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Energy Procedia 63 (2014) 6120 – 6128

GHGT-12

Current Status of MHI CO2 Capture Plant technology, 500 TPD

CCS Demonstration of Test Results and Reliable Technologies
Applied to Coal Fired Flue Gas
Takuya Hirataa, Hiromitsu Nagayasua, Takahito Yonekawab *, Masayuki Inuib,
Takashi Kamijoa, Yasuo Kubotaa, Tatsuya Tsujiuchia, Daisuke Shimadaa,
Todd Wallc, and Jerrad Thomasc
a
Mitsubishi Heavy Industries, Ltd., 3-3-1, Minatomirai, Yokohama 220-8401, Japan
b
Environmental Systems & Chemical Plant Division, Mitsubishi Heavy Industries America, Inc.,
20 Greenway Plaza, Suite 600, Houston, TX 77046, United States
c
Southern Company Services, Inc., 600 North 18th Street / 14N-8195, PO Box 2641, Birmingham, AL 35291-8195, United States

Abstract

Mitsubishi Heavy Industries, Ltd. (MHI) has developed a high efficiency chemical solvent process, the KM-CDR® Process, in
collaboration since 1990 with Kansai Electric Power Co., Inc.. The process has been applied to eleven (11) commercial CO2
capture plants for natural gas-fired boilers. For coal-fired boilers, Southern Company and MHI successfully started the 500 TPD
carbon capture demonstration plant in June 2011 in Alabama. This operational experience and lessons learned of the actual plant
has helped facilitate scale-up CO2 capture plant. This experience has resulted in the world largest CO2 capture and compression
plant for coal fired boiler, the 4,776 MTPD-class unit in Texas, which is now under construction.
© 2013 The
© 2014 TheAuthors.
Authors.Published
Publishedby by Elsevier
Elsevier Ltd.Ltd.
This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of GHGT.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: CO2 Recovery; Coal Fired; Power Plant; Carbon Capture and Storage (CCS); Enhanced Oil Recovery (EOR); KM-CDR Process

* Corresponding author. Tel.: +1-713-351-6419.

E-mail address: takahito_yonekawa@mhiahq.com

1876-6102 © 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.644
 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128 6121

1. Introduction

It is now widely agreed that capturing CO2 from flue gases and the subsequent injection into geological
formations can significantly contribute to reducing CO2 emissions, the principal greenhouse gas. As well as having
benefits in terms of reducing CO2 emissions into the atmosphere, the deployment of Carbon Capture and Storage
(CCS) can also allow nations around the world to continue using important domestic fossil fuels, such as coal, in an
economic and environmentally sustainably way.
Among the CCS technology, Enhanced Oil Recovery (EOR) utilizing anthropogenic CO2 is believed to be an
effective use of CO2. EOR using natural CO2 was commercialized during the 1970s. Infrastructure of CO2 transport
pipelines is especially advanced in the U.S..
For commercialization of CCS and EOR, scale-up of equipment and energy reduction for CO2 capture and
compression are essential considerations. Therefore, MHI is continuing to develop demonstration testing and scale-
up of CO2 capture plant utilized for flue gas from coal fired boilers.

2. Development of MHI’s CO2 Capture Technology

The conventional monoethanolamine (MEA) absorption solvent, which has been used for several decades, has the
following shortcomings:
x it requires a high amount of energy for regeneration
x the amount of absorption solvent loss is significant
x it generates a large amount of degraded product, such as Heat Stable Salts (HSS), requiring frequent reclaiming
to remove the degraded product and HSS
In order to overcome these issues, MHI investigated the molecular structure of the absorption solvent and tested a
number of available amine compounds. Consequently, MHI developed the KS-1™ absorption solvent, jointly
developed together with Kansai Electric Power Co., Inc., which features low energy consumption, minimal solvent
loss and low corrosivity.
Figure 1 shows MHI’s commercial CO2 recovery plant operational experience and R&D experience. MHI has
developed further energy-saving measures for the process. To further reduce the amount of steam consumed, an
energy-saving process that utilizes the heat of the lean solvent and steam condensate repeatedly to regenerate the
absorption solvent has been developed.
MHI has already commercialized CO2 recovery technology targeting exhaust gas from natural gas-fired boilers,
oil-fired boilers and gas turbines and to date, eleven (11) units have been delivered for commercial application and
are currently under operation.
The commercial plant in Malaysia was started up in 1999 as the first plant employing our unique technology, and
recovered CO2 has been used to increase urea production. This plant has operated smoothly and continuously for
more than 10 years, proving its reliability. In August 2014, the plant in Qatar started operation for enhancement of
methanol production.
These commercial experiences are the results of the testing of long standing by R&D. For application to coal
fired boilers, MHI accumulated technology and know-how from many pilot plants. As a result, the world largest CO2
capture and compression plant for coal fired boiler, the 4,776 MTPD-class unit in Texas, is now under construction
as twelfth commercial application of KM-CDR® process.
6122 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128

1990 1995 2000 2005 2010 2015

Plant Operation Malaysia (200t/d)
Japan (330t/d)
India (450t/d)
Natural Gas India (450t/d)
India (450t/d)
CO2 Recovery (CDR) Plant –
IFFCO AonlaUnit (India)
CO2 Recovery (CDR) Plant –
IFFCO Phulpur Unit (India)
Bahrain (450t/d)
UAE (400t/d)
Vietnam (240t/d)
Pakistan (340t/d)
India (450t/d)
Qatar (500t/d)

Hiroshima Pilot (1t/d)

Coal Japan Pilot(10t/d)
USA Demo (500t/d)
USA Commercial (4,776t/d)

R&D Laboratory
Solvent Nanko Pilot (2 t/d)

Packing Packing

Amine Loss Amine Loss Amine Loss Emission Reduction

Process System Control Regeneration Dynamic Simulation

Scale Up

Impurities Treatment (SOx) Impurities Treatment (Dust, SO3)

Cost Reduction

Fig. 1. MHI’s commercial CO2 recovery plant operational experience

3. Considerations for CO2 Capture from a Coal Fired Boiler

The flue gas of coal fired boilers includes SOx, dust, and other impurities. Furthermore, coal fired boilers
operational load is frequently changed in accordance with electricity demand. The flue gas condition, such as the
flow rate and CO2 concentration, are changed with the boiler operation load. Therefore, the following considerations
for CO2 capture from a coal fired boiler need to be carefully verified with long term demonstration and testing.

x Understanding the influences of dust accumulation in system

x Amine emission increase caused by SO3 in flue gas
x Influence of coal fired boilers operation load

4. Considerations for CO2 Capture from a Coal Fired Boiler

4.1. Project Overview

The 500 MTPD coal fired demonstration project is part of a start-to-finish CCS project (Figure 2). The
demonstration plant is installed at Southern Company’s Plant Barry, and the flue gas is drawn from the main duct
downstream of the existing Flue-Gas Desulfurization (FGD) prior to CO2 capture.
The CO2 capture and compression demonstration project has been predominantly self-funded by Southern
Company and MHI and collaboratively executed by Southern Company Services, Inc. (SCS) and Mitsubishi Heavy
Industries America, Inc. (MHIA). Figure 3 shows an aerial photo of the plant. The captured and compressed CO2
was supplied to a pipeline which is part of the Department of Energy (DOE) funded Southeast Regional Carbon
Sequestration Partnership (SECARB) phase III “Anthropogenic Test”. SECARB transported CO2 to the Citronelle
field 12 miles from Plant Barry. The CO2 was injected into the Citronelle field, operated by Denbury Resources, at
roughly 9,500 ft. CO2 injection operations will continue in 2014, and post-injection monitoring will take place
through 2017.
 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128 6123

CO2
Absorber

SCS/MHI SECARB Regenerator

Alabama Power Plant Barry

Boiler SCR ESP FGD

CO2 CO2 Compressor
Sequestration
CO2
CO2
Compression
Recovery Inlet
Dehydration
Gas
From
Utilities FGD

Fig. 2. Block Flow of the Project Fig. 3. Aerial Photo.

4.2. Operation Achievement

The plant was successfully started in June 2011, and the captured and compressed CO2 has been injected since
August, 2012. Table 1 shows the basic flue gas condition and Table 2 shows the operation results summary. Figure 4
also shows the operation history. The plant had been operated for a cumulative 10,600 hours. During that time
198,000 tons of CO2 capture and 100,600 tons of CO2 storage were achieved while maintaining stable operation in
October 2013. The operation was conducted with a high reliability (>98%).

Table 1. Operation Results Summary

Items Operation Results
Capacity 25 MW equivalent
Flue gas flow rate 73,805 SCFM (116,840 Nm3/hr)
CO2 concentration in flue gas 10.1 mol%-wet
CO2 removal efficiency 90 %
CO2 production (CO2 capture rate) 500 MTPD (150,000 MTPY)

Table 2. Operation Results Summary (as of end of October 2013)

Items Operation Results (as of the end of October 2013
Total operation time 10,600 hrs
Total amount of captured CO2 198,000 metric tons
Total amount of stored CO2 100,600 metric tons
CO2 capture plant reliability >98 %
6124 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128

200,000
180,000 CO2 Captured
CO2 Captured[ton]
[ton] Boiler Off-line

160,000 CO2 Transportation

CO2 Transportation [ton]
[ton]
10,000 tons
140,000
Injected
120,000
CO2 [metric ton]

100,000
80,000
60,000
40,000 Injection Begins
8/20/12
20,000
0
Jun-11 Sep-11 Dec-11 Mar-12 Jun-12 Sep-12 Dec-12 Mar-13 Jun-13 Sep-13 Dec-13

Fig. 4. Operation History

4.3. Test Achievement

Emissions and Waste Streams Monitoring

Through numerous amine emission test campaigns in the small pilot test plant and laboratory scale test, MHI
discovered that the solvent emission increased significantly with SO3 concentration in the flue gas at the CO2
absorber inlet. SO3 in the flue gas, which is introduced into the CO2 absorber, is in the form of mist as the flue gas
temperature is lower than the acid dew point. SO3 mist absorbs the amine vapor while passing through the CO2
absorber, the mist, including the amine, is then discharged from the CO2 absorber top. This is the mechanism for the
amine emission increase caused by SO3.
This phenomenon should be considered and the amine emission caused by SO3 mist must be minimized for the
commercial plant. MHI has developed an amine emission reduction system for the KM-CDR® process and the
system was evaluated at the demonstration plant.
In Plant Barry, a sulfur burner was installed to supply
SO3 to the flue gas. Figure 5 shows the amine emission 100
MHI Conventional Technology
KS-1TM Concentration [ppm]

test results under the various SO3 concentrations in the

Amine Emission Reduction Technology
flue gas. SO3 concentration at the inlet of the quencher
and amine concentration in the treated flue gas leaving the
absorber tower were measured during the 2011-2013
emission testing campaign. The amine emission clearly
increased with SO3 concentration at the quencher inlet, 50
especially in the case of conventional washing and
demister system. MHI amine emission reduction
technology was tested and amine emissions were
significantly reduced to less than 1/10 compared with the
conventional system. MHI also measured total Volatile
Organic Compound (VOC) emissions and verified that the 0
commercial scale CO2 capture plant using KM-CDR® 0 1 2 3 4
Process will be acceptable. SO Concentration [ppm] 3

Fig. 5. KS-1TM Emission under the various SO3 concentrations

 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128 6125

Dynamic Response Evaluation Test

In general, coal fired boilers operational load is frequently changed in accordance with electricity demand. The
flue gas condition, such as the flow rate and CO2 concentration, are changed with the boiler operation load. However
the CO2 concentration can fluctuate even if the boiler operation load is stable. Again, the flue gas flow rate designed
for large scale CO2 capture plant can be larger than the actual flue gas flow rate from the boiler in the low load
operation, and the flue gas can be mixed with ambient air from the stack. For this reason, it is not easy to adjust the
operation condition manually and an automated operation control system is effective in following the flue gas
condition. The purpose of the control system is to optimize the operation condition following the boiler.
MHI developed the proprietary operation control system and demonstrated two (2) control systems in this project.
Figure 6 shows the concept of these control systems. Auto Load Adjustment Control System (ALAC) is the system
that changes the operation condition automatically and Optimized Operation Condition Control System (OOCC) is
the system that continuously follows the flue gas condition. The results of ALAC have been explained in previous
papers.
ALAC OOCC
(Auto Load Adjustment Control) (Optimized Operation Condition Control)

Optimized Operation Condition

Operation Load

Set Point
Actual Operation Condition

ON (Start to load up)

Time

Fig. 6. Concept of Dynamic Simulation Models

Figure 7, 8 and 9 shows comparison between manual operation and the Optimized Operation Condition Control
(OOCC). Figure 7 shows manual operation results and CO2 removal efficiency fluctuated as the flue gas condition
fluctuated. Figure 8 shows the operational trend under the OOCC, the CO2 capture rate was constant and the flue gas
flow rate was changed to keep the optimized operation condition. In addition, Figure 9 shows the operational trend
under the OOCC, the CO2 removal efficiency was constant and the flue gas flow rate was adjusted in accordance
with CO2 concentration in the flue gas. The above results highlight that KM-CDR® process was continuously
optimized by the control system and that MHI’s proprietary operation control system can be applied to the future
commercial plants.
550 100 16 100

500 95 15 95
CO2 Removal Efficiency [%]
CO2 Capture Rate [ton/d]

Flue Gas Flow Rate [%]

CO2 Concentration [%]

450 90 14 90

400 85 13 85

350 80 12 80
CO2 Capture Rate [ton/d] CO2 Concentration [%]
300 75 11 75
CO2 Removal Efficiency [%] Flue Gas Flow Rate [%]

250 70 10 70
0 2 4 6 8 10 0 2 4 6 8 10
Time [hr] Time [hr]

Fig. 7. Manual Operation (10 hrs)

6126 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128

550 100 16 100

CO2 Capture Rate [ton/d] 500 95 15 95

CO2 Removal Efficiency [%]

Flue Gas Flow Rate [%]

CO2 Concentration [%]
450 90 14 90

400 85 13 85

CO2 Capture Rate [ton/d]

350 80 12 80
CO2 Removal Efficiency [%]
CO2 Concentration [%]
300 75 11 75
Flue Gas Flow Rate [%]

250 70 10 70
0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3
Time [hr] Time [hr]

Fig. 8. OOCC Control Operation (CO2 injection following mode)

550 100 16 100

500 95 15 95
CO2 Removal Efficiency [%]
CO2 Caputure Rate [ton/d]

Flue Gas Flow Rate [%]

CO2 Concentration [%]

450 90 14 90

400 85 13 85

350 80 12 80

CO2 Caputure Rate [ton/d] CO2 Concentration [%]

300 75 11 75
CO2 Removal Efficiency [%]
Flue Gas Flow Rate [%]
250 70 10 70
0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3
Time [hr] Time [hr]

Fig. 9. OOCC Control Operation (Boiler Load Following Mode)

Long Term Impurities Influence Test

Coal fired flue gas has various impurities that influence the CO2 capture plant. This is the biggest concern to the
plant. MHI verified the influence of the impurities to KM-CDR® process in the demonstration project.
One of the impurities which affects CO2 capture plant is SO3. As shown in Figure 5, SO3 mist increases amine
emission significantly. To reduce amine emission from CO2 capture plant SO3 must be removed from the flue gas
upstream of CO2 capture plant, if SO3 concentration is high.
MHI verified that some impurities accumulated in the solvent however no critical issues, such as fouling to
impede the long term stable operation, were found. This means that the KM-CDR® Process could control impurities
in the solvent using a solvent purification system including a reclaimer. In addition, the corrosion in the plant was
within the expectation based on the material evaluation test, proving the material selection concept for KM-CDR®
Process was reasonable.

5. Road map for Commercialization of CO2 Recovery Technology for a Coal Fired Boilers

MHI’s long term strategy and road map to commercialization of CO2 recovery technology for coal fired boilers, is
based on know how gained from prior R&D, ongoing development activities, commercial CO2 recovery plant
 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128 6127

operational experience and other MHI coal based demonstration projects (Figure 10). As a result, MHI has received
an order for a large-scale commercial CO2 capture and compression plant for coal fired boiler.
For commercialization of CCS and EOR, the scale-up technology of equipment is required, and it is important to
demonstrate some tests of laboratory, bench, pilot and demonstration scale on a step-by-step basis. Regarding
commercial technology maturity, MHI is continuing to develop demonstration testing with Sothern Company and to
accelerate commercial viability of CCS/EOR.

MHI’s Experiences
9Commercial plant deployment
9Long term operational plant experience
9Large scale plant design complete

MHI’s Operating Experiences (More than 20 years: 1990-2014)

9Pilot plants (1-2 tpd)

9Small scale demonstration plant (10 tpd)
9Commercial plants (200-500 tpd)
9Experience with coal & natural gas
Plant
Barry

Matsushima

1 tpd 2 10 200 240 330 340 400 450 450 450 450 450 500 500 >3,000
Pilot scale experience Commercial Experience Commercial
5
(Natural Gas & Coal) (Natural Gas) (Natural Gas)
Pilot Demonstration Commercial
(Coal) (Coal) (Coal)

Fig. 10. Evolution and road map for commercialization of MHI CO2 recovery technology for coal fired boilers

The world largest CO2 capture and compression plant designed to capture CO2 from a 240 MW equivalent flue
gas from existing coal fired WA Parish Generation Station located in Thompsons, Texas. This project is provided
financial assistance by the U.S. Department of Energy (DOE) through the Clean Coal Power Initiative (CCPI).
Captured CO2 will be utilized for EOR at mature oil fields in the Gulf Coast region. This CO2 capture plant
consists of pre-treatment, CO2 absorption and regeneration, CO2 compression with dehydration and utility system.
The host power unit will not be decreased power efficiency because the electric power and steam for the CO2 capture
and compression system will be provided
by a cogeneration plant comprised of a
combustion turbine with a heat recovery
boiler. These advances are anticipated to
reduce captured CO2 costs and increase
system flexibility and efficiency.
This plan is expected to be
operational in 4th quarter, 2016. It is
expected that oil production will be
enhanced from 500 barrels/day to approx.
15,000 barrels/day. Furthermore, 1.4
million metric tons of greenhouse gas
will be used annually or injection into
geological formations.

Fig. 11. Rendering of WA Parish CO2 Project

6128 Takuya Hirata et al. / Energy Procedia 63 (2014) 6120 – 6128

6. Conclusion

MHI’s CO2 recovery technology has reached commercial level of large scale plant for coal fired boiler. MHI has
started to construct the world largest CO2 recovery and compression plant. This is the results of the know-how
gained from prior R&D, ongoing development activities, commercial CO2 recovery plant operational experience and
other MHI coal based demonstration projects.

The world largest CO2 capture and compression plant for coal fired boiler, the 4,776 MTPD-class unit in Texas, is
expected to be operational in 4th quarter, 2016.

For commercial technology maturity (optimization of steam utilization, energy reduction for CO2 capture and
compression and reduction of capital cost), MHI is continuing to develop demonstration testing with Sothern
Company and to accelerate commercial viability of CCS/EOR more.

References

[1] Hirata, T., Nagayasu, H., Kamijo, T., Kubota, Y., Tsujiuchi, T., Yonekawa, .T, Wood, P., Ivie, M., Irvin, N., Project Update of 500 TPD
Demonstration Plant for Coal-fired Power Plant , 11th international conference on Greenhouse Gas Control Technologies (2013)
[2] Yonekawa, .T, Inui, M., Kamijo, T., Tsujiuchi, T., Nagayasu, H., Nakagawa, Y., Jerrad, T., Todd, W., Project Update of 500 TPD
Demonstration Plant for Coal-fired Power Plant , Paper #39, Power Plant Pollutant Control “MEGA” Symposium, Baltimore, MD, 2014