentration is always higher and hydro-
gen concentration lower than our model

Pulgarín et al., Innovaquímica, 2009
6
0.0
0.1
0.2
0.3
0 2 4 6 8 10 12
distance along reactor (m)
C
H
4

(
m
o
l

f
r
a
c
t
i
o
n
)
a.
Zamaniyan et al.
this paper
0.2
0.3
0.4
0.5
0 2 4 6 8 10 12
distance along reactor (m)
H
2
O

(
m
o
l

f
r
a
c
t
i
o
n
)
b.
Zamaniyan et al.
this paper
0.0
0.1
0.2
0.3
0 2 4 6 8 10 12
distance along reactor (m)
H
2

(
m
o
l

f
r
a
c
t
i
o
n
)
Zamaniyan et al.
this paper
c.
0.0
0.1
0.2
0.3
0 2 4 6 8 10 12
distance along reactor (m)
C
O

(
m
o
l

f
r
a
c
t
i
o
n
)
d.
Zamaniyan et al.
this paper

Figure 2. Comparison of concentration profiles as predicted by the model described by Zamaniyan et al. [20] and by this paper. (a)
CH
4
, (b), H
2
O, (c) H
2
and (d) CO.


Pulgarín et al., Innovaquímica, 2009
7
results, at short distances inside the reac-
tor. This result is not surprising as Zama-
niyan et al. [20] considered mass-transfer
limitations inside the catalyst (using an
effectiveness factor) and our model consi-
dered a pseudo-homogeneous approach.
Neglecting mass transfer limitations caus-
es the observed overestimation of methane
conversion at short distances in the reac-
tor. As stated above, future model ver-
sions should consider mass transfer limita-
tion in the catalyst.
3.2 Simulation of industrial methane
steam reformer.
Once the model was validated against
literature data, the ability of the model to
predict the behavior in an industrial re-
former was addressed. Table 6 compares
the exit concentrations (in mole fractions)
as reported by the reformer operator with
model predictions. Although there are
some differences, particularly in CO, the
agreement between predictions and the
data for the industrial reformer is deemed
as excellent, considering some of the
crude approximations taken with the pres-
sure and temperature profiles.
Table 6. Comparison of exit concentrations
(mole fraction) in an industrial reformer with
model predictions
Industrial
reformer
Model
CH
4
0.0110 0.0145
H
2
O 0.4536 0.4878
H
2
0.4121 0.3885
CO 0.0600 0.0419
CO
2
0.0620 0.0657
N
2
0.0013 0.0015

3.3 Sensitivity analysis
To make an additional validation of the
model and get a better understanding of
the reforming reaction, a sensitivity analy-
sis of the model response to variations in
temperature profile, steam-to-carbon ratio
( )
in
C S (in molar units) and residence
time was carried out. There are different
variables that can be used to evaluate the
performance of a methane steam reformer
(e.g. mass flow hydrogen produced, con-
version of different species, rate of coke
deposition, rate of H
2
to CO at the reactor
exit). Among those and for clarity of the
discussion we selected only two: conver-
sion of methane ( )
4 CH
X defined as the
ratio of methane moles converted in the
reactor to those entering the reformer and
the fractional conversion of hydrogen
( )
4 2
CH H | defined in E 8.
( )
( )
(moles)
converted CH
moles reactor
the leaving H
CH H
4
2
4 2
= |
E 8

Figure 3 shows the variation of methane
conversion ( )
4 CH
X and hydrogen fraction-
al conversion ( )
4 2
CH H | with changes in
nominal reactor temperature. Because
there is a temperature profile, the abscissa
in Figure 3 represents a nominal tempera-
ture that reflects the mean temperature in
the profile.
As expected, in Figure 3 methane conver-
sion increases with temperature. However,
( )
4 2
CH H | decreases, with temperature,
as thermodynamic restrictions on the for-
ward reaction in R 3 augment with tem-
perature. Figure 3 suggests that a temper-
ature of the order of 1100 K guarantees
acceptable methane conversion, while the
fractional hydrogen conversion remains at
an acceptable value of 2.8. It is important
to note that according R 1 to R 3, the max-
imum possible value of ( )
4 2
CH H | is 4.
A value of 2.8, such as that obtained
around 1100 K, seems a good compromise
between methane conversion and hydro-
gen production.
As Figure 4 shows, a higher value in the
steam to carbon ratio ( )
in
C S favors both,
methane conversion and fractional con-
version to hydrogen. This happens be-
cause a higher steam concentration favors

Pulgarín et al., Innovaquímica, 2009
8
equilibrium toward hydrogen production
in E 3. Favoring hydrogen production
increases as well methane conversion.

0.0
0.2
0.4
0.6
0.8
1.0
700 900 1100 1300
temperature (K)
X
C
H
4
2.4
2.6
2.8
3.0
3.2
Ф
(
H
2
/
C
H
4
)

Figure 3. Predicted variation of methane con-
version ( )
4 CH
X and fractional conversion of
hydrogen ( )
4 2
CH H | with changes in no-
minal reactor temperature
0.0
0.2
0.4
0.6
0.8
1.0
4 5 6 7 8
(S/C)
in
(mol/mol)
X
C
H
4
2.4
2.6
2.8
3.0
3.2
Ф
(
H
2
/
C
H
4
)

Figure 4. Predicted variation of methane con-
version ( )
4 CH
X and hydrogen fractional con-
version ( )
4 2
CH H | with steam-to-carbon
ratio ( )
in
C S
Figure 4 suggests that the use of a higher
value of ( )
in
C S would be advisable, as
higher methane conversion and fractional
conversion of hydrogen are desirable out-
comes. However, as Figure 5 shows, the
total mass flow of hydrogen ( )
2
H
m de-
creases as the steam to carbon ratio in-
creases. Therefore, a balance between a
reduction on hydrogen production and an
increase in methane conversion and frac-
tional conversion of hydrogen needs to be
performed during reactor design. A final
sensitivity analysis was conducted for
residence time (Figure 6). The model
predicts a reduction on methane conver-
sion and fractional selectivity of hydrogen
as the residence time in the reactor de-
creases. This is an expected result. How-
ever, Figure 6 gives very important infor-
mation for model validation as shows that
for typical conditions (residence time of
0.11 s) methane conversion and the frac-
tional conversion of hydrogen present a
plateau that favors stable operation.

900
1000
1100
1200
1300
3.5 4.5 5.5 6.5 7.5
(S/C)
in
(mol/mol)

(
)
h
/
k
g
m
2
H


Figure 5. Predicted variation of hydrogen mass
flow
2
H
m with changes in the steam-to-carbon
ratio ( )
in
C S
0.0
0.2
0.4
0.6
0.8
1.0
0.00 0.02 0.04 0.06 0.08 0.10 0.12
residence time (s)
X
C
H
4
2.4
2.6
2.8
3.0
3.2
Ф
(
H
2
/
C
H
4
)

Figure 6. Predicted variation of methane con-
version ( )
4 CH
X and hydrogen fractional con-
version ( )
4 2
CH H | with residence time in the
reactor

4. Conclusions
A model that integrates complex chemical
kinetics into ASPEN using a FORTRAN
subroutine correctly predicts the behavior
of an industrial methane steam reformer.
The model, validated against literature and
industrial data, was used to conduct a sen-

Pulgarín et al., Innovaquímica, 2009
9
sitivity analysis of methane conversion
and fractional conversion to hydrogen
with temperature, steam to carbon ratio
and residence time. Although the higher
the temperature, the higher the methane
conversion, thermodynamic restrictions
decrease methane and steam conversion to
hydrogen as temperature increases. A
nominal temperature of 1100 K seems to
give a reasonable balance between me-
thane conversion and factional conversion
of hydrogen. Higher steam to carbon ratio
favors both methane conversion and fac-
tional conversion of hydrogen, however it
decreases the mass flow of hydrogen. It is
necessary to establish a balance on prod-
uctivity and conversion to assure optimal
reformer behavior. The model gives in-
formation on the variation of methane
conversion and fractional conversion of
hydrogen with residence time. The results
suggest that for the industrial reformer
analyzed, a residence time close to 0.12 s
is optimal because it guarantees that varia-
tions in residence time do not have a ma-
jor impact in conversion.
Acknowledgment
We acknowledge Aspen Technology for
having granted special permission for the
use of the ASPEN. PLUS under the condi-
tion of the academic licensing agreement.

References
1. Ríos, J.A., Modelo matemático y simulación de
un reformador de metano, 1981, M.Sc. Ingeniería
Química. Universidad Industrial de Santander,
Ingeniería Química: Bucaramanga. p. 242.
2. Murray, A.P. and Snyder, T.S., Steam-methane
reformer kinetic computer model with heat trans-
fer and geometry options. Ind. Eng. Chem. Proc.
Des. Dev., 1985. 24(2): p. 286-294.
3. Soliman, M.A., El-Nashaie, S.S.E.H., Al-Ubaid,
A.S., and Adris, A., Simulation of steam reformers
for methane. Chem. Eng. Sci., 1988. 43(8): p.
1801-1806.
4. Murty, C.V.S. and Murthy, M.V.K., Modeling
and simulation of a top-fired reformer. Ind. Eng.
Chem. Res., 1988. 27(10): p. 1832-1840.
5. Xu, J. and Froment, G.F., Methane steam re-
forming: Ii. Diffusional limitations and reactor
simulation. AIChE J, 1989. 35(1): p. 97-103.
6. Alatiqi, I.M., Meziou, A.M., and Gasmelseed,
G.A., Modelling, simulation and sensitivity analy-
sis of steam-methane reformers. Int. J. Hyd. Ener-
gy, 1989. 14(4): p. 241-256.
7. Xu, J. and Froment, G.F., Methane steam re-
forming, methanation and water-gas shift: I. In-
trinsic kinetics. AIChE J, 1989. 35(1): p. 88-96.
8. Rajesh, J.K., Gupta, S.K., Rangaiah, G.P., and
Ray, A.K., Multiobjective optimization of steam
reformer performance using genetic algorithm.
Ind. Eng. Chem. Res., 2000. 39(3): p. 706-717.
9. Pina, J., Schbib, N.S., Bucala, V., and Borio,
D.O., Influence of the heat-flux profiles on the
operation of primary steam reformers. Ind. Eng.
Chem. Res., 2001. 40(23): p. 5215-5221.
10. Prasad, P. and Elnashaie, S.S.E.H., Novel
circulating fluidized-bed membrane reformer for
the efficient production of ultraclean fuels from
hydrocarbons. Ind. Eng. Chem. Res., 2002.
41(25): p. 6518-6527.
11. Snoeck, J.W., Froment, G.F., and Fowles, M.,
Steam/co2 reforming of methane. Carbon forma-
tion and gasification on catalysts with various
potassium contents. Ind. Eng. Chem. Res., 2002.
41(15): p. 3548-3556.
12. Nandasana, A.D., Ray, A.K., and Gupta, S.K.,
Dynamic model of an industrial steam reformer
and its use for multiobjective optimization. Ind.
Eng. Chem. Res., 2003. 42(17): p. 4028-4042.
13. Prasad, P. and Elnashaie, S.S.E.H., Coupled
steam and oxidative reforming for hydrogen pro-
duction in a novel membrane circulating fluidized-
bed reformer. Ind. Eng. Chem. Res., 2003. 42(20):
p. 4715-4722.
14. Acuña, A., Simulación de un reactor para
generar hidrógeno y desarrollo de un sistema de
control avanzado, 2004, Ph.D. Thesis. Universidad
Industrial de Santander, Ingeniería Química: Buca-
ramanga. p. 205.
15. Posada, A. and Manousiouthakis, V., Heat and
power integration of methane reforming based
hydrogen production†Ind. Eng. Chem. Res.,
2005. 44(24): p. 9113-9119.
16. Rakib, M.A. and Alhumaizi, K.I., Modeling of
a fluidized bed membrane reactor for the steam
reforming of methane: Advantages of oxygen addi-
tion for favorable hydrogen production. Energy
Fuels, 2005. 19(5): p. 2129-2139.
17. Patil, C.S., van Sint Annaland, M., and Kui-
pers, J.A.M., Design of a novel autothermal mem-
brane-assisted fluidized-bed reactor for the pro-
duction of ultrapure hydrogen from methane. Ind.
Eng. Chem. Res., 2005. 44(25): p. 9502-9512.
18. Sarvar-Amini, A., Sotudeh-Gharebagh, R.,
Bashiri, H., Mostoufi, N., and Haghtalab, A., Se-

Pulgarín et al., Innovaquímica, 2009
10
quential simulation of a fluidized bed membrane
reactor for the steam methane reforming using
aspen plus. Energy Fuels, 2007. 21(6): p. 3593-
3598.
19. Abashar, M.E.E., Alhabdan, F.M., and Elna-
shaie, S.S.E.H., Staging distribution of oxygen in
circulating fast fluidized-bed membrane reactors
for the production of hydrogen. Ind. Eng. Chem.
Res., 2007. 46(17): p. 5493-5502.
20. Zamaniyan, A., Ebrahimi, H., and Moham-
madzadeh, J.S.S., A unified model for top fired
methane steam reformers using three-dimensional
zonal analysis. Chem. Eng. Proc., 2008. 47(5): p.
946-956.
21. Schwaab, M., Alberton, A.L., Fontes, C.E.,
Bittencourt, R.C., and Pinto, J.C., Hybrid modeling
of methane reformers. 2. Modeling of the industri-
al reactors. Ind. Eng. Chem. Res., 2009.
22. Alberton, A.L., Schwaab, M., Fontes, C.E.,
Bittencourt, R.C., and Pinto, J.C., Hybrid modeling
of methane reformers. 1. A metamodel for the
effectiveness factor of a catalyst pellet with com-
plex geometry. Ind. Eng. Chem. Res., 2009.
23. Haldor, T., Some aspects of catalytic cracking.
1965, Insittute of gas engineers.
24. Morley, C. Gas-eq: A chemical equilibrium
program for windows. 2003 [cited 2003 August];
Available from:
http://www.c.morley.ukgateway.net/.
25. Barrera-Zapata, R., Villa de P, A.L., and Mon-
tes de Correa, C., Modelado y simulación de la
epoxidación de limoleno con aspen plus, in XXIV
Conferencia Internacional Ingeniería Química,
A.C.d.I. Química, Editor. 2007: Cali.

Sign up to vote on this title
UsefulNot useful