Water-Gas shift

reaction
Group WGS B
David Chen, Carl-Robert Florn, Richard Johansson and Fredrik Edman

Water-Gas Shift Reaction(WGS)

Group B

Introduction
Because of todays increased electricity usages the importance for conversion of
chemical energy into electrical energy has grown. Through fuel cells, the free
energy of a chemical reaction is converted into electrical energy. This has led to
increased interest of high purity H 2 in the exhaust from a combustion engine,
because it is used to power the fuel cells. H 2 can be obtained from synthesis gas
that mostly consists of H2, CO, CO2 and H2O. There is a requirement for the fuel
cells that the concentration of CO must be held below 100 ppm or else its
electrodes will be poisoned. This project is involving Water-Gas Shift (WGS)
reaction which is one way to keep a low CO concentration. It is also possible to
increase the quantity of H2 by changing the composition of the synthesis gas by
using WGS as a method. The WGS reaction reacts in multiple stages, but the
overall reaction can be described as seen below:

CO+H 2 O K eq CO2 +H 2

where its equilibrium constant, K eq is highly affected by the temperature. The

conversion of CO is generally equilibrium limited during characteristic reaction
conditions within industrial processes. Catalysts based on copper and zinc or iron
is often used in WGS but their efficiency is reduced because of air exposure.
Therefore new catalysts less sensitive to air have been developed consisting of
noble metals such as platinum, ruthenium or rhodium supported on oxides like
Al2O3, CeO2 and ZrO2.
The used catalyst in this project consists of 1.4 weight% Pt and 8.3 weight% CeO 2
on an Al2O3 layer. The aim is to design a WGS reactor system reducing the CO
concentration in a gas mixture below 1 mole%. A monolith reactor will be used
with the catalyst as a washcoat and it is important that the total reactor volume
and catalyst load becomes as small as possible.
To optimize the reactor volume, different values of the diameter, length, inflow
temperature and catalyst load will be simulated. This is to find working conditions
so that the outflow reaches a maximum concentration of CO at 1 mol%.

Methodology
The simulations were run in MATLAB as a single-channel model where all
channels are considered identical and radial variation in the monolith reactor is
neglected. The cross-sectional of the monolith for the single channel is illustrated
in Figure 1: dw is the catalyst thickness, dH is the channel dimension and w/2 is
the thickness of the monolith wall. The monolith is considered to operate
adiabatically and the reactor contains 400 channels per square inch. Each
monolith channel is modeled as a tanks-in-series of 15 tanks where the catalyst is
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Water-Gas Shift Reaction(WGS)

Group B

washcoated onto the channel walls in 5 layers. By discretizing the catalyst in

layers, pore mass transport resistance in the washcoat is accounted for. To
account for the radial gas phase temperature and concentration gradients in the
channels, a film models is introduced in the simulation, as well as the heat
transport in monolith and washcoat are taken into account.

Figure 1: The cross-sectional of the monolith for a single channel

The tanks-in-series is modeled by the following mass and heat balances for
component i in tank k:

Fi , k1Fi , k i ,k ,0 c tot ,k ( y i , k, 0 y i , k ,1 )=

dy i , k ,0
c tot , k V k , 0
dt

c P ,i dT
T g , k
T g ,k1

Fi , k

h k A k ( T s ,k )=

T g, k

d yi , k ,0
c tot, k V k ,0
dt

where

i , k ,0=

is the lumped mass transfer coefficient

Ak
for layer n=0
0.5 x 0
1
+
k c ,i , k D eff ,i , k

Water-Gas Shift Reaction(WGS)

Group B

Washcoat mole balance for component i in tank k and washcoat layer n:

i , k ,n1 ctot , k ( y i , k ,n1 yi , k ,n ) i , k ,n c tot, k ( y i ,k , n y i ,k , n+1 ) + i , j r j ,k , nw k ,n=

j

d y i ,k , n
c (tot , k ) V
dt

k,n

with

i , k ,n=

Deff ,i , k A k
for layers 1 n N1
0.5 x n+ 0.5 x n +1

For the bottom washcoat layer:

i , k ,N =0 for layer n=N

hk A k ( T g , k T s ,k ) A s ( q k+1qk ) + r j , k ,n w k ,n ( H R , j , k )=
n

d T s ,k
c w
dt Ps n k , n

where the axial heat flux for a given tank k is:

q k = s

T s , k T s ,k1
for layers 2 k K1
0.5 z k + 0.5 zk 1

Radiative heat transfer for the first and last tanks (axial heat flux) is accounted
for as:

q1 = m ( T 4g ,feed T 4s ,1 )

and

q K = m (T s ,K T g , K )

The heat and mass transport coefficients

and

kc

are estimated from the

equations above through correlations with Sherwood and Nusselt number as an

asymptotic value [R.D. Hawthorn, AIChE Symp. Ser. 70 (1974) 428].

Water-Gas Shift Reaction(WGS)

Group B

The effective diffusivities in the washcoat are estimated from the Bosanquet
formula [G.F. Froment, K.B. Bischoff, J. De Wilde, Chemical Reactor Analysis and
Design, third ed., John Wiley & Sons, New York, 2010, p. 175]:

Deff , i=

fD

1
i

D + D1
k,i

where fD is the ratio of internal void fraction and tortuosity factor and is set to
0.1.
Originally the generic program simulated another type of catalytic reaction, but
used the same type of monolith reactor. Therefore changes had to be made in
order to simulate the water-gas shift reaction. First the reaction taking place in
WGS is a reversible reaction. Due to that the MATLAB program requires two
reactions the reversible reaction is divided into one forward (r1) and one
backward (r2) reaction.
The necessary properties of the catalyst that were not given had to be calculated.
However, the catalyst heat capacity and heat conductivity was assumed to be
the same since the values are hard to find for porous materials.
In order to find accurate data Tref was changed to 293.15K from where the
properties could be found. The total pressure was set to 1 atm and assumed to
be constant over the reactor. Due to a change in reference temperature new k ref
had to be calculated from the Arrhenius equation:

k ref =Aexp

E a
RT ref

The equilibrium relationship [A.A. Phatak et al., Catalysis Today 123 (2007) 224
234] that relating the forward and the backward reaction is expressed as:

K eq =exp

4.33 )
( 4577.8
T

The diffusivities are taken at STP from [Atmospheric Environment, 32A 11111127. 1998. Massman, WJ] and calculated for our temperature and pressure
assuming

P0
T

P
T0

1.81

( )( )

D (T , P )=D ( 273.15, 101325 )

All the necessary data that had to be changed in MATLAB is summarized in Table
1.
The dimensionless numbers Sherwood (Sh), Nusselt (Nu), Reynolds (Re), Schmidt
(Sc) and Prandtl (Pr) are assumed constant throughout the reactor. They are
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Water-Gas Shift Reaction(WGS)

Group B

assumed to be the same as from the generic program. The mass and heat
transfer coefficients are calculated in the program from correlations using these
dimensionless numbers.

Table 1: The input data for the simulation of the monolith reactor for
water-gas shift process
Catalyst properties
Channel dimension [m]
Wall thickness of
monolith [m]
Catalyst layer thickness
[m]
Density of catalyst
[kg/m3]
Bulk density [kg/m3]
Catalyst surface are per
monolith volume
[m2/m3]
Fraction of open area to
total cross sectional
area
Catalyst mean pore
diameter [m]
Kinetic properties [1]
kref, forward [mol/kg/s]
kref, backward

1.1176e-3
1.524e-4
25e-6
1100
74.5155
2647.7

0.7067

10e-9

6.1598e-10
6.1598e-10
5

Water-Gas Shift Reaction(WGS)

[mol/kg/s]
Ea (forward) [J/mol] [1]
Ea (backward) [J/mol]
[1]
A (pre-exp. factor)
Standard enthalpies
of formation [2]
Hf [kJ/mol]
Physical properties

Group B

86 000
86 000
2.9245e-25

1.51e-5

CH4
inert
0
CH4
inert
2.168e-5

2.032e-5

2.02e-3

44e-3

16.04e-3

28.01e-3

CO

H2O

H2

CO2

-110.54
CO

-241.818
H2O

0
H2

-393.422
CO2

Diffusivity [m2/s] [3]

1.856e-5

6.1e-5

Molar mass [kg/mol]

28e-3

2.4752e5
18e-3

Cp =
A+B*T+C*T2+D*T3+E*
T4
CO
H2O
H2

29.56
33.93
25.40

-6.58e-3
-8.42e-3
2.02e-2

2.01e-5
2.99e-5
-3.85e-5

-1.22e-8
-1.78e-8
3.19e-8

CO2

27.44

4.23e-2

-1.96e-5

4.00e-9

CH4
N2

34.94
29.34

-4.00e-2
-3.55e-3

1.92e-4
1.01e-5

-1.53e-7
-4.31e-9

2.26e-12
3.69e-12
-8.76e12
-2.99e13
3.93e-11
2.59e-13

N2 inert
0
N2 inert

Results and Discussion

The totals of 2 series monolith reactors are required as to reduce the CO mole
fraction lower than 1 mol%. The temperature of the outlet gases from the first
reactor will increase due the exothermic catalytic reaction. Hence, proper cooling
system should be installed at the outlet of the first reactor in order to cool down
the gases before feeding into the second reactor. Both of the reactors are
designed in such a way that they will have the same dimensions. Different
combinations of the designs (dimension, catalyst mass and operating
temperature) for the both of the monolith reactors are shown in Table 2 below.
The optimization is performed as to minimize the volume of reactor and the total
catalyst mass required for the WGS reaction.
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Water-Gas Shift Reaction(WGS)

Group B

Table 2: Different settings are set and tested to optimize the design of the
monolith reactor in converting carbon monoxide to the level lower than 1 mol %
for the water gas shift (WGS) process

Basic Settings
the 1st reactor
Catalyst thickness
(x10-6 m)
Length (x 10-2 m)
Diameter (x 10-2
m)
Volume (x10-6 m3)
Mass of catalyst
(kg)
Inlet temperature
(oC)
Outlet mole
fraction of CO
(mole %)

25

25

25

25

35

50

75

6
20

6
20

6
20

6
20

6
18

6
14

9
10

1885
0.14
05
300

1885
0.140
5
310

1885
0.14
05
290

1885
0.140
5
310

1524
0.15
78
310

924
0.134
5
310

707
0.150
2
310

1.53

1.53

2.00

1.53

1.53

1.77

2.05

25

25

25

25

35

50

75

6
20

6
20

6
20

6
20

6
18

6
14

9
10

1885
0.14
05
300

1885
0.140
5
310

1885
0.14
05
290

1885
0.140
5
290

1524
0.15
78
290

924
0.134
5
290

707
0.150
2
290

0.70

0.74

0.83

0.69

0.68

0.81

0.95

The 2nd reactor

Catalyst thickness
(x10-6 m)
Length (x 10-2 m)
Diameter (x 10-2
m)
Volume (x10-6 m3)
Mass of catalyst
(kg)
Inlet temperature
(oC)
Outlet mole
fraction of CO
(mole %)

First optimization is performed to obtain the best combination of temperatures to

operate the series monolith reactors. (Run 1- 4). The Run 2 and 3 have shown
that it is not favorable to operate both of the reactors at either higher or lower
than 300 oC as it will result in lower conversion. However, if the operating
temperatures for the reactor 1 and reactor 2 are set at 310 oC and 290 oC
respectively as in the run 4, the mole fraction of CO could be reduced to 0.69 mol
% for the same reactor dimensions of: length= 6 cm, diameter= 20 cm and
volume= 1885 cm3 with the total catalyst mass of 0.1405 kg.
The aforementioned phenomena could be explained by the water-gas shift
equilibrium behavior. The forward reaction of the water-gas shift process is an
exothermic reaction while the backward reaction is an endothermic reaction.
Although high temperature will enhance the catalytic activity of the catalyst, the
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Water-Gas Shift Reaction(WGS)

Group B

rate of the forward reaction will be decreased as the equilibrium will be actually
shifted back to the left under these high temperature conditions. The rate of
endothermic backward reaction will increase with temperature and reverse the
produced CO2 back to CO and therefore it is not recommended to run the reactor
at high temperature. It is important to operate the reactor at the temperature
where the forward reaction rate is always higher than the backward reaction rate
to enhance the production of CO2.

Figure 2: The effectiveness factor changes along the first monolith reactor (Run
4)

Water-Gas Shift Reaction(WGS)

Group B

Figure 3: The effectiveness factor changes along the second monolith reactor
(Run 4)

Figure 4: The effectiveness factor changes along the first monolith reactor (Run
7)

Figure 5: The effectiveness factor changes along the second monolith reactor
(Run 7)

As shown in Figure 2 and 3, the effectiveness factors obtained from the Run 4 for
both of the reactors are close to unity which means that the internal mass
transfer resistance within the catalyst layer is not significant. In other words, all
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Water-Gas Shift Reaction(WGS)

Group B

the catalysts coated on the monolith inner wall layer are almost fully utilized for
the water-gas reactions. Thereby, the catalyst thickness could be increased
further while the volume of the reactor could be reduced as to have more
catalyst mass per volume. Series of optimization (Run 5-7) are performed as to
have more compact design for both of the monolith reactors by increasing the
catalyst thickness and reducing the volume of the reactor (diameter and length)
in the same time while maintaining the low catalyst load. In order to have low
catalyst load, the effectiveness factor need to be maintained at the value close to
unity along the reactor length as to ensure that the coated catalyst is fully
utilized for reaction and not wasted.
The total volume of the reactor had been reduced to 707 cm 3 each through the
optimization process (Run 5-7). The total catalyst mass coated on the monolith
for both of the reactor is 0.1502 kg each and the outlet CO mole fraction
becomes slightly higher to 0.95 mole% but still below the desired value of 1 mole
%. The values of the effectiveness factor obtained for the forward reaction for
both of the first and second reactor are close to unity as illustrated in Figure 4
and 5. Moreover, the values only drop slightly approximately by 0.10 and 0.02 for
first and second reactor respectively if comparing the Run 4 to the Run 7. It can
be noticed that the values of effectiveness factor for the backward reaction for all
the runs are higher than unity and this reflects that the rate of reaction occurred
within the catalyst layer is higher than the rate of reaction on the catalyst
surface. This can be explained by the endothermic reaction characteristic of the
backward reaction. During the water- gas shift reaction, the heat is accumulated
within the catalyst pore due to the highly exothermic forward reaction and this
will result in high temperature conditions. The backward reaction will be favored
at high temperature conditions. Therefore, it is also crucial to ensure that the rate
of the backward reaction is always lower than the forward reaction along the
reactor to have better conversion of CO. In order to achieve the aforementioned
condition, the dramatically temperatures change along the reactor is not
recommended. Thereby, good heat transfer is required to remove the
accumulated heat within the catalyst layer.

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Water-Gas Shift Reaction(WGS)

Group B

Figure 6: The average of the forward and backward reaction along the first
monolith reactor (Run 7)

Figure 7: The average of the forward and backward reaction along second
monolith reactor (Run 7)

As illustrated in Figure 6 and 7, the average of forward reaction rate is always

higher than the average of the backward reaction rate and the equilibrium is not
achieved along the first and second reactor for the Run 7. By comparing Figure 6
to Figure 8 or Figure 7 to Figure 9, it can be seen that the rates of reaction for
both backward and forward reaction are increasing with temperature along the
reactor. However, it is also noted that the backward rate increases much faster
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Water-Gas Shift Reaction(WGS)

Group B

than the forward rate due to the backward reaction is endothermic and the
increasing concentration of CO2 along the reactor, this further drives the speed of
the backwards reaction.

Figure 8: The temperature profiles of gas and catalyst surface along the first
reactor (Run 7). No significant difference for the temperatures of gas and
catalyst surface.

Figure 9: The temperature profiles of gas and catalyst surface along the second
reactor (Run 7). No significant difference for the temperatures of gas and
catalyst surface.

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Water-Gas Shift Reaction(WGS)

Group B

Therefore, the overall rate of reaction (rate of forward reaction-rate of backward

reaction) will actually decrease when moving from the inlet to the outlet for both
of the reactor. It is not recommended to have extreme low overall rate of reaction
along the reactor. The average overall reaction rates in the Run 7 are reasonable
high.

Figure 10: The concentration profile of CO changes along the first reactor (Run
7)

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Water-Gas Shift Reaction(WGS)

Group B

Figure 11: The concentration profile of CO changes along the second reactor
(Run 7)

From the Figure 8 and 9, it can be seen that there is not significant difference
between the gas temperature and the temperature at the catalyst surface. This
means that the heat transfer occurred between the gas and the solid catalyst at
the catalyst surface is excellent with monolith design done in the Run 7. The heat
transfer resistance is relatively low.
The concentration surface plot for the first reactor and second reactor are shown
in Figure 10 and 11 respectively. From the plot, it can be noticed that the
difference between the surface concentration (x=0) and the concentration within
the catalyst layer (0<x<7.5x10 -5) is insignificant. These results are justified by
the values of effectiveness factor evaluated previously which are close to unity.
The internal mass transfer limitation is relatively small and all the coated catalyst
could be utilized fully well without any wastage.
For further reference, all the details of the simulation could be found in the zip file
named as WGS_GROUP_B along with the attachment.

Conclusion
The target was to reach a total concentration of CO below 1 mole%, which was
achieved with the result of 0.0095-mole%. Two reactors were used in series and
the dimensions are 0.09 m in length, 0.1 m in diameter and a layer thickness of
75x10-6 m for each of the reactors. The total volume for these reactors was
0.0014 m3 which proved to be realistic dimensions of real catalysts in moving
vehicles.
The possible improvements could be done on this project by adding more sets of
reactors, this will give stricter control over the temperature rise over the reactor,
and also the overall reaction rate. The control could be performed by cooling the
feed between the reactors. By observing the derivate for the reaction rates, a
condition could be held when |drforward|<|drbackwards| is reached; the temperature of
the feed could be then lowered so that |drforward|>|drbackwards| and improve the
overall reaction. By doing so, it is also possible to have a smaller total reactor
volume by reducing the length of the reactors..

References
[1] A.A. Phatak et al., Catalysis Today 123 (2007) 224234
[2] Yaws, Carl L., Yaws' Handbook of Thermodynamic and Physical Properties of
Chemical Compounds (2003)
[3] Massman, WJ, Atmospheric Environment (1998), 32A 1111-1127

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Water-Gas Shift Reaction(WGS)

Group B

15