A Review of The WGS Reaction Kinetics

I NTERNATIONAL J OURNAL OF C HEMICAL
R EACTOR E NGINEERING
Volume 8
2010
Review R4
A Review of the Water Gas Shift Reaction

Kinetics
Byron Smith R J
Muruganandam Loganathan
Murthy Shekhar Shantha
Vellore Institute of Technology University, [email protected]


ISSN 1542-6580
c
Copyright 2010
The Berkeley Electronic Press. All rights reserved.
A Review of the Water Gas Shift Reaction Kinetics

Byron Smith R J, Muruganandam Loganathan, and Murthy Shekhar Shantha
Abstract
The worlds progression towards the Hydrogen economy is facilitating the
production of hydrogen from various resources. In the carbon based hydrogen
production, Water gas shift reaction is the intermediate step used for hydrogen enrichment and CO reduction in the synthesis gas. This paper makes a critical review
of the developments in the modeling approaches of the reaction for use in designing and simulating the water gas shift reactor. Considering the fact that the rate of
the reaction is dependent on various parameters including the composition of the
catalyst, the active surface and structure of the catalyst, the size of the catalyst, age
of the catalyst, its operating temperature and pressure and the composition of the
gases, it is difficult to narrow down the expression for the shift reaction. With different authors conducting experiments still to validate the kinetic expressions for
the shift reaction, continuous research on different composition and new catalysts
are also reported periodically. Moreover the commercial catalyst manufacturers
seldom provide information on the catalyst. This makes the task of designers difficult to model the shift reaction. This review provides a consolidated listing of the
various important kinetic expressions published for both the high temperature and
the low temperature water gas shift reaction along with the details of the catalysts
and the operating conditions at which they have been validated.
KEYWORDS: water gas shift reaction, reaction kinetics
Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics
1. INTRODUCTION
The Water Gas Shift Reaction (WGSR) is a reaction traditionally used for the
production of Hydrogen from synthesis gas which is further used for ammonia
production in the fertilizer industry, petroleum refineries for a variety of
operations and recently as fuel for power generation and transportation. The use
of gasification for power generation has also increased the use of water gas shift
reactors multifold. The earliest recording of the reaction dates back to 1888
[Rhodes et al., 1995], and its prominence came with the Haber ammonia synthesis
process and development of catalyst by Bosch and Wilde in 1912 [Twigg, 1989].
The catalyst developed containing iron and chromium was capable of catalyzing
the reaction at 4000C to 5000C and reduced the exit carbon monoxide content to
around 2%.
Water gas shift reaction is a moderately exothermic reversible reaction and
is expressed by
CO + H2O CO2 + H2
H0298 = -41.09 kJ/mol
(1)
The equilibrium constant of the reaction decreases with increasing temperature.

The reaction is thermodynamically favoured at low temperatures and kinetically
favoured at high temperatures. Since there is no change in the volume from
reactants to products, the reaction is not affected by pressure. The WGSR can be
catalyzed by both metals and metal oxides. Historically, in the ammonia plant, the
iron oxide chromium oxide catalyst in an adiabatic single reactor produced an exit
composition of carbon monoxide at 2 4% as the temperature increases along the
length of the reactor and approaches equilibrium [Twigg, 1989]. At lower
temperatures, these catalysts lose their activity and hence to reduce the CO levels
to less than 1 %, multiple beds with inter cooling was necessary. Since these
catalysts could work in only high temperatures, the iron oxide chromium oxide
catalysts were called High Temperature (HT) shift catalysts. Later copper based
catalysts were developed to operate at lower temperatures in the range of 2000C
and these reactors could achieve exit CO concentrations of 0.1 to 0.3%. The
temperature limitation is enforced due to the dew point of the gaseous mixture.
These catalysts were known as Low Temperature (LT) shift catalysts.
Commercially the water gas shift reaction is carried out in two adiabatic stages,
namely the high temperature shift followed by low temperature shift with inter
cooling to maintain the inlet temperatures [Twigg, 1989]. This configuration is
necessitated because, the copper based catalyst can be easily poisoned by sulphur
compounds which comes from coal or hydrocarbon sources whereas the iron
based catalyst are sulphur tolerant. If sulphur is available in the feed, a guard bed
should also be used to concentrate and remove the sulphur compounds to protect
Published by The Berkeley Electronic Press, 2010
International Journal of Chemical Reactor Engineering
Vol. 8 [2010], Review R4
the catalyst. Pasel et al. (2005) has suggested using isothermal reactors based on
his experiments.
Both the high temperature and low temperature catalysts are available
commercially and every vendor has a specific composition and characteristics for
the catalysts. Active research is also carried out across the globe to develop better
catalysts for the reaction. With the commercialization of fuel cell powered
vehicles and fuel cell based power generation, the need for active water gas shift
catalyst is felt as this reaction consumes the bulk space requirements in the power
generation system. Moreover designing the reactor for this reaction requires the
prediction of the rate of the reaction which in turn is predicted by the kinetics of
the reaction. Hence it is imperative that the kinetics of the reaction be known to
designers. Keeping in mind this requirement, a literature search was carried out to
list the various kinetic expressions available in the open literature that could help
in determining the rate of the reaction. Even though the focus was on the kinetic
parameters, the details of the catalysts and the operating conditions on which
these models were developed were also consolidated to help understand the
reaction conditions.
2. HIGH TEMPERATURE SHIFT CATALYSTS
The high temperature catalyst can operate in the temperature range of 3100C to
4500C and are called ferrochrome catalysts because of their composition [Rhodes
et al., 1995]. The reaction is operated adiabatically in the industrial scale where
the temperature increases along the length of the reactor. Hence to prevent the
catalyst bed temperature from going higher that damages the catalyst, the inlet
temperature is normally maintained at 3500C. This inlet temperature can give a
maximum temperature of approximately 5500C at the exit. Newsome (1980) has
reported the typical composition of high temperature shift catalyst as 74.2% Fe2O3,
10.0% Cr2O3, 0.2% MgO and the remaining being volatiles. The Cr2O3 acts as a
stabilizer and prevents the sintering of the iron oxide and its optimal content in the
catalyst is reported by Newsome (1980) to be 14%. To prevent the compromise
on surface area, 8% is used industrially [Rhodes et al., 2002]. The high
temperature reactor is capable of reducing the CO concentration to 3%, which is
the equilibrium concentration at 4500C. The industrial reactors can operate from
atmospheric pressure to 8375 kPa and varying compositions of gases with CO
composition ranging from 3% to 80% [Newsome, 1980]. Rase (1977) has listed
inorganic salts, Boron, Oils, Phosphorous compounds, liquid water (temporary
poison) and sulphur compounds greater than 50 ppm as poisons for the iron
chromia catalyst.
The pretreatment of HT shift catalyst is carried out by partially reducing
the Hematite (Fe2O3) to Magnetite (Fe3O4) using the addition of the process gas
http://www.bepress.com/ijcre/vol8/R4
mixtures to activate the catalyst [Rhodes et al., 1995]. This also converts any
CrO3 present in the catalyst to Cr2O3. The reactions are
3Fe2O3 + H2 2Fe3O4 + H2O
3Fe2O3 + CO 2Fe3O4 + CO2
H = -16.3 kJ/mol
H = +24.8 kJ/mol
(2)
(3)
This partial reduction process should be controlled by controlling the gas feed
mixture concentrations of the constituent gases to achieve the required reduction.
Over reduction of the catalyst can cause damage to the catalyst pellets. A
convenient tool to control the reduction process is the reduction factor proposed
by Rhodes et al. (2002). The typical value of the reduction factor (R) should be
less than 1.2 and values more than 1.6 can cause over reduction.
R = ({[CO] + [H2]} / {[CO2] + [H2O]}]
(4)
In high temperature shift reaction, the ratio of steam to CO is an important

parameter and operating the reaction at low ratios could lead to formation of
metallic iron, methanation, carbon deposition and Fischer Tropsch reaction
[Twigg, 1989]. Callaghan et al. (2003) suggests a contact time of approximately
3-9 seconds for the reaction.
Publications on newer composition of the catalysts and newer catalysts are
continuously emerging. Grenoble and Estadt (1981) analyzed the catalytic effect
of group VIIB, VIII and IB metals coated on alumina, silica and carbon on WGSR.
They found that the support for the metal or metal oxide should be acidic in
nature to help the reaction. The turnover number decreased in the order of Cu, Re,
Co, Ru, Ni, Pt, Os, Au, Fe, Pd, Rh and Ir supported on alumina. Salmi et al.
(1988) and Hakkarainen et al. (1993) have reported that the commercial cobalt
molybdenum oxide catalyst was capable of catalyzing the reaction above 3500C
and can be sulphur tolerant. The studies by Rhodes and Hutchings (2003) using
different promoters for the high temperature catalyst have shown higher
conversions. The study involved addition of 2 wt% of B, Pb, Cu, Ba, Ag and Hg
to the high temperature catalyst and studying the effect of the promoters on the
conversion. The activity of the promoters obtained in the temperature range of
3500C to 4400C were, Hg >Ag, Ba > Cu > Pb > unpromoted >B. Various studies
have showed the promotion by Cu, Au and Ru of the iron chromia catalyst as
promising. The replacement of chromia by other less toxic component has not
been so far commercially successful.
3. LOW TEMPERATURE SHIFT CATALYSTS

The low temperature shift reaction occurs at 200 0C to 250 0C and the catalyst is a
mixture of ZnO, CuO and Cr2O3/Al2O3 at varying composition depending on the
manufacturer. The typical composition of the catalyst are 68 73 % ZnO, 15
20% CuO, 9 14 % Cr2O3, 2 5 % Mn, Al and Mg oxides [Newsome, 1980] and
32-33% CuO, 34-53% ZnO, 15-33% Al2O3 [Callaghan et al., 2003 and Rhodes et
al., 1995]. Recent catalysts can also be operated at medium temperatures of
around 3000C. The active species in the catalyst is the copper metal crystallites.
ZnO and Cr2O3 provide the structural support for the catalyst and Al2O3 is largely
inactive and helps in the dispersion and minimizes pellet shrinkage. Copper is
more susceptible to thermal sintering and hence should not be operated at higher
temperature [Twigg, 1989]. The lower temperature of operation is restricted by
the dew point of the mixture in industrial conditions. The catalyst is sulphur,
Halogen and unsaturated hydrocarbon intolerant and hence needs to be protected
from these compounds [Rase, 1977]. The ZnO is effective in reducing the
poisoning of copper by sulphur [Twigg and Spencer, 2001]. To prevent the
sulphur poisoning usually a guard bed of ZnO is always used before the low
temperature shift reactor. The exit concentration of CO from the low temperature
reactor will be 0.1% which is desirable in industrial practice. The advantages of
the LT catalyst are its selectivity and fewer side reactions occurring at higher
operating pressures. The normal life time of the low temperature catalyst is 2 3
years [Rase, 1977].
Similar to the HT catalyst, the LT catalyst needs to be activated and hence
the catalyst is exposed to the process stream with dilute H2 [Rhodes et al., 1995].
The CuO is reduced to copper by the following reaction and the catalyst gets
activated.
CuO + H2 Cu + H2O
H = - 80.8 kJ/mol
(5)
Since the reduction reaction is exothermic, the catalyst should be exposed to the
process stream at temperatures of 2300C and higher temperatures will lead to
sintering of the catalyst [Callaghan et al., 2003]. Moreover the process stream
should contain Hydrogen and steam is not preferable as condensation could affect
the catalyst. Tanaka et al. (2003) found CuMn2O4 and CuAl2O4 mixed oxide
catalyst having conversion of CO more than the commercial catalyst. Henrik
Kusar et al. (2006) have found the copper ceria catalyst to be non-pyrophoric and
stable. Studies on Mn promoted Cu/Al2O3 by Dinesh et al. (2006) showed that
with 8.55 wt% of Mn, 513 K and space time of 5.33 hour, CO conversion of 90%
could be achieved. Many more studies on various modifications in the catalysts
are being proposed routinely in the literature. But the mainstay of all the catalysts
still is copper.
4. NOBLE METAL CATALYSTS
For compact fuel cell applications, several authors have listed the inherent
disadvantages with the existing commercial catalysts and hence have tried the use
of noble metals as catalysts. In the transportation sector, efforts are on to integrate
reforming of fossil fuel and water gas shift reaction with the fuel cell technologies
to improve modularity, reduce the emission and increase the efficiency of fuel
utilization. The commercial Iron based catalysts are prone to coke formation in
the presence of excess fuel from the reformer [Wheeler et al., 2004]. The use of
the commercial copper based catalysts, due to kinetic limitations will occupy
more volume. Moreover the Cu catalyst is pyrophoric in reduced state and gets
deactivated in the presence of condensed water due to leaching of active
component or formation of surface carbonates [Henrik Kusar et al.(2006),
Wheeler et al.(2004), Mhadeshwar and Vlachos (2005)]. The catalysts should also
be capable of withstanding thermal cycling and faster response during startup and
shutdown. Hence the search for a better noble metal or promoted catalyst is still
being carried out.
Hilaire et al. (2001) found the ceria supported transition metals acting as
catalysts for the water gas shift reaction. Apanee et al. (2003) found the Pt/CeO2
catalyst more active than Au/CeO2 and Au/Fe2O3. Wheeler et al. (2004) studied
the possibility of the WGSR using noble metals and metals with Ceria in the
temperature range of 3000C to 10000C and found the activity of the metals in the
order, Ni>Ru>Rh>Pt>Pd. The measured frequency factor and activation energy
are given in Table 4. Phatak et al. (2007) carried out experiments on Pt supported
on alumina and ceria at varying compositions and reported their order of reactions
and activation energy. Pt exhibited lower turnover rate than Cu.
Gonzaleza et al. (2010) studied the effect of Pt catalysts supported on TiO2,
CeO2 and CeTiO2 and found the Pt supported on Ce-modified TiO2 support
exhibiting better activity than those corresponding to individual ceria and titania
supported catalysts. Most of the recent studies have been directed in using any of
the precious metals like Pt, Rh, Pd and Au deposited on Ceria, Zirconia, Alumina,
Titania, Thoria or Magnesia supports [Andrea et al., 2010]. Latest research works
have started using mixed oxides of the above supports with the precious metals
dispersed in them to effect the low temperature water gas shift reaction.
Ratnasamy and Wagner (2009) have recently published a comprehensive review
on the latest developments on the catalysts for the water gas shift reaction.
5. REACTION KINETICS
The kinetic models provide the easiest way to represent the reaction and help the
designers in determining the rate of the reaction and thus design the reactors.
Basically the kinetic expressions can be classified as microkinetic approach and
the empirical method. The microkinetic method is based on the knowledge about
the elementary steps that are involved in the reaction and its energetics. This
method explores the detailed chemistry of the reaction. Using this method it is
possible to estimate the surface coverage, reaction order and activation enthalpy.
This method provides the accurate pathway and prediction of the reaction, but is
computationally intensive. On the other hand, the empirical models are based on
the experimental results and are typically expressed in the Arrhenius model and
provide an easy and computationally lighter way to predict the rate of reaction.
Most of the design works use the empirical models. The WGSR has been
explained through both the microkinetic approach and empirical approach.
5.1 Micro Kinetic Models
The WGSR mechanism over the metal oxide catalyst has been broadly classified
as
1. Regenerative Mechanism and
2. Associative Mechanism
In the regenerative mechanism also known as the redox mechanism, the oxidation
reduction cycle occurring on the catalyst surface is responsible for the reaction. In
the redox mechanism it is proposed that the catalyst surface is oxidized by H2O,
producing H2 as by product followed by reduction of surface to convert CO to
CO2 as represented in equations 6 and 7.
H2O + red H2 + ox
(6)
CO + ox CO2 +red
(7)
The redox mechanism is used to explain the high temperature water gas shift
reaction. The low temperature shift reaction has been explained by several authors
using both the regenerative mechanism and the associative mechanism.
The mechanism for the water gas shift reaction has been elucidated from
single copper crystal studies. Ovesen et al. (1992) proposed an eight step model
based on surface redox mechanism using single crystal studies on copper. Citing
his studies, he found the reaction structure sensitive with the reaction more on Cu
(1 1 0) than Cu (1 1 1). Wang et al. (2003) investigated the kinetic properties for
both the forward and reverse reactions and supported the surface redox
mechanism at low temperatures. In their energetic analysis they found the
dissociation of water as the rate controlling step. They too supported the
sensitivity of the reaction to Cu structure. Rhodes et al. (1995) has questioned the
redox mechanism by showing that the reduction reaction as possible and raised
doubt about the possibility of the oxidative step.
The associative mechanism is an adsorption - desorption model where the
adsorbed species interact to form an adsorbed intermediate which then
decomposes to form H2 and CO2 as explained in reaction step 8.
CO + H2 (intermediate) CO2 + H2
(8)
Even though many authors support this mechanism, there is still no convergence
of idea on the nature of the intermediate. The conflict basically in the associative
mechanism is based on the nature of the intermediate formed namely Formate
intermediate mechanism and Carboxyl intermediate mechanism.
Rhodes et al. (1995) explained the associative mechanism of Cu
Chromite as a Langmuir Hinshelwood process with the reaction steps 9 to 13.
CO(g) CO(ads)
(9)
H2O(g) H2O(ads)
(10)
CO(ads) +H2O(ads) [*] CO2(ads) + H2(ads)
(11)
CO2(ads) CO2(g)
(12)
H2(ads) H2(g)
(13)
They found the intermediate species to be formate. Grenoble and Estadt (1981)
proposed formic acid as the intermediate based on the fact that the principal
decomposition pathways for formic acid involved both the reactants and products
of the water gas shift reaction. Ovesen et al., (1996) further modified the 8 step
microkinetic model he proposed in 1992 based on redox mechanism, by adding 3
more steps to account for the formate mechanism and suggested that the formate
coverage was negligible at atmospheric conditions and was significant at higher
pressures. He found the water dissociation and carbon monoxide oxidation as the
rate limiting steps. Gideon Botes (2007) listed out three different mechanisms and
applied them to the data generated from SASOL (South African Coal, Oil and Gas
Corporation) and found the associative formate mechanism providing better fit for
the data. Waugh (1999) using the microkinetic approach has questioned the
formate mechanism and supported the redox mechanism. Sun et al. (2005) studied
the mechanism of precious metals for the water gas shift reaction and found the
Langmuir Hinshelwood model giving better predictions.
Salmi et al. (1989) carried out transient studies on the water gas shift
reaction and observed that H2 is liberated slowly which contradicted with the
associative mechanism and put forth a mechanism with both adsorptive and
regenerative reaction steps. Hakkarainen et al. (1994) found the reaction
mechanisms different for the ferrochrome catalyst and the Co Mo catalysts
using transient response studies. Keiski et al. (1996) carried out stationary and
transient studies on the high temperature water gas shift reaction and found that
the CO adsorption, CO2 desorption and H2 formation were rate determining steps
in the transient studies. Fishtik and Dutta (2002) found out that the formate and
associative mechanisms were dominant in the low temperature region whereas the
redox mechanism was dominant at higher temperatures.
Gokhale et al. (2008) has proposed the carboxyl mechanism as the
intermediate route for the water gas shift reaction based on studies with Cu(1 1 1).
They found the formate species non reactive and at high pressure contribute to
blocking of active sites which explained the loss in activity with increase in CO2
concentration. Mao et al. (2008) using the Density Functional Theory
investigation has reported that the formate mechanism had low probability
whereas the carboxyl and the redox mechanisms had higher probability on copper
catalyst. Grabow et al. (2008) carried out studies on low temperature water gas
shift reaction on Pt (1 1 1) and found the carboxyl mechanism better suited than
the formate mechanism. Tang et al. (2009) using density functional method and
slab models studied the mechanism of the water gas shift reaction on Cu (1 1 1).
They found the carboxyl and redox mechanisms feasible rather than the formate
and associative mechanisms. Thus an undisputed conclusive mechanism is not
available for the water gas shift reaction so far with many researchers taking sides
for these mechanisms based on their studies. So to carry out the microkinetic
simulation of the water gas shift reaction, the kinetics of the elementary steps can
be used. The 18 step microkinetic model to explain the water gas shift reaction
based on Cu (1 1 1) is given by Callaghan et al. (2003), Fishtik and Dutta (2002)
is listed out in Table 1.
Table 1 Microkinetic model for forward water gas shift reaction on Cu(1 1 1)
[Callaghan et al. (2003), Fishtik and Dutta (2002)]
Ko
Elementary Step
Adsorption/desorption(1/atm s)
Surface reaction (1/s)

CO + S CO.S
1.5 x 106
H2O + S H2O.S
1.0 x 106
H2O.S + S OH.S +H.S
1.0 x 1013
CO.S + O.S CO2.S + S
1.0 x 1013
CO.S + OH.S HCOO.S + S
1.0 x 1013
OH.S + S O.S + H.S
1.0 x 1013
CO.S + OH.S CO2.S + H.S
1.0 x 1013
HCOO.S + S CO2.S + H.S
1.0 x 1013
HCOO.S + O.S CO2.S + OH.S
1.0 x 1013
H2O.S + O.S 2OH.S
1.0 x 1013
H2O.S + H.S OH.S + H2.S
1.0 x 1013
OH.S + H.S O.S + H2.S
1.0 x 1013
HCOO.S + OH.S CO2.S + H2O.S
1.0 x 1013
HCOO.S + H.S CO2.S + H2.S
1.0 x 1013
CO2.S CO2 + S
4.0 x 1012
H.S + H.S H2.S + S
1.0 x 1013
H2.S H2 + S
6.0 x 1012
H.S + H.S H2 + 2S
6.0 x 1012
(S is the vacant site and X.S is the adsorbed X species)
Ea
(kcal/mol)
0
0
25.4
10.7
0
15.5
0
1.4
4
29
26.3
1.3
0.9
14.6
5.3
15.3
5.5
15.3
5.2 Macro Kinetic Models

There are a number of kinetic expressions published since the use of WGSR in the
ammonia process. Since it is difficult to list out the variations in the models, only
the commonly used models are listed out in Table 2. In general the associative
mechanism is represented by the Langmuir Hinshelwood (LH) model and the
Eley Rideal type model.
The equilibrium constant for the WGS reaction is a function of
temperature and various approaches are used to calculate the value at the required
temperature of operation. Table 3 lists out the numerical values of the equilibrium
constant at various temperatures in the regions of concern and a complete listing
of equilibrium constants for the water gas shift reaction over a temperature range
of 2000C to 11990C is provided by Twigg (1989).
10
Table 2 Kinetic Expressions for WGSR

Model
Kodama et al.
Kinetic Expression
High Temperature Shift [Ref. Twigg (1989)]
[CO 2][ H 2]
k [CO][ H 2O]
r=
(1 + KCO[CO] + KH 2O[ H 2O] + KCO 2[CO 2] + KH 2[ H 2])
Hulburt - Vasan
r=
k [ H 2O ]
1 + K [ H 2O ] / [ H 2 ]
Langmuir
Hinshelwood Model
[CO 2][ H 2]
kKCOKH 2O [CO][ H 2O ]
r=
2
(1 + KCO[CO] + KH 2O[ H 2O] + KCO 2[CO 2] + KH 2[ H 2])
Oxidation
Model
k 1k 2{[CO][ H 2O] [CO 2][ H 2] / K }

k 1[CO] + k 2[ H 2O] + k 1[CO 2] + k 2[ H 2]
r = kPaCOPbH2OPcCO2P d H2
Reduction
Bohlboro et al.
r=
Low Temperature Shift [Ref. Van Herwijnen and De Jong (1980)]

Campbell et al.
PCOPH 2O (1 )
r=k
(1 + KCOPCO + KH 2OPH 2O + KCO 2 PCO 2 + KH 2 PH 2) 2
Shchibrya et al.
kPH 2OPCO (1 )
r=
APH 2O + PCO 2
Moe
r = kPCOPH2O(1-)
0.5
Kulkova and Temkin
PH 2O
r = kPCO
(1 )
PH 2
Goodgidge and Quazi r = kPaCOPbH2OPcCO2P d H2
The equation used by Twigg (1989) to calculate the equilibrium constants was
Keq = exp (Z (Z (0.63508-0.29353Z) +4.1778) +0.31688)
(14)
Z = (1000/T)-1, Temperature (T) is in Kelvin
(15)
11
Table 3 Equilibrium constants for WGSR (Twigg, 1989)

T (0C)
Keq
200
250
300
350
400
450
500
550
210.82 83.956 38.833 20.303 11.723 7.3369 4.9035 3.4586
The equilibrium constant for the reaction derived from thermodynamics is given
in equation 16.
ln( Keq ) =
5693.5
49170
+ 1.077 ln(T ) + 5.44 104 T 1.125 107 T 2
13.148
T
T2
(16)
Moe (1962) has derived a simple to use empirical model to represent the
equilibrium constant which is sufficiently good for design computations and is
given by
Keq = exp (
4577.8
4.33)
T
(17)
The detailed kinetic expressions for the high temperature, low temperature
and noble metal catalysts were compiled and consolidated in Tables 4 and 5. In
table 4, the kinetic parameters corresponding to the power law type kinetic
expression are listed. These parameters are segregated based on the type of
catalysts and similar catalysts are grouped together. Rhodes et al. (2003) has
carried out a series of experiments on the high temperature catalysts and have
reported their arrhenius parameters which are listed in Table 4. The table also lists
the parameters put forth by Keiski et al. (1996) and San et al. (2009). The power
law type reaction rates for the low temperature catalysts for different conditions
are also listed in Table 4. Choi and Stenger (2003) and Koryabkina et al. (2003)
have provided a comprehensive analysis of the previously published parameters.
A good review of the noble metal catalysts was available in the work of Grenoble
and Estadt (1981), Wheeler et al. (2004) and Phatak et al. (2004). By substituting
the pre exponential factor, activation energy and the powers of the component
gases, the rate of reaction can be computed for various catalysts.
Apart from the power law type of kinetic expression where the orders of
the components are listed, complex kinetic expressions have also been developed
to represent the water gas shift reaction. Podolski and Kim (1974) made a detailed
study of the available models and concluded that their experimental data was
reproduced by both the Langmuir Hinshelwood type model and the power law
type model. The same is supported by Newsome (1980) where he has listed the
12
power law model by Bohlboro. This model was capable of predicting the rate in
the presence of H2S. Rase (1977) has provided a kinetic expression for both the
high temperature and low temperature shift reactions in his book which has been
used by Elnashaie and Elshishini (1993) in their modeling works on the shift
reaction. Singh and Saraf (1977, 1980) extended the kinetics of laboratory
catalysts for both low temperature and high temperature to industrial scale by
using factors for diffusion limitation, age of catalyst, pressure correction and
effect of exposure to H2S. San et al. (2009) carried out the high temperature
reaction for varying catalyst composition and derived two rate equations. Keiski
et al. (1996) too has provided an expression for the high temperature shift reaction.
Thomas and Barton (2009) have recently used the models of San et al. and Keiski
et al. for modeling the heterogeneous reactor by introducing correction factors for
porosity.
Earlier, the kinetic expressions for High temperature were applied to the
low temperature shift also. Newsome (1980) has reported the Temkin model for
the low temperature range. Van Herwijnen and De Jong (1980) have listed the
various kinetic models for the low temperature WGSR. Among them are the
models by Campbell and Moe based on industrial data, Shchibrya, Kulkova and
Temkin based on the redox mechanism and the power law model by Goodridge
and Quazi. Ovesen et al. (1992) introduced a factor to account for the pressure
correction in a power law expression. A pressure correction formulae is also
provided by Rase (1977) to extrapolate the experimental data normally carried out
at atmospheric pressure to industrial data. Amadeo and Laborde (1995) made an
analysis of five model equation, 2 representing redox mechanism and 3
representing Langmuir Hinshelwood model. They found the LH model which
included the adsorption of the four components and surface reaction controlling
the reaction provided best fit to their experimental results.Based on their
experimental results, they provided a modified LH model for the low temperature
shift reaction.
Zhao et al. (1999) using the reduced rate method analyzed the pressure
effects and found the LH model to be better than the other models. Choi and
Stenger (2003) tested the validity of two adsorptive, two regenerative and one
empirical model using Cu/ZnO/Al2O3 catalyst and found that all the models
giving good results with the best fit provided by the single step regenerative
model. They also developed their own empirical equation which is listed in Table
5. Wei et al. (2008) has included the steam to CO ratio in the kinetic expression.
The noble metal catalysts are still evolving and have not reached the
commercial stage. Hence a large number of newer catalyst combinations are being
reported in the literature. The nole metal that shows more promise is platinum and
the kinetic expressions derived for platinum has been reported by Ding and Chan
(2008). Another expression is by Sun et al. (2005) for noble metals.
13
Table 4 Power Law parameters for various WGSR catalysts and operating conditions
Catalyst
Fe3O4/Cr2O3
8 wt% Cr2O3
Fe3O4/Cr2O3
180 -250m
Fe3O4/Cr2O3
180 -250m
Fe3O4/Cr2O3
180 -250m
Fe3O4/Cr2O3
89%Fe2O3,
9% Cr2O3
80-90%Fe2O3,
8-13% Cr2O3,
1-2%CuO,
80-95%Fe2O3,
5-10% Cr2O3,
1-5%CuO,
CuO/Fe3O4/Cr2O3
180 -250m
CuO/Fe3O4/Cr2O3
180 -250m
CuO/Fe3O4/Cr2O3
180 -250m
Operating
Conditions
Ko
Arrhenius Parameters
Ea
Order of reaction
m
n
q
Reference
0.53
0.47
-0.18
Rhodes et al
( 2003)
Rhodes et al
( 2003)
Rhodes et al
( 2003)
Rhodes et al
( 2003)
Keiski et al.
(1996)
Keiski et al.
(1992)
San et al.
(2009)
1 atm, 3500C 4400C

1 bar, 3800C
4500C
6 bar, 3800C
4500C
27 bar, 3800C
4500C
3 5 bar
5730C - 6330C
575 to 675 K
High Temperature Catalyst

lnKo=11.5
112
(kJ/mol)
lnKo=10.10.2
1181
(kJ/mol)
lnKo=12.00.2
1241
(kJ/mol)
lnKo=7.40.1
1111
(kJ/mol)
1.1
2.16 x 1011 (s-1) 95
(lnKo=26.1)
(kJ/mol)
ln k0 = 14.78
E/R = 9598
0.74
1 atm, 4500C
6mm x 6mm
102.845
(mol/ gcat s)
111
(kJ/mol)
-0.36
-0.09
1 atm, 4500C
6mm x 6mm
100.659
(mol/ gcat s)
88
(kJ/mol)
0.9
0.31
-0.156
-0.05
San et al.
(2009)
751
(kJ/mol)
852
(kJ/mol)
851
(kJ/mol)
Rhodes et al
( 2003)
Keiski et al.
(1992)
Keiski et al.
(1992)
1 bar, 3800C lnKo=2.00.1

4500C
6 bar, 3800C lnKo=5.50.1
4500C
27 bar, 3800C lnKo=4.00.1
4500C
14
Power gas pilot

plant data
Girdler pilot
plant data
ICI pilot plant data
1/4 x 3/8 , 9.4 x 107 (1/s)

2.20 g/cm3
1/4 x 1/4
1.47 x 108 (1/s)
1.25 g/cm3
11.3 x 8.5 4.5 x 109 (1/s)
mm,
1.36 g/cm3
Rase (1977)
Rase (1977)
Rase (1977)
Low Temperature Catalysts

1
3.99 x 106 (s-1) 52.8
(lnKo=15.2)
(kJ/mol)
1 atm, 2000C
1 atm, 2500C
k = 5.37 x 10-7 (mol/m2s)/atml+m

k = 4.40 x 10-5 (mol/m2s)/atml+m
0.45
1.07
0.07
0.55
41.8
(kJ/mol)
47.4
(kJ/mol)
Choi
and
Stenger
(2003)
Salmi and
Hakkarainen
(1989)
Choi
and
Stenger
(2003)
Choi
and
Stenger
(2003)
71
(kJ/mol)
Henrik et al.
(2006)
67
(kJ/mol)
79
(kJ/mol)
0.2
0.6
0.8
0.8
-0.9
-0.9
Koryabkina
et al. (2003)
Koryabkina
et al. (2003)
ICI CuO-ZnO- Al2O3

ICI 52-1 (Copper
based catalyst)
density= 5.83g/cm3
CuO-ZnO-Al2O3
200 -250 m 2.96 x 105 (s-1)

size, 120 (lnKo=12.6)
2500C,
1:2
CO-H2O
42%
CuO-ZnO- 396 to 448K
4.9 x 106 (s-1)
Al2O3
(G-66A) CO/H2O =1/3
Sud Chemie
Cu-ZnO- Al2O3
1 atm, 2000C
Cu-ZnO- Al2O3
(EX-2248)Sud
Chemie
40%CuO-ZnO
Al2O3(United
Catalysts)
1 atm, 1900C
21.4
(kCal/g mol)
23.8
(kCal/g mol)
27.0
(kCal/g mol)
Cu-ZnO- Al2O3
Cu/ Al2O3
1 atm,
1800C-2000C
-
10%Cu- Al2O3
1 atm, 1300C
8%CuO-Al2O3
1 atm, 2000C
CuO/MnO2
8%CuO-CeO2
1 atm, 2400C
8%CuO15%CeO2- Al2O3
Cu(111)
1 atm, 2000C
1 atm, 3400C
Cu(110)
1 atm, 3400C
Ru
Ru/ceria
Ni
Ni/Ceria
15
86
(kJ/mol)
69.3
(kJ/mol)
1.4
-0.7
-0.9
1.9
55
(kJ/mol)
62
(kJ/mol)
55
(kJ/mol)
0.3
0.38
0.9
0.8
-0.7
-0.8
0.9
0.4
-0.6
-0.6
0.7
0.6
-0.6
-0.6
0.5-1
(2003)
56
(kJ/mol)
32
(kJ/mol)
71
(kJ/mol)
42
(kJ/mol)
Noble Metal Catalysts

- 1.6 x 107 (s-1)
80
(kJ/mol)
5.0 x 107 (s-1)
80
0.008 to 0.05 s
(kJ/mol)
contact time
8.0 x 107 (s-1)
85
(kJ/mol)
Coated
on 1.7 x 108 (s-1)
85
3000C
10000C
Koryabkina
et al. (2003)
Choi and
Stenger
(2003)
Koryabkina
et al. (2003)
Koryabkina
et al. (2003)
Choi and
Stenger
Koryabkina
et al. (2003)
Koryabkina
et al. (2003)
Koryabkina
et al. (2003)
Koryabkina
et al. (2003)
Wheeler
al. (2004)
Wheeler
al. (2004)
Wheeler
al. (2004)
Wheeler
et
et
et
et
16
Rh
alumina
support
3.0 x 109 (s-1)
Rh/Ceria
5wt% loading
1.5 x 1010 (s-1)
Rh/ Al2O3
3300C
Rh/ SiO2
3500C
Pd
1.66%Pt/ Al2O3
3000C
10000C
0.008 to 0.05 s
contact time
Coated
on
alumina
support
5wt% loading
1atm, 2250C 2850C
1atm,2850C
3450C
1atm, 2850C
1.66%Pt/ Al2O3
1atm, 3000C
2%Pt/ Al2O3
1atm, 2700C
0.9%Pt/ Al2O3
1atm, 1000C
Pd/Ceria
Pt
Pt/Ceria
1%Pt/ Al2O3
1%Pt/ Al2O3
5.10 x 106
(molecules/s/ site)
3.23 x 105
(molecules/s/ site)
- 4.0 x 106 (s-1)
4.0 x 107 (s-1)
1.0 x 106 (s-1)
2.5 x 107 (s-1)
-
(kJ/mol)
130
(kJ/mol)
130
(kJ/mol)
23.01.3
-0.10
0.44
-0.24
0.53
0.1
1.1
-0.07
-0.44
0.06
-0.09
-0.44
0.11
0.82
-0.06
-0.49
0.1
0.77
-0.08
-0.46
-0.21
0.75
0.02
0.55
-0.22
(kcal/mole)
22.82.5
(kcal/mole)
100
(kJ/mol)
100
(kJ/mol)
80
(kJ/mol)
80
(kJ/mol)
68
(kJ/mol)
84
(kJ/mol)
81
(kJ/mol)
81
(kJ/mol)
82
(kJ/mol)
al. (2004)
Wheeler
al. (2004)
Wheeler
al. (2004)
Grenoble
al. (1981)
Grenoble
al. (1981)
Wheeler
al. (2004)
Wheeler
al. (2004)
Wheeler
al. (2004)
Wheeler
al. (2004)
Phatak et
(2007)
Phatak et
(2007)
Phatak et
(2007)
Phatak et
(2007)
Phatak et
(2007)
Phatak et
(2007)
et
et
et
et
et
et
et
et
al.
al.
al.
al.
al.
al.
0.4%Pt/ Al2O3
1atm, 5440C
Pt/ Al2O3
2700C
1%Pt/ CeO2
1atm, 2000C
1.9 x 106
(molecules/s/ site)
-
1%Pt/ CeO2
1atm, 2400C
1% Pt/CeO2
Pt/SiO2
3400C
Pt/C
3400C
1% Pt/TiO2
1.18 x 105
(molecules/s/ site)
3.84 x 106
(molecules/s/ site)
-
1.4%Pt8.3%
CeO2/Al2O3
2%Pt1%
Re/CeO2-ZrO2
CuO.2CeO.8O2-y
(Cu ceria)
1atm, 2600C
1atm,
2100C-2600C
473 K 623K 1.8 x 103 (s-1)
CO/H2O =1/3
CuO.1CeO.9O2-y
(Cu ceria)
Ce(La)Ox
573 K 623K 4.0 x 103 (s-1)

CO/H2O =1/3
375 475 0C
-
5
at.%
Cu- 175 300 0C
Ce(10%La)Ox
CO/H2O=1.5
5
at.%
Ni- 275 300 0C
Ce(10%La)Ox
CO/H2O=1.5
17
39
(kJ/mol)
19.61.3
0.45
0.37
-0.73
-0.21
0.75
-0.03
0.44
-0.09
-0.38
0.14
0.66
-0.54
-0.08
-0.08
0.69
0.13
0.35
0.3
0.85
-0.67
0.13
0.49
-0.12
-0.45
-0.05
-0.32
0.85
-0.05
(kcal/mole)
75
(kJ/mol)
46
(kJ/mol)
91
(kJ/mol)
19.10.8
(kcal/mole)
25.51.4
(kcal/mole)
59
(kJ/mol)
86
(kJ/mol)
71
(kJ/mol)
61
(kJ/mol)
78
(kJ/mol)
58.5
(kJ/mol)
30.4
(kJ/mol)
38.2
(kJ/mol)
Phatak et al.
(2007)
Grenoble et
al. (1981)
Phatak et al.
(2007)
Phatak et al.
(2007)
Thinon et al.
(2009)
Grenoble et
al. (1981)
Grenoble et
al. (1981)
Thinon et al.
(2009)
Phatak et al.
(2007)
Phatak et al.
(2007)
Henrik et al.
(2006)
Henrik et
(2006)
Li et
(2000)
Li et
(2000)
Li et
(2000)
al.
al.
al.
al.
18
For Table 4, the rate is given by r = kPlCOPmH2OPnCO2Pq H2 (1-), rate constant k =Ko exp (-Ea/RT), Ko is pre
exponential or frequency factor, Ea is activation energy and is the approach to equilibrium and is given by
= PCO2PH2/KeqPCOPH2O
Table 5 Macro kinetic Rate expressions for WGSR
Catalyst
information
Operating
Conditions
Rate Expression
High Temperature Catalysts
Girdler(G3-b)
particle size 0.62 Reference: Elnashaie and Elshishini(1993)

cm
equivalent
XC XD
XAXB
diameter
K
r = k
, k = exp(15.95 4900/T)
(1/4 x 1/4)
379 b
= 0.816+0.184P
for P11.8
= 1.53 + 0.123 P for 11.8 < P 20
= 4.0
for P > 20
r is rate of reaction (lb mol CO reacted/lb catalyst. hr ), Xi is the dimensionless
concentration for component i (Ci/Cref), T is temperature (K), P is Pressure (atm)
and K is equilibrium constant, b is bulk density of catalyst (lb/ cu. ft), is
activity factor
72% Fe2O3
8% Cr2O3
Density
g/cm3
19
4.561 Reference: Singh and Saraf (1977)

r = Eff x 2.32 x 1013 (XCO - XCO*) exp(-27760/RT) x Ra x Agf x Pf x fs
Keq = exp[((9998.22/T) 10.213 + 2.7465x10-3T 0.453x10-6T2 0.201 ln T)/R]
Ra = exp(-8.91 + (5.553 x 104/T)

Log Agf = (14.66 x 10-4 2 x 10-6)
Pf = P(0.5 P/250)
fs = -0.276 log([H2S] + 2.78) + 1.127
Xco* = XH2XCO2 / XH2Okeq
Sud Chemie
SHT-4
Density =
7633.65 kg/m3
r is rate of reaction (cm3/gcat h), XCO is mole fraction of CO, XCO* is mole
fraction of CO in equilibrium condition P is pressure (atm), Keq is equilibrium
constant, R is gas constant(cal/gmol K), T is temperature (K), Eff is effectiveness
factor, Ra is relative activity, Agf is aging factor, Pf is pressure factor, fs is rate
reduction factor due to H2S concentration, [H2S] is H2S concentration in ppm and
is age of catalyst in days
Reference: Wei et al. (2008)
r = k (PCOPH2O PCO2PH2 /keq)
k = 1.78 x 1022 (1+ 0.0097 1.1364 2) T-8 exp(-70/RT)
r is rate of reaction, Pi is partial pressure of species ( kPa), Keq is equilibrium
constant, R is gas constant, T is temperature (K) and is steam to CO ratio
20
ferrochrome
catalysts
Bohlboro
Power Law
Model
0.8 to 1.2 mm Reference: Newsome (1980), Elnashaie and Elshishini(1993)

particle size
3300C-5000C
r = k [CO]0.9[H2O]0.25[CO2]-0.6[H2]0(1-)
= [CO2][H2] / Keq[CO][H2O]
Ea = 114.6 kJ/mol
With H2S
Reference: Newsome (1980), Elnashaie and Elshishini(1993)
addition
3800C-5000C
Average Equation r = k [CO]0.8 [H2O]0.45[CO2]-0.1[H2]-0.1(1-)
For specific H2S concentrations l, m, n and q are powers of CO, H2O, CO2 and
H2 respectively
Ea at 2000 ppm H2S is 94.6 kJ/mol
ppm H2S l
m
n
q
0
0.25
-0.6
25
0.75 0.8
0.50
-0.10
-0.15
0.40
-0.10
-0.10
2000
For small
Catalysts
(crushed/experi
mental)
For Large
Catalysts
(Commercial)
0.93
0.85
0.24
r = k [CO] [H2O]
Ea=105.9 kJ/mol
-0.31
[CO2]
[H2] (1-):
[ ] represents the species concentration

r = k [CO]0.87 [H2O]0.26[CO2]-0.18[H2]0(1-)
Ea=59.8 kJ/mol
80-90wt%
Fe2O3,
8-13 % Cr2O3,
1-2% CuO
375 0C to 475
0
C
Temkin Model
21
Reference: Boon et al. (2009)

(112 2) 103 1
1 0.84 0.04 1.17 0.12 0.36 0.05 0.09 0.05 0.3 0.03
(1 )
r = (3.2 1.3) 106 exp
PH 2O PCO 2
PH 2
PH 2 S
PCO
R
T 678
r is rate of reaction (mol/kg s), Pi is partial pressure of species (kPa) and T is temperature (K)
= PCO2PH2 / KeqPCOPH2O
Low Temperature Catalysts
Reference: Newsome (1980)
kPH 2OPCO (1 )
4577.8
, Equilibrium Constant, Keq = exp

4.33
APH 2O + PCO 2
T
26800
Rate Constant, k = 6 1011 exp
1/atm s
1.987 T
21500
Constant, A = 2.5 109 exp
1.987 T
r is rate of reaction (1/s), Pi is partial pressure of species (Pa), T is
temperature(K)
r=
22
Langmuir Hinshelwood Model
Reference: Criscuoli et al. (2000)

PCO 2 PH 2
kKCOKH 2O PCOPH 2O
cat
Keq
r=
2
(1 + KCOPCO + KH 2OPH 2O + KCO 2 PCO 2 ) 60
4577.8
Equilibrium Constant Keq = exp

4.33
T
40.32
29364
Rate Constant k = exp
+
mol/g cat. Min
1.987 T 1.987
6.74
6216
12.77
3064
KCO = exp
+
, KH 2O = exp
1.987 T 1.987
1.987 T 1.987
18.45
12542
KCO 2 = exp
1.987 T 1.987
r is rate of reaction (mol/cm3s), Pi is partial pressure of species (Pa), cat is
density of catalyst(g cat/cm3), T is temperature(K)
Empirical Model based on

Industrial Data Moe Kinetic
Model
Reference: Seo et al. (2006)

r = k PCO PH2O [1 (PCO2 PH2/Keq PCO PH2O)],
4577.8
Equilibrium Constant, Keq = exp

4.33
T
1855.5
Rate constant k = 1.85 105 exp 12.88

mol/g.min
T
r is rate of reaction (mol/g min), Pi is partial pressure of species (bar)
Girdler(G3-b)
Catalyst
composition,
(%p/p) CuO
(32.7), ZnO
(47) and Al2O3
(11)
particle size
0.62 cm
equivalent
diameter
(1/4 x 1/4)
1 atm,
453 K - 503 K
23
Reference: Elnashaie and Elshishini(1993)

XC X D
K
r = k
379 b
k = exp (12.88 2002.6/T)
= 0.86 + 0.14 P
for P 24.8
= 4.33
for P > 24.8
r is rate of reaction (lb mol CO reacted/lb catalyst. hr ), Xi is the dimensionless
concentration for component i (Ci/Cref), T is temperature (K), P is Pressure (atm)
and K is equilibrium constant, b is bulk density of catalyst (lb/ cu. ft), is
activity factor
Reference: Amadeo and Laborde (1995)
XAXB
454.3
0.92 e
PCOPH 2O(1 )
T
r=
2
101.5
158.3
2737.9
1596.1
1
2.2
0.4
e
P
e
P
P
P
+
+
CO
H
CO
H
2 O + 0.0047e
2 + 0.05e
2
T
T
T
T
r is rate of reaction (mol/g min), T is temperature (K), Pi is partial pressure of the

components (Pa) and = PCO2PH2 / KeqPCOPH2O
24
1 atm,
Sud Chemie
120 0C - 2500C,
(EX-2248)
Cu/ZnO/ Al2O3 particle size 200
250 m,
CO:H2 1:2
Reference: Choi and Stenger(2003)

PCO 2 PH 2
47400
r = 2.96 105 exp
PCOPH 2O
RT
Keq
r is the rate of reaction (mol/gcat h), Pi is partial pressure of component (atm), T

is temperature (K), R is universal gas constant (J/mol K)
Girdler/Sud
Chemie (G66
b). unreduced
wt% - CuO
(32.2),
ZnO(61.8) and
Fe2O3(1.6)
0.35 0.42 mm Reference: Van Herwignen and De Jong (1980)

particle size,
Surface area
PCOPH 2O
16000
3
22.3(m2/g), pore r = 25.9 10 exp RT (1 + 127 PCOPH 2O + 26 PCO )
diameter 12.5nm
r is rate of reaction (mol/g s), Pi is partial pressure (atm), R is gas constant and T
is temperature (K)
CuO (33%)
ZnO (66%)
5.09g/cm3
Reference: Singh and Saraf (1980)

r = Eff x 2.955 x 1013 exp(-20960/RT) x Agf x Pt (Xco-Xco*)
Eff is effectiveness factor
Agf is aging factor, log Agf = (4.66 x 10-4 1.6 x 10-6 T)
Pt is effect of Pressure, Pt = P(0.5 P/250)
Xco* = XH2XCO2 / XH2Okeq
r is rate of reaction (cm3/gcat h), XCO is mole fraction of CO, XCO* is mole
fraction of CO in equilibrium condition, is age of catalyst in days, P is pressure
(atm) and T is temperature(K)
25
Sud Chemie
MDC 7
Cu-Zn based
catalyst
Reference: Wei et al. (2008)
General Empirical equation for

Large Catalysts 4.5 x 4.5 mm,
Bohlboro
Reference: Newsome (1980)
Cu/ZnO/Al2O3
40%Cu,
22%Zn, 5%Al
r = k (PCOPH2O keq-1PCO2PH2)
k = 1.74 x 1017 (1- 0.1540 + 0.008 2) T-8.5exp(-35/RT)
r is rate of reaction, Pi is partial pressure (Pa), Keq is equilibrium constant, R is
gas constant, T is temperature (K) and is steam to CO ratio
Copper surface
area =10m2/g
r = k [CO]0.8 [H2O]0.5[CO2]-0.15[H2]0(1-)
Reference: Ovesen et al. (1992)
r = A exp(-Ea/RT)PlCOPmH2OPnCO2PqH2Ptot(1-)
is fudge factor correcting total pressure dependence, = PCO2PH2 / KeqPCOPH2O
Catalyst
P(bar)
Ea(kJ/mol)
l
m
n
q
Cu/ZnO/Al2O3
5
86.5
1
1.4
-0.7
-0.9
Cu/ZnO/Al2O3
20
78.2
1
1.5
-0.7
-0.7
Cu/Al2O3
20
59.3
1.9
-1.4
-0.9
26
Platinum
Precious
Metals
Particle Size =
3.3 mm
Surface area =
80 m2/g
Noble Metal Catalysts

Reference: Ding and Chan (2008)
PCO 2 PH 2
k PCOPH 2O
Keq
r=
2
(1 + KCOPCO + KH 2OPH 2O + KCO 2 PCO 2 + KH 2 PH 2 )
Ko (mol/kgcat s) = 748.824/bar2
Ea (J/mol) = 53,821
KCO2=0.036 (1/bar), KCO=2.222(1/bar)
KH2=2.197 x 10-5(1/bar), KH2O=2.006 x 10-5(1/bar)
Reference: Sun et al. (2005)
PCOPH 2O (1 )
Ea
r = A exp
H 1
H 2
RT
1 + A1 exp RT PCO 1 + A2 exp RT PH 2
7
3
2
-3
A=9 x 10 mol/m atm s, Ea = 44 kJ/mol, A1= 1 x 10 1/s, H1=-46 kJ/mol,
A2=43 1/s, H2=11 kJ/mol
27
Almost similar kinetic expressions have been proposed for both the high
temperature and low temperature catalysts. The kinetic models that have been
endorsed by many authors from their experiments with various catalysts have
been the Langmuir Hinshelwood model and the power law model. The recent
literature publications use the kinetic expressions of Keiski et al. (1996), San et al.
(2009) for high temperature and Choi and Stenger (2003) for low temperature
water gas shift reaction.
The difference in opinion on the nature of kinetics for the water gas shift
reaction has been attributed to the presence of impurities, mass transfer limitations,
experiments carried out at atmospheric pressure and the use of integral reactor for
kinetic studies rather than the differential reactor [Levent, 2001]. Since all the
experiments were reported at atmospheric pressures, the kinetic models can be
corrected for pressure using the modification recommended by Rase (1977) which
also takes care of the diffusional effects of the catalysts or the pressure correction
factor of Singh and Saraf (1977).
6. CONCLUSION
The use of water gas shift reaction is growing due to the shift towards the
Hydrogen economy. This necessitated the need for designers to have kinetic
expressions for the reaction to help them in designing the water gas shift reactors.
A detailed view of the various catalysts used in the high temperature shift, low
temperature shift and the noble metal catalysts was made. The microkinetic
approach towards the WGSR was explained. A comprehensive listing of the
various kinetic models for the high temperature shift, low temperature shift and
noble metal shift reaction was provided in Table 4 and 5 along with the relevant
numerical values. This consolidated table could provide a ready reference for
computing the rate of the water gas shift reaction. Even though different authors
have obtained different ranges of rates by these models for their experimental data,
most of the works conform to the power law type of kinetic expression and hence
can be conveniently used for design calculations.
28
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What is the water gas shift reaction?

What is the water gas shift reaction?

What are the catalysts used for the water gas shift reaction?

What are the catalysts used for the water gas shift reaction?

I NTERNATIONAL J OURNAL OF C HEMICAL

A Review of the Water Gas Shift Reaction

Murthy Shekhar Shantha

Vellore Institute of Technology University, [email protected]

Vellore Institute of Technology University, [email protected]

A Review of the Water Gas Shift Reaction Kinetics

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

H0298 = -41.09 kJ/mol

The equilibrium constant of the reaction decreases with increasing temperature.

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

In high temperature shift reaction, the ratio of steam to CO is an important

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

3. LOW TEMPERATURE SHIFT CATALYSTS

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

CO(ads) +H2O(ads) [*] CO2(ads) + H2(ads)

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

Surface reaction (1/s)

5.2 Macro Kinetic Models

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

Table 2 Kinetic Expressions for WGSR

k 1k 2{[CO][ H 2O] [CO 2][ H 2] / K }

Low Temperature Shift [Ref. Van Herwijnen and De Jong (1980)]

Z = (1000/T)-1, Temperature (T) is in Kelvin

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

Table 3 Equilibrium constants for WGSR (Twigg, 1989)

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Review R4

Smith R J et al.: A Review of the Water Gas Shift Reaction Kinetics

1 atm, 3500C 4400C

High Temperature Catalyst

1 bar, 3800C lnKo=2.00.1

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Power gas pilot

1/4 x 3/8 , 9.4 x 107 (1/s)

Low Temperature Catalysts

k = 5.37 x 10-7 (mol/m2s)/atml+m

ICI CuO-ZnO- Al2O3

200 -250 m 2.96 x 105 (s-1)

Vol. 8 [2010], Review R4