1 s2.0 S0009250910004860 Main
1 s2.0 S0009250910004860 Main
1 s2.0 S0009250910004860 Main
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.
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
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:
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
Table 1
Physical properties of the fixed bed reactor and catalyst bed applied for simulation.
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.
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. 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 6347
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. 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).
Finally, based on the proposed graph representation it can be can generally be compensated by the temperature effect on the
concluded that the operating temperature for the kinetic conversion. This evidences an important potential since it
determination of catalyst 2 should in fact be extended in order performs not only at the same yield level and methane
to reach the highest absolute achievable area. 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.
4.2. Performance of a conventional packed-bed membrane reactor
However, by increasing temperature beyond a certain value, the
combustion will be accelerated. Thus, in order to control
Distributed oxygen feed is one of the basic ideas in order to undesired consequences of selectivity reduction, the thickness
improve the yield in most of the processes for partial oxidation of should be increased again. In this manner, in case of the highest
hydrocarbons. Concerning this particular topic, theoretical studies achievable yield, the optimum area could be identified in the
have concluded that using this feeding policy with some catalysts upper center of Fig. 8.
can improve the yield significantly (Lu et al., 1997, 1996; Hamel Fig. 9 visualizes the same theoretical background. By increas-
et al., 2003). The reaction order of oxygen in the coupling reaction ing the operating temperature, a lower oxygen concentration in
plays an important role in the efficiency of the distribution policy. the shell side could be used so as to reach the same yield level.
If the reaction order of oxygen in the coupling reaction for one This behavior is rather expected since a temperature increase,
reaction kinetics is lower than for the combustion reactions, the results in a selectivity increase, which can compensate the
distributed oxygen policy is followed by an increase of yield. undesired effect of oxygen on the selectivity. Fig. 10 shows the
Otherwise, the distribution of the oxygen feed will not improve shell flow rate influence on the CPBMR performance. The oxygen
the yield in comparison to the fixed bed reactor (Coronas, 1994). concentration in the shell side is manipulated along with the shell
In order to simulate and analyze the effect of the distributed flow in order to investigate the influence of the total oxygen
feeding policy, the three types of kinetic models and catalysts are availability on the reactor performance. In general, since these
again tested in the packed bed membrane reactor model. Same two parameters reflect the amount of accessible oxygen, which is
data of Table 2 is used. Reactors are fed with the same flow in the required to have a constant yield level, the increase of one of them
tube side, which contains the same amount of methane. However, should be compensated by decreasing the other one. Conse-
thickness of the diffusion layer in the membrane, oxygen quently, by increasing the shell volume flow rate, the correspond-
concentration in the shell side, total shell side flow-rate, and ing oxygen fraction is declined along the curve, which represents
temperature are all manipulated within the wide range of a constant yield (Fig. 11). The effect of the oxygen fraction can in
operating conditions. Although the influence of all of these particular be identified better at average shell flow rates, where C2
independent variables cannot be presented simultaneously, their formation and combustion are in balance due to the accessible
influence can properly be visualized by changing two of them oxygen.
each time while keeping the other two constant. In this manner, Moreover, using a low oxygen fraction in the shell stream
all variables are covered and their influence can be represented in implies the use of more diluents (e.g. Nitrogen) in the shell. If the
three individual graphs for each catalyst. same shell and tube flow rate are used, the dilution of oxygen in
Especially in this reactor type, the influence of gas phase the shell side has a negative effect on the achievable yield because
reactions in the shell side (oxygen rich side) is important and has it decreases methane conversion. It can also be concluded that a
to be taken into account. Yield over prediction of 5–12% was high yield is only obtainable (red line of methane conversion
noticed in the vicinity of the highest achievable yields. X¼0.9 in Fig. 10) for an oxygen amount higher than the
stoichiometrical such that almost all methane is used. However,
4.2.1. Performance with catalyst 1 the observed yields of around 60% for this catalyst and reactor
The performance of the OCM process in the CPBMR structure concept are much higher than all reported yields in literature.
with catalyst 1 is presented in Figs. 8–10. This feeding policy Even though such high yield has been obtained with undiluted
improves normally the yield mainly because of the selectivity oxygen feed, it should be noticed that when 50% or more dilution
improvement. In this structure, the membrane thickness deter- is applied using smaller shell flows, yield is limited to less than
mines the accessibility to oxygen in the reaction side; therefore, 35%. Moreover, when methane conversion of 50% or less is
increasing the membrane thickness improves the achievable achieved, no more than 25% yield can be obtained with this
yield. However, this improvement in yield is only obtained at catalyst. Unfortunately, all experimental studies were conducted
the cost of increasing the required reactor length for such a in this operational range so far. However, when practical aspects
performance. A further yield improvement might still be possible are considered, dilution of the shell stream is necessary because of
with a less permeable membrane, this is however not a practical safety reasons. So, for instance, because of the back permeation of
and efficient approach for a yield improvement. This is due to the methane, an explosive mixture of oxygen and methane can be
fact that the required reactor length will then be increased formed, which can cause a hazard in an oxygen-rich environment.
drastically if the permeable layer is thicker than d ¼100 mm. Gas phase reactions are very important because of their
As shown in Fig. 8, even a thinner membrane could be used to influence on process performance. When gas phase reactions are
achieve the same yield level when increasing temperature. It not included in the reactor model, the highest achieved yield is
means that a reduction in selectivity due to the thickness decrease 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
Table 2
Simulation conditions in the reaction side (tube side) of all reactor concepts.
model can only predict the competition between selective and
non-selective reactions involving methane and oxygen as reac-
Tube diameter 7 mm tants, but not in the presence of ethane and ethylene. Conse-
Bed porosity 0.36 quently, this model is fairly accurate only in case of low
Shell diameter 21 mm
concentrations of ethane and ethylene in the gas stream and
Tube flow rate 4 cm3n =s
Methane content in the tube 50%
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 6349
in this simulation. It should however be noticed that if the ethane 4.2.4. Comparison between the predicted performances of different
and ethylene reactor concentration are considerable, it is catalysts in a conventional porous membrane reactor
necessary to include their combustion reactions in the model in The comparison of kinetic models developed for three different
order to evaluate properly the total effect of gas phase reactions. catalysts shows that their yield, conversion, and reactor size are
Thus, a model considering all relevant gas phase reactions, and quite different. Qualitative similarity and difference observed for
which is not based on elementary steps, is to be developed so as to these catalysts were described based on the difference between their
improve the accuracy of similar simulation studies. 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.
4.2.2. Performance with catalyst 2 Instead catalyst 3 is less sensitive to the effect of membrane
The conclusions derived for this catalyst are similar to those for thickness in comparison to catalyst 1 but it is much more sensitive
catalyst 1. Therefore, only the effect of membrane thickness is than catalyst 2. It can be concluded that the performance of catalyst
depicted in Fig. 11. Moreover, the same behavior in terms of 1, catalyst 3, and catalyst 2 is controlled by diffusion aspects,
influence of the total oxygen availability can be derived, where reaction-diffusion aspects, or reaction mechanism, respectively.
methane conversion has to be significant, if a high yield is to be However, in all of them the increase of membrane thickness results
obtained. Undiluted feed of oxygen was proved to provide the in a much bigger reactor size than required for fine oxygen
highest attainability because of the same reasons described above. distribution. For all investigated cases, oxygen dilution decreases
The main difference between this catalyst and the previous one is its the yield. Thus, it can be concluded that there is a need to operate
intrinsic activity. The average reaction rate for this catalyst is 1 to 2 with more than a stoichiometrical amount of oxygen.
orders of magnitude smaller than in the previous case, which results The quantitative results in terms of reported yield can be found
in a reactor length of 30–80 cm for the best performance. This is on the higher activity of catalyst 1 in comparison to other catalysts.
significant in comparison to the length of around 10 cm for the This property enables oxygen to react rapidly and to remain at a low
catalyst 1. Furthermore, the activity of this catalyst affects the level in the reaction side. Consequently, it makes reaction more
observed maximal yield as well. Smaller reaction rate allows more selective towards coupling products. Furthermore, fast reaction and
oxygen being present in the tube side of the reactor, which low contact times will not allow methane to permeate significantly
consequently affects the selectivity. Therefore, a membrane thick- to the oxygen rich shell side and combusting further. Lower yields
ness of more than 100 mm is needed in order to further decrease the reported for catalyst 2 are due to the slower reaction rate, and
oxygen permeability and to increase further the selectivity. How- therefore, longer contact times and better distribution of oxygen is
ever, such manipulation would have a strong negative effect on the needed. For both catalyst 1 and catalyst 2 significant yield
reactor size (Fig. 8) as shown in our simulation. improvement is obtained using a conventional porous membrane
The temperature was limited to that range, in which the reactor. For catalyst 1 this improvement it accounted to 40% (from
kinetic model was developed (around 780 1C). This has already 20% in FBR to 60% in CPBMR) and for catalyst 2 up to 13% (from 17%
been addressed in the discussion related to the fixed bed reactor. in FBR to 30% in CPBMR). An interesting observation is that although
The gas phase reactions did not have a critical influence on this catalyst 2 shows an evident higher ‘‘differential selectivity’’ (j), as
reactor performance. This is mainly due to the lower selectivity and discussed previously, due to its lower activity the achievable yield is
lower fraction of C2 + compared to the previous case, which could lower in a membrane reactor. Therefore, a less selective but more
not be affected significantly by the gas phase combustion reactions. 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
4.2.3. Performance with catalyst 3 catalysts, quantitatively speaking no improvement in the achievable
The performance of the OCM process in a conventional yield was observed by using this catalyst in a CPBMR structure.
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 4.3. Performance of the proposed packed bed membrane reactor
only the influence of membrane thickness and temperature are
investigated. Fig. 12 shows also the same trend as in the The third reactor structure PPBMR, which has recently been
previously discussed catalysts. However, a smaller sensitivity to proposed by Godini et al. (2009, 2010), has the same structure as
the effect of membrane thickness is observed in comparison to CPBMR, but the feeding policy is more comparable to the FBR
catalyst 1. This is due to the smaller reactivity of catalyst 3 and structure. The tube gas stream contains all the reactants
the comparable rates of both reaction and diffusion through the (N2-Diluent, CH4, O2) and the shell stream contains mainly
membrane. This catalyst is though much more sensitive to the N2-Diluent and CH4. Along this reactor, reactants and products
effect of membrane thickness in comparison to the reaction are removed from the reaction side according to their concentra-
controlled with catalyst 2. tion gradient. This offers the possibility for higher oxygen
For this catalyst, the gas phase reactions do not have a concentration in the feed entrance section, which then enhances
significant effect on the performance. A maximal yield with and the absolute yield and gives the opportunity to remove products
without implementation of gas phase reactions in the shell side is (such as ethane and ethylene) from critical areas in the reaction
18.7% and 19.8%, respectively. It can be concluded that the side, and thus, selectivity improvement. Therefore, in case of flow-
performance of this catalyst in the CPBMR structure is mainly rate this structure has a higher capacity because of the co-feeding.
determined by the reaction orders of oxygen in combustion and Moreover, due to reactants removal it shows a satisfactory level of
coupling reactions. These parameters describe the kinetic model selectivity and can handle a higher oxygen feed in comparison to
for this catalyst as ‘‘non-favorable’’ for the oxygen feeding policy. the FBR structure. Moreover, in the PPBMR structure, the methane
It has to be noted here that the experimental study of Lu et al. available in the shell side can compensate the undesired effect of
(2000) obtained 27.8% yield for the same catalyst. Therefore, it has methane reduction due to reaction in the tube side. It increases the
been shown that this catalyst is able to be used in distributed methane-to-oxygen ratio, which is a critical parameter and when
oxygen conditions, and thus, it gives a doubt on the validity of this this is optimally applied, it then enhances both the yield and the
kinetic model. 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.
However, shell side has only a slightly lower temperature, and temperatures and membrane thickness. Catalyst 3 shows its best
thus, a heat transfer is very inefficient. Shell side provides here performance in the proposed PPBMR structure.
unwanted heat insulation, because the heat must penetrate Non-isothermal simulations show that FBR is impossible to
through the membrane wall, shell side and a reactor wall. In this run isothermally and that severe hot spots appear even with high
manner the biggest portion of the heat is kept inside the tube side dilution of feed and catalyst. Membrane reactor in its classical
of the reactor, and an adiabatic behavior occurs. configuration offers better control over the reaction heat.
In order to control the reaction heat, tube and shell side were However, hot spots of around 100 K are still observed. By
exchanged such that the reaction occurs in the shell side of the manipulating the reactor geometry, it is possible to maintain
membrane reactor so as to increase the heat transfer area as well the reaction temperature almost isothermal. This shows that a
as the driving force a for heat exchange. This results in almost membrane reactor can be used in industry not only because of the
isothermal operation, where hot spot of only 9 K was observed for enhanced yield, but also because of the isothermal operation. The
the optimal feed conditions. Moreover, no more than 15 K hot most important parameter for the reactor performance was found
spot is observed in additional simulation studies, which testifies to be the membrane thickness. The thicker the membrane, the
the validity of previous isothermal investigations. Simulations for better distribution of oxygen and consequently the higher yield
other catalyst types gave results which are very similar to the can be achieved. The second most important parameter is the
ones already shown on Figs. 17 and 18. Moreover, same oxygen concentration. It was found that the larger the oxygen
conclusions which were derived for the non-isothermal behavior concentration, the better the yield.
of CPBMR could be extended to the proposed PPBMR structure. 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
5. Conclusions has no significant effect neither in the performance of the PPBMR
nor in a FBR structure.
In this contribution, a comparative analysis of attainable In order to analyze the highest achievable performance in each
performance has been presented for three different reactor case, a novel graph-based approach has been proposed. In this
structures and their feeding policies. In these structures the manner, individual and synergic effects of all variables over the
efficiency is strongly affected by the availability of reactants (i.e. OCM process performance are evaluated. These graphs represent
methane, ethylene, and oxygen). In the FBR structure, there is no not only a sensitivity analysis but they also depict the effects of
diffusion aspect involved in the operation, and thus, the reactants diffusion and reaction parameters according to the catalyst
availability cannot be manipulated. Therefore, the intrinsic activity and the limiting step under a certain range of operating
difference between reactivity and inherent selectivity of the three conditions. Based on these graphs, the effect of parameters such
catalysts cannot be exploited optimally. Hence, they show as temperature, membrane thickness, shell flow-rate, methane,
relatively the same quantitative and qualitative behavior. and oxygen concentration in the shell side could then be
The CPBMR structure offers potentially the highest achievable compensated. Thus, the trends of achievable yield can be
yield and provides a comparative flexible operating mode. However, predicted by any scenario including the manipulation of these
this reactor concept has to confront methane back-permeation, and parameters. The graph-based approach has also the potential to
very long required contact times. Due to its feeding policy, the provide alternative path towards improving the process perfor-
highest achievable yield in the PPBMR structure is almost the same mance, and thus, it can simply be used for reactor design and
as for the FBR structure. The feeding policy is limited because of optimization tasks. Thus, kinetic-analysis based on the proposed
diffusion aspects. However, it is much more flexible than the FBR graphical approach enables determination of the suitable range of
structure. In addition, back-permeation does not represent a operating conditions for any kinetic study and possible operation
problem in this configuration. to cover and reach the highest achievable area.
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 Acknowledgements
a high conversion in the FBR structure or obtaining a high selectivity
in the CPBMR structure, where oxygen is supplied in a more The authors acknowledge the support from the Cluster of
controllable way, are the potential of these structures, respectively. Excellence ‘‘Unifying Concepts in Catalysis’’ coordinated by the
It should though be pointed out that among the investigated kinetic Berlin Institute of Technology – Technische Universität Berlin and
models; the one developed for catalyst 1 shows a better perfor- funded by the German Research Foundation – Deutsche For-
mance in the CPBMR structure under intermediate range of 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
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).
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