Refereed Proceedings

The 13th International Conference on

Fluidization - New Paradigm in Fluidization
Engineering
Engineering Conferences International Year 2010

REACTION CHARACTERISTICS OF
TWO WATER GAS SHIFT
CATALYSTS IN A BUBBLING
FLUIDIZED BED REACTOR FOR
SEWGS PROCESS
Ho-Jung Ryu∗ Sung-Ho Jo†
Young Cheol Park‡ Chang-Keun Yi∗∗

∗ KoreaInstitute of Energy Research, [email protected]

† KoreaInstitute of Energy Research
‡ Korea Institute of Energy Research
∗∗ Korea Institute of Energy Research

This paper is posted at ECI Digital Archives.

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 Ryu et al.: REACTION CHARACTERISTICS OF TWO WATER GAS SHIFT CATALYSTS IN A BU

REACTION CHARACTERISTICS OF TWO WATER GAS SHIFT

CATALYSTS IN A BUBBLING FLUIDIZED BED REACTOR FOR
SEWGS PROCESS
Ho-Jung Ryu1†, Sung-Ho Jo2, Young Cheol Park3 and Chang-Keun Yi4
Korea Institute of Energy Research
71-2 Jang-dong, Yuseong-gu, Daejeon 305-343
†
Corresponding author: T: 82-42-860-3794; F: 82-42-860-3134; E: [email protected]

ABSTRACT

Reaction characteristics of two WGS catalysts for SEWGS process were

investigated in a bubbling fluidized bed reactor. The commercial low temperature
WGS catalyst produced by Süd-chemie and new catalyst produced by spray-drying
method were used as bed materials. Reaction temperature, steam/CO ratio, and
gas velocity were considered as experimental variables. Moreover, long-term
operation results of two WGS catalysts were compared as well.

INTRODUCTION

Hydrogen production is the most fundamental part of the hydrogen energy system,
and has always been the object of intense and vigorous research and development.
World hydrogen production has been growing rapidly at 8-10% per annum for many
years (1). At present, hydrogen is produced mainly from fossil fuels, water and
biomass. However, more than 90% of the hydrogen is produced from fossil fuels (2).

Series of gasification of coal, water gas shift, and CO2 separation is the predominant
production route to hydrogen from coal for commercial scale application. However,
this process needs multiple-steps such as high- and low-temperature water gas shift
reaction as shown in eq. (1) to improve hydrogen yield, and CO2 separation process
to separate almost pure hydrogen from the gas mixture of CO, CO2, and H2. To
separate CO2 from the exhaust gas, additional energy and equipments are required.
More than 22% of hydrogen generation cost comes from CO2 separation process for
purifying hydrogen (3). Although the previous process has been used for many
years, there are some areas for improvement. The previous process requires many
reactors and many kinds of catalysts and/or sorbents. Therefore, it will be extremely
desirable if new concepts can be developed which can reduce the capital and
operating cost of the conventional process (4). To overcome these disadvantages,
SEWGS (Sorption Enhanced Water Gas Shift) system has been developed.
Equation (2) and (3) explain concept of SEWGS system. The thermodynamic
equilibrium in the shift reaction can be enhanced to give more hydrogen yield by
adding a CO2 absorbent into the shift reactor. Carbon dioxide is then captured as a
solid carbonate as soon as it formed, shifting the reversible water-gas shift reactions
beyond their conventional thermodynamic limits as shown in eq. (2). Regeneration
of the sorbent releases pure CO2 suitable for sequestration as shown in eq. (3) (4). It
is important that the gas composition of the exhaust gas from the SEWGS reactor

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 The 13th International Conference on Fluidization - New Paradigm in Fluidization Engineering, Art. 49 [2010]

contains only highly concentrated H2 and excess water vapor. Therefore, H2 can be
easily recovered by cooling the exhaust gas without any extra energy consumption
for H2 separation. Moreover, the exhaust gas from the regeneration reactor
contains only carbon dioxide and water vapor if we use steam as fluidization gas.
After water condensation, almost pure carbon dioxide can be obtained with little
energy loss for component separation.

Water gas shift reaction CO + H2O  H2 + CO2

(1)
SEWGS reaction CO + H2O + MO  H2 + MCO3
(2)
Regeneration reaction MCO3  MO + CO2
(3)
where, MO: metal oxide, MCO3: metal carbonate

In this study, the reaction characteristics of two WGS catalysts for SEWGS have
been investigated in a bubbling fluidized bed reactor, as a preliminary research. The
commercial low temperature WGS catalyst (MDC-7) produced by Süd-chemie and
new WGS catalyst (PC) produced by KEPRI (Korea Electric Power Research
Institute) by means of spray-drying were used as bed materials. Reaction
temperature, steam/CO ratio, and gas velocity were considered as experimental
variables. Moreover, long-term operation results of two WGS catalysts were
compared as well.

EXPERIMENTAL

The reactivity tests were carried out in a bubbling fluidized bed reactor. A schematic
of the reactor is provided in Figure 1. The major components consist of a gas input
system, a fluidized bed, a condenser, a hot gas filter, a gas sampling/analyzing unit,
and water feeding pump. The fluidization column is 0.7 m high with an internal
diameter of 0.05 m. A perforated gas distributor plate separates the fluidization
column and air box. Reactant gas was fed to the air box. An electric heater could be
controlled by a thermocouple and a heater controller. Temperature and pressure
data were recorded by a data acquisition system. The exit stream from the fluidized
bed reactor was sampled at the outlet of the reactor. The CH4, CO, CO2, H2, NO,
and O2 concentrations were monitored using an on-line gas analyzer and recorded
by a data acquisition system. Further details of the reactor system are available in
our previous paper (5).

Two water gas shift catalysts, the commercial low temperature WGS catalyst (MDC-
7) produced by Süd-chemie and new WGS catalyst (PC) produced by KEPRI (Korea
Electric Power Research Institute) were used. MDC-7 catalyst had pellet shape and
we crushed the pellets to 106~212 m. However, PC catalyst has spherical shape
and the same particle size range was prepared. Figure 2 shows photos of two WGS
catalysts. The PC catalyst shows spherical shape and the MDC-7 catalyst shows
irregular shape.

The static bed height was 0.4 m in all cases, and initial solid masses were 0.57 kg
for PC catalyst (b=724.7 kg/m3) and 0.88 kg for MDC-7 catalyst (b=1117 kg/m3),
respectively. The fluidized bed reactor operated with a total inlet gas flow of 2.0
Nl/min in all cases, except for tests to check effect of gas velocity. The total inlet gas

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 Ryu et al.: REACTION CHARACTERISTICS OF TWO WATER GAS SHIFT CATALYSTS IN A BU

contained 50% of syngas and 50% of nitrogen. The syngas composition was 60.5%
of CO, 27.2% of H2, 9.9% of CO2 and N2 as a balance.

Figure 1. Schematic of a bubbling fluidized bed reactor.

Figure 2. Photos of PC and MDC-7 catalysts.

RESULTS AND DISCUSSION

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 The 13th International Conference on Fluidization - New Paradigm in Fluidization Engineering, Art. 49 [2010]

Prior to the start of each experiment, catalysts were reduced by H2 gas (57%, N2
balance) at 400oC. Figure 3 shows breakthrough curves of hydrogen concentrations
during pretreatment (reduction) of catalysts. A breakthrough of hydrogen
concentration marked the end of reduction. As shown in Figure 3, since MDC-7
catalyst showed sharper breakthrough curve than PC catalyst, and therefore, we
could expect that the MDC-7 catalyst would show better reactivity than PC catalyst.
100 100

90 (a) PC catalyst 90 (b) MDC-7 catalyst

Bed mass = 0.57 kg Bed mass = 0.88 kg
80 80
H2 concentration [%]

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 20 40 60 80 0 20 40 60 80

Time [min] Time [min]

Figure 3. H2 breakthrough curves during pretreatment of catalysts.

Figure 4 shows effect of temperature on CO conversion of catalysts. The CO

conversion to H2 and CO conversion to CH4 were calculated by mass balance based
on the output gas concentration and the tie component (N2). For MDC-7 catalyst,
high CO conversion up to 99.4% was observed in the range of 220~240oC at 4.0 of
steam/CO ratio. For PC catalyst, lower CO conversion than MDC-7 catalyst was
observed even at higher temperature (380~400oC) and at higher steam/CO ratio
(=5).

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 Ryu et al.: REACTION CHARACTERISTICS OF TWO WATER GAS SHIFT CATALYSTS IN A BU

100 100

90 90

80 80
CO conversion [%]

70 70

60 60

50 50
(a) PC catalyst (b) MDC-7 catalyst
40 Steam/CO ratio = 5 40 Steam/CO ratio = 4
30 Total CO conversion 30 Total CO conversion
CO to H2 conversion CO to H2 conversion
20 20
CO to CH4 conversion CO to CH4 conversion
10 10

0 0
280 300 320 340 360 380 400 420 440 140 160 180 200 220 240 260 280 300 320

Temperature [ C]
o
Temperature [oC]

Figure 4. CO conversion versus reaction temperature.

Figure 5 shows effect of steam/CO ratio on CO conversion of two catalysts. For
MDC-7 catalyst, CO conversion increased slightly as the steam/CO ratio increased
up to 2.0, and maintained at high level thereafter. However, CO conversion of PC
catalyst increased continuously as the steam/CO ratio increased up to 5.0. MDC-7
catalyst showed higher CO conversion at the same steam/CO ratio and at lower
temperature. Moreover, PC catalyst generated higher CH4 at lower steam/CO ratio.

100 100

90 90

80 80
CO conversion [%]

70 70

60 60
(a) PC catalyst (b) MDC-7 catalyst
o o
50 (at 360 C) 50 (at 200 C)
40 Total CO conversion 40 Total CO conversion
CO to H2 conversion CO to H2 conversion
30 30
CO to CH4 conversion CO to CH4 conversion
20 20

10 10

0 0
1 2 3 4 5 1 2 3 4 5
Steam/CO ratio [-] Steam/CO ratio [-]

Figure 5. CO conversion versus steam/CO ratio.

Figure 6 shows long-term test results of two catalysts. The reactivity of MDC-7
catalyst was maintained more than 8 hours but that of PC catalyst decreased as the
reaction time increased. As a conclusion, MDC-7 catalyst showed better reactivity
than PC catalyst from the viewpoints of reaction temperature, seam/CO ratio, CO
conversion, and long-term durability.

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 The 13th International Conference on Fluidization - New Paradigm in Fluidization Engineering, Art. 49 [2010]

100 100
gas
90 analyzer 90
trouble
80 80
CO conversion [%]

70 70

60 60

50 50

40 (a) PC catalyst 40 (b) MDC-7 catalyst

o
at 380 C at 200oC
30 steam/CO ratio = 5 30 steam/CO ratio = 4
20 Total CO conversion Total CO conversion
20
CO to H2 conversion CO to H2 conversion
10 CO to CH4 conversion 10 CO to CH4 conversion

0 0
0 100 200 300 400 500 0 100 200 300 400 500
Time [min] Time [min]

Figure 6. CO conversion versus time.

To check effects of syngas concentration and gas velocity, supplementary tests were
performed using MDC-7 catalyst in the same reactor and the results are provided in
Figure 7. The CO conversion of MDC-7 catalyst decreased slightly as the syngas
concentration increased, but increased as the gas velocity decreased. However,
these values are much higher than the results from the fixed bed with the same
catalyst (6).

100

98
CO conversion [%]

96

94

Steam/CO ratio=2, U=0.05 m/s

92 Steam/CO ratio=4, U=0.05 m/s
Stema/CO ratio=4, U=0.025 m/s

90
0 20 40 60 80 100

Syngas concentration [%]

Figure 7. CO conversion to H2 versus syngas concentration (MDC-7 catalyst).

CONCLUSIONS

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