Energy Convers. MgratVol. 37, Nos 6-8, pp.

929-933, 1996
Pergamon Copyright © 1996 Elsevier Science Ltd
0196-8904(95)00279-0 Printed in Great Britain. All rights reserved
0196-8904/96 $15.00 + 0.00

TECHNOLOGY FOR REMOVING CARBON DIOXIDE FROM POWER PLANT

FLUE GAS BY THE PHYSICAL ADSORPTION METHOD

MICHIO ISHIBASHI, HIROMITSU OTA, NOBUO AKUTSU,

SATOSHI UMEDA, MOTOAKI TAJIKA,

JUN IZUMI, AKINORI YASUTAKE, TATSUO KABATA, YASUO KAGEYAMA

Tokyo Electric Power Company,

4-1 Egasaki-cho, Tsurumiku, Yokohama, Kanagawa 230, Japan
Mitsubishi Heavy Industries, Ltd.
5-717-1 Fukahori-machi, Nagasaki 851-03, Japan

Abstract -Research into technology for removal of CO2 considered to be the major
cause of global warming, was applied to electric power plant flue gas. Our method was
to use zeolite as adsorbent for physical adsorption, progressing from the previously used
PSA (Pressure Swing Adsorption) method to the more advanced PTSA (Pressure and
Temperature Swing Adsorption) method. ~ have been conducting basic research since
the 1980s, and in 1991 built a 1000m3N/h scale pilot plant, where we are continuing
research through trial operation. Trial operation of the pilot plant has been mainly for
acquisition of scale up data, as well as improvement in the decrease in the power
consumption of PTSA units. As a result, we have seen a better than 20% improvement in
that area. In addition, the pilot plant completed 2000 hours of continuous operation
without incident between October and December, 1994. The total hours of operation of
the plant have topped 4000 hours, but we have seen no decrease in the effectiveness of
the CO2 adsorbent. The SOx in the flue gas was trapped in the lower part of desiccant in
PSA-H20 before the process. Some of desiccant reacts to that, but we have prevented
any ill effects on the process that might be caused by main units. At this point we would
like to report on the results of our research, as well as outline our plants for the future.

1. INTRODUCTION

Increased concentration of carbon dioxide (CO2) in the atmosphere has been attracting attention
worldwide as one factor contributing to global warming. In order to separate and remove CO2 from
flue gases produced in coal-fired power plants, as one of the methods for inhibiting this CO2
increase, Tokyo Electric Power Company and Mitsubishi Heavy Industries, Ltd. have been
conducting experimental research at a pilot plant, using actual flue gases from the utility power
plant, to examine technology of the physical adsorption method[I],[2]
In this work, the Pressure & Temperature Swing Adsorption (called "VISA" hereinafter), CO2
929
930 ISHIBASHI et al.: REMOVING CO2 FROM POWER PLANT FLUE GAS

adsorption by pressure and temperature swing, has been employed. In the FrSA method, CO2 is
adsorbed on an adsorbent at near the normal pressure, and then the adsorbent is heated and CO2 is
regenerated under depressurization. Addition of a moderate temperature swing can increase
regenerative capacity and reduce power consumption (mainly for the vacuum pump). This system
can be expected to be an economically effective system by providing maximized utilization of yet-
unused energy within the thermal power plant as the heat source for this system.
A series of tests performed up to now clarified subjects leading to further possibilities of
reducing the required energy consumption, such as problems of co-adsorption of COs on the
desiccant, wash-down of CO2 due to the regenerative purge and the heat purge, and some review of
the heating method for the first stage PTSA adsorption towers. This paper presents how we coped
with such problems and the results obtained up to the present stage of this research.

2. DEVELOPMENT OF AN ADSORBENT SUITABLE TO THE PTSA METHOD

X-type zeolite, A-type zeolite and mordenite were listed as candidate adsorbents, and preliminary
selection of an optimum adsorbent for the PTSA method was carried out using a small column test
apparatus. The preliminary selection test showed that three types of adsorbents, including two kinds
of Ca-X type and one kind of Ca-A type, would be promising. In order to choose an optimal
adsorbent for PTSA from the three types of zeolites selected, a small column test for PTSA
operation was conducted. Although results of Fig.1 showed almost the same COs selectivity with the
three types of zeolite, the Ca-X type zeolite showing the highest CO2 adsorption was eventually
chosen as the adsorbent for FrSA.
From a bench scale test of this process, it was found that the regeneration temperature could be
considerably effective at the relatively low temperatures of 50 to 100°C.

~2°I~
1•5,
< .o .-= /..~..---"f/ ~ Ca-X(a)
O-~3 Ca-X(B)
• ~ A(Baseline Data)

"F, Adsorption Press. : 1.2ata

~o 0.5 ~- Adsorption Temp. : 50"C
Regenerative Press• : 0.4arm
&J *~ [ Inlet CO2 Cone. : 15 9~
a & B Denote Different Ratios of Si/Ag
0 i i i
50 75 i00
Regenerative Temperature (*C)

Fig. 1 Example of Test Data on Characteristics

of Three Kinds of Zeolite for PTSA-C02

3. PILOT PLANT

The pilot plant was designed, based on the mass balance data obtained from the bench scale test
and on the temperature swing test results. A schematic diagram of the pilot plant is shown in Fig. 2.
For the FFSA process, it is considered that addition of temperature swing introducing gas to the
adsorption column using a steam gas heater should be most effective if added to the first stage of low
concentration CO2. Because of the required heating and cooling processes, the four-tower type was
chosen for the first stage of adsorption towers. Also, the four-tower type PSA process was chosen for
the second stage because it was considered that the effect of temperature swing would be small in the
second stage, because CO2 would be concentrated at nearly 60% at the inlet of the second stage, and
also for the purpose of smooth operation between the first stage and the second stage.
 ISHIBASHI et al.: REMOVINGCO2 FROM POWER PLANTFLUE GAS 931
Dehumidification Ist Adsorption 2nd Adsorption
Stage Stage (PTSA) Stage (PSA)
1"
I ! ! I _ m~coverea

Flue
. +

I ]1 ll ]1 J I I I I 1 1 1 ~
Outlet ~=
Gas

Fig. 2 Schematical Flow Diagram of Pilot Plant of PTSA Method

The pilot plant was installed within the enclosure of the Yokosuka Thermal Power Station owned
by Tokyo Electric Power Company, and the test was started in December, 1991. This pilot plant was
intended to separate and recover 032 from flue gas of 1000m3N/h emitted from No.1 & 2 Units
firing COM (Coal & Oil Mixture). The target was set at 99% concentration of the recovered 0 3 2 and
a recovery ratio of 90%.

4. TEST RESULTS FROM THE PILOT PLANT

Utilization of simulation calculations

Prior to starting tests using this pilot plant, we performed simulation calculations on various
parameters, and based on the simulation results and on the fundamental test results, the desorption
pressure was set between 0.3 arm and 0.5 atm to raise the PTSA effect. However, re-calculations were
carried out based on the pilot plant test results obtained in 1992, which showed that it would be better
to reduce the desorption pressure to 0 . 0 5 ~ 0 . 1 5 atm, at which pressure the amount of the
regenerative purge gas can be minimized, in order to minimize power consumption required for 032
recovery[3]. The results of the pilot plant test demonstrated that making this change reduced the
power consumption by about 12%.

Reeirculation of the second stage PSA parallel-flow purge outlet gas

The parallel flow purge outlet gas in the second stage PSA process contains CO2 concentrations
of 20% to 80% (40% on an average). This outlet gas had been reeireulated to the plant inlet for CO2
recovery at that location, but this was now reeirculated to the inlet of the second stage PSA in order to
reduce power consumption. As a result, the amount of gas passing through auxiliary equipment, etc.,
could be reduced, leading to an improved effect of reducing the required power by about 5%.

CO2 recovery from the dehumidifier tower

In this pilot plant, alumina is used as the desiccant, which can cause co-adsorption of CO2 on this
desiccant at a good dew point (D.P., around -50°C) and a yield of this co-adsorption reaching several
percentage points of the overall CO2 recovery has occurred. Although we are now investigating an
alternative desiccant with a smaller co-adsorption potential of O32, CO2 recovery was attempted by
recireulating some of the desorbed gas from the dehumidifier tower to the inlet of the pilot plant, for
an improvement in terms of the system configuration. As a result, about 3% curtailment of the
required power consumption could be obtained.

Energy consumption required for 032 removal

In the test results, the target removal efficiency of 90% and 99% purity of the removed CO2 were
achieved.
932 ISHIBASHI et al.: REMOVING CO2 FROM POWER PLANT FLUE GAS

Although the required power consumption had been 708 kWh/t-CO2 in the initial period of a
series of these tests, it was reduced by about 21% to 560 kWh/t-COz in the most recent test results,
As described in a previous paper[2], efficiencies of auxiliary equipment and the like are
relatively low in this pilot plant, and it can fully be expected that their efficiencies will be raised
considerably when more efficient equipment is used in a full scale plant, which will lead to the
possibility of reducing the required power consumption to almost a half of the present value.

Effect of temoerature swing

For the temperature swing in the first stage of PTSA operation, a part of the product Co2 is
heated by steam and the parallel-flow purge is used to heat the interior of the towers. Comparison
between I operation and PSA operation using the parallel-flow purge alone, without using steam
heating, showed that addition of this temperature swing reduced the electric power consumption by
about 11% (in Fig.3). The main reason for this is that heating can cause the adsorbed Co2 to be
desorbed more readily, reducing the required amount of the regenerative purge gas and thus, the
required power consumption for the vacuum pump.

Effect of CO2 concentration in flue eases

In the case of physical adsorption, it is estimated that concentration of the process gas can
greatly affect the plant performance, and in this test about a 1.5% increase from 10% of the CO2
concentration in flue gases led to about a 25% drop in the electric power consumption, and thus, it
was found that the CO2 removal efficiency greatly depended on the CD2 concentration in the flue
gases (in Fig.3).

COz Concentration (~01% dry base)

Fig. 3 Comparison of Power Consumptions

for PSA and PTSA at Pilot Plant

Recycle Mode
600 - I I I 1 I
Several Conditions
z
Zo^
,E.z$$
8aa Recycle IMode
70 I I 1

T#$-----M.l,
28s- 0 400 800 1200 1600 2000
Time (hr)

Fig. 4 Continuous Operation Test

 ISHIBASHI et al.:REMOVING CO2 FROM POWER PLANT FLUE GAS 933
Continuous operation test
A continuous operation test over a period of 2000 hours was conducted to confirm stability of
the PTSA system. Auxiliary equipment such as the blower and the vacuum pump, etc. worked
satisfactorily without showing any particular problems and the performance could also be maintained
at a given point throughout this test period. The results are shown in Fig.4. Based on these results, it
was judged that practicability of this system could be shown.

Influence of SOx
Investigation was carried out to evaluate how SOx contained in flue gases affects the
adsorben[4].
Alumina as the desiccant in the primary stage captured sulfuric acid in a form of aluminium
sulfate at its lower part without showing changes in dehumidifier performance and no accumulation
of SOx was found in the CO2 adsorbent removed after operation of 2000h, and thus, it was judged
that the desiccant could play a role of a guard filter. Furthermore, since a large drop in CO2
adsorption performance could not be observed after 4000h of operation, it was also judged that
durability of the CO2 adsorbent was high.

5. CONCLUSIONS

The PTSA method was investigated as one of techniques to remove CO2 from flue gases in
thermal power plants.
In our fundamental research, an optimal CO2 adsorbent was selected and the PTSA system
demonstration could be performed in a pilot plant.
A promising outlook to future reduction of power consumption for CO2 removal could be
obtained and from a verification test on stability of this system using 2000 hours of a continuous
operation, it was found that this system had a high practicability.
In a further research, we will work on the research of high performance adsorbent, on the scale
up possibility of this system and on methods to reduce the required power consumption.

REFERENCES

1. N. Nishikawa, Proceeding of 26th Annual Meeting of SCEJ, Q103 (1993).

2. N. Nishikawa, M. lshibashi, H. Ohta, A. Yasutake, H. Nohara and H. Nawata, Proceeding of 26th
Annual Meeting of SCEJ, Q108 (1993).
3. M. Ishibashi, H. Ohta, N. Akatsu, S. Umeda, A. Mori, N. Oda, M. Yamada, A. Yasutake, H.
Nohara, J. lzumi and Y. Kageyama, Proceeding of CSPE-JSME-ASME ICOPE-95,990 (1995).
4. N. Nishikawa, M. Ishibashi, H. Ohta, J. Izu mi, A. Yasutake, H. Nohara and Y. Kageyama,
Proceeding of 27th Annual Meeting of SCEI , K314 (1994).