Catalyst development for water-gas shift

J. R. Ladebeck and J. P. Wagner

Volume 3, Part 2, pp 190–201

in

Handbook of Fuel Cells – Fundamentals, Technology and Applications

(ISBN: 0-471-49926-9)

Edited by

Wolf Vielstich
Arnold Lamm
Hubert A. Gasteiger

 John Wiley & Sons, Ltd, Chichester, 2003

Chapter 16
Catalyst development for water-gas shift
J. R. Ladebeck and J. P. Wagner
Süd-Chemie Inc., Louisville, KY, USA

1 HISTORIC PERSPECTIVE Since the early 1940s the WGS reaction has represented
an important step in the industrial production of hydrogen:
◦
1.1 Introduction CO + H2 O ←−→ CO2 + H2 ,
H298 = −41.1 kJ mol−1
(1)
The essential role of the industrial WGS reaction is to
For many years the development of fuel efficient low or increase the production of hydrogen for refinery hydro-
zero emission engines has been a major objective of auto- processes, bulk storage and redistribution. This includes the
mobile, refinery and catalyst industries. Although important need for gases of appropriate H2 /CO ratios in the produc-
improvements in fuel economy and emission control of tion of organic bulk chemicals such as ammonia, methanol,
internal combustion engines has been achieved, further and alternative hydrocarbon fuels through Fischer–Tropsch
steps are necessary in order to meet the coming strin- synthesis. These gas mixtures applied in industry are usu-
gent legislation. Of all the fuel cell concepts discussed, the ally referred to as synthesis gas, or syngas, and are produced
development of the polymer electrolyte membrane (PEM) in large scale facilities by high temperature reaction of
fuel cell technology for transport applications appears to carbonaceous materials in presence of water or oxygen
be most promising however they are deactivated by low where supported nickel catalysts are in use (see equa-
levels of carbon monoxide.[1, 2] Obviously the technical tions (2)–(4)):
challenges with hydrogen production capacity, storage, and
distribution must be addressed. To achieve an accept- CH4 + H2 O −−−→ CO + 3H2 (2)
able and economic lifetime of the fuel cell it is essential
to reduce the amount of carbon monoxide entering the Cn Hm + nH2 O −−−→ nCO + (n + m/2)H2 (3)
cell. Latest technology anodes are typically tolerant up CH4 + 12 O2 ←−→ CO + 2H2 (4)
to 100 ppm CO in the feed gas but the typical refor-
mate coming from a fuel processor contains hydrogen, or by gasification of coal (equation (5)):[6]
carbon dioxide and 1–3 vol% of carbon monoxide.[3–5] In
order to minimize the reformate CO concentration for PEM C + H2 O −−−→ CO + H2 (5)
fuel cell applications, methanation of the excess CO, the
selective oxidation in the presence of oxygen or water In the subsequent WGS reaction the composition of
has been considered. The topic of the following sum- the so-called water gas can be adjusted to the desired
mary is the oxidation reaction of carbon monoxide with ratio of hydrogen and carbon monoxide. More detailed
steam herein referred to as the water gas shift (WGS) reviews on synthesis gas generation and application can
reaction. be found elsewhere.[7–10] Although the WGS reaction is

Handbook of Fuel Cells – Fundamentals, Technology and Applications, Edited by Wolf Vielstich, Hubert A. Gasteiger, Arnold Lamm.
Volume 3: Fuel Cell Technology and Applications.  2003 John Wiley & Sons, Ltd. ISBN: 0-471-49926-9.
 Catalyst development for water-gas shift 191

not the primary reaction, it must be considered in methanol systems motivated further investigations. In the work of
synthesis, hydrocarbon conversion by reforming, Fischer– Bohlbro, the CO2 partial pressure in the reacting gas was
Tropsch synthesis, automotive exhaust catalysis, and selec- found to exert a retarding effect on the forward reaction
tive CO oxidation for fuel cells. rate constant of the WGS reaction.[11] Experiments demon-
strated that the effect of CO2 was negligible on the forward
reaction rate constant over copper based catalysts devel-
1.2 Industrial applications oped by Larson and patented as early as 1931.[12] The
unsupported metallic copper catalysts or copper supported
Two stage CO conversion systems employing WGS using
on Al2 O3 , SiO2 , MgO, pumice or Cr2 O3 of the early days
Fe/Cr oxide catalysts and methanation using nickel based
were characterized by relatively short life (6–9 months) and
catalysts with CO2 removal between the stages was the
common and economical design for ammonia synthesis gas low space velocity operation (400–1000 h−1 ). Important
up to the late 1950s. Most of these plants employed the progress was made by the addition of ZnO or ZnO/Al2 O3 ;
Fe/Cr oxide high temperature shift (HTS) catalyst as well in not only did the lifetime of these catalysts increase consid-
the second stage converter at temperatures as low as 320 ◦ C erably, but also due to a strong support effect an increase
but more typically at 330◦ . The conventional HTS catalysts of the turnover numbers in the order of magnitudes were
worked extremely well in these applications. The success of observed.[13] For example, the turnover number of cop-
these catalysts at low temperature led to its use as a second, per on alumina is approximately three orders of magnitude
lower temperature bed. This became the basis for the next higher than in the case of iron on alumina.
evolution in ammonia plant design. The two stage converter Today the industrial realization of WGS takes place in
systems easily and consistently reduced the CO level to a series of adiabatic converters where the effluent from
3000–4000 ppm compared to the single stage converters the reformer system is converted in two steps with the
that could not reduce the CO to much less than 1%. second at a significantly lower temperature in order to
The relatively poor performance of the Fe/Cr HTS cata- shift the equilibrium towards the favored hydrogen product
lyst applied in the lower temperature second bed of these (Figure 1).

Steam Air

HC feed

HTS

Purification Pre reformer Primary reformer Secondary reformer

CO2
Reforming

Ammonia

HT CO shift LT CO shift CO2 removal Methanation NH3 synthesis loop

Figure 1. Syngas generation for ammonia synthesis: reforming, HTS, LTS.

192 Part 2: Hydrogen storage and hydrogen generation

In the first step, promoted Fe/Cr oxide catalysts are resistance and good selectivity especially in the case when
applied at a reactor inlet temperature of 300–360 ◦ C and a low steam to CO ratios are applied where the formation
total pressure between 10 and 60 bar. Due to the exothermic of hydrocarbons is favored.[7] The commercially available
nature of the reaction and depending on the origin of catalysts are applied in the form of pellets, containing
the synthesis gas, which determines the inlet concentration 8–12% Cr2 O3 and a small amount of copper as an activity
of CO, great care has to be taken to avoid overheating and selectivity enhancer. Cu/Zn/Al commercial catalysts are
the catalyst, e.g., by intercooling the catalyst beds or by applied in the form of tablets, extrusions, or spheres and
the addition of quench water. Under normal operating are usually produced by co-precipitation of metal nitrates.
conditions the temperature rises progressively through the Summers et al. describes as well the replacement of Al2 O3
converter bed and can increase to 500 ◦ C especially if by rare earth metal oxides like La2 O3 and Ce2 O3 ; sufficient
the CO inlet concentration is about 45 vol%. At exit gas crush strength was obtained by the addition of cement.[16]
temperatures of 400–500 ◦ C the CO content can be reduced It is important to note that the commercial Fe/Cr/Cu and
in an industrial HTS converter to 4 vol% or lower. Similar Cu/Zn/Al catalysts must be activated before operation using
to HTS the low temperature shift (LTS) is performed in a specific process to control reduction of the oxides to the
industrial scale using adiabatic converters. Here the inlet catalytically active state. Improper activation detrimentally
temperatures range between 190 and 230 ◦ C at a total effects the activity and life of the catalysts. Care must
pressure up to 60 bar in some special applications, but be taken to avoid steam condensation and to minimize
usually not exceeding 40 bar. Inlet CO concentrations vary the re-oxidization of the catalysts upon shutdown. One of
between 1 and 5% depending on the performance of the the greatest impacts on increasing the lives of industrial
HTS installed upstream. Exit temperatures can reach 280 ◦ C WGS catalysts was the training of plant operators on the
and the CO content is typically reduced to <0.5%. Due careful startup, inert purging to prevent condensation and
to its industrial importance, the WGS catalysts were the sequestration during shutdown of industrial reactors. These
topic of numerous studies. Newsome in 1980 and later other process improvements increased the lives of WGS catalysts
authors published important and comprehensive reviews on dramatically from months to years.
the industrial application of the WGS reaction.[6, 7, 14, 15] As seen in Table 1, the typical plant size for Syngas
Industrial HTS converters exclusively apply Fe-based generation cover a wide range of scale depending on the
catalysts because of their excellent thermal stability, poison application.[10] Present commercialized stationary fuel cell

Fuel cell processor Stack

(autothermal reformer) off-gas

Off-gas
combustion
Fuel cell
Hydrocarbon Steam Air Air stack
feed

Product
hydrogen

Desulfurization HTS Selective

oxidation

Figure 2. Fuel processor: reforming, WGS.

 Catalyst development for water-gas shift 193

Table 1. Syngas application typical plant sizes.[10] the high CO concentrations expected from the reforming
reaction. The WGS reaction is very desirable for fuel pro-
Plant capacity Reformer cessing as it provides two benefits. In addition to effectively
catalyst reducing the CO concentration, a mole of H2 is produced
volume (m3 )
for every mole of CO that is converted in the WGS reac-
Gas-to-liquids/FT 20 000 Bbl day−1 240
tion (equation 1). The WGS reaction increases the fuel cell
Methanol 2700 t day−1 85 efficiency by generating H2 from water. A detailed under-
Refinery hydrogen 50 t day−1 21 mmscfd 12 standing of the thermodynamics and kinetic limitations of
Ammonia 1000 t day−1 30 the catalyst must be mastered to fully utilize the benefits
Reducing gas (DRI) 1000 t day−1 109 of the WGS reaction. Temperature, water concentration and
Carbon monoxide 40 t day−1 2
methods of reforming must be considered when designing
Stationary fuel cells 250 kW 0.1
Mobile fuel cells 25 kW 0.01 a WGS reactor system and catalysts.

power units on the order of 100–500 kW use hydrogen 2.1 Thermodynamic aspects
generated from natural gas or liquid fuel. International Fuel
Cell (IFC) for instance, is manufacturing phosphoric acid
Due to the exothermic nature of the WGS reaction, higher
fuel cell based systems where the hydrogen is generated
CO conversions are favored at lower temperatures. The
by internal catalytic steam reforming and WGS reactions.
WGS equilibrium constant is nearly 80 times greater when
Although the design of fuel processors for stationary fuel
the temperature is decreased from 600 to 200 ◦ C. The WGS
cells are less constrained by the need for compactness and
equilibrium constants at various temperatures are summa-
fast response as it is for automotive applications, compared
rized in Table 2.[18] The water content has a strong influence
to industrial systems a reduction in reformer size and
in converting CO. The water entering the WGS reactor
other catalytic reactors of over three orders of magnitude
can be varied by controlling the amount added at the
is necessary. The transition to the new age of hydrogen
reformer or by injecting water before or between stages of
production will only be successful with the development of
the WGS reaction. In contrast, the CO, CO2 and H2 con-
novel reactor technology and new catalyst inventions.
centrations are more dependent on the reformer operation,
In 1994 Jamal and Wyszynsky reviewed the onboard gen-
which in turn determines the thermodynamic limitations.
eration of hydrogen as an alternative fuel for combustion
The effect of temperature and water concentration on the
engines.[17] Applying hydrogen as a combustion fuel is still
equilibrium CO concentration is shown in Figures 3 and
an attractive alternative; only slight modifications of spark
4 for a typical HTS and LTS gases. The gas composi-
ignition engines are necessary and car manufacturers have
tion used for these calculations are shown in Table 3 and
already demonstrated performing engines. The application
represent a syngas generated from autothermal reforming
of hydrogen for onboard fuel cells requires much purer
and excludes any residual hydrocarbon. By increasing the
hydrogen that can only be directly delivered in the desired
molar steam to dry gas ratio (S/G) from 0.25 (20% H2 O) to
purity by voltaic decomposition of water. The processing of
0.75 (42.9% H2 O) the equilibrium temperature increases by
methane and other hydrocarbon fuels requires highly selec-
100 ◦ C while maintaining 1% CO. By operating at 100 ◦ C
tive processes and catalysts as well as additional purification
higher temperature a significant reduction of the reactor size
steps in order to supply the needed purity. Figure 2 gives a
can be achieved by utilizing more favorable kinetics.
scheme of a fuel processor where the WGS part is located
Single stage WGS is desired but difficult to accomplish
between reforming and selective oxidation.
due to the adiabatic temperature rise. To account for the

Table 2. WGS equilibrium constants.[18]

2 THEORY
Temperature Kp Temperature Kp
The WGS reaction is a critical step in reducing the CO ( ◦ C) ( ◦ C)
concentration for low temperature fuel cells that are not
tolerant to CO. In most fuel processor designs the WGS 93.3 4523 426.7 9.030
reaction must deliver a CO concentration of <1% to the 148.9 783.6 482.2 5.610
selective CO oxidation reactor. Any further reduction in 204.4 206.8 537.8 3.749
260.0 72.75 593.3 2.653
CO concentration eases the load on the CO oxidizer. High
315.6 31.44 648.9 1.966
temperature fuel cells are not as dependent on the WGS 371.1 15.89 704.4 1.512
shift reaction to reduce CO since they are able to withstand
194 Part 2: Hydrogen storage and hydrogen generation

Table 3. Representative inlet gas compositions approximately equal to that needed to operate a 50 kW
for HTS and LTS reactions, from autothermal fuel cell, the adiabatic temperature rise can be calculated.
reforming, methane free.
At a moderate S/G ratio of 0.50, an inlet temperature of
243 ◦ C is needed to achieve the equilibrium CO concen-
HTS gas (%) LTS gas (%)
tration of 1% at an exit temperature of 334 ◦ C. However
CO 9 3 when the S/G ratio is reduced to 0.25, an inlet temperature
CO2 7 13 of 143 ◦ C needed to achieve 1% CO at an exit temperature
H2 24 30 of 260 ◦ C. In this case the WGS catalyst will be kinetically
N2 28 28 limited. Commercial LTS catalysts are kinetically limited
H2 O 32 26
at <190 ◦ C even at moderate space velocities. An actively
cooled reactor can operate in a quasi-isothermal mode to
increase the inlet temperature. In this case the reactor vol-
14
ume and complexity increase to account for heat exchange
Inlet dry gas S/G = 0.25
12 surface area and reactor control, respectively.
13.2 % CO
10.3 % CO2 Two stages of WGS are traditionally used to take advan-
% CO equilibrium, dry

10 35.3 % H2 tage of kinetics and thermodynamics. By operating an HTS

41.2 % N2 S/G = 0.50 catalyst at higher temperatures the favorable kinetics can be
8
exploited and the volume of the catalyst can be minimized.
6 By cooling the syngas between the HTS and LTS stages an
S/G = 0.75 active catalyst can take advantage of the thermodynamic
4 equilibrium at low temperature. A two-stage WGS config-
uration can produce an exit CO concentration of much less
2
than 1%. At this time both single and two bed concepts are
0 being considered in fuel processor designs.
100 200 300 400 500 600 700 800 The method of producing the syngas will effect the WGS
Temperature (°C) equilibrium. Autothermal reforming produces a syngas with
lower H2 concentration due to the dilution of nitrogen as
Figure 3. CO equilibrium of HTS gas from auto thermal reformer compared to steam reforming. The lower H2 concentration
(ATR) at various S/G ratios.
improves the equilibrium CO conversion whereas the high
H2 concentration expected with steam reforming lowers
4.0 the WGS reaction equilibrium conversion. Figures 5 and 6
Inlet dry gas S/G = 0.5 show the equilibrium CO as a function of H2 content at con-
3.5
4.1% CO stant CO and CO2 concentrations for HTS and LTS gases.
% CO equilibrium, dry

3.0
17.6% CO2 S/G = 0.25
40.5% H2
2.5 37.8% N2
S/G = 0.75 12
2.0 Inlet dry gas 73.5 % H2
10 13.2 % CO 2.9 % N2
1.5
% CO equilibrium, dry

10.3 % CO2
1.0 8 S/G = 0.50

0.5 35.3% H2
6 41.2 % N2
0.0
0 200 400 600 800 1.0
4
Exit temperature (°C)
0.5
Figure 4. CO equilibrium of LTS gas from ATR at various S/G 2
0.0
ratios. 100 200 300
0
100 200 300 400 500 600 700 800
increasing temperature, the inlet temperature to the catalyst Temperature (°C)
must be relatively low where existing catalysts may reach
kinetic limitations. Assuming a H2 flow rate out of the Figure 5. CO equilibrium of HTS gas from autothermal vs steam
WGS catalyst of 500 standard liter per minute, which is methane reformer (SMR): effect of H2 concentration.
 Catalyst development for water-gas shift 195

4 conditions the catalysts available today are kinetically lim-

Inlet dry gas ited at the low temperatures needed for high CO conversion
4.1% CO
17.6% CO2 75.7% H2 40.5% H2 while striving to minimize reactor volumes.
% CO equilibrium, dry

3 S/G = 0.50 2.7% N2 37.8% N2

2.2 Mechanisms and kinetics

2
0.6
The kinetics and mechanisms of the WGS reaction with
0.4
various catalyst systems were studied in the past by many
1 0.2 authors and excellent summaries can be found in “Hand-
0.0 book of Heterogeneous Catalysis” by Ertl, Knözinger and
100 200 300 Weitkamp and also by Barbier and Duprez.[7, 19]
0
0 100 200 300 400 500 600 700 800
Based on kinetic results two types of mechanisms were
proposed.[6] The oxidation-reduction, or regenerative mech-
Temperature (°C)
anism of Rideal-Elay type, in which water oxidizes the
Figure 6. CO equilibrium of LTS gas from ATR vs SMR: effect surface and CO re-reduces the oxidized surface.[15, 19] Oth-
of H2 concentration. ers describe a bi-functional process where the adsorbed CO
on the precious metal or mixed metal oxide is oxidized
Table 4. Effect of pressure on equilibrium CO concentrations by the support and then water fills the support oxygen
(inlet dry gas: 13.2% CO, 10.3% CO2 , 35.3% H2 , 41.2% N2 , vacancy:[19–21]
S/G = 0.5).
H2 O+∗ ←−→ H2 + O∗ (6)
Temperature P = 3 atm P = 30 atm P = 300 atm
( ◦ C) (% CO) (% CO) (% CO) CO + O∗ ←−→ CO2 +∗ (7)

200 0.12 0.12 0.07 where ∗ is an active metal site. The multi-step
300 0.68 0.65 0.48 Langmuir–Hinshelwood type or “associative” mechanism
400 1.98 1.94 1.61 where adsorbed or dissociated water form reactive hydroxyl
500 3.93 3.88 3.46 groups that combine with CO to produce a formate that
600 6.15 6.10 5.68
700 8.38 8.34 7.95 decomposes to CO2 and H2 . Others describe the bi-
functional nature where CO adsorbed on the reduced
metal migrates to react with hydroxyl groups to produce
To achieve 1% CO the temperature must be decreased by the formate intermediate.[13, 19] FTIR analysis has been
nearly 40 ◦ C when the H2 is increased from 35% to 74%. commonly used to confirm the presence of the formate
Or in other words the CO concentration would be 1.66% intermediate:
for steam reforming at the same temperature required to
achieve 1% CO for autothermal reforming. The effect of CO + ∗ ←−→ CO∗ (8)
∗ ∗
H2 concentration is not as significant as the S/G ratio, but H2 O + 2a ←−→ H + OH (9)
it is not trivial and must be considered when trying to max-
imize efficiency and minimize volume of the WGS reactor OH∗ + CO∗ ←−→ HCOO∗ +∗ (10)
∗ ∗ ∗ ∗
volume. HCOO + ←−→ CO2 + H (11)
Since the WGS reaction is equimolar (equation 1) the
effect of pressure is minimal considering the range of pres- CO2 * ←−→ CO2 +∗ (12)
sure used for fuel processing. By increasing the pressure 2H∗ ←−→ H2 + 2∗ (13)
from 3 to 30 atm there is negligible effect on the thermo-
dynamic CO conversion (Table 4). But if the pressure is The rate-determining step was found to be the decomposi-
increased to 300 atm the equilibrium CO concentration is tion of the formate. An increase in the water partial pressure
lower. However it is not practical to increase the pressure increased the rate of formate decomposition and the acti-
to take advantage of the slightly higher equilibrium CO vation energy decreased.[22]
conversion. Based on adsorption/desorption measurements and inter-
From a thermodynamic perspective, the efficiency of the conversion of CO and CO2 by isotope exchange on a Fe/Cr
WGS reaction is maximized at low temperature, high water catalyst, Tinkle and Dumesic concluded that the WGS on
and a low hydrogen concentration. However under some Fe/Cr catalyst proceeds via the regenerative mechanism.[23]
196 Part 2: Hydrogen storage and hydrogen generation

The question of the reaction mechanism over Cu based 1000

catalysts is still debated today. The catalyst composition,
Acu / Apd = 10
catalyst precursors, its resulting surface properties as well

Relative rate: Cu vs Pd
as the reaction conditions obviously play a decisive role. 100
Most authors propose the regenerative mechanism, which HTS gas
is in good agreement with results obtained from WGS LTS gas
10
reaction performed on single crystal Cu surfaces and water
adsorption experiments on poly-crystalline copper.[24–27]
Several different kinetic expressions used for the WGS 1
reaction over copper catalysts have been summarized previ- Acu / Apd = 0.1 HTS gas
ously.[26] Ovensen et al. showed the influence of pressure LTS gas
on the activation energy and reaction orders based on 0
macro and microkinetic models for Cu/Zn/Al catalysts.[28] 100 200 300 400 500 600
Grenoble et al. studied the WGS reaction over a number Temperature (°C)
of supported metals in detail at atmospheric pressure and
in a temperature range from 270 to 380 ◦ C.[13] Alumina Figure 7. Relative reaction rates of Cu and Pd catalysts with
supported Group VIIB, VIII, and IB metals were examined variation of pre-exponential factors and gas composition. P =
3 atm, (
, ž) ACu /APd = 10; (, Ž) ACu /APd = 0.1. ACu and
and for these metals the range of activity differed by more APd are the pre-exponential factors for copper and palladium,
than three orders of magnitude and the reaction orders of respectively.
water varied from 0 to +0.8 and from −0.4 to +0.6 for
carbon monoxide. Alumina supported metals exhibit much the Pd catalyst viable. The activation energies reported by
higher activity than catalysts prepared on silica or active Grenoble for Cu/Al and Pd/Al will be used and are 55.6,
carbon. The turnover number of Pt supported on Al2 O3 79.9 kJ mol−1 respectively and are relatively consistent with
is an order of magnitude higher than the turnover number other references.[13, 28, 31] The ratio of pre-exponential fac-
of Pt on SiO2 and almost two magnitudes higher than Pt tors were varied from ACu /APd = 10 to ACu /APd = 0.1.
on active carbon. Other researchers have shown carbon Figure 7 shows the relative reaction rates with different gas
monoxide reaction order of 0 and water order from 0 to compositions and over a broad temperature range. Nominal
0.5 and −0.5 for carbon dioxide and −1 for hydrogen over HTS and LTS gas compositions are used for this compari-
Pd/CeO2 catalysts.[22, 29] son (Table 2). By comparing the effect of temperature and
Equation (14) represents the rate expression from Moe gas composition the relative rate of copper versus palladium
et al.[30] and is considered for discussion.[34] Equation (15) is greatest at lower temperatures and higher CO content.
is used to represent Pd/CeO2 and is based on the reaction The kinetic limitations of the current WGS catalyst tech-
orders reported by Hilaire et al.:[29] nology at low temperature where thermodynamics are most
favorable was also described by Sun.[32] It is safe to say
rCu = kCu PCO PH2 O (1 − β) (14)
that precious metal catalyst activity must be improved by
kPd (PH0.5
2O
) at least two orders of magnitude to become useful in fuel
rPd = (1 − β) (15) processing.
(PCO
0.5
P )
2 H2

where
3 ROLE OF WGS FOR AUTOMOTIVE
(PCO2 PH2 ) 1
β= EXHAUST GAS CLEANING SYSTEMS
(PCO PH2 O ) Keq
rCu k In contrast to conventional base metal catalysts, supported
= Cu PCO PH0.5 P 0.5 P (16) precious metal catalysts have been known to be active
rPd kPd 2 O CO2 H2

for the WGS reaction for many years with early research
To compare the relative rate of copper and palladium cat- performed in 1925 by Prichard and Hinshelwood[33] who
alysts, equations (14) and (15) are divided resulting in studied the reverse WGS reaction over supported Pt.[31]
equation (16). The relative WGS rate of supported Pd Much attention was focused on the WGS reaction as it
catalyst compared to copper is negatively effected by pres- applied to automotive exhaust catalysts with respect to CO
sure, a higher activation energy and to a lesser extent the emissions in the 1970s and 1980s.[19, 34–40] Detailed and
gas composition. The activity can be calculated by eval- excellent reviews of the early work are given by Kummer
uating the relative reaction improvement needed to make and Taylor.[34, 35, 41]
 Catalyst development for water-gas shift 197

Many have reported that CeO2 promoted the WGS cells are far different from the traditional industrial appli-
reaction.[34, 36, 41, 42] It was shown that Pt was most active cations (Table 5). The requirements for mobile applications
for WGS reaction followed by Pd and Rh on alumina and must compete with the standards set by internal combus-
activity was improved with the incorporation of 12% CeO2 tion engines, therefore the operability, size, weight and cost
with alumina.[36, 42] Currently CeO2 is generally added to targets are rigorous. For stationary applications the catalyst
three-way catalysts in order to promote the WGS reac- attributes are less constrained and larger volumes and higher
tion and to store oxygen under lean conditions for use costs are acceptable to compete with the cost of electricity
under rich conditions.[16, 43, 44] The literature provides use- from the grid, especially in premium power applications.
ful information for the development of precious metal WGS But it is clear that catalyst and reactor technology devel-
catalysts for fuel processing but there are important differ- oped for mobile fuel cells will be integrated into stationary
ences that must be noted. Most WGS activity evaluations applications making them more economically viable.
made with respect to exhaust catalyst typically were studied Industrial WGS catalysts are designed to operate at
in an oxidative atmosphere and at temperatures >400 ◦ C. steady state conditions for months to years on end with-
The effect of CO2 and H2 were not often considered. The out interruption. It is expected that fuel processor WGS
WGS fuel processing environment is more reducing where catalysts will be exposed to many startup/shutdown cycles
the partial pressures of CO2 and H2 are much greater and where the catalyst will be exposed to redox cycles and
operating temperatures are generally lower, 180–450 ◦ C. condensing steam. As mentioned previously, care must be
taken to prevent such exposure to industrial WGS catalysts.
A commercial Cu/Zn/Al catalyst was exposed to condens-
4 WGS CATALYSTS FOR FUEL
ing synthesis gas. The results show dramatic deactivation
PROCESSING when tested as a powder in a micro-activity test after a
few condensation cycles. Figure 8 shows the CO conver-
Compared to the industrial use of WGS catalyst the require-
sion dropping 40–50% of the fresh catalyst activity after 3
ments for fuel processing are quite different. Industrially the
cycles.
Fe/Cr and Cu/Zn/Al catalysts are activated before operation
It has been shown that the Cu/Zn/Al catalysts also deacti-
by a slow and controlled reduction process. Also upon shut-
vate rapidly when exposed to an oxidizing environment.[45]
down the catalysts must be purged with inert gas to prevent
In addition, the catalyst activity per volume and mass must
condensation and re-oxidation. If any of these conditions
be increased orders of magnitude over conventional tech-
are not met, the performance of the catalyst is significantly
nology to meet automotive targets. The WGS reactor targets
limited. Ease of operation is the key for WGS catalyst for
based on Department of Energy projections for 2004 trans-
fuel processing applications.
portation fuel cells are <0.1 l kWe−1 , < 0.1 kg kWe−1 at a
cost of <$1 kWe−1 . These targets are at least 10 times lower
4.1 Catalyst requirements than expected using conventional WGS catalysts.[46] Based
on the desired attributes for WGS catalysts used for fuel
To apply WGS catalysts successfully to fuel processing processing, new catalysts must be developed.
many obstacles must be overcome. The desired require- Conventional Cu/Zn/Al and Fe/Cr/Cu WGS catalysts
ments of WGS catalysts used to produce hydrogen for fuel may continue to have a place in fuel processing due to

Table 5. WGS catalyst requirements for mobile and stationary applications.

WGS catalyst attribute Mobile application Stationary application

Volume reduction Critical, <0.1 l kW−1 Not as constrained

Weight reduction Critical, <0.1 kg kW−1 Not as constrained
Cost Critical, <$1 kW−1 Not as critical
Rapid response Critical, <15 s Load following
Nonpyrophoric Important Eliminate purging
Attrition resistance Critical No constraint
Selectivity Critical Important
No reduction required Critical Important
Oxidation tolerant Critical Important
Condensation tolerant Important Important
Poison tolerant Desired Desired
Pressure drop Important Important
198 Part 2: Hydrogen storage and hydrogen generation

% of equilibrium CO conversion
100% 120% 2.0

100%
80%

% methane make
1.5
% activity loss

204 °C 80%
60%
193 °C 60% 1.0
40% 182 °C
40%
0.5
20% 20%

0% 0% 0.0
0 1 2 3 4 250 300 350 400 425 450 475

Number of condensation cycles Temperature (°C)

Figure 8. Effect of condensing synthesis gas on commercial

Cu/Zn/Al catalyst. Figure 9. Selectivity of WGS catalysts. (
, ) Commercial
Fe/Cr/Cu, (ž, Ž) 2% Pt/CeO2 . HTS syngas, total gas SV =
their proven success with long term performance. Fe/Cr/Cu 45 000 h−1 , S/G = 0.5.
catalysts are known to be poison tolerant, selective and
stable at high temperature. The low temperature activ-
ity of commercial Cu/Zn/Al catalysts continue to be the was detected. The selectivity at high temperatures is even
benchmark for new developments. The Cu/Zn/Al cata- more critical when considering fuel processors will have
lyst has been used successfully in the ONSI Corpo- to operate at 5–100% power ratings. The methane leak-
ration/International Fuel Cell commercial PC25 200 kW age will increase when operating at lower turndown ratios
power plants with several million hours operating expe- due to the longer contact time. It is apparent that precious
rience. As well, new interest in Cu/Zn/Al catalysts for fuel metal catalysts have potential to replace conventional cat-
processing has been generated with the application of low alysts, however the activity must be increased greatly to
temperature oxygen assisted WGS that combines the WGS overcome the implied high cost while maintaining high
and CO oxidation reactions.[47] Even though the conven- selectivity.
tional catalysts must be treated with special care, engineered Not all WGS catalyst development has focussed on
solutions are possible that take advantage of the low tem- precious metals. Several groups have investigated lower
perature activity, low cost, and proven performance. cost base metal formulations while striving to overcome
the pyrophoricity of commercial catalysts. Alternative con-
cepts include transition metal carbides, copper or nickel
4.2 Catalyst developments
supported on ceria, cobalt on perovskite and other pro-
Recently new formulations have been studied specifically prietary base metal formulations.[21, 46, 55] In general the
to meet fuel processing requirements. A majority of the activities at higher temperature, typically >300 ◦ C show
published work has focussed on precious metal catalysts. dramatic improvement compared to Fe/Cr catalysts. In
Ru/Fe2 O3 , Au/Fe2 O3 and Au/TiO2 all were reported to some cases the low temperature activities are compara-
have high CO conversion activity at 200 ◦ C.[48–50] As ble to commercial Cu/Zn/Al catalysts, but they offer no
found by Gorte et al. and other groups, precious met- relief in reducing the low temperature WGS catalyst vol-
als supported on ceria exhibit surprisingly high WGS ume. The interest in these formulations is to develop a
activities.[20, 22, 29, 51, 52] Other groups investigated precious catalyst that requires no activation and does not generate
metals supported on zirconia.[45, 52–54] As opposed to the significant heat when exposed to air at elevated temper-
very selective conventional catalysts, the formation of atures. This simplifies the control of the fuel processor
methane can be significant for precious metal catalysts and allows air to be used as a purge gas during shut-
causing a decrease in hydrogen production and extreme down cycles. Precious metal catalysts are typically suc-
heat release.[52, 54] The selectivity of commercial Fe/Cr/Cu cessful meeting these criteria, but it is the low cost of
and a model 2% Pt/CeO2 catalyst is compared in Figure 9. the base metal formulations that make them attractive. It
At moderately high space velocity the ceria catalyst oper- is clear that no WGS catalyst system has met all crite-
ated at equilibrium but produced nearly 2% CH4 at 400 ◦ C ria demanded for fuel processing especially at low tem-
in the dry gas. In comparison the Fe/Cr/Cu catalyst did peratures where low CO concentrations are favored by
not reach equilibrium conversion until 450 ◦ C but no CH4 thermodynamics.
 Catalyst development for water-gas shift 199

4.3 Catalyst poisons and contaminants when using autothermal reforming or partial oxidation due
to the addition of nitrogen and high temperature operation.
The lifetime of industrial Cu/Zn/Al WGS catalysts is typi- Also it is likely that unconverted hydrocarbons may slip
cally determined by deactivation due to sulfur poisoning.[15] from the reforming section especially when using heavy
Commercially natural gas feedstocks are desulfurized using hydrocarbon feedstocks. The exposure of a Pt/ZrO2 cat-
a Co/Mo or Ni/Mo hydrotreating catalyst with ∼5% H2 alyst to low levels of ethylene or benzene did not show
in the feed. The resulting H2 S is readily removed over any significant deactivation.[54] Possible contaminants such
ZnO operating at ∼370 ◦ C. Zinc oxide is very effective for as chloride, sulfate, calcium, magnesia, etc., may be intro-
H2 S sorption but removal is not complete. Approximately duced from the air and water fed to the reforming section or
50 ppb H2 S slips through hot zinc oxide and enters the if quench water is added before the WGS reactor. Care must
reformer. Due to the high temperatures in the reformer and be taken to purify these feeds to eliminate potential poisons
the low capacity of Fe/Cr/Cu catalysts for sulfur adsorption, of the WGS or eventually the fuel cell stack itself. Recently
nearly all sulfur is removed by the Cu/Zn/Al low temper- Hilaire described the formation of a carbonate or bicarbon-
ature WGS catalyst. After the volume expansion due to ate species on Pd/CeO2 after exposure to a WGS reaction
the reforming reaction the resulting H2 S concentration is gas.[29] The implication is that the carbonate species may
about 10 ppb entering the WGS catalyst reactor. Normally impair the reducibility of the support and therefore decrease
the Cu/Zn/Al LTS catalyst reactors are designed at a space the activity. More research is needed to develop a better
velocity of 1000–2500 h−1 to account for sulfur poison- understanding of the effects of poisons and contaminants
ing. This represents approximately three times the kinetic on the WGS catalysts before reactor volumes and catalyst
volume. The Cu/Zn/Al WGS catalyst acts as a total sul- lives can be predicted with any certainty.
fur purifier protecting downstream processes in industrial
applications.[56] Cu/Zn/Al WGS catalysts are highly suscep-
tible to sulfur poisoning but they do provide a purification 5 SUMMARY AND OUTLOOK
step that still may be of interest for fuel processing depend-
ing on the sulfur removal philosophy. Even if Cu/Zn/Al To achieve the maximum performance, opportunities exist
catalysts are not applied as WGS catalysts they may find to apply novel reactor concepts to fuel processing. If the
application as a total sulfur removal sorbent where sulfur exothermic heat of reaction can be removed from the
adsorption continues even at zero WGS activity. reactor, the thermodynamics can be exploited by driving
down the exit temperatures. Micro-channel reactors appear
The desired desulfurization operating conditions for fuel
to be able to accomplish the formidable heat transfer task
processing are ambient temperature without hydrogen recy-
while achieving small reactor volumes.[52] However, it will
cle. There is also interest to reform sulfur bearing fuels
require high performance catalysts to take advantage of the
followed by sulfur removal in the resulting wet syngas. In
favorable low temperature equilibria.
either case it is safe to assume that the WGS catalyst will
The catalyst cost is worth some discussion especially
be exposed to H2 S during its lifetime. Only a few publica-
when considering precious metal formulations. Making the
tions have investigated the effect of H2 S poisoning on WGS
following assumptions an estimate about the relative costs
catalyst under fuel processing conditions.[45, 53, 54] The lit-
of precious metal vs conventional catalysts can be made:
erature indicates that the Pt/ZrO2 catalysts are deactivated
by the presence of H2 S, but once the sulfur is removed • cost of Fe/Cr/Cu and Cu/Zn catalysts are $10.6 l−1 and
from the reaction gas the fresh catalyst activity is regained. $17.3 l−1 , respectively
A similar observation was made for Fe/Cr catalyst however • precious metal loading at 2 wt% and washcoat loading
they were relatively less susceptible to sulfur poisoning. In of 150 g l−1
comparison the Cu/Zn catalyst was rapidly deactivated to • precious metal cost is 40% of the total catalyst cost
zero WGS activity with the deactivation being irreversible • precious metal cost $600 troy ounce−1 .
once the sulfur was removed from the gas stream. It is sur-
prising to note that the Pt/ZrO2 catalyst exhibited a higher On an equal volume basis the precious metal is about 14
activity at 50 ppm H2 S than the fresh Fe/Cr catalyst even times that of Fe/Cr/Cu catalyst and is sensitive to precious
when operated at 50 ◦ C higher temperature. It is encourag- metal price. Therefore the precious metal catalyst activity
ing that the activity can be maintained at reasonable levels must be increased at least 10 times to be competitive on
even under extremely high H2 S concentrations and that the a cost basis, but previous discussion has shown that the
effect is reversible. activity must be improved over 100 times to meet activity
Other poisons or contaminants may be present in the requirements for fuel processing. Precious metal catalysts
fuel processor. It is likely that ammonia will be produced may offer benefits over the Cu/Zn and Fe/Cr/Cu catalysts
200 Part 2: Hydrogen storage and hydrogen generation

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