Chemical Engineering Science 65 (2010) 6341–6352

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Analysis of attainable reactor performance for the oxidative methane

coupling process
S. Jašo a, H.R. Godini a,b, H. Arellano-Garcia a,n, M. Omidkhah b, G. Wozny a
a
Berlin Institute of Technology, Str. des 17. Juni 135, Sekr. KWT9, D-10623 Berlin, Germany
b
Chemical Engineering Department, Tarbiat Modares University, 14155-143 Tehran, Iran

a r t i c l e in fo abstract

Article history: In this work, a comparative analysis of attainable performance is presented for three different reactor
Received 2 February 2010 structures including a fixed-bed reactor, and two different feeding structures of packed bed membrane
Received in revised form reactors. For this purpose, three types of kinetic models, namely La2O3/CaO, Mn/Na2WO4/SiO2, and
29 July 2010
PbO/Al2O3 have been used under a wide range of operating conditions. Thus, the effect of several
Accepted 20 August 2010
variables such as operating temperature, membrane thickness, methane-to-oxygen ratio, feed flow rate,
Available online 27 August 2010
gas streams composition, and reactor length are investigated.
Keywords: Moreover, kinetic-analysis based on a proposed graphical approach enables determination of the
Oxidative coupling of methane suitable operational condition range and allows analysis of the feasible and optimal performance that
Membrane reactor
corresponds to the effect of several dependent operating variables. The results show that tracking the
Chemical processes
optimum area of operation has a monotonic direction under some range of operating conditions, while
Reactor design
Attainable analysis it reflects qualitative trade-offs under some other ranges of operating conditions. For all investigated
Graphical approach reactor concepts and catalysts, optimal operating conditions and the best corresponding performance
are presented.
& 2010 Elsevier Ltd. All rights reserved.

1. Introduction Recently, there have been a number of investigations (Liu et al.,

Oxidative coupling of methane (OCM) is an alternative route
for obtaining directly high-valued hydrocarbons from natural gas
feedstock. The corresponding process has a potential to become a
key technology for petrochemical and chemical industry. Thus,
the interest for the OCM process has re-emerged in the last years.
Most of the previous works were oriented towards finding a
suitable catalyst for the selective methane conversion. Although
there is still a debate over the most suitable catalyst, there is a
general agreement that basic metal oxides promoted by alkali and
earth–alkali metals show an acceptable performance as OCM
catalysts. Recently, the performances of different types of
catalysts were compared under different reaction conditions
(Oliver et al., 2008). The best performance in this work was
observed for the La–Sr system supported on CaO with a yield of up
to 20% along with 42% methane conversion.
One of the very first catalysts proposed for the OCM process
was Li + -doped MgO, which showed promising yields to higher
hydrocarbons. Thus, it has been used extensively and recom-
mended in research applications. However, this catalyst deacti-
vates rapidly under operating temperatures higher than 800 1C.
n
Corresponding author.
E-mail address: arellano-garcia@tu-berlin.de (H. Arellano-Garcia).
2008; Ji et al., 2002; Chua et al., 2008; Daneshpayeh et al., 2009;
Salehoun et al., 2008) on Mn/Na2WO4/SiO2 showing that this
catalyst is even able to provide around 25% yield of C2 + products
per pass without significant deactivation (Liu et al., 2008; Salehoun
et al., 2008). The previously contemplated catalysts are among the
few ones reported to allow for more than 50% selectivity and under
30% or higher methane conversion. In order to find new catalysts,
alternative stochastic approaches have also been applied. For
instance, Huang et al. (2003) applies a combination of genetic
algorithm and neural networks using six metal components for
catalyst synthesis. Following this, a sample was found, which was
able to give 27.8% yield of C2 + products per pass.
However, obtaining high C2 + yields in OCM confronts some
difficulties, in particular, because of the competition between
coupling and combustion reactions. Hence, a typical parallel
series reaction scheme emerges because of the series of combus-
tion, coupling, and dehydrogenation reactions. This type of
reaction scheme has theoretically been investigated by Lu et al.
(1997, 1996) concluding that in comparison to the combustion
steps, if the reaction orders for oxygen is lower in the coupling
step, an optimal distributed oxygen feed can significantly improve
the yield of the desired product. The same authors emphasize that
up to 100% of yield is obtainable, if continuous feeding of oxygen
and removal of C2 + products is done simultaneously. Using a
membrane for the oxygen distribution shows a comparable

0009-2509/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2010.08.019
6342 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352

performance as the optimal oxygen feeding policy. However,

Hamel et al. (2003) indicates that the use of a membrane reactor
for OCM may require extremely long contact times for the
required conversions under low oxygen concentrations. Never-
theless, yields of at least 30–35% per pass, which are required for
an industrial application, have not been obtained experimentally
so far. Therefore, improved reaction engineering is needed to
overcome the low yields limitation even for a membrane reactor.
The application of different concepts of oxygen feeding policy
has proved to improve the yield significantly in both theory (Lu
et al., 1997, 1996; Hamel et al., 2003; Kao et al., 2003; Cheng and
Shuai 1995; Kiatkittipong et al., 2005) and practice (Tonkovich
et al., 1996; Lu et al., 2000; Coronas et al., 1997a, b; Bhatia et al.,
2009; Oliver et al., 2009). One way to distribute oxygen is through
dense ionic conductive membranes, which are perm-selective
towards oxygen (Kiatkittipong et al., 2005; Bhatia et al., 2009;
Oliver et al., 2009), and non-permeable for other species. In this
manner, oxygen is finely distributed along the reactor, and Fig. 1. General framework for analyzing the effect of the reactor performance on
methane loss due to back-permeation is prevented. Moreover, the whole OCM process.
air can be used as a source of oxygen and the process can thus be
operated in a safer mode. However, because of the low oxygen 2. Kinetic model analysis
concentration in the reaction side, the reaction rate is rather slow,
and consequently, a long contact time is required for high
Different reactor concepts for the OCM process have been
methane conversion. Furthermore, due to ionic oxygen conduc-
studied both theoretically and experimentally by Mlezko and
tion mechanisms and low fluxes, the catalytic activity of
Baerns (1995). One of the main remarks in their report is a lack of
membranes is of crucial importance. Although fine oxygen
detailed kinetic models for the OCM catalysts. For the develop-
distribution is obtained and back permeation is prevented, so
ment of a new or existing reactor concept, the validity of a kinetic
far only yields of less than 35% have been obtained (Bhatia et al.,
model is of vital importance. In spite of several available micro-
2009). The use of porous ceramic membranes for oxygen
kinetic models based on elementary steps (Simon et al., 2007;
distribution seems to be a promising alternative (Tonkovich
Couwenberg et al., 1996; Sun et al., 2008), there is certainly a lack
et al., 1996; Lu et al., 2000; Coronas et al., 1997a, b). Although
of applicable kinetic models for reaction engineering studies.
there is a permeation of methane and C2 + products to the oxygen
Most of the available proposed models have only a few reaction
rich side of the membrane, the oxygen distribution to the catalyst
steps—mostly the primary ones. Moreover, in these models
side of the reactor has been proved to educe enhanced yields.
ethane and ethylene are lumped together as C2 + products,
However, the highest reported yield of 27.5% by Lu et al. (2000)
whereas CO and CO2 are presented as combustion products COx.
using this concept should still be improved further, if any
Besides, the produced hydrogen is not accounted, and thus, water
industrial application is expected. In the open literature, there
produced by combustion reactions is overestimated and the
are only few simulation studies on porous membrane reactors for
oxygen reaction stoichiometry is disturbed. Consequently, these
OCM (Kao et al., 2003; Cheng and Shuai 1995; Santamaria et al.,
models cannot be used for the development of OCM down-stream
1992) and these simulations were all conducted using simplified
processes and their economical evaluation.
kinetic models.
In this work, the attainable performance of the OCM process is
studied in diverse configurations of fixed bed and porous 2.1. Kinetic models selection
membrane reactors using different catalysts in a wide range of
operating conditions. Thus, a relevant overview of the porous One of the most comprehensive kinetic models available in
membrane reactor performance is given using kinetic models literature has been developed by Stansch et al. (1997) for the
developed for different catalysts. Moreover, the effect of the La2O3/CaO catalyst. This model consists of three primary and
reactor feeding policies will also be analyzed in detail. For this seven consecutive reaction steps. It basically considers all relevant
purpose, a new graph-phased approach is introduced, which can chemical species. Different effects such as gas phase dehydro-
be considered as an efficient complementary tool for general genation of ethane, ethylene steam reforming, and reaction
rector design and optimization activities. Accordingly, this work inhibition by CO2 and O2 have been taken into consideration.
provides a more accurate prediction of the outlet gas composition, Because of very high catalyst activity, this model will be later
which can directly be applied for the development of OCM down- referred to as ‘‘fast’’ reaction kinetics. Based on its developed
stream processes as well as their economical evaluation. There- reaction network, two additional models have recently been
fore, the performance of the reactor section (e.g. selectivity or proposed for the Mn/Na2WO4/SiO2 catalyst (Daneshpayeh et al.,
conversion) should be analyzed in a general framework consider- 2009; Shahri and Alavi, 2009). Another suitable catalyst for OCM
ing separation and purification sections as shown in Fig. 1. This is Li + /MgO, but except for the kinetic model proposed by Tung
represents the basis of an ongoing experimental research work for and Loban (1992), there is no detailed kinetic model available.
which a mini-plant is currently being built. This mini-plant Although this kinetic model is based on the surface reaction
consists of different reactor types including all structures of mechanism, it has however only two main reaction paths.
membrane reactors discussed in this paper, fixed bed reactor, and Therefore, this model is not appropriate for a detailed simulation
fluidized bed reactor as well as the purification section (CO2 study. For a comprehensive OCM simulation, some authors used
removal in absorption and desorption columns). The goals of such the kinetic developed for PbO/Al2O3 (Hinsen et al., 1985). This
project include finding the best reactor concept, validation of the kinetic represents one of the few complete expressions for OCM
simulation results, and designing an efficient OCM process based and it has been used in this work as well. This model has
on an extensive experimental basis. commonly been used for the simulation of a porous membrane
 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352 6343

reactor and fixed bed reactors in some studies (Lu et al., 1997).
This particular kinetic model will be later referred to as ‘‘slow’’
reaction kinetics.
In this work, the three kinetic models developed for La2O3/CaO
by Stansch et al. (1997), Mn/Na2WO4/SiO2 by Daneshpayeh et al.
(2009), and PbO/Al2O3 by Hinsen et al. (1985) are used for the
reactor simulation studies. The corresponding catalysts will
further be referred within the text as follows:

Catalyst 1 Catalyst 2 Catalyst 3

La2O3/CaO PbO/Al2O3 Mn/Na2WO4/SiO2

These three different kinetic models have different levels of

complexity. For instance, only the kinetic model for catalyst 1
reflects the effect of CO2 adsorption on the reaction rates for the
initial and some consecutive steps as well. This aspect was not
noticed when the model for catalyst 3 was developed. However, the
reaction network is the same as for the previous catalyst. Therefore,
it includes steam reforming of ethylene, and gas phase ethane
dehydrogenation. The kinetic model for catalyst 2 consists of only
four reactions, and thus, it cannot predict the mentioned effects
above. Nevertheless, a basic reaction network is preserved so that all
important aspects are covered. Consequently, the chosen kinetic
model is able to predict soundly the reaction behavior.
2.2. Kinetic models comparison
The evaluation of the kinetic models with different levels of
complexity allows comparing their effect on the process attain-
ability. Thus, it is possible to understand the intrinsic properties of
the kinetic models, which help to follow the observed behavior in
the reactor. For this comparison, the so called ‘‘differential
selectivity’’ or ‘‘instantaneous fractional yield’’ (in the text further
referred to as j), is used (Levenspiel, 1999)
P P 
2 j ¼ ethane ni,j ri þ j ¼ ethylene ni,j ri
j¼ P ð1Þ
j ¼ methane ni,j ri
In this definition, ni,j and ri are the stoichiometric matrix and
the reaction rate for the ith reaction and jth component,
respectively. This value generally represents the production rate
of desired products against the consumption rate of the main
reactant. For the OCM process, j is the ratio of the net rate of
formation of C2 + products against the consumption of methane.
For a basic analysis, we use a fixed temperature of 800 1C,
methane partial pressure of 30 kPa, and a CO2 partial pressure of
3 kPa (as an average partial pressures in the reactor). Partial
pressures of ethylene and oxygen are changed in the range of
(0.01–10 kPa) and (0.1—15 kPa), respectively, while keeping a
total pressure of 1 bar. This procedure enables the coverage of
normal operating conditions.
The analysis of the dependence of j on the partial pressures of
ethylene and oxygen for catalyst 1 and catalyst 2 shows
surprisingly similar results. As it was expected, decreasing the
oxygen partial pressure results in an increase of j for both
catalyst 1 and catalyst 2, as depicted in Fig. 2. However, after a
certain value, a decrease of the oxygen partial pressure shows a
decrease of j for catalyst 3. This feature will prove to be crucial
later for the membrane reactor design. The analysis of the kinetic
model for catalyst 3 shows that the adsorption of oxygen has a
much more important effect on the coupling reaction in
comparison to the kinetics of catalyst 1. This can be seen by
comparing the oxygen adsorption constants and adsorption
enthalpies. Furthermore, for the catalyst 3, the oxygen reaction
order of the coupling reaction is lower than the reaction orders for
Fig. 2. Influence of ethylene and oxygen concentration on the differential
selectivity for different catalysts.
the combustion reactions. This type of kinetic models is referred
to as ‘‘non-favorable’’ for the oxygen distribution (Lu et al., 1997,
1996; Hamel et al., 2003). In other words, the manipulation of
oxygen concentration will not yield a significant improvement in
the reactor performance. This is not the case for the kinetics of
catalyst 1 and catalyst 2. Besides, in the developed kinetic model
for catalyst 3, ethylene combustion is not sensitive to the oxygen
concentration as the coupling reaction. Therefore, a negative
value of j can be observed for catalyst 3, when low oxygen and
high ethylene concentrations are applied, which is not observed
for other two kinetics. A temperature increase is accompanied by
a small increase of j-surfaces for all investigated catalysts and
conditions. The same can be concluded for an increase of the
methane concentration.
In summary, all observed differences between the applied
kinetic models are to be addressed appropriately and considered
for any efficient reactor selection and reactor design approach.
2.3. Gas phase reactions
In order to model the OCM process in particular concerning the
membrane reactors and to explain the reaction rate in the gas
phase (shell side of the membrane reactor), the kinetic model
reported by Lane and Wolf (1988) is used and integrated in the
model structure. This model predicts the formation of all relevant
components in the gas phase. Despite the fact that reactions in the
gas phase are significantly slower than catalytic reactions, when a
distributed oxygen policy is used, these reactions should not be
neglected. However, fine oxygen distribution weakens the
reactivity in the catalyst bed, when reaction rates of catalytic
and gas phase reactions are compared, in particular, when long
contact times are applied. This is a very important issue in the
case of porous membrane reactors because of the methane
permeation to the shell side and the high probability of
combustion in the oxygen rich environment.
The model used in this study is not based on elementary steps
(Lane and Wolf, 1988). Moreover, this model does not include
combustion of ethane/ethylene in the gas phase, which might
influence the accuracy of the final results. Nevertheless, some
general recommendations for the operation of different reactor
concepts will be given for each reactor concept based on the effect
of gas phase chemistry.
6344 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352

3. Reactor models material balances applied for the co-current configuration of the
catalyst-bed and the shell side in each reactor structure.
In this work, a general model has been developed in order to The following assumptions are considered in order to establish
analyze the reactor performance as well as their feeding policies. the governing equations:
The three reactor structures considered are: a fixed bed reactor
(FBR), a conventional packed bed reactor (CPBMR), and a novel Axial diffusion dispersion was neglected
proposed packed bed membrane reactor (PPBMR). The general All components can diffuse across the porous membrane
structure of these three reactor concepts along with their Since the membrane diameter is small, each cross section of
specifications are depicted in Fig. 3. The model includes mass the reactor is represented by a unique concentration for the
and momentum balance equations in both tube and shell sides of component i. Therefore, the bulk gas stream in the tube and
the corresponding reactor as well as other individual character- the shell side does not change with the radial distance from
istics for each reactor structure. The FBR represents a very simple the membrane wall.
structure and consists of only one catalyst bed. All the reactants
are co-fed into the catalyst bed, where all the reactions take place. The mass balance for the components along the FBR is given as
In the CPBMR structure, a porous tubular membrane separates the follows:
shell side and the tube side. The latter contains the catalyst bed,
dFi
where methane reacts with the diffused oxygen supplied from the ¼ rc,i A ð2Þ
dl
shell side. In the PPBMR structure, all reactants are fed into the
tube side and extra methane is fed into the shell side. where Fi (mol/s) and A (m2) are the molar flow-rate for
Here the combustible products are removed along the reactor component i and the cross sectional area of the tubular reactor,
from the reaction side as soon as they are produced. Simulta- respectively. The catalytic production rate of the component i is
neously, the shell side methane stream improves the ratio of denoted by rc,i. The mass balances for the components along the
methane to oxygen along the catalyst-bed. The removal of the PBMR are generally formulated as follows:
reactants and products from the reaction side is based on their dFit
concentration gradient (Godini et al., 2009, 2010). ¼ rc,i At Ni pdt ðTube sideÞ ð3Þ
dl

3.1. Mass balance dFis

¼ Ni pdt þ rg,i As ðShell sideÞ ð5Þ
dl
A generic model has been developed for the different types of here rg,i is the gas phase production rate of the component i and dt
reactors in such a way that it can be reduced to the fixed bed (m) represents the tube side diameter of the reactor. The reaction
model when there is no mass and heat transfer across the rates are substituted in these equations based on the applied
membrane. Fig. 4 describes schematically the control volume and kinetic relations. Besides, it has been assumed that the diffusion
mechanism for the gas components across the membrane is
dominated by the Knudsen diffusion regime. Therefore, the
following equations are used to determine the diffusivity and
mass transfer across the membrane
DK
Ni ¼ ðCit Cis Þ ð5Þ
d
rffiffiffiffiffiffiffiffiffi
2e 8RT
DK ¼ r ð6Þ
3t pM

The general membrane characteristics used in the equations

Fig. 3. Three reactor concepts for the OCM process: Set ‘‘I’’: CPBMR; methane-to- above are defined in Table 1. The details of the algebraic
oxygen ratio is kept high by providing a low oxygen concentration; Ft ¼ N2 +CH4; expressions that reveal the role of contact time, gas flow rates,
Fs ¼ N2 +O2; Ps ¼ mainly O2 + N2; Set ‘‘II’’: FBR; Pt ¼N2 + CH4 + O2; Set ‘‘III’’: PPBMR; reactors dimension, and other design parameters in the governing
methane-to-oxygen ratio is kept high by providing a high methane concentration; mass balance are defined as follows:
Ft ¼ N2 + CH4 + O2; Fs ¼ N2 +CH4; Ps ¼All components (mainly removed pro-
ducts+ CH4); tube side product stream for all three reactor (Pt) contains all dCit At DK t p
components (reactants, products, and inert). ¼ rc,i  ðC C s Þ ð7Þ
dl vt d i i vt
here At is the cross sectional area for the reactor tube side in m2
and vt is the volumetric flow-rate of the gas stream in m3/s. The
available membrane area perimeter for mass transfer in meter is
denoted by P. In Eq. (7), the contact time for reaction corresponds
to the ratio A/vt while P/vt reflects the contact time for diffusion in
each reactor segment (dl).

Table 1
Physical properties of the fixed bed reactor and catalyst bed applied for simulation.

Reactor tube diameter, dt 7 mm

Membrane porosity e and tortusity t 0.5, 2.95
Bulk bed porosity, e 0.36
Density of catalyst 1 3600 kg/m3
Density of catalyst 2 2000 kg/m3
Fig. 4. Material balance in the tube and shell side of the reactor concepts in Density of catalyst 3 1100 kg/m3
co-current configuration.
 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352 6345

3.2. Momentum balance the corresponding set of operating conditions can be found but
also process sensitivities towards each of these variables can be
In this work, analysis and evaluations have been performed tracked as well by simply following process performance trends
based on isothermal conditions just to stress on the effect of along with the variation of each parameter. Moreover, it provides
structural and conceptual parameters. However, the momentum a basis to guide the search direction in any reactor optimization
balance for the tube side in all three structures is applied as task. This can be done by tracking the attainability trend for the
follows: predefined process performance (e.g. objective function). These
are very important information (sensitivities) in any reactor
dPtotal rg G2
¼ f ð8Þ design and optimization task. Figs. 5–16 have been created based
dl dP on this idea.

The coefficient f is described by

4.1. Performance of a fixed bed reactor for different catalysts
ð1eÞ1:2 dP rg G
f ¼ 6:8 Re0:2 with Re ¼ ð9Þ
e3 mg ð1eÞ Figs. 5–7 show the performances of different catalysts in a
fixed bed reactor. Since the feeding policy in a fixed bed reactor
Moreover, the model includes some dimensional character- does not include any diffusion, the most general independent
istics of the catalyst, reactor, and membrane e.g. diffusivity etc., variables for such a graph representation are methane conversion
see Table 1. The resulting equation system is implemented and and temperature. Besides, the required reactor length for the
solved using a modified implicit Runge–Kutta method for stiff reported yield and operating parameters such as the ratio of
problems in Matlab 2008s. methane to oxygen are all represented in the same graph.
In Figs. 6–8, symmetrical distributions of yield are observed
3.3. Energy balance when temperature and conversion are manipulated. For instance,
when the temperature effect is investigated, a trade-off effect over
yield is noticed. For lower temperatures, methane combustion
Although all performance evaluation were carried out based on
an isothermal model, for the sake of the practical implementation,
few most promising conditions have been evaluated with a non-
isothermal model as well so as to investigate whether hot-spot
formation is possible. The energy balance is made up of heat
balance equations for tube and shell side
!
dT t 1 X n
¼ ðri DHR i Þ þht,s ðT t T s Þ ðTube sideÞ ð10Þ
dl rt cp,t wt i ¼ 1
!
dT s 1 X
n
¼ ðri DHR i Þht,s ðT t T s Þ þ hs,e ðT s T e Þ ðShell sideÞ
dl rt cp,t wt i¼1
ð10Þ

The heat transfer coefficients have been estimated by a

correlation of Dixon (1988). The environment temperature has
been fixed to be equal to the inlet temperature.

4. Reactor performances: results and discussion Fig. 5. Influence of the methane conversion and operating temperature on the
achievable yield of C2 + products for catalyst 1 in the FBR structure.
In order to provide comparable results for all catalysts and
reactor feeding policies, reactor, and catalysts characteristics are
maintained constant in all studies as shown in Table 1. Further-
more, in this study, a new graphical representation form has been
developed in order to visualize the simulation results such that
both qualitative and quantitative process behavior can be
analyzed appropriately. In this manner, the highest achievable
process performance (yield) is represented in one graph along
with as many variables as possible. For instance, when tempera-
ture and feed composition are manipulated simultaneously, it
affects the conversion, yield, and the required reactor length
(catalyst amount). These trends can now be followed and
represented together in one graph. It should though be empha-
sized that the operating conditions are evaluated in the same
range in which the kinetic models have been developed.
This approach enables one not only to track the behavior of the
OCM process for a set of integer variables such as the type of
reactor and catalyst, but also to cover a wide range of process
variables such as reactor size, temperature, and inlet concentra- Fig. 6. Influence of the methane conversion and operating temperature on the
tion. Herewith, not only the highest achievable performance and achievable yield of C2 + products in for the catalyst 2 in the FBR structure.
6346 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352

Fig. 7. Influence of the methane conversion and operating temperature on the

achievable yield of C2 + products in for the catalyst 3 in the FBR structure.
Fig. 10. Influence of the oxygen concentration in the shell side and shell flow rate
on the achievable yield for catalyst 1; T ¼820 1C; d ¼ 20 mm.

Fig. 8. Influence of the membrane thickness and operating temperature on the Fig. 11. Influence of the membrane thickness and operating temperature on the
achievable yield for catalyst 1; vsh (Shell flow rate) ¼ 4 cm3n =s (STP); yO2 ¼1 achievable yield for catalyst 2; vsh (Shell flow rate) ¼4 cm3n =s (STP); yO2 ¼ 1
(undiluted oxygen in the shell side). (undiluted oxygen in the shell side).

Fig. 9. Influence of the oxygen concentration in the shell side and operating
temperature on the achievable yield for catalyst 1; vsh (Shell flow rate) ¼ 4 cm3n =s Fig. 12. Influence of the membrane thickness and operating temperature on the
(STP); d ¼20 mm. achievable yield for catalyst 3; vsh (Shell flow rate) ¼4 cm3n =s (STP); yO2 ¼ 1
(undiluted oxygen in the shell side).

reactions have a significant contribution. This is due to the Therefore, a further increase of temperature enhances the coupling
temperature sensitive coupling reactions, which have higher reactions. However, when high temperatures are applied, product
activation energy in comparison to the combustion reactions. combustion is inevitable, which results in a steep decrease of yield.
 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352
Fig. 13. Influence the membrane thickness and operating temperature on the
achievable yield for catalyst 1 (PPBMR structure); vsh (Shell flow rate) ¼4 cm3n =s
(STP); yO2 ¼1 (undiluted oxygen in the shell side).
Fig. 14. Influence of the methane concentration in the shell side and operating
temperature on the achievable yield for catalyst 1 (PPBMR structure); vsh (Shell
flow rate) ¼ 4 cm3n =s (STP); d ¼ 20 mm.
Fig. 15. Influence of a membrane thickness and operating temperature on the
achievable yield for catalyst 2 (PPBMR structure); vsh (Shell flow rate) ¼4 cm3n =s
(STP); yO2 ¼1 (undiluted oxygen in the shell side).
The same is true for the effect of methane conversion. Up to some
level, a conversion increase is also followed by an increase of the
achievable yield because of the higher amount of C2 formation.
6347
Fig. 16. Influence of the membrane thickness and operating temperature on the
achievable yield for catalyst 3 (PPBMR structure); vsh (Shell flow rate) ¼ 4 cm3n =s
(STP); yO2 ¼ 1 (undiluted oxygen in the shell side).
However, a high methane conversion requires high oxygen
concentrations in the inlet. Therefore, the concentration of both
desired products and oxygen is significant since formed products
can be combusted easily. Consequently, the highest achievable
area of yield is just right in the center of the mentioned graph
above.
Since several kinetic models have been evaluated, the proposed
overview is much more comprehensive and complete. The highest
C2 + yield for catalyst 1 was found to be 20.11%, which is comparable
to the highest yield reported in the literature for this catalyst. For
catalyst 3 or catalyst 2, the highest achievable yields are 19.46% and
17.4%, respectively. These predicted yields are in a reasonable range
as well. Since no empty space was available, the influence of gas
phase reactions was not considered in this case.
In fixed bed reactors, the reaction aspects affect the process
performance in a straightforward way and there is no applicable
diffusion concept. Therefore, the qualitative behavior of these
catalysts in FBR is quite similar, in other words the dependence of
yield on conversion and temperature follows the same trend for
all kinetic models. Optimum values of yield are obtained for both
catalysts 1 and 3, but not for catalyst 2 because of the
temperature range under which its kinetics has been developed.
Hence, another characteristic of the proposed graph-based
approach is the ability to determine whether the range of
operation during the kinetic experiments has been designed
properly or not. Moreover, the inlet conditions affect also the
quantity of the highest achievable yield. For instance, for catalyst
1 and catalyst 2 a maximum yield value has been found for an
inlet ratio of methane to oxygen between 1.1 and 0.8 (Figs. 5 and 6).
However, for catalyst 3 the maximum value of yield corresponds
to an inlet ratio of 2 (Fig. 7). Besides, the contact times needed for
a full oxygen conversion for catalyst 2 and catalyst 3 are similar
and the corresponding required reactor length is in the range of
few centimeters, whereas for catalyst 1 only few millimetres are
required for a full oxygen conversion. This is because of much
faster reaction rates observed for this catalyst in comparison to
the other catalysts, which have also been reported in literature
(Oliver et al., 2008). Therefore, reactor designed for one catalyst
type may not work properly under similar operating conditions,
when other catalysts are applied. Furthermore, the efficiency of
the reactor concept in order to perform the OCM process depends
strongly on the catalyst activity as the only effective aspect of the
FBR structure.
6348 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352
Finally, based on the proposed graph representation it can be
concluded that the operating temperature for the kinetic
determination of catalyst 2 should in fact be extended in order
to reach the highest absolute achievable area.
4.2. Performance of a conventional packed-bed membrane reactor
Distributed oxygen feed is one of the basic ideas in order to
improve the yield in most of the processes for partial oxidation of
hydrocarbons. Concerning this particular topic, theoretical studies
have concluded that using this feeding policy with some catalysts
can improve the yield significantly (Lu et al., 1997, 1996; Hamel
et al., 2003). The reaction order of oxygen in the coupling reaction
plays an important role in the efficiency of the distribution policy.
If the reaction order of oxygen in the coupling reaction for one
reaction kinetics is lower than for the combustion reactions, the
distributed oxygen policy is followed by an increase of yield.
Otherwise, the distribution of the oxygen feed will not improve
the yield in comparison to the fixed bed reactor (Coronas, 1994).
In order to simulate and analyze the effect of the distributed
feeding policy, the three types of kinetic models and catalysts are
again tested in the packed bed membrane reactor model. Same
data of Table 2 is used. Reactors are fed with the same flow in the
tube side, which contains the same amount of methane. However,
thickness of the diffusion layer in the membrane, oxygen
concentration in the shell side, total shell side flow-rate, and
temperature are all manipulated within the wide range of
operating conditions. Although the influence of all of these
independent variables cannot be presented simultaneously, their
influence can properly be visualized by changing two of them
each time while keeping the other two constant. In this manner,
all variables are covered and their influence can be represented in
three individual graphs for each catalyst.
Especially in this reactor type, the influence of gas phase
reactions in the shell side (oxygen rich side) is important and has
to be taken into account. Yield over prediction of 5–12% was
noticed in the vicinity of the highest achievable yields.
4.2.1. Performance with catalyst 1
The performance of the OCM process in the CPBMR structure
with catalyst 1 is presented in Figs. 8–10. This feeding policy
improves normally the yield mainly because of the selectivity
improvement. In this structure, the membrane thickness deter-
mines the accessibility to oxygen in the reaction side; therefore,
increasing the membrane thickness improves the achievable
yield. However, this improvement in yield is only obtained at
the cost of increasing the required reactor length for such a
performance. A further yield improvement might still be possible
with a less permeable membrane, this is however not a practical
and efficient approach for a yield improvement. This is due to the
fact that the required reactor length will then be increased
drastically if the permeable layer is thicker than d ¼100 mm.
As shown in Fig. 8, even a thinner membrane could be used to
achieve the same yield level when increasing temperature. It
means that a reduction in selectivity due to the thickness decrease
Table 2
Simulation conditions in the reaction side (tube side) of all reactor concepts.
Tube diameter 7 mm
Bed porosity 0.36
Shell diameter 21 mm
Tube flow rate 4 cm3n =s
Methane content in the tube 50%
can generally be compensated by the temperature effect on the
conversion. This evidences an important potential since it
performs not only at the same yield level and methane
conversion, but decreases also the reactor size. Fig. 8 shows also
at which extent the temperature has to be increased in order to
compensate the effect of a decrease in membrane thickness.
However, by increasing temperature beyond a certain value, the
combustion will be accelerated. Thus, in order to control
undesired consequences of selectivity reduction, the thickness
should be increased again. In this manner, in case of the highest
achievable yield, the optimum area could be identified in the
upper center of Fig. 8.
Fig. 9 visualizes the same theoretical background. By increas-
ing the operating temperature, a lower oxygen concentration in
the shell side could be used so as to reach the same yield level.
This behavior is rather expected since a temperature increase,
results in a selectivity increase, which can compensate the
undesired effect of oxygen on the selectivity. Fig. 10 shows the
shell flow rate influence on the CPBMR performance. The oxygen
concentration in the shell side is manipulated along with the shell
flow in order to investigate the influence of the total oxygen
availability on the reactor performance. In general, since these
two parameters reflect the amount of accessible oxygen, which is
required to have a constant yield level, the increase of one of them
should be compensated by decreasing the other one. Conse-
quently, by increasing the shell volume flow rate, the correspond-
ing oxygen fraction is declined along the curve, which represents
a constant yield (Fig. 11). The effect of the oxygen fraction can in
particular be identified better at average shell flow rates, where C2
formation and combustion are in balance due to the accessible
oxygen.
Moreover, using a low oxygen fraction in the shell stream
implies the use of more diluents (e.g. Nitrogen) in the shell. If the
same shell and tube flow rate are used, the dilution of oxygen in
the shell side has a negative effect on the achievable yield because
it decreases methane conversion. It can also be concluded that a
high yield is only obtainable (red line of methane conversion
X¼0.9 in Fig. 10) for an oxygen amount higher than the
stoichiometrical such that almost all methane is used. However,
the observed yields of around 60% for this catalyst and reactor
concept are much higher than all reported yields in literature.
Even though such high yield has been obtained with undiluted
oxygen feed, it should be noticed that when 50% or more dilution
is applied using smaller shell flows, yield is limited to less than
35%. Moreover, when methane conversion of 50% or less is
achieved, no more than 25% yield can be obtained with this
catalyst. Unfortunately, all experimental studies were conducted
in this operational range so far. However, when practical aspects
are considered, dilution of the shell stream is necessary because of
safety reasons. So, for instance, because of the back permeation of
methane, an explosive mixture of oxygen and methane can be
formed, which can cause a hazard in an oxygen-rich environment.
Gas phase reactions are very important because of their
influence on process performance. When gas phase reactions are
not included in the reactor model, the highest achieved yield is
around 75%. In contrast to this, a yield of 62% is obtained when
they are considered. However, according to Lane and Wolf (1988),
all combustion reactions in the gas phase are calculated based on
methane and oxygen consumption. Therefore, this gas phase
model can only predict the competition between selective and
non-selective reactions involving methane and oxygen as reac-
tants, but not in the presence of ethane and ethylene. Conse-
quently, this model is fairly accurate only in case of low
concentrations of ethane and ethylene in the gas stream and
when the combustion of those species is not significant. There-
fore, the obtained yield for this catalyst might be over-predicted
 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352
in this simulation. It should however be noticed that if the ethane
and ethylene reactor concentration are considerable, it is
necessary to include their combustion reactions in the model in
order to evaluate properly the total effect of gas phase reactions.
Thus, a model considering all relevant gas phase reactions, and
which is not based on elementary steps, is to be developed so as to
improve the accuracy of similar simulation studies.
4.2.2. Performance with catalyst 2
The conclusions derived for this catalyst are similar to those for
catalyst 1. Therefore, only the effect of membrane thickness is
depicted in Fig. 11. Moreover, the same behavior in terms of
influence of the total oxygen availability can be derived, where
methane conversion has to be significant, if a high yield is to be
obtained. Undiluted feed of oxygen was proved to provide the
highest attainability because of the same reasons described above.
The main difference between this catalyst and the previous one is its
intrinsic activity. The average reaction rate for this catalyst is 1 to 2
orders of magnitude smaller than in the previous case, which results
in a reactor length of 30–80 cm for the best performance. This is
significant in comparison to the length of around 10 cm for the
catalyst 1. Furthermore, the activity of this catalyst affects the
observed maximal yield as well. Smaller reaction rate allows more
oxygen being present in the tube side of the reactor, which
consequently affects the selectivity. Therefore, a membrane thick-
ness of more than 100 mm is needed in order to further decrease the
oxygen permeability and to increase further the selectivity. How-
ever, such manipulation would have a strong negative effect on the
reactor size (Fig. 8) as shown in our simulation.
The temperature was limited to that range, in which the
kinetic model was developed (around 780 1C). This has already
been addressed in the discussion related to the fixed bed reactor.
The gas phase reactions did not have a critical influence on this
reactor performance. This is mainly due to the lower selectivity and
lower fraction of C2 + compared to the previous case, which could
not be affected significantly by the gas phase combustion reactions.
4.2.3. Performance with catalyst 3
The performance of the OCM process in a conventional
membrane reactor with catalyst 3 is presented in Fig. 12. The
effect of oxygen availability is similar as for catalyst 1. Therefore,
in Fig. 12 undiluted stoichiometrical oxygen feed is applied. Here
only the influence of membrane thickness and temperature are
investigated. Fig. 12 shows also the same trend as in the
previously discussed catalysts. However, a smaller sensitivity to
the effect of membrane thickness is observed in comparison to
catalyst 1. This is due to the smaller reactivity of catalyst 3 and
the comparable rates of both reaction and diffusion through the
membrane. This catalyst is though much more sensitive to the
effect of membrane thickness in comparison to the reaction
controlled with catalyst 2.
For this catalyst, the gas phase reactions do not have a
significant effect on the performance. A maximal yield with and
without implementation of gas phase reactions in the shell side is
18.7% and 19.8%, respectively. It can be concluded that the
performance of this catalyst in the CPBMR structure is mainly
determined by the reaction orders of oxygen in combustion and
coupling reactions. These parameters describe the kinetic model
for this catalyst as ‘‘non-favorable’’ for the oxygen feeding policy.
It has to be noted here that the experimental study of Lu et al.
(2000) obtained 27.8% yield for the same catalyst. Therefore, it has
been shown that this catalyst is able to be used in distributed
oxygen conditions, and thus, it gives a doubt on the validity of this
kinetic model.
6349
4.2.4. Comparison between the predicted performances of different
catalysts in a conventional porous membrane reactor
The comparison of kinetic models developed for three different
catalysts shows that their yield, conversion, and reactor size are
quite different. Qualitative similarity and difference observed for
these catalysts were described based on the difference between their
performance governing-mechanisms. For catalyst 1, the reaction is
fast and the achievable yield will be affected considerably by
manipulating diffusion parameters such as membrane thickness.
Instead catalyst 3 is less sensitive to the effect of membrane
thickness in comparison to catalyst 1 but it is much more sensitive
than catalyst 2. It can be concluded that the performance of catalyst
1, catalyst 3, and catalyst 2 is controlled by diffusion aspects,
reaction-diffusion aspects, or reaction mechanism, respectively.
However, in all of them the increase of membrane thickness results
in a much bigger reactor size than required for fine oxygen
distribution. For all investigated cases, oxygen dilution decreases
the yield. Thus, it can be concluded that there is a need to operate
with more than a stoichiometrical amount of oxygen.
The quantitative results in terms of reported yield can be found
on the higher activity of catalyst 1 in comparison to other catalysts.
This property enables oxygen to react rapidly and to remain at a low
level in the reaction side. Consequently, it makes reaction more
selective towards coupling products. Furthermore, fast reaction and
low contact times will not allow methane to permeate significantly
to the oxygen rich shell side and combusting further. Lower yields
reported for catalyst 2 are due to the slower reaction rate, and
therefore, longer contact times and better distribution of oxygen is
needed. For both catalyst 1 and catalyst 2 significant yield
improvement is obtained using a conventional porous membrane
reactor. For catalyst 1 this improvement it accounted to 40% (from
20% in FBR to 60% in CPBMR) and for catalyst 2 up to 13% (from 17%
in FBR to 30% in CPBMR). An interesting observation is that although
catalyst 2 shows an evident higher ‘‘differential selectivity’’ (j), as
discussed previously, due to its lower activity the achievable yield is
lower in a membrane reactor. Therefore, a less selective but more
active catalyst proves to be a better choice for the CPBMR. Although
catalyst 3 qualitatively shows a moderate reaction rate in a
conventional membrane reactor in comparison to two other
catalysts, quantitatively speaking no improvement in the achievable
yield was observed by using this catalyst in a CPBMR structure.
4.3. Performance of the proposed packed bed membrane reactor
The third reactor structure PPBMR, which has recently been
proposed by Godini et al. (2009, 2010), has the same structure as
CPBMR, but the feeding policy is more comparable to the FBR
structure. The tube gas stream contains all the reactants
(N2-Diluent, CH4, O2) and the shell stream contains mainly
N2-Diluent and CH4. Along this reactor, reactants and products
are removed from the reaction side according to their concentra-
tion gradient. This offers the possibility for higher oxygen
concentration in the feed entrance section, which then enhances
the absolute yield and gives the opportunity to remove products
(such as ethane and ethylene) from critical areas in the reaction
side, and thus, selectivity improvement. Therefore, in case of flow-
rate this structure has a higher capacity because of the co-feeding.
Moreover, due to reactants removal it shows a satisfactory level of
selectivity and can handle a higher oxygen feed in comparison to
the FBR structure. Moreover, in the PPBMR structure, the methane
available in the shell side can compensate the undesired effect of
methane reduction due to reaction in the tube side. It increases the
methane-to-oxygen ratio, which is a critical parameter and when
this is optimally applied, it then enhances both the yield and the
selectivity. The gas phase chemistry plays only a minor role in this
6350 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352

reactor concept because the oxygen availability is very small in the the necessary operating conditions required for a safe reactor
empty space of the reactor (shell side). operation, a non-isothermal studies are carried out on the most
The behavior of the OCM process performance in a PPBMR promising reaction conditions.
structure is presented on Figs. 13 and 14 for catalyst 1. Since For the fixed bed reactor it was found that the reaction occurs
membrane thickness determines the possibility to withdraw almost adiabatically. Even with a cooling of the reaction wall, the
reactants and products from the reaction side, increasing the hot spot temperature increases up to approximately adiabatic
thickness of the membrane permeable layer has a dual effect on temperature rise. Simulation results for catalyst 1 are shown in
yield. On the other hand, decreasing the membrane thickness Fig. 17. Whenever optimal feed composition and an optimal
facilitates the removal of the desired products from the reaction temperature (Fig. 5) together with a catalyst dilution of 1:4 is
side, but this policy has a practical limitation since at least some applied, significant hot spots were observed (Fig. 17). Similar
parts of the reactants should be kept on the reaction side in order results were obtained by Tye et al. (2002). Isothermal tempera-
to have a level of conversion. As shown in Fig. 13, at two ture profile could not be observed even with feed dilution of 85%.
temperature ranges, membrane thickness does not affect the In case of catalysts 2 and 3, this temperature rise was significantly
achievable yield. At low temperatures, the combustion of reactants smaller being only about 30–50 K for the same operating
is favorable regardless how fast diffusion is. On the other hand, conditions with high dilution. This testifies the importance of
combustion of products always occurs at very high temperatures the controlled reaction rate on the reactor performance. Catalyst
before any possible removal. Consequently, an absolute maximum 1, which has a greater activity compared to other catalysts by 1 to
yield could be achieved in an intermediate range of temperatures. 2 orders of magnitude, is therefore not recommendable for its use
Moreover, membrane diffusion can be the limiting and governing in the PFR without significant feed or catalyst dilution.
mechanism when using this catalyst. Nevertheless, it is clear that In case of a membrane reactor, when the conditions in Fig. 8
only for very thin membrane, the effect of removal is identified. are applied for the analysis of a non-isothermal performance, it
However, very thin membranes decrease yield by allowing can be noticed that a hot spot of around 100 K occurs (blue lines
oxygen to permeate out from the reaction side. On the other hand, in Fig. 18). Such behavior is observed for almost all conditions
very thick membranes prevent removal of combustible reaction with high temperature and in an oxygen rich environment
products. By increasing temperature or by decreasing membrane because of the insufficient heat transfer rate. The tube side of
thickness, the reactants are leaving the reaction side either through the membrane reactor can exchange heat only with its shell side.
removal or via direct methane combustion. In consequence, yield is
decreased. Fig. 14 shows the effect of the methane available in the
shell side w.r.t. the attainable yield. In Fig. 14, it can be seen that for a
lower methane fraction in the shell side, the reaction determines the
reactor performance. Therefore, membrane thickness has no con-
siderable effect within this range. However, the reaction will be
saturated and the diffusion becomes more dominant over the process
performance in case of a higher range of methane concentration.
Fig. 15 illustrates the performance of the OCM process for the
PPBMR, using catalyst 2, where the reaction rate is relatively slow
and it controls the process performance. This catalyst behaves
similarly like catalyst 1. Therefore, this graph does not imply a
significant sensitivity towards the effect of membrane thickness.
A similar behavior like catalyst 1 can also be noticed when
different methane concentration was applied. Generally, the
membrane thickness is a less sensitive parameter in comparison
to catalyst 1. Due to the temperature range for catalyst 2, the dual
effect of membrane thickness could not be observed.
The attainable performance in the PPBMR structure is Fig. 17. Hot spots formation in the fixed bed reactor under different feed dilution
presented in Fig. 16. The behavior of catalyst 3 is comparable to conditions.
the previous catalysts regarding temperature effect, membrane
thickness, and methane fraction in the shell side. Catalyst 3 shows
a similar qualitative behavior and performs moderately due to its
intermediate reaction rate. The performance of catalyst 3 is
controlled by a combination of diffusion and reaction. The effect
of membrane thickness is not as sensitive as for catalyst 1, but it is
more sensitive than for catalyst 2.
Because of the operational aspects of the PPBMR structure, the
achievable yield is affected by both high and low reactive
catalysts. In this proposed configuration, reactants are removed
from the reaction side either via diffusion or due to combustion.
The OCM performance for all three catalysts in the PPBMR
structure is quantitatively more similar to the FBR structure, but
with a higher degree of flexibility.

4.4. Non-isothermal simulation

Fig. 18. Temperature distribution in the classical membrane reactor geometry
(blue lines) and modified geometry (red lines). (For interpretation of the
In order to evaluate the performance of all reactor types in references to colour in this figure legend, the reader is referred to the web version
terms of heat effects and hot spot formation as well as to suggest of this article.)
 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352 6351

However, shell side has only a slightly lower temperature, and
thus, a heat transfer is very inefficient. Shell side provides here
unwanted heat insulation, because the heat must penetrate
through the membrane wall, shell side and a reactor wall. In this
manner the biggest portion of the heat is kept inside the tube side
of the reactor, and an adiabatic behavior occurs.
In order to control the reaction heat, tube and shell side were
exchanged such that the reaction occurs in the shell side of the
membrane reactor so as to increase the heat transfer area as well
as the driving force a for heat exchange. This results in almost
isothermal operation, where hot spot of only 9 K was observed for
the optimal feed conditions. Moreover, no more than 15 K hot
spot is observed in additional simulation studies, which testifies
the validity of previous isothermal investigations. Simulations for
other catalyst types gave results which are very similar to the
ones already shown on Figs. 17 and 18. Moreover, same
conclusions which were derived for the non-isothermal behavior
of CPBMR could be extended to the proposed PPBMR structure.
5. Conclusions
In this contribution, a comparative analysis of attainable
performance has been presented for three different reactor
structures and their feeding policies. In these structures the
efficiency is strongly affected by the availability of reactants (i.e.
methane, ethylene, and oxygen). In the FBR structure, there is no
diffusion aspect involved in the operation, and thus, the reactants
availability cannot be manipulated. Therefore, the intrinsic
difference between reactivity and inherent selectivity of the three
catalysts cannot be exploited optimally. Hence, they show
relatively the same quantitative and qualitative behavior.
The CPBMR structure offers potentially the highest achievable
yield and provides a comparative flexible operating mode. However,
this reactor concept has to confront methane back-permeation, and
very long required contact times. Due to its feeding policy, the
highest achievable yield in the PPBMR structure is almost the same
as for the FBR structure. The feeding policy is limited because of
diffusion aspects. However, it is much more flexible than the FBR
structure. In addition, back-permeation does not represent a
problem in this configuration.
Each of the presented reactor structures shows relevant
efficiency aspects concerning the OCM process (selectivity, yield,
or conversion) and its specific feeding policy. So, for instance, getting
a high conversion in the FBR structure or obtaining a high selectivity
in the CPBMR structure, where oxygen is supplied in a more
controllable way, are the potential of these structures, respectively.
It should though be pointed out that among the investigated kinetic
models; the one developed for catalyst 1 shows a better perfor-
mance in the CPBMR structure under intermediate range of
temperatures and membrane thickness. Catalyst 3 shows its best
performance in the proposed PPBMR structure.
Non-isothermal simulations show that FBR is impossible to
run isothermally and that severe hot spots appear even with high
dilution of feed and catalyst. Membrane reactor in its classical
configuration offers better control over the reaction heat.
However, hot spots of around 100 K are still observed. By
manipulating the reactor geometry, it is possible to maintain
the reaction temperature almost isothermal. This shows that a
membrane reactor can be used in industry not only because of the
enhanced yield, but also because of the isothermal operation. The
most important parameter for the reactor performance was found
to be the membrane thickness. The thicker the membrane, the
better distribution of oxygen and consequently the higher yield
can be achieved. The second most important parameter is the
oxygen concentration. It was found that the larger the oxygen
concentration, the better the yield.
In terms of catalyst selection, it has been shown that in
comparison to slower catalysts, an ‘‘intrinsically fast’’ catalyst is
better for its use in the CPBMR structure. The activity of a catalyst
has no significant effect neither in the performance of the PPBMR
nor in a FBR structure.
In order to analyze the highest achievable performance in each
case, a novel graph-based approach has been proposed. In this
manner, individual and synergic effects of all variables over the
OCM process performance are evaluated. These graphs represent
not only a sensitivity analysis but they also depict the effects of
diffusion and reaction parameters according to the catalyst
activity and the limiting step under a certain range of operating
conditions. Based on these graphs, the effect of parameters such
as temperature, membrane thickness, shell flow-rate, methane,
and oxygen concentration in the shell side could then be
compensated. Thus, the trends of achievable yield can be
predicted by any scenario including the manipulation of these
parameters. The graph-based approach has also the potential to
provide alternative path towards improving the process perfor-
mance, and thus, it can simply be used for reactor design and
optimization tasks. Thus, kinetic-analysis based on the proposed
graphical approach enables determination of the suitable range of
operating conditions for any kinetic study and possible operation
to cover and reach the highest achievable area.
Acknowledgements
The authors acknowledge the support from the Cluster of
Excellence ‘‘Unifying Concepts in Catalysis’’ coordinated by the
Berlin Institute of Technology – Technische Universität Berlin and
funded by the German Research Foundation – Deutsche For-
schungsgemeinschaft.

Table A1
Kinetic constants for catalyst 1 (left column) and catalyst 3 (right column).

Step k0,j [mol/(gm s Pam + n)] Ea,j [kJ/mol] Kj,CO2 ½Pa1  DHads,CO2 Kj,O2 ½Pa1  DHads,O2 m n
½kJ=mol ½kJ=mol

1 0.2  10  5 3.07  10  7 48 98.54 0.25  10  12  175 0.24 0.85 0.76 0.5

2 23.2 29.4 182 212.6 0.83  10  13  186 0.23  10  11 4.39  10  11 124 121.9 1 1 0.4 0.75
3 0.52  10  6 6.65  10  8 68 146.8 0.36  10  13  187 0.57 0.5 0.85 1.57
4 0.11  10  3 5.26  10  4 104 114.6 0.40  10  12  168 1 0.5 0.55 0.5
5 0.17 2.70  10  3 157 153.5 0.45  10  12  166 0.95 0.91 0.37 0.5
6 0.06 0181 166 174.4 0.16  10  12  211 1 0.72 0.96 0.4
7 1.2  107 1.08  107 266 291.9 1 0.88
8 1.2  103 461 300 394.2 0.97 1.62 0 0.71
9 0.19  10  3 5.24  10  3 173 158.0 1 1 1 1
10 0.26  10  1 5.77  10  6 220 131.1 1 1 1 1
6352 S. Jašo et al. / Chemical Engineering Science 65 (2010) 6341–6352

Appendix A. Reaction kinetics

The reaction kinetics for catalyst 1 and 3 are given below. In case of catalyst 3, the enthalpy of adsorption and adsorption constants for
CO2 are not included in the expressions for reactions 1–6 (Table A1).

CH4 + 2O2-CO2 + 2H2O (1) k0,j e

ðEaj =RTÞ
ðKO2 ,j e
ðDHads O ,j =RTÞ
2
n m
pO2 Þ j pc j
rj ¼  2 j¼2
2CH4 + 0.5O2-C2H6 + H2O (2) 1 þ ðKO2 ,j e
ðDHads O ,j =RTÞ
2
nj
pO2 Þ þ KCO2 ,j e
ðDHads CO ,j =RTÞ
2 pCO2

CH4 + O2-CO+ H2O + H2 (3) k0,j e

ðEaj =RTÞ nj mj
pO pc
CO +0.5O2-CO2 (4) rj ¼  2
ðDHads CO ,j =RTÞ
 2 j ¼ 1,36
1 þ KCO2 ,j e 2 pCO2

C2H6 + 0.5O2-C2H4 + H2O (5)

C2H4 + 2O2-2CO+ 2 H2O (6)
C2H6-C2H4 +H2 (7) r 7 ¼ k0,7 eðEa7 =RTÞ pm 7
C2 H6
C2H6 + H2O-2CO +4H2 (8) r8 ¼ k0,8 eðEa8 =RTÞ pm n8
C2 H4 pH2 O
8

CO +H2O-CO2 + H2 (9) r9 ¼ k0,9 eðEa9 =RTÞ pm 9 n9

CO pH2 O
CO2 + H2-CO+ H2O (10) r10 ¼ k0,10 eðEa10 =RTÞ pm 10 n10
CO2 pH2

Reaction kinetics for catalyst 2

CH4 + 2O2-CO2 + 2H2O (1) 0:4 0:5

r 1 ¼ 0:015eð6:134=TÞ CCH C
4 O2

2 CH4 + 0.5O2-C2H6 + H2O (2) 0:8 1:1

r 2 ¼ 0:6eð11908=TÞ CCH C
4 O2

C2H6 + 0.5O2-C2H4 + H2O (3) r 3 ¼ 1  104 eð772=TÞ CC0:8 C 1:0

2 H6 O2

C2H4 + 3O2-2CO2 + 2H2O (6) r 4 ¼ 1  1016 e26461=T CC0:8 C 1:6

2 H4 O2

Gas phase kinetics reactions are as follows:

CH4 + 2O2-CO2 + 2H2O (1) r 1 ¼ 3:23  1011 e71:6=RT PCH

0:53 3:7
PO2
4

CH4 + 1.5O2-CO+ 2H2O (2) r 2 ¼ 1:02  102 e29:5=RT PCH

0:95 1:33
PO2
4

2CH4 + 0.5O2-C2H6 + H2O (3) r 3 ¼ 3:95  105 e51:8=RT PCH

1:04 1:78
PO2
4

2CH4 + O2-C2H4 +H2O (6) r 4 ¼ 9:75  104 e52:1=RT PCH

1:16 1:62
PO2
4

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