Applied Catalysis A: General 236 (2002) 3553

Investigation of low temperature decomposition of ammonia

using spatially patterned catalytic membrane reactors
M.E.E. Abashar , Y.S. Al-Sughair, I.S. Al-Mutaz
Reaction and Environmental Engineering Group (REEG), Department of Chemical Engineering, College of Engineering,
King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia
Received 18 February 2002; received in revised form 28 March 2002; accepted 3 May 2002

Abstract
A mathematical model is used to simulate a bench-scale membrane reactor for the decomposition of ammonia over
Ni/Al2 O3 catalyst. Since the reaction is equilibrium limited the removal of the product hydrogen by the membrane derives
the thermodynamic equilibrium. For further displacement of the thermodynamic equilibrium, auxiliary methanation reactions
over Ni/Mg Al2 O4 catalyst are used to remove part of hydrogen. The two catalysts are loaded together in different pattern
configurations. The purpose of this study is to investigate the effect of catalyst patterns on ammonia decomposition. Optimal
conditions are observed and explanations offered. An effective length criterion for the optimal conditions is presented. The
results show that the pattern strategies have 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 a part of the rich characteristics of this system.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Ammonia; Catalyst patterns; Mathematical modeling; Membrane reactor

1. Introduction
The problem of air pollution grows steadily with
the sharp increases in population, industrialization
and urbanization. As a result the atmosphere has
been damaged irreversibly. The main sources of the
air pollutants are fossil fuels (natural gas, coal, and
oil), industry and motor vehicles. Air pollutants such
as: carbon dioxide, carbon monoxide, nitrogen oxides (NOx ), sulfur dioxide, ammonia and tiny solid
particles are responsible for ozone depletion, global
warming (the greenhouse effect), acid rain and serious
problems to public health [1].
Corresponding author. Fax: +9661-4678770.
E-mail address: mabashar@ksu.edu.sa (M.E.E. Abashar).

Power generation plants are responsible for 29%

of all NOx emissions [2]. Synthesis gas is utilized as
fuel in the gas turbine power generation plants. The
synthesis gas that produced by coal gasification contains small but potentially harmful amount of ammonia
[3,4]. Under combustion conditions ammonia forms
NOx . Nitric oxide (NO) and NO2 are the main oxides
of nitrogen. The sum of these two is known as nitrogen oxides (NOx ). In the presence of atmospheric
moisture NOx turn into nitric acid the main component of acid rain. The NO reacts with ozone to form
NO2 (NO + O3 NO2 + O2 ) and hence, contributes
to the depletion of ozone [5]. Moreover, ammonia can
react with other common pollutants like sulfur dioxide
or nitrous oxide (N2 O) and forms tiny particles that
contribute to the formation of smog.

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 2 7 2 - 7

36

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Nomenclature
List of symbols
A
membrane area (m2 )
Fi
molar flow rate of component
i (kmol/s)
Fio
initial molar flow rate of component
i (kmol/s)
k1
reaction rate constant of reaction
(1) (kmol Pa0.674 /m3 s)
k2
reaction rate constant of reaction
(2) (kmol Pa0.5 /kg s)
k3
reaction rate constant of reaction
(3) (kmol Pa1 /kg s)
k4
reaction rate constant of reaction
(4) (kmol Pa0.5 /kg s)
KCH4 ,
KH2 , KCO adsorption constant for CH4 , H2
and CO (Pa1 )
adsorption constant for H2 O
KH2 O
K1
equilibrium constant of reaction
(1) (Pa1 )
equilibrium constant of reaction
K2
(2) (Pa2 )
K3
equilibrium constant of reaction (3)
K4
equilibrium constant of reaction
(4) (Pa2 )
LBi
dimensionless bed i length
Leff
dimensionless effective reactor
length
Lo
reactor length (m)
Pi
partial pressure of component i (Pa)
QH2
hydrogen permeation rate (kmol/s)
Qo
permeability constant
(kmol m/m2 s Pa0.5 )
rate of reaction (1) (kmol/m3 s)
R1
R2 , R3 , R4 rate of reaction (2), (3) and (4)
(kmol/kg s)
RCO
reaction rate of carbon monoxide
(kmol/kg s)
RCO2
reaction rate of carbon dioxide
(kmol/kg s)
RH2
reaction rate of hydrogen (kmol/kg s)
S
cross sectional area of the catalyst
bed (m2 )
SR
sweep ratio
T
temperature (K)

Xi
Z

conversion of component i
dimensionless reactor length

Greek symbols

kinetic parameter

membrane thickness (m)

i
volume fraction of catalyst i
catalyst particle density (kg/m3 )
p
Subscripts
p
particle
s
shell side
t
tube side
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 significant amount of
ammonia from the synthesis gas streams but still the
amount released to the atmosphere is unacceptable
(400 ppm) [6]. For clean air, the power generation
plants must meet the air pollution performance standards. Therefore, new technologies, improved processes and designs are needed to supply clean fuels
by reducing or eliminating the harmful traces of air
pollutants from the synthesis gas streams.
In the last decade membrane catalytic reactors have
received increasing attention as multi-functional reactors [712]. Some attractive features of membrane
reactors are: combining reaction and separation of
products in a single unit, equilibrium shifting, favorable effects on the conversion and selectivity, control
of reactants distribution and low costs. Despite the
significant 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.
Gobina et al. [3] reported that the application of
the catalytic membrane reactor process is an efficient
method for the elimination of dilute concentrations of
ammonia from coal gasification streams. They were
able to attain far higher ammonia decomposition rate
than those obtained by fixed bed catalytic reactors. It
was shown that the complete decomposition of ammonia by a co-current mode of operation was achieved
at high temperatures.
In a recent work, Cote et al. [13] have shown that
for equilibrium limited reactions the performance of

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

fixed bed catalytic reactors has improved significantly

by introduction of the dual-functionality via structured
pattern (either mixed or layered configuration) 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
of 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
[11]. Moreover, the energy operating costs is high at
elevated temperatures. In this investigation the concept
of the dual-functionality via spatial catalyst patterns is
implemented in an experimental co-current composite
membrane reactor for the decomposition of ammonia.
The objective is to explore the decomposition of ammonia at low temperatures. A mathematical model is
utilized to identify the key parameters that are likely
to affect the pattern strategies and the performance of
the membrane reactors. Methanation reactions are selected as auxiliary reactions and two calalyst layers
are considered.

2. Rate expressions

37

developed more general and realistic intrinsic rate

equations for methanation reactions using an integral flow reactor and a commercial catalyst (Haldor
Topose Ni/Mg Al2 O4 spinel). The catalyst contains
15.2% nickel. A reaction network consisting of three
representative reactions were obtained:
3H2 + CO
CH4 + H2 O

(3)

H2 + CO2
CO + H2 O

(4)

4H2 + CO2
CH4 + 2H2 O

(5)

The corresponding rate expressions are:

 3

PH2 PCO /K2 PCH4 PH2 O
k2
R2 = 2.5
DEN2
PH2
(kmol/kg s)


k3 PH2 PCO2 /K3 PCO PH2 O
R3 =
PH2
DEN2
(kmol/kg s)
 4

PH2 PCO2 /K4 PCH4 PH22 O
k4
R4 = 3.5
DEN2
PH2

(6)

(kmol/kg s)

(8)

(7)

where
2.1. Primary reaction
The decomposition of ammonia is carried out over
a Ni/Al2 O3 catalyst
NH3
21 N2 + 23 H2

(1)

The TemkinPyzhev rate expression [3] is used in

this study, as follows:


 3 1
2
PNH
PH2
3

R1 = k1
K12 PN2
3
2
PNH
PH2
3
(kmol/m3 s)

(2)

DEN = 1 + KCO PCO + KH2 PH2 + KCH4 PCH4

KH O PH2 O
+ 2
PH2

The kinetic rate coefficients and adsorption equilibrium constants are given as follows:
2.3. Rate coefficients



2771.23
k1 = 5.744 1016 exp
T
(kmol/m3 s Pa0.674 )

(10)


where = 0.674

k2 = 8.336 1014 exp

2.2. Auxiliary reactions

(kmol Pa0.5 /kg s)

The literature contains large numbers of kinetic

models of methanation reactions and different rate
expressions are available. Xu and Froment [14] have

(9)

28879.0
T

(11)


k3 = 1.219 102 exp

(kmol Pa1 /kg s)

8074.3
T

(12)

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M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

29336.0
k4 = 2.012 10 exp
T

14

(kmol Pa0.5 /kg s)

(13)

2.4. Adsorption equilibrium constants

KCH4 = 6.65 109 exp

4604.28
T

10666.35
KH2 O = 1.77 10 exp
T


9971.13
14
KH2 = 6.12 10
exp
T


8497.71
KCO = 8.23 1010 exp
T

(Pa1 ) (14)


(15)

where T is the absolute temperature (K).

(Pa1 ) (17)

4. Model development

2250.322
1.51049 log T
T
(18)
25.898 105 T (Pa1 )

log K1 = 5.859117 +

K4 = K2 K3

(kmol m/m2 s Pa0.5 )

(Pa1 ) (16)

2.5. Equilibrium constants

K2 = 10266.76 10


26830.0
exp
+ 30.11
T


4400.0
K3 = exp
4.063
T

where QH2 is the hydrogen permeation rate, A is the

membrane area available for flow (m2 ), is PdAg
alloy film 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. [7], as follows


767.38
Qo = 1.0061 1012 exp
T

(Pa2 )

(Pa2 )

(19)
(20)
(21)

where T is the absolute temperature (K).

3. Hydrogen permeation rate
The composite membrane used in this study is made
of a very thin layer of palladiumsilver alloy. The
membrane is deposited as a continuous layer on the
outer surface of thermostable support. The details of
the membrane are given by Gobina et al. [7]. The
permeation rate of hydrogen through the composite
membrane is assumed to obey the half power pressure
law [15,16]
 


QH2 = Qo
(kmol/s)
(PH2 )t (PH2 )s

(22)

(23)

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 PdAg 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 and
isothermally with negligible pressure drop [3].
2. The reactions are considered to take place only in
the tube side.
3. One dimensional model i.e. radial variations in the
tube and shell sides are negligible.
4. Negligible diffusion resistance within the catalyst
particles.
5. The gas in the tube and shell sides is assumed in
plug flow.
6. The membrane has exclusive selectivity for hydrogen. This assumption is justified by the experimental evidence of Gobina et al. [7].
7. The ideal gas law is obeyed.
8. Axial diffusion in the membrane is negligible.
4.1. Tube side
The differential mass balance equations are given
by
d(FNH3 )t
= S1 R1 Lo
dZ

(24)

d(FH2 )t
3
= S2 p RH2 Lo + S1 R1 Lo QH2 (25)
dZ
2

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

39

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

d(FCO )t
= S2 p RCO Lo
dZ
d(FCO2 )t
= S2 p RCO2 Lo
dZ
RH2 = 3R2 + R3 + 4R4

(26)

(37)
(27)
(28)

RCO = R2 R3

(29)

RCO2 = R3 + R4

(30)

where i is the volume fraction of catalyst i and is

given by:
volume of catalyst i in a well mixed catalyst bed
i =
volume of a well mixed catalyst bed
(31)
The conversion of NH3 , CO and CO2 at any cross
section of the bed are given by
XNH3 =

XCO =
XCO2 =

o ) (F
(FNH
NH3 )t
3 t
o )
(FNH
3 t

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

(32)

(33)

(34)

The molar flow rates of N2 , CH4 and H2 O at any

cross section of the bed can be written as
(FN2 )t = (FNo2 )t + 21 (FNo2 )t XNH3

o
o
)t XCO + 2(FCO
)X
(FH2 O )t = (FHo2 O )t + (FCO
2 t CO2

(35)

o
o
o
(FCH4 )t = (FCH
) + (FCO
)t XCO + (FCO
)X
4 t
2 t CO2

(36)

The molar flow 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)

Table 1
Data for the simulation [3]
Feed (typical composition of coal gasification stream)
Component

Mol%

H2
N2
NH3
CO
CO2
CH4
H2 O
H2 S

20.0
48.0
00.3
13.0
13.0
04.2
01.0
00.5

Experimental reactor data

Volume of the catalyst bed (m3 )
Reactor length (m)
PdAg alloy film thickness (m)
Diameter of catalyst pellets (m)
Pressure of synthesis gas (MPa)
Pressure of sweep gas (MPa)
Flow rate of synthesis gas (m3 (STP)/s)
Flow rate of sweep gas stream (m3 (STP)/s)

6.689 106
0.14
6.0
(0.150.2) 102
3.6477
0.1013
5.833 105
5.000 105

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M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

5. Solution of the model equations

The composition of the coal gasification stream and
the initial feed temperature, flow rate, pressure and
the volume of the catalyst bed are taken from the
work of Gobina et al. [3] and shown in Table 1. The
initial value differential Eqs. (2427) and (38) are
integrated directly using an IMSL subroutine called
DGEAR.

6. Catalyst bed patterns

A brief illustration of the idea of the catalyst patterns
is presented by considering two types of catalysts. The
catalyst patterns are depicted in Fig. 2. Fig. 2(a) shows
a catalyst bed that contains only one type of catalyst.
Fig. 2(b) shows a well-mixed pattern in which two
catalysts are involved in the reactions. The 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 [13]. The final pattern involves 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 fluid
alternates between different catalyst regions. Among
the potential advantages of the patterns: shift of thermodynamic equilibrium, tune the feed for the primary
reactions and eliminate environmentally harmful
by-products. The shift of the thermodynamic equilibrium allows the reactions to take place at reduced
temperatures, thus, minimizing energy operating
cost.

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 one and that used for
the methanation reactions (the auxiliary reactions) is
catalyst two.

Fig. 2. Catalyst bed patterns: (a) single-catalyst pattern, (b) well-mixed pattern: (i) composite pellets; (ii) discrete pellets, (c) spatial pattern:
(i) single-catalyst spatially layered; (ii) single well-mixed spatially layered; (iii) well-mixed spatially layered.

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

7.1. Comparing the fixed bed reactor to the

co-current membrane reactor
In this section, a comparison of the performance
of fixed bed and co-current membrane reactors is
presented. The comparison is made for identical feed
conditions and catalyst mass. The effect of the sweep
gas on the performance of the membrane reactor is
also considered. Here, the primary reaction proceeds
alone i.e. the reactors are packed with one type of the
catalyst that is catalyst one (1 = 1, 2 = 0). Fig. 3
compares the performance of the fixed bed reactor
and the co-current membrane reactor without (sweep
ratio (SR) = 0) and with sweep gas (SR = 0.857).
It can be seen that the fixed bed reactor gives negative conversions i.e. the equilibrium is shifted toward
ammonia formation. The poor performance shown
by the fixed bed reactor indicates that the fixed bed
reactor is not suitable for ammonia decomposition at
these operating conditions. It is clearly shown that
significant 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

41

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, the sweep gas has an overall positive effect on 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).
7.2. Catalyst patterns in the membrane reactor
7.2.1. Well-mixed pattern
The well-mixed pattern involves loading the reactor with catalyst one and two after physically well
mixed. The configuration with mixed catalysts is utilized for the investigation of the effect of the auxiliary
reactions (methanation reactions) on the performance
of the fixed bed reactor with and without membrane.
A comparison of these cases at a temperature of
720 K is shown in Fig. 4. In Fig. 4, the exit ammonia
conversion varies as a function of the catalyst bed
composition. The trend is an initial steep rise in exit

Fig. 3. Comparison of fixed bed and membrane reactors.

42

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Fig. 4. Effect of auxiliary reactions (methanation reactions) on exit ammonia conversion for different concentrations of catalyst two for
the fixed bed reactor with and without membrane.

ammonia conversion and the rise attains a maximum.

As it can be seen that the auxiliary reactions alone
increase the ammonia conversion from 9.36% at
2 = 0 (fixed bed reactor without auxiliary reactions)
to a maximum conversion of 69.66% at 2 = 0.158.
The fixed bed membrane reactor without auxiliary
reactions (2 = 0) achieves 81.04% conversion. The
fixed bed membrane reactor with auxiliary reactions
achieves a maximum conversion of 99.999% at 2 =
0.04. These results demonstrate that the auxiliary reactions and the membrane have pronounced effects in
enhancing the ammonia conversion. However, none
of them alone achieves complete conversion of ammonia. From these results we may then conclude that,
the combined effect of the auxiliary reactions and
membrane is necessary for the complete decomposition of ammonia at low temperature. In the analyses
that follow the membrane reactor with sweep gas is
considered for the catalyst patterns study.
Fig. 5 shows how the exit ammonia conversion
varies as a function of the bed composition for several different temperatures. It can be seen that at

all temperatures the exit ammonia conversion passes

through a maximum with increasing the concentration
of catalyst two ( 2 ). The occurrence of the maximum
could be due to the interaction of the equilibrium,
hydrogen permeation driving force and composition
of the catalyst bed. It appears that the amount of catalyst two in the bed plays a key role in determining
the overall effect. It is also shown that the increase of
the temperature shifts the maxima towards low concentrations of catalyst two and the maxima are much
more temperature-sensitive at high concentrations of
catalyst two as shown at 645 and 648 K.
The conversion profiles along the length of the
reactor at 720 K and different catalyst bed compositions are presented in Fig. 6. It can be observed that
addition of a little amount of catalyst two to catalyst
one has significant improve of ammonia conversion
at the exit of the reactor. 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 beneficially.

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Fig. 5. Well-mixed patterns: exit ammonia conversion vs. catalyst two concentration for various temperatures.

Fig. 6. Well-mixed pattern: ammonia conversion along the reactor for different concentrations of catalyst two.

43

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M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

7.2.2. Spatially layered patterns

The total volume of the catalyst used is kept constant and the catalyst bed is divided into two distinct
beds (layers). Various configurations of the layers are
considered and investigated in this section.
7.2.2.1. Configuration 1. In this configuration, the
first bed (layer 1) contains catalyst two (1 = 0, 2 =
1) in which the methanation reactions take place and
the second bed (layer 2) contains catalyst one (1 =
1, 2 = 0) in which ammonia reaction takes place.
The volumes of the catalyst in bed first (layer 1) and
second (layer 2) are expressed by their corresponding
dimensionless lengths LB1 and LB2 (LB1 + LB2 =
1.0), respectively. The effect of the bed volumes on
ammonia conversion are shown in Fig. 7. It can be
seen that by increasing the length of the first bed (LB1 )
and decreasing the length of the second bed (LB2 ),
the complete decomposition of ammonia is attained at
shorter total reactor lengths as shown by profiles C and
D (LB1 = 0.02, LB1 = 0.05). Further increase of LB1
beyond a certain length has a negative effect on the

total length required for the complete decomposition

of ammonia and the conversion as shown by profiles
E, F and G (LB1 = 0.10, 0.40, 0.60). This indicates
that an optimum total length exists.
Fig. 8(a) shows the exit ammonia conversion versus
the length of the first bed (LB1 ). A plateau is shown
which indicates that a wide range of LB1 can achieve
complete decomposition of ammonia at the exit of the
reactor. However, in some cases the complete decomposition of ammonia occurs far from the exit of the
reactor i.e. at shorter total lengths as shown in Fig. 7.
In order to investigate the optimum conditions, we
defined an effective reactor length (Leff ) as the total
reactor length that gives 99.8% conversion of ammonia. This criterion is fair enough to find the optimum
conditions. Fig. 8(b) shows the profile of the dimensionless effective length. As the length of the first bed
increases the plot tends to assume an inflection point
of a minimum value of 0.2963 at LB1 = 0.0264.
Sensitivity analysis for the optimum value is shown
in Fig. 9(a and b). Fig. 9(a) shows that the temperature has a pronounced effect on the minimum values.

Fig. 7. Spatially layered pattern (configuration 1): ammonia conversion along the reactor for different beds lengths.

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

45

Fig. 8. Spatially layered pattern (configuration 1): (a) exit ammonia conversion vs. dimensionless length of the first bed; (b) dimensionless
effective reactor length as a function of the dimensionless length of the first bed.

46

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Fig. 9. Spatially layered pattern (configuration 1): (a) effect of temperature on the dimensionless effective reactor length; (b) effect of SR
on the dimensionless effective reactor length.

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

It appears that the effect of the SR on the minima

is less pronounced as shown in Fig. 9(b). It is interesting to note that a little layer of catalyst two at
the entrance of the reactor improves significantly the
performance of the reactor and reduces the effective
length required for the complete decomposition of
ammonia.
7.2.2.2. Configuration 2. In this configuration, the
first bed contains catalyst one (1 = 1, 2 = 0) and
the second bed contains catalyst one and two in a
well-mixed form (1 + 2 = 1). In order to investigate
the effect of the composition of bed second on the
overall performance of the reactor, the length of bed
first is kept constant at two different values (LB1 =
0.05, LB1 = 0.5) as shown in Fig. 10(a and b), respectively. Fig. 10(a) shows that the effect of the composition of the second bed on the conversion has the same
general trend of that shown by the well-mixed bed
(Figs. 5 and 6) i.e. there exists an optimal exit conversion with the increase of the concentration of catalyst
two in bed second. This behavior is expected because
the first bed in this case is very thin. Fig. 10(b) shows
that the behavior of the second bed is totally different
when the length of the first bed is kept at 0.5. When
the concentration of catalyst two in bed second is increased, a steady increase in the exit conversion and
a steady decrease in the effective length are observed.
It appears that there is a critical point at a certain
length of bed first (LB1 ) after which the trend of the
concentration profiles changes from those shown in
Fig. 10(a) to (b). To investigate this more, the effective
length (Leff ) versus the length of bed first at different compositions of bed two (2 = 0.1, 0.2, 0.8) are
presented in Fig. 11. It can be seen that for each composition of bed second there is a range for the length
of bed first in which the effective length exists i.e.
the criterion of effective length is satisfied. Within the
start and the end of each range there is and inflection
point of a minimum nature and the minima are located
at different positions along the length of the reactor.
This may explain the different behaviors shown in
Fig. 10(a and b).
7.2.2.3. Configuration 3. In this configuration,
bed first is loaded with the well-mixed catalyst
(1 + 2 = 1) and bed second is loaded with catalyst
one (1 = 1, 2 = 0). The effective length at different

47

compositions of bed first is shown as a function of

bed first length (LB1 ) in Fig. 12. It can be observed
that the profiles show minima. For each composition
there exists a region in which the effective length
criterion is satisfied (conversion >99.8%). The region
shrinks and is shifted up with the decrease of the concentration of catalyst two in bed first. It appears also
that there is a composition beyond which the effective
length criterion cannot be satisfied i.e. the condition
at which the profiles converge to a point. Two compositions (2 = 0.2, 0.8) for bed first are selected to
show the conversion profiles along the length of the
reactor at different bed lengths. Fig. 13(a) shows the
conversion profiles when the concentration of catalyst two in bed first is low (2 = 0.2). The positions
of the shift points from bed first to bed second are
located at S1 S4 . The profiles show high ammonia
conversion but do not satisfy the effective length
criterion and this is may be due to the fact that the
concentration of catalyst two in bed first is not within
the effective region as shown in Fig. 12. Fig. 13(b)
shows the conversion profiles when the concentration
of catalyst two in bed first is high (2 = 0.8). When
bed first lengths at S1 = 0.05, S2 = 0.2 and S3 = 0.4,
the profiles satisfy the effective length criterion. It
is clear that the complete decomposition of ammonia is achieved with a very short effective length by
introducing a little layer of the well-mixed catalyst
in front of bed second. The effect of temperature on
the conversion is shown in Fig. 14(a and b). Here,
the length of bed first is kept constant at S1 = 0.05
which gives the best performance among the profiles
presented in Fig. 13(b). The effect of the temperature
is investigated for two cases. In the first case, the two
beds are maintained at the same temperature. The
effect of the increase of temperature is pronounced
as shown in Fig. 14(a). In the second case, the first
bed temperature is kept constant at 720 K while the
temperature of the second bed is varied. It is clearly
shown from Fig. 14(b) that the complete decomposition of ammonia is achieved at low temperatures
>680 K. This implies that to maintain the two beds at
different temperatures has a distinct advantage over
the case in which the two beds are maintain at the
same temperature. Comparing configuration 2 and 3,
it becomes clear that the reactor performance is much
better when the mixed layer is introduced in the first
bed.

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M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Fig. 10. Spatially layered pattern (configuration 2), ammonia conversion along the reactor for different compositions of bed second and
constant lengths of the beds: (a) LB1 = 0.05, LB2 = 0.95; (b) LB1 = 0.50, LB2 = 0.50.

Fig. 11. Spatially layered pattern (configuration 2): dimensionless effective reactor length as a function of the dimensionless length of the
first bed for various compositions of the second bed.

Fig. 12. Spatially layered pattern (configuration 3): dimensionless effective reactor length as a function of the dimensionless length of the
first bed for various compositions of the first bed.

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M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

Fig. 13. Spatially layered pattern (configuration 3), ammonia conversion along the reactor for different dimensionless lengths of the beds
and constant compositions of the beds: (a) first bed (1 = 0.8, 2 = 0.2), second bed (1 = 1, 2 = 0); (b) first bed (1 = 0.2, 2 = 0.8),
second bed (1 = 1, 2 = 0).

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

51

Fig. 14. Spatially layered pattern (configuration 3), effect of temperature on ammonia conversion along the reactor: (a) two beds at the
same temperature; (b) two beds at different temperature.

Fig. 15. Spatially layered pattern (configuration 4): dimensionless effective reactor length as a function of the dimensionless length of the
first bed for constant composition of the first bed and various compositions of the second bed.

Fig. 16. Spatially layered pattern (configuration 4): dimensionless effective reactor length as a function of the dimensionless length of the
first bed for various compositions of the first bed and constant composition of the second bed.

M.E.E. Abashar et al. / Applied Catalysis A: General 236 (2002) 3553

7.2.2.4. Configuration 4. In this configuration, bed

first and bed second are loaded with the well-mixed
catalysts (1 + 2 = 1). Two cases are considered. In
the first case, the composition of the first bed is kept
constant at (1 = 0.96, 2 = 0.04) while the composition of bed second is varied as shown in Fig. 15. It
is observed that for each profile there is a region in
which the effective length criterion is satisfied. The
effective regions shrink and are shifted down showing
that the increase of the concentration of catalyst two
in bed second improves the optimal effective length
value as shown by profiles A, B and C. However,
profile D shows that the increase of the concentration
of catalyst two in bed second has a slight negative
effect on the optimal effective length. In the second
case, the composition of bed second is kept constant
at (1 = 0.80, 2 = 0.20) while the composition of
bed first is varied as shown in Fig. 16. It appears that
very weak concentrations of catalyst two in bed first
are enough to produce effective regions with minima.
As shown, local minima is presented in profile D. It
is also clearly shown that the effective regions are
very sensitive to the concentration of catalyst two
in bed first and the increase of the concentration of
catalyst two has a negative effect on the optimal effective length i.e. the performance of the reactor. It is
interesting to note that the behavior shown in Fig. 16
is opposite to the behavior shown in Fig. 15.
8. Conclusions
In this investigation, the concept of dual-functionality
via structure pattern is implemented into a catalytic
membrane reactor. A mathematical model is involved
to simulate the performance of the membrane reactor
at different conditions. Various configurations of catalyst patterns are investigated. These configurations
demonstrate significant improvement of the reactor
performance in terms of high conversions, low temperatures and reduced total reactor length. The results
show that the complete decomposition of ammonia
could be achieved at low temperatures within regions

53

of effective lengths. The effective length versus the

length of the first bed determines the optimal configuration and operating conditions. It is also shown that
the spatially layered patterns offer the flexibility of
controlling each bed temperature independently. Appreciable improve is shown by maintaining the layers
at different temperatures. Future interest should focus in experimental validation, rigorous mathematical
modeling and optimization.
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