CO2 Conversion to Methane Project

Author: Aujchara Weerawong

Specialist, Technology Development, PTT Exploration and Production PCL

1. Introduction

The effect of greenhouse gas (GHG) content in the atmosphere is currently well-accepted by the public as the
reasons for extreme weathers the mankind are facing. Therefore, all authorities in the international and national
levels focus on the effective plan to mitigate or manage these GHG emissions.

For Thailand, natural gas in the gulf of Thailand is the key energy resource to power the country growth and
support extensive industry initiatives. However, as this natural gas resource contains variable content of the key
GHG i.e. carbon dioxide (CO2) over the sales specification of 23% CO2. It is, therefore, required that some field
development plan includes bulk CO2 removal prior to export into the pipeline. Producing CO2 along with natural
gas, PTTEP has a record of high CO2 (GHG) emission as compared to operators with same production level as
shown in Figure 1. Several GHG emission reduction projects are initiated, for example, hydrocarbon loss
reduction in the CO2-separation membrane, energy efficiency and waste heat recovery.

Figure 1 Forecast Green House Gas Emission in PTTEP Thailand Operations Source: Ref.1

Among the three key CO2 management options which are a) Afforestation and reforestation, b) CO2
capture and storage (CCS), and c) CO2 capture and recycle (CCR), PTTEP explores and/or pursues all these
CO2 management options as follows:

a) Afforestation and Reforestation: PTTEP has 10-year reforestation project with the 200,000 rais target.
The expected CO2 absorption is 620,000 CO2 ton equivalent in 2022. At present, the project already achieved
100,000 rais plantation in 2013-2014.
 PTTEP 10-Year Reforestation Project (2013-2022)
10 Year (2013-2022) 200,000 rai (6 Year Plantation)
2013 50,000
2014 50,000
2015 5,000
2016 15,000
2017 40,000
2018 40,000
2014-2020 Maintenance 200,000 Rai
2022 620,000 ton CO2 (absorption target)
Figure 2 PTTEP 10-year Re-forestation Project

b) CO2 Capture and storage (CCS): The option to re-inject the separated CO2 into depleted reservoir or
aquifers were studied in coordination with Government Authority and the key technical issues being the highly-
faulted, small reservoir sizes and the high re-injection pressures leading to high energy consumption and
unacceptably high product gas price.

c) CO2 Capture and Recycle (CCR): Table 1 gives the key advantages of CCR as compared to CCS
which is the available product to be used especially fuel or energy storage.

Table 1 Key Consideration for CO2 Management

CCS Carbon Capture and CCR Carbon Capture and
Storage Recycle
CO2 Purification Required Yes Yes
Product available for use No Yes
Continuous liability for CO2 Yes No
Leakage : onshore / offshore
Support Energy Demand No Yes
Large Geological Structure Yes No
Required

CO2 can be recycled or utilized with or without conversion reaction in various ways as shown in
Figure 3. However, the progress of CO2 conversion technology development towards the large/commercial
scale is quite different as shown in Table 2.

Figure 3 CO2 Utilization Options Source : Ref. 2

Table 2 Current Major CO2 Conversion Technology Development
Methane Methanol Liquid Fuel Polymer
Basic Reaction CO2 + 4H2  CH4 CO2 + 3H2  CH4 + CO2  C5- Polypropylene
+ 2H2O CH3OH + H2O 10Hn + H2O carbonate
H2 Source Water electrolysis Geothermal energy Methane -
Product Familiarity + Toxicity Equal amount of Unfamiliarity
consideration Infrastructure CH4 required
Pilot Scale Yes Yes Yes Yes
Industrial Scale No Yes** No Yes *
Note * [Ref. 3]
**
[Ref. 4]

As methane is widely accepted by the public as flexible and clean fuel e.g. compressed natural gas
(CNG) for automobiles and fuel for power plant, PTTEP pursues the CO2 conversion to Methane (CCM)
technology development with Hitachi Zosen Corporation that has developed the CCM catalyst since early
1980’s. The inventor for this catalyst is Prof. Koji Hashimoto of Tohoku Institute of Technology. CO2
conversion to methane (CCM) reaction follows the equation:

CO2 + 4H2  CH4 + 2H2O 300° C 1 atm

The reaction was discovered by Sir Paul Sabatier in 1912 using Ni-based catalyst. The reaction is
therefore called Sabatier reaction and Sir Paul Sabatier received Nobel Prize in chemistry after several years of
experimental work.[Ref. 5] With the green objective to reuse the CO2, it is necessary to use “green” H2 i.e. H2
that is generated from green source or from water electrolysis using renewable energy.

H2 Generation 
Renewable  from 
Energy 
Power Water 
Electrolysis

CO2
Methanation
Reactor

Figure 4 Key Technologies for CO2 Conversion to Methane Project

The known use of Sabatier reactor in the spacecraft converts CO2 from astronaut’s breath to generate
water and this water can be electrolyzed to obtain O2 (2 H2O  2 H2 + O2). The reaction and the catalyst had
been studied further for the application on Mars Expedition. Since Mars atmosphere contains 95% CO2 with no
known source of H2, the plan is to carry H2 to Mars to begin the reaction with the produced CH4 to be used for
the exploration vehicle engine and the H2O for use or as the source of O2 for breathing. [Ref. 6]

2. CCM Technology Application

The benefit of CCM technology can be shown in its various application as follows:

a) Renewable Energy (RE) Storage and Distribution

As the H2 used in the reaction comes from renewable energy (RE) which is uncertain/fluctuating in
nature, the key CCM technology application is for the RE (electrical power) storage and distribution in the form
of methane (chemical power). This adds the “distribution” benefit over the battery which allows only storage.
Also, as the higher heating value of methane product vs the much-lower heating value content of H2, the storage
is smaller. The Germany government concluded that CCM is the technology to be adopted to store and
distribute the vast amount of RE generated from solar and wind power. CCM is now critical path towards
Germany plan of 100 % RE use in the future.[Ref. 7]

Figure 5 shows the RE storage with CH4 generated from the surplus RE and this methane is used when
the RE is insufficient.

Figure 5 Basic Concept of Renewable Energy Storage with CCM Technology Source: Ref. 7

Figure 6 shows the scheme in which the high RE potential Hokkaido (both solar and wind power) can serve the
power demand in Tokyo metropolitan area using the RE to generate H2 for CO2 conversion to methane reaction
and CH4 can then be transported to Tokyo without the need for long and high-capital-investment transmission
line.

Figure 6 Wind Energy potential in Hokkaido and opportunity to serve Tokyo using CCM Technology.
Source : Modified Ushiyama, I, Wind Power Development in Japan, Mar 2012.
b) Biogas Upgrading

As the biogas is a mixture of CO2 and CH4, CCM technology offers more efficient single process
towards higher content of CH4 as compared to CO2 separation by the chemical absorption or membrane which
usually requires 2-steps or more and larger footprint.

c) Coal Gasification Product Gas upgrading

The Coal gasification technology is developed so that the large coal resource can be used with much
less GHG emission. However, the produced “syngas” (Mixture of H2, CO and CO2) cannot be readily used by
the public due to toxicity and other safety concerns. The conversion of this produced syngas to methane allows
well-accepted product of methane or synthetic natural gas (SNG).

Figure 7 Coal Gasification product upgrade to synthetic natural gas (SNG) readily usable by the public

d) High CO2 Natural Gas field Development

Several large natural gas resources contain high CO2 content e.g. 14% CO2 in Gorgon Field (Australia)
shown in Figure 8 and 71% CO2 in East Natuna Field (Indonesia). CCM technology allows the produced CO2
to be utilized instead of being re-injected (CCS) which incurs continuous risks of leakage.
Figure 8 Gorgon Field Development with CO2 re-injection to 2,500 m. depth beneath the Barrow Island
Source : Ref. 9

3. Joint R&D Project with Hitachi Zosen Corporation

R&D Cooperation in the CCM technology development commences in early 2012 with the 3 key areas of work

a) Catalyst binding agent study

Several binding agents are tested for optimum physical properties and durability in the high temperature
environment of CCM reactor.

b) Feed and Product cases consideration and catalyst testing

PTTEP and Hitachi Zosen Corp. jointly constructed the integral reactor (Figure 9) allowing the study of
reaction behavior similar to that of the actual reactor design.

Figure 9 Integral Methanation Reactor constructed in the CCM Project – December 2012
c) Conceptual design of the Reactor and Heat recovery systems

As the Sabatier reaction is exothermic reaction, waste heat recovery technology is also reviewed to
optimally capture and utilize the released energy in the process.

The reactor system conceptual design includes main equipment such as

 Feed gas pre-treatment

 Reactor
 Waste heat recovery system
 Product treatment

The results from catalyst testing and reaction rate examination were used as input to the process simulation
and conceptual design of 1,000 Nm3/h CH4 production system.

4. The Next Step of Pilot Unit Development

PTTEP and Hitachi Zosen will continue this critical technology development to next step of prototype or pilot
plant to be designed and constructed in Thailand, Rayong province. The technology development in this phase
will allow design optimization for operation reliability leading to larger / commercial unit size in 4-5 years.

5. Conclusions
With the focus on the green technology that manages CO2 from the reservoir, PTTEP believes in the great
benefit of CO2 conversion to methane which is using the GHG to become useful fuel or the renewable energy
storage or additional energy resources adding to the country energy independence for the benefit of the country.

The Cooperation between our partner, Hitachi Zosen Corporation, and PTTEP allows significant value towards
the scientific and corporate collaboration to mitigate the GHG emissions effect and create renewable energy
storage options for all.
 References
[1] Forecast of PTTEP Domestic Operations Green House Gas Emissions 2012-2020 TSH, January, 2015.

[2] Carbon Dioxide Utilization – Electrochemical Conversion of CO2 – Opportunities and Challenges, DnV
Research and Innovation, Position Paper 07-2011.

[3] Recycling Carbon Dioxide to make Plastics, Gizmag magazine, May 20, 2013.

[4] George Olah CO2 to Renewable Methanol Plant, Reykjanes, Iceland

http://www.chemicals-technology.com/projects/george-olah-renewable-methanol-plant-iceland/

[5] Nobel Lecture by Sir Paul Sabatier in 1912.

[6] In-situ Propellant Production on Mars : A Sabatier / Electrolysis Demonstration Plant, David L. Clark,
Lockheed Martin Astronautics, Denver Colorado 80201.

[7] Bioenergy and renewable power methane in integrated 100% renewable energy systems, Sterner, M.,
Renewable Energies and Energy Efficiency, Vol. 14, Fraunhofer, IWES, p. 106.

[8] Wakeyama, T., and Ehara, S., Estimation of Renewable Energy Potential and Use – A Case
Study of Hokkaido, Northern-Tohoku Area and Tokyo Metropolitan, Japan, World Renewable
Energy Congress 2011 – Sweden, 8-13 May 2011.

[9] Gorgon Fact Sheet : Carbon Dioxide Capture and Storage Project,
http://sequestration.mit.edu/tools/projects/gorgon.html, January 2015.