Chemical Engineering and Processing 41 (2002) 403 412 www.elsevier.

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Integrated catalytic membrane reactors for decomposition of ammonia

M.E.E. Abashar *
Department of Chemical Engineering, College of Engineering, King Saud Uni6ersity, PO Box 800, Riyadh 11421, Saudi Arabia Received 25 June 2001; accepted 25 July 2001

Abstract A model is presented for the simulation of an integrated catalytic membrane reactor for the removal of toxic ammonia traces from coal gasication streams. Heat integration and equilibrium shifting are achieved by introducing integrated reaction network and various catalyst pattern strategies. Different congurations of spatially patterned catalytic beds (layers) have been investigated. Two important reactions were considered namely, the decomposition of ammonia as a primary reaction and methanation reactions as secondary reactions. An effective length criterion is used to evaluate the performance of the reactor. Optimal conditions were observed and explanations offered. The results show substantial improvement in the reactor performance in terms of high conversions, low temperatures and reduced mass of the catalyst used. The investigation, although is restricted to two catalyst layers, has uncovered some of the rich characteristics of this system. 2002 Published by Elsevier Science B.V.
Keywords: Membrane reactor; Catalyst patterns; Mathematical modeling; Ammonia

1. Introduction Addition of air pollutants to the atmosphere results in depletion of ozone in the upper layers of the stratosphere, global warming (the greenhouse effect), acid rain and is harmful to public health. The main sources of the air pollutants are fossil fuels (natural gas, coal, oil) and industry. Among the harmful air pollutants are carbon dioxide, carbon monoxide, nitrogen oxides, sulfur dioxide, ammonia and tiny solid particles [1]. The major sources of nitrogen oxides include power generation plants and motor vehicles. The power generation plants are responsible for about 29% of all nitrogen oxide emissions [2]. Gas turbine power generation plants depend on synthesis gas as fuel. The synthesis gas that comes from coal gasication streams contains small but potentially harmful amount of ammonia [3]. Under combustion conditions ammonia forms nitrogen oxides (NOx ), which are mainly nitric oxide (NO) and nitrogen dioxide (NO2). The nitrogen oxides are known to be radiative and chemically active gases and have
* Fax: + 966-1-4678770. E -mail address: mabashar@ksu.edu.sa (M.E.E. Abashar).

signicant contribution to the greenhouse effect and main components of acid rain [4]. Moreover, ammonia can react with other common pollutants like sulfur dioxide or nitrous oxide (N2O) and forms tiny particles that contribute to the formation of smog. The problem of ammonia in the power generation plants has been addressed by implementation of water removal systems. Although the water based ammonia removal systems remove signicant amount of ammonia from the synthesis gas streams but still the amount released to the atmosphere is unacceptable ( : 400 ppm) [5]. Thus, the regulation and reduction of the present air pollution and the elimination of future air pollutants can be achieved by introducing new technologies, design, improved industrial processes and operations. In the last few years, research interest has been focused on catalytic membrane reactors as multi-functional reactors [611]. The main advantages of the membrane reactors are: shift of the thermodynamic equilibrium, simultaneous reaction and separation of products, enhancement of yield and selectivity, control of reactants distribution and low costs. Gobina et al. [3] reported that the catalytic membrane reactors provide new and improved processes for purifying emissions

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from combustion processes. In application to removal of dilute concentrations of ammonia from coal gasication streams, they were able to attain far higher ammonia decomposition rate than those obtained by xed bed catalytic reactors. It was also shown that the complete decomposition of ammonia by a co-current mode of operation was achieved at relatively high temperatures. Despite the signicant advantages of the membrane catalytic reactors, still the membrane reactor is not fully understood and the technology is limited to certain kind of reactions and is not commercially utilized. In the domain of xed bed catalytic reactors, the subject of spatially patterned catalytic reactors and the dual-functionality of the catalyst bed has attracted growing interest in the chemical engineering research literature in recent years [12]. Cote et al. [12] have shown that for equilibrium limited reactions the performance of xed bed catalytic reactors has improved signicantly by introduction of the dual-functionality via structured pattern (either mixed of layered conguration) of the catalyst bed. The purpose of these patterns is to introduce secondary reactions in order to improve the performance of a primary (main) reaction by a drain off mechanism i.e. adding another factor to help in shifting the thermodynamic equilibrium. Excessive temperatures are known to have destructive effects on the catalyst and the mechanical and chemical stability of the membranes and the reactors [10]. Moreover, the energy operating costs is high at elevated temperatures. The objective of this investigation is to explore the potential application of integrated catalytic membrane reactors for removal of ammonia at low temperatures. The concept of spatially patterned catalytic reactors and the dual-functionality of the catalyst bed is implemented in an experimental co-current composite membrane reactor. The energy integration and equilibrium shifting are investigated by coupling the endothermic ammonia reaction with highly exothermic methanation reactions. A mathematical model is utilized to study the inuence of various parameters and to identify the key parameters that are likely to affect the pattern strategies and the performance of the membrane reactors. This preliminary investigation is restricted to two catalyst layers.

2.2. Auxiliary reactions

3H2 + CO X CH4 + H2O H2 + CO2 X CO + H2O [ DH2 = 206.0 kJ/mol] (2) [ DH3 = 41.0 kJ/mol] (3) [ DH4 = 164.9 kJ/mol] (4)

4H2 + CO2 X CH4 + 2H2O

The rate expression for ammonia reaction is given by Gobina et al. [3], and the rate expressions for methanation reactions are given by Xu and Froment [13]. The corresponding rate expressions are:
3 h 3 2 1h 2 R1 = k1[(P 2 ] NH3/P H2) K 1PN2(P H2/P NH3)

kg mol m3 s (5)

where h = 0.674 R2 = R3 = R4 =

k2 P 3 H2PCO PCH4PH2O 2.5 P H2 K2 k3 PH2PCO2 PCOPH2O PH2 K3

k4 P 4 H2PCO2 PCH4P 2 H2O 3.5 P H2 K4

  

, , ,

DEN2

kg mol kg s kg mol kg s kg mol kg s

(6) (7) (8)

DEN2

DEN2

where DEN = 1 + KCOPCO + KH2PH2 + KCH4PCH4 + KH2OPH2O/PH2 (9)

The kinetic rate coefcients and adsorption equilibrium constants are given below.

2.3. Rate coefcients

k1 = 5.744 1016exp k2 = 8.336 1014exp

k3 = 1.219 10 2exp k4 = 2.012 1014exp

   

2771.23 T 28879.0 T 8074.3 T

2. Rate expressions

29336.0 T

    

kg mol m s Pa 0.674
3

(10) (11) (12) (13)

kg mol Pa0.5 kg s kg mol Pa 1 kg s kg mol Pa0.5 kg s

2.1. Primary reaction

1 3 NH3 X N2 + H2 2 2 [ DH1 = 54.6 kJ/mol] (1)

2.4. Adsorption equilibrium constants

KCH4 = 6.65 10 9exp

4604.28 T

Pa 1

(14)

KH2O = 1.77 102exp KH2 = 6.12 10 14exp

M.E.E. Abashar / Chemical Engineering and Processing 41 (2002) 403 412

KCO = 8.23 10 10exp

 

10666.35 T

9971.13 T

8497.71 T

 

405

Pa 1

(15) (16) (17)

where T is the absolute temperature (K).

Pa 1 Pa 1

4. Model development A one-dimensional model is developed for the decomposition of ammonia in a co-current packed bed membrane reactor. A schematic diagram of the composite Pd Ag membrane reactor is given in Fig. 1. The following simplifying assumptions are used in the derivation of the conservation equations of the model. 1. The reactor operates at steady state conditions with negligible pressure drop [3]. 2. One dimensional model i.e. radial variations in the tube and shell sides are negligible. 3. The gas in the tube and shell sides is assumed in plug ow. 4. The membrane has exclusive selectivity for hydrogen. This assumption is justied by the experimental evidence of Gobina et al. [6]. 5. The reactions are considered to take place only in the tube side. 6. Negligible diffusion resistances within the catalyst particles. 7. Axial diffusion in the membrane is negligible. 8. Heat transfer to the shell side is negligible. 9. The ideal gas law is obeyed.

2.5. Equilibrium constants

logK1 = 5.859117 + 2250.322 1.51049logT 25.898 T

10 5T Pa 1

K2 = 10266.76 106exp K3 = exp

4400.0 4.063 ( ) T

 

26830.0 + 30.11 Pa2 T

(18) (19) (20) (21)

K4 = K2K3 Pa2 where T is the absolute temperature (K).

3. Hydrogen permeation rate The permeation rate of hydrogen through the composite membrane was assumed to obey the half power pressure law [14,15] QH2 = Qo



A kg mol [
(PH2)t
(PH2)s] l s

4.1. Tube side

(22)

where QH2 is the hydrogen permeation rate, A is the membrane area available for ow (m2), l is Pd Ag alloy lm thickness, and (PH2)t and (PH2)s are the hydrogen partial pressures (Pa) in the tube and shell sides, respectively. The permeability constant of hydrogen (Qo) has been determined experimentally by Gobina et al. [6], as follows Qo = 1.0061 10 12exp

4.1.1. Mass balance The differential mass balance equations on the jth catalyst layer (bed) are given by
d(FNH3)t = Sm1jR1Lo dZ d(FH2)t 3 = Sm2jz PRH2Lo + Sm1jR1Lo QH2 2 dZ d(FCO)t = Sm2jz PRCOLo dZ (24) (25) (26)

767.38 T

kg mol m m2 s Pa0.5

(23)

Fig. 1. Schematic representation of the co-current catalytic membrane reactor.

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d(FCO2)t = Sm2jz PRCO2Lo dZ RH2 = 3R2 + R3 + 4R4 RCO = R2 R3 RCO2 = R3 + R4

(27) (28) (29) (30)

Table 1 Data for the membrane reactor [3] Component

Mol%

4.1.2. Energy balance The differential energy balance equation on the jth catalyst layer (bed) is given by
% Fi CPi
i=1 8 4 dT = (DH1)Sm 1jR1 + % ( DHn ) Sm2jzsRn dZ n=2 (31)

Feed (typical composition of coal gasication stream) H2 20.0 N2 48.0 00.3 NH3 CO 13.0 CO2 13.0 CH4 04.2 H2O 01.0 00.5 H2S Experimental reactor data Volume of the catalyst bed (m3) Reactor length (m) Palladiumsilver alloy lm thickness (mm) Diameter of catalyst pellets (m) Pressure in tube side (atm) Pressure of sweep gas (atm) Flow rate of synthesis gas (m3 (STP)/s) Flow rate of sweep gas stream (m3 (STP)/s) 6.689106 0.14 6.0 (0.150.2)102 36.0 (3.6477 MPa) 1.0 (0.1013 MPa) 5.833105 5.000105

Where mkj is the volume fraction of catalyst k in the jth catalyst layer. The conversion of NH3, CO and CO2 at any crosssection of the layer are given by XNH3 = XCO = (F o NH3)t (FNH3)t (F o NH3)t (32) (33)

(F o CO)t (FCO)t (F o CO)t (F o CO )t (FCO2)t 2 (F o CO2)t

6. Catalyst layer congurations (34) The performance of the xed bed catalytic membrane reactor depends on the catalyst size, structure, shape and layer congurations. A brief idea about the catalyst layer congurations can be shown by considering two types of catalysts and two layers. The suggested patterns are depicted in Fig. 2. Fig. 2(a) shows a single layer that contains only one type of catalyst. Fig. 2(b) shows a single layer in which two types of catalysts are well mixed. This well-mixed pattern can be made of composite pellets i.e. the two catalysts are co-extruded into composite pellets or two discrete types of pellets that are physically well mixed [12]. The nal pattern involves two distinct layers spatially patterned as shown in Fig. 2(c). The distinct layer can contain a single catalyst or more than one catalyst well mixed. In this case the reaction uid alternates between different catalyst regions. Among the potential advantages of the patterns: (a) shift of thermodynamic equilibrium, (b) tune the feed for the primary reaction, and (c) eliminate environmentally harmful by-products.

XCO2 =

The molar ow rates of N2, CH4 and H2O at any cross-section of the layer can be written as 1 o (FN2)t = (F o N2)t + (F N2)tXNH3 2
o o (FCH4)t = (F o CH4)t + (F CO)tXCO + (F CO2)tXCO2

(35) (36) (37)

(FH2O)t = (F

o H2O t

) + (F

o CO t

) XCO + 2(F

o CO2 t

) XCO2

The molar ow rate of the inert is obtained by difference.

4.2. Shell side

The differential mass balance on hydrogen gives d (FH2)s = QH2 dZ (38)

5. Solution of the model equations The composition of the coal gasication stream and the initial feed temperature, ow rate, pressure and the volume of the catalyst bed are and shown in Table 1 [3]. The initial value differential equations (24 27, 31 and 38) are integrated directly using an IMSL subroutine called DGEAR. Automatic step size in the integration was used to ensure accuracy. Needless to say, double precision used throughout all the computation. 7. Results and discussion In order to distinguish between the catalysts employed in this investigation, the catalyst used for the decomposition of ammonia (the primary reaction) is considered to be catalyst 1 and that used for the methanation reactions (the auxiliary reactions) is catalyst 2.

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407

Fig. 2. Catalyst layer conguration. (1) Single catalyst layer. (a) Single catalyst pattern, and (b) two catalysts pattern (i) well-mixed composite pellets; (ii) well-mixed discrete pellets. (2) Two layers spatially patterned. (i) Single catalyst spatially layered; (ii) well-mixed spatially layered; and (iii) well-mixed single spatially layered.

7.1. Single layer (bed)

The single layer is investigated for two cases. The rst case involves one type of catalyst and the second case involves two types of catalysts, which are well mixed. Also, a comparison between the performance of a xed bed reactor (permeation of hydrogen through the membrane is not allowable) and a membrane reactor is included. The comparison is made for identical feed conditions, catalyst mass and co-current mode of operation.

the conversion by enhancing the permeation driving force for the hydrogen due to the reduction of the partial pressure of hydrogen in the shell side and therefore complete decomposition of ammonia is attained. In fact, the complete destruction of ammonia occurs at high temperatures (T \ 873 K).

7.1.1. Single catalyst pattern In this case, the xed bed reactor and the membrane reactor are packed with catalyst 1 only i.e. the decomposition reaction of ammonia (the primary reaction) proceeds alone. Since this reaction is highly endothermic, the comparison is made at isothermal conditions. The effect of sweep gas on the performance of the membrane reactor is also considered. Fig. 3 compares the performance of the xed bed reactor and the membrane reactor without and with sweep gas. It can be seen that the xed bed reactor gives negative conversions i.e. the equilibrium is shifted toward ammonia formation. The poor performance shown by the xed bed reactor indicates that the xed bed reactor is not suitable for ammonia decomposition at these operating conditions. It is clearly shown that signicant improve in the conversion is achieved by the membrane reactor without and with sweep gas. For the membrane reactor without sweep gas, the net driving force for the permeation of hydrogen along the length of the reactor approaches zero and hence the complete decomposition of ammonia cannot be achieved. In the case of the membrane reactor with sweep gas (sweep ratio (SR) = 0.857), the sweep gas has an overall positive effect on

7.1.2. Two catalysts pattern This case represents the well-mixed pattern, which involves loading the two reactors with discrete types of pellets of catalysts 1 and 2 after physically well mixed. The reactors are operated under non-isothermal conditions. Fig. 4(a) and (b) show how the exit ammonia conversion varies as a function of the layer composition

Fig. 3. Single catalyst pattern. Comparison of xed bed and membrane reactors.

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that the increase of catalyst 2 in the layer at the expense of catalyst 1 as shown by the sharp drop of the conversion as m21 1. It can be observed that the increase of the feed temperature shifts the beginning of the plateaus towards low concentrations of catalyst 2 and the plateaus are much more temperature-sensitive at high concentration of catalyst 2 as shown by the proles at the feed temperatures of 585 and 588 K. Fig. 5 shows the conversion proles along the length of the reactor at constant bed composition (m21 = 0.40) and feed temperatures of 600, 630 and 670 K. It can be seen that high ammonia conversions are achieved in wide ranges of the reactor length and in some cases far form the reactor exit. Therefore, in order to investigate the performance of the reactor in a unied way, we dened a dimensionless effective reactor length as the total length of the reactor that gives 99.5% conversion of ammonia. Fig. 6(a) shows the effective length versus the layer composition for several different feed temperatures. It is shown that at a specic feed temperature the effective length passes through a minimum with the increase of catalyst 2 concentration in the layer. The occurrence of the minimum could be due the interaction of many factors such as hydrogen driving forces, thermodynamic equilibrium, temperature and the catalysts composition. The removal of hydrogen by the auxiliary reactions (reactions (2) (4)) has a positive effect in shifting the thermodynamic equilibrium toward ammonia decomposition (reaction (1)) and a negative effect on the hydrogen permeation driving force by reducing the partial pressure of hydrogen in the tube side. The increase of the temperature has a positive effect on the ammonia decomposition reaction (endothermic) and a

Fig. 4. Two catalysts pattern. Comparison of xed bed and membrane reactors.

for several different feed temperatures for the xed bed and membrane reactors respectively. Fig. 4(a) shows that the performance of the xed bed reactor is enhanced substantially by the secondary reactions. The reaction network is controlled by the thermodynamic equilibrium and a maximum conversion of 88.8% is obtained. It appears that the drain off mechanism alone is not sufcient to shift more the thermodynamic equilibrium in order to achieve higher ammonia conversion. Therefore, in the following analyses, we focused on the membrane reactor. Fig. 4(b) shows that high ammonia conversions are obtained by using the catalytic membrane reactor with sweep gas (SR = 0.857). It is clearly shown that the exit ammonia conversion forms a plateau due to the fact

Fig. 5. Two catalysts pattern. Inuence of feed temperature on the performance of the membrane reactor.

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409

that these parameters have a pronounced effect on the effective length. It can be concluded that for the mixing pattern there exist optimal conditions under which the complete decomposition of ammonia is achievable. The potential application of the mixing pattern strategy can be benecially.

7.2. Two layers spatially patterned

The total volume of the catalyst used is kept constant and the catalyst bed is divided into two distinct layers (beds). A feed temperature of 670 K, total pressure in the tube side of 36 atm and SR of 0.857 are selected for this part of the study. Two congurations of the layers are considered in this section.

Fig. 6. Two catalysts pattern for the membrane reactor. (a) Effect of feed temperature on the dimensionless effective reactor length; and (b) effect of feed temperature on the effective temperature.

negative effect on the methanation reactions (exothermic reactions). Another factor could be the increase of the concentration of catalyst 2 in the layer at the expense of catalyst 1. It is also shown that for each feed temperature there exists a region in which the effectiveness length criterion is satised. The regions shrink with the decrease of the feed temperature. It is interesting to observe that the locus of the minima with feed temperature and the layer composition passes through an optimum value. The corresponding effective temperature proles are shown in Fig. 6(b). Sensitivity analysis for the effect of the SR and the total pressure in the tube side (P) on the effective length is shown in Fig. 7(a) and (b) respectively. It appears

Fig. 7. Two catalysts pattern for the membrane reactor. (a) Effect of SR on the dimensionless effective reactor length; and (b) effect of pressure in the tube side on the dimensionless effective reactor length.

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Fig. 8. Two layers spatially patterned, conguration 1: inuence of second bed (layer) catalyst composition on the dimensionless effective reactor length.

7.2.1. Conguration 1 In this conguration, the rst layer (bed 1) and the second layer (bed 2) are loaded with well mixed catalysts and spatially layered. Two cases are considered. In the rst case, the composition of the rst bed is kept constant at m21 = 0.03, while the catalyst composition of the second bed is varied. The composition of the rst bed is chosen at the optimal conditions shown in Fig. 6(a) (Tf = 670 K, m21 = 0.03). The effective length at different composition of bed 2 is shown as a function of bed 1 length (LB1) in Fig. 8. It can be seen that when the composition of the second bed is less than the composition of the rst bed (m22 B m21) there exist regions in which the behavior of the spatially layered pattern (proles 1 and 2) is much better than a single well mixed layer (prole 3). It is also shown that at a certain length of bed 1, the two layers behavior converges to a single layer behavior (prole 3) and becomes independent of the composition of bed 2. In the second case, the composition of the second bed is kept constant at m21 = 0.03 while the composition of the rst bed is varied as shown in Fig. 9. It is also shown that when the composition of the rst bed is less than the composition of the second bed (m21 B m22) there exist regions with optimal conditions in which the behavior of the spatially layered pattern (proles 1 and 2) is much better than a single well mixed layer (prole 3). These results indicate that the composition and the volume of the catalyst layers should be controlled carefully.

7.2.2. Conguration 2 In this conguration, the rst bed contains wellmixed catalyst (m11 + m21 = 1) and the second bed contains catalyst 1 only (m12 = 1, m22 = 0). This conguration is a well-mixed single pattern. Fig. 10(a) shows that the effective length versus dimensionless length of the rst bed for several different compositions of the rst bed. A signicant decrease in the effective length is observed by increasing the composition of the rst bed. This could be due to the fact that the increase of the amount of catalyst 2 in rst bed increases the heat generated by the auxiliary reactions and maintain high feed temperature to the second layer as shown in Fig. 10(b). It is clear that conguration 2 is superior to conguration 1. The effect of varying the feed temperature and the total pressure in the tube side on the effective length can be seen in Fig. 11(a) and (b), respectively. Fig. 11(a) shows that the increase of the feed temperature decreases the effective length and the length of the rst bed. It is interesting to observe that there exists a region in which the effect of varying the feed temperatures on the effective length becomes insignicant. Fig. 11(b) shows that the increase of the total pressure in the tube side decreases the effective length and increases the length of the rst bed.

8. Conclusions The results presented in this paper show that the integrated catalytic membrane reactor with catalyst pattern strategies are attractive application for the

Fig. 9. Two layers spatially patterned, conguration 1: inuence of rst bed (layer) catalyst composition on the dimensionless effective reactor length.

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Fig. 10. Two layers spatially patterned, conguration 2. (a) Inuence of rst bed (layer) catalyst composition on the dimensionless effective reactor length; (b) inuence of rst bed (layer) catalyst composition on the effective temperature.

Fig. 11. Two layers spatially patterned, conguration 2. (a) Inuence of feed temperature on the dimensionless effective reactor length; (b) inuence of pressure in the tube side on the dimensionless effective reactor length.

removal of ammonia from coal gasication streams. The introduction of catalyst patterns mixed or spatially layered into the membrane reactor has appreciable improve of the reactor performance in terms of high conversions, low temperatures and reduced total reactor lengths. Effective operating regions with optimal conditions were observed. It has been also shown by simulation that the composition, volume, congurations of the catalyst layers should be considered with care. We have compared the performance of a conventional xed bed reactor with the membrane reactor and in light of the results presented the membrane reactor is shown to be superior to the xed bed reactor.

Further studies are needed to focus on the experimental validation, rigorous mathematical modeling and optimization.

Appendix A. Nomenclature List of symbols A membrane area (m2) Cpi heat capacity of component i (kJ/kg mol K) Fi molar flow rate of component i (kg mol/s)

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F0 i DHi k1 k2 k3 k4 KCH4, KH2O, KH2, KCO K1 K2 K3 K4 Lo Pi P Ps Qo QH2 R1 R2, R3, R4 RH2 RCO RCO2 S T Xi Z

initial molar flow rate of component i (kg mol/s) heat of reaction i (kJ/mol) reaction rate constant of reaction (1) (kg mol/m3 s Pa0.674) reaction rate constant of reaction (2) (kg mol Pa0.5 /kg s) reaction rate constant of reaction (3) (kg mol Pa1 /kg s) reaction rate constant of reaction (4), (kg mol Pa0.5 /kg s) adsorption constant for CH4, H2O, H2 and CO (Pa1) equilibrium constant of reaction (1) (Pa1) equilibrium constant of reaction (2) (Pa2) equilibrium constant of reaction (3) () equilibrium constant of reaction (4) (Pa2) reactor length (m) partial pressure of component i (Pa) pressure in tube side (Pa) pressure of sweep gas (Pa) permeability constant (kg mol m/m2 s Pa0.5) hydrogen permeation rate (kg mol/s) rate of reaction (1) (kg mol/m3 s) rate of reaction (2), (3) and (4) (kg mol/kg s) reaction rate of hydrogen (kg mol/kg s) reaction rate of carbon monoxide (kg mol/kg s) reaction rate of carbon dioxide (kg mol/kg s) cross-sectional area of the catalyst bed (m2) temperature (K) conversion of component i dimensionless reactor length

zP Subscripts P s t

catalyst particle density (kg/m3)

particle shell side tube side

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Greeks symbols h kinetic parameter l membrane thickness (m) mkj volume fraction of catalyst k in the jth catalyst layer