W
Water Gas Shift (WGS)
Giuseppe Barbieri
Institute on Membrane Technology, Italian
National Research Council, Rende CS, Italy
In the last decades, great attention has been paid
to hydrogen as a carrier to be used for the pro-
duction of clean energy by means of new tech-
nologies, designed to enhance efficiency and
environmental sustainability, especially for
power generation. Hydrogen is also utilized in a
large amount in the chemical and petrochemical
industry for ammonia synthesis, hydrocracking,
hydroreforming, etc. Currently, hydrogen is
mainly produced from fossil fuels (96 %): the
stream coming out from a reformer or a coal
gasification plant contains about 50 % H2 that
has to be recovered and 40–45 % CO which can
be utilized for producing more hydrogen. Thus,
an upgrading stage is required, and the water gas
shift (WGS) reaction is the most feasible one for
this purpose. The water gas shift reaction is
CO þ H2 O ¼ CO2 þ H2
DH0298 ¼ 41 kJ mol1
# Springer-Verlag Berlin Heidelberg 2015
E. Drioli, L. Giorno (eds.), Encyclopedia of Membranes,
DOI 10.1007/978-3-642-40872-4_598-1
Low temperatures thermodynamically favors CO
conversion, but pressure (in a traditional reactor)
does not affect it since the reaction is exothermic
and characterized by no variation of the mole
number.
Kinetics is promoted by a high temperature
and slightly depends on the feed pressure.
WGS process is conventionally operated in
two fixed-bed adiabatic reactors, in series, with
a cooler interposed between them. So the WGS
traditional process consists of:
1. A first reactor operating at high temperatures
(300–450  C) and GHSV (20,000 h1, gas
hourly space velocity), using Fe2O3-Cr2O3
catalyst (Bustamante et al. 2004; Keiski
et al. 1996; Ullman’s Encyclopedia of Indus-
trial Chemistry & 5th Completely Revised
Edition 1995) which shows high kinetic activ-
ity when operated at a temperature higher than
300  C. Taking advantage of the high reaction
rate, this reactor converts the most of CO.
2. A heat exchanger for cooling the stream from
400–450  C down to 200  C ca.
3. A second reactor operating at lower tempera-
tures (210–300  C) and GHSV (2,000 h1) for
reducing the CO fraction in the gaseous stream
to less than 1 %. This reactor uses CuO-ZnO-
(Bustamante et al. 2004; Ullmann’s
2 Water Gas Shift (WGS)
Encyclopedia of Industrial Chemistry & 5th
Completely Revised Edition 1995; Amadeo
and Laborde 1995) or CuO-CeO2-based cata-
lysts and takes advantage of the low tempera-
tures displacing the equilibrium, since the
exothermic character of the WGS reaction.
H2O/CO feed molar ratio typically ranges
from 2 to 5 for shifting the thermodynamic equi-
librium conversion and increases the reaction rate
and thus hydrogen yield. The WGS is often
followed by a further step of remaining CO elim-
ination since CO is a poison for many industrial
catalysts. Thus, this H2-rich stream is usually
directed to a CO selective/preferential oxidation
reactor and then to a pressure swing adsorption
unit for separating H2 from the other gases.
For providing a better exploitation of raw
materials together with the reduction of the reac-
tion/separation/purification stages and related
loads, the use of membrane reactors (MRs) is a
promising approach, as they combine the reaction
and the H2 separation by means of a selective
membrane (Brunetti et al. 2012a; Shu
et al. 1991; Uemiya et al. 1991; Dittmeyer
et al. 2001; Brunetti et al. 2012b).
The presence of the membrane allows the
recovery of a hydrogen-rich/pure stream which
does not require any additional separation. More-
over, the removal of the hydrogen, which is a
product, from the reaction volume shifts the reac-
tion toward a further conversion.
The removal of hydrogen by a membrane
gives many advantages: the reverse reaction rate
is depleted owing to the lower H2 concentration;
the residence time of reactants is increased; the
thermodynamic equilibrium of a membrane reac-
tor exceeds that of a traditional reactor; the pres-
sure has a positive effect on conversion in a
membrane reactor, even if no variation in the
number of mole is involved in the WGS reaction
(Marigliano et al. 2003). Therefore, the use of a
membrane reactor allows obtaining a higher con-
version also at higher temperature where the ther-
modynamic conversion is low, acting positively
on the kinetics. Consequently, the amount of
catalyst necessary for a given conversion can be
significantly reduced (Barbieri et al. 2011). In
fact, one membrane reactor operating at high
temperature was demonstrated replacing the two
reactors of the traditional process (Fig. 1), giving
the same final conversion or higher.
Among the several membrane types, the
Pd-alloy membranes are the most used for the
selective removal of hydrogen in applications
such as dehydrogenation reactions, thanks to
their infinite H2 selectivity. An important aspect
in the use of Pd-alloy MR is the good exploitation
of whole the available membrane area, which
allows the improvement of the global perfor-
mance, with higher CO conversion and more H2
recovered in the permeate side (Barbieri
et al. 2008).
Currently, self-supported Pd-Ag membranes
are produced at commercial level, and, when
used to investigate experimentally the WGS reac-
tion at a laboratory scale, they showed a high
durability and performance stability for more
than 2 years operating at 330  C and up to
10 bar (Barbieri et al. 2008).
The results obtained at a laboratory scale con-
cretized in some cases in various patents. For
example, United Technologies Corp. patented
the use of a WGS MR, comprising a WGS reac-
tion region a permeate volume, separated by an
H2-separation membrane which allows H2
formed over a catalyst in the reaction region to
be passed selectively to the permeate region
(Gummalla et al. 2010).
Water Gas Shift (WGS) 3

b Pd-based MR Feed (e.g., reformer down-stream)

300 °C
Pd-based Membranes
Retentate stream Blind (upper end)

440 °C

440 °C
Pure hydrogen
-1
GHSV = 20 000 h
No sweep gas

a Traditional process

210 °C
Second stage LT-WGS
GHSV = 3 000 h-1 Feed (e.g., reformer down-stream)
LT-WGS Heat exchanger
First stage 300 °C
HT-WGS
GHSV = 20 000 h-1
LT-WGS
ca. 10 GHSV
380 °C
Converted stream
Containing Hydrogen
260 °C

Water Gas Shift (WGS), Fig. 1 Schemes of “Pd-based membrane reactor” and “traditional process” for WGS reaction
(Marigliano et al. 2003)

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