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Energy Procedia 105 (2017) 2022 – 2027

The 8th International Conference on Applied Energy – ICAE2016

CO2 methanation: the effect of catalysts and reaction

conditions
Kristian Stangeland1, Dori Kalai1, Hailong Li2, Zhixin Yu1*
1
Department of Petroleum Engineering, University of Stavanger, 4036 Stavanger, Norway
2
Department of Energy, Building and Environment, Mälardalen University, 73123 Västerås, Sweden

Abstract

Great attention has been paid to develop non-fossil fuel energy sources to reduce carbon emissions and create a
sustainable energy system for the future. Storing the intermittent energy is one of the challenges related to electricity
production from renewable energy resources. The Sabatier reaction produces methane from carbon dioxide and
hydrogen, with the latter produced by electrolysis. Methane could be stored and transported through the natural gas
infrastructure already in place, and be a viable option for renewable energy storage.
Current technology for biogas upgrading focuses on removing carbon dioxide from the biogas. However, the biogas
could potentially be used directly as feed gas for the Sabatier reaction, thereby removing the cost associated with
carbon dioxide removal and increasing the methane yield and carbon utilization from biological sources.
Carbon dioxide methanation requires a catalyst to be active at relatively low temperatures and selective towards
methane. Nickel based catalyst are most widely investigated, and commercial catalysts are typically nickel on
alumina support. Focus on catalyst development for carbon dioxide methanation is predominantly related to support
modification, promoter addition, as well as utilizing new class of materials such as hydrotalcite-derived catalysts.
© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2016 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and/or
Peer-review responsibilityunder
under peer-review of the responsibility of ICAE
scientific committee of the 8th International Conference on Applied Energy.

Keywords: Sabatier reaction; CO2 methanation; energy storage; biogas upgrading; reaction conditions; nickel catalyst

1. Introduction

A major part of today’s energy derives from fossil fuels, which result in increased carbon dioxide
(CO2) concentration in the atmosphere and thereby causing global warming through the greenhouse
effect. Significant efforts are being made to replace the conventional fossil fuels by renewable energy
sources such as wind or solar energy. One of the main challenges with the growth of renewable energy
production is intermittency, which requires balancing of the electricity production and/or storing of the

* Corresponding author. Tel.: +47-5183-2238; fax: +47-5183-2050

E-mail address: zhixin.yu@uis.no

1876-6102 © 2017 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/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
doi:10.1016/j.egypro.2017.03.577
 Kristian Stangeland et al. / Energy Procedia 105 (2017) 2022 – 2027 2023

excess energy [1]. On the other hand, CO2 emissions result in large amounts of carbon being wasted,
which is the building block of fossil fuels and petrochemicals. The most commonly studied technology to
reduce CO2 emissions is Carbon Capture and Sequestration (CCS), which consists of CO2 capture,
transportation and underground storage. Alternatively, the captured CO2 could be utilized and converted
into fuels and chemicals, such as dry reforming of methane for synthesis gas production, or CO2
hydrogenation to CH4, methanol or higher alcohols.
The methanation reaction, also called the Sabatier reaction, was first studied by Sabatier and
Senderens in the beginning of the last century [2]. Early use of the technology was to remove trace carbon
oxides from the feed gas for ammonia synthesis [3]. Recently, the CO2 methanation has gained renewed
interest due to its application in the so-called power-to-gas technology [4] as well as biogas upgrading
[5]. In power-to-gas technology, hydrogen produced from excess renewable energy is reacted with CO2
(from power plants, industrial or biogenic processes) and chemically transformed to methane, which can
be stored and transported through the well-developed natural gas infrastructure already in place.
Technology related to biogas upgrading mainly consists of CO2 removal [6]. However, the biogas
consisting of a mixture of CH4 and CO2 could potentially be used directly as feedstock for CO2
methanation. In this way the biogas is upgraded to high purity methane and can meet natural gas grid
standards without CO2 removal. Removal of certain impurities, such as sulfur containing compounds,
from the biogas appears necessary to avoid catalyst deactivation [7]. The CH4 present in the biogas could
be beneficial with regards to temperature control in the exothermic process, where the CH4 could act as a
diluent.
On the other hand, challenges related to implementation of the reaction still have to be resolved. The
process parameters and catalyst affect the product yield. Considerable efforts have been devoted to
investigate various aspects of CO2 methanation ranging from the catalytic aspect to process design and
challenges related to implementation [4, 7]. The catalysts being developed today normally show high
selectivity for CH4, but improving the conversions at lower temperatures is still of importance.
Furthermore, the effect of the reaction conditions such as temperature, pressure, gas hourly space velocity
(GHSV), as well as initial CH4 concentration will affect the CO2 conversion and methane selectivity. This
review briefly summarizes the effect of these reaction conditions and recent advances in catalyst
development for CO2 methanation.

2. The effect of reaction conditions

2.1. Thermodynamics: effect of temperature and pressure

Methanation of CO2 is an exothermic reaction in which H2 and CO2 react to form CH4 and H2O. The
reaction stoichiometry is shown in equation 1.

CO2 + 4H2 → CH4 + 2H2O ∆H = -165 kJ/mol (1)

The most widely accepted mechanism of the methanation reaction is the combination of an
endothermic reversed water gas shift (RWGS) reaction and an exothermic CO methanation, as shown in
equation 2 and equation 3, respectively.

H2 + CO2 → CO + H2O ∆H = 41 kJ/mol (2)

3H2 + CO → CH4 + H2O ∆H = -206 kJ/mol (3)

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The overall reaction in equation 1 is favored at lower temperature, but due to kinetic limitations, a
catalyst needs to be utilized [8]. Analysis of equilibrium composition in COx (x = 1, 2) methanation by
the Gibbs free energy minimization method was performed by Gao et al. [9] and the end product fractions
are shown in Fig. 1 (a). Theoretically, the optimal operating window for CO2 methanation is at low
temperatures, where the conversion of CO2 and CH4 selectivity can reach close to 100 %. However, the
reaction rate increases with temperature. Increasing the temperature above 500 oC is favorable for the
RWGS reaction and therefore the reaction is not investigated above 500-600 oC. Additionally, high
temperatures require increased catalyst stability and can result in carbon deposition [5].
According to le Chatelier’s principle, the CO2 methanation is favored at elevated pressures. The effect
of pressure on equilibrium conversion of CO2 was calculated and is shown in Fig. 1 (b) [9]. As can be
seen, in the typical temperature range of 200-500 oC, increasing the pressure is effective up to a certain
point and further increase of pressure is less effective. A pressure of 10 to 30 atm is considered mild in
terms of stress on the catalyst and should therefore not cause sintering for the catalyst.
Carbon deposition theoretically does not occur if the H 2/CO2 ratio is equal to or higher than the
stoichiometric ratio [9]. On the other hand, thermodynamic simulations performed by Jürgensen et al. [5]
found that elevated pressure increased the temperature at which carbon deposition would occur from 365
o
C at 1 bar to 515 oC at 11 bar. Additionally, the selectivity for methane was improved at elevated
pressure in both studies.

Fig. 1. (a) Equilibrium product fraction for CO2 methanation calculated at 1 atm; (b) the effect of pressure on CO2 conversion at
different temperatures. [9]

Catalyst evaluation is mostly conducted at atmospheric pressure. However, pressure is of great

importance in terms of optimizing the process. Temperatures above 500 oC can cause sintering and
increase carbon deposition, leading to catalyst deactivation. Thus, temperature control is vital as the
exothermic methanation reaction will result in apparent temperature increase in large-scale operations [5].

2.2. Effect of Gas Hourly Space Velocity (GHSV)

GHSV is defined as the ratio of the volumetric flow rate of reactants at standard conditions (25 °C and
1 atm) to the total catalyst volume. If the quantities of catalyst and reactants are in the same units, GHSV
is frequently expressed in h-l (inverse time). For a granule catalyst, GHSV is frequently expressed in SmL
(gcat.h)-l. A higher GHSV implies a shorter time that the reactants are in contact with catalyst.
Abate et al. [10] investigated the effect of GHSV on a Ni/Al 2O3-TiO2-CeO2-ZrO2 catalyst at
temperatures from 250 to 400 oC. The feed gas consisted of a H2/CO2 ratio of 4, and was diluted in 87.5%
N2. The GHSV was varied between 20000, 25000, and 30000 h-1. At temperatures above 350 oC the CO2
 Kristian Stangeland et al. / Energy Procedia 105 (2017) 2022 – 2027 2025

conversion and CH4 yield was found to be almost identical and close to equilibrium, which is apparently
limited by thermodynamics. However, substantially higher CO2 conversion and methane yield was
observed at temperatures below 350 oC as the GHSV was reduced. This is expected because the reaction
is operated below thermodynamic equilibrium and a higher GHSV will result in lower CO2 conversions.
The CO selectivity data is quite close at different GHSVs, while a higher GHSV will give a slightly
higher CO yield, which could be explained by the reduced chance for the hydrogenation of CO.

2.3. Effect of initial CH4 concentration

The CH4 content in the gas mixture does not significantly affect the conversion, but an increase in
carbon deposition will occur at temperatures above 400 oC due to the methane cracking reaction [9]. The
influence of CH4 in the biogas feed was investigated by Jürgensen et al. [5] by thermodynamic
calculations. The conversion of CO2 decreased from 96% to 92% at 1 bar when the CH4 fraction was
increased from 0% to 64%. However, by increasing the pressure, this influence was compensated quickly.
At a constant pressure of 10 bar, the conversion decreased from 98% at 0% CH4 mole fraction to 97% at
64% CH4 fraction in the biogas feed stream. Above 8 bar there is just a very small influence of the CH4
content in the feed stream on the conversion of CO2. The results clearly indicate that CH4 removal before
the Sabatier is not necessary if the operation pressure is elevated. The CH4 cracking reaction was again
proposed to be the main cause of carbon deposition.

3. Catalyst development

Ni and Ru based catalysts produce almost exclusively CH4, while less reactive metal catalysts of Pd,
Pt, Rh, Mo, Re and Au simultaneously produce CH4, CH3OH and CO (by RWGS) in CO2 methanation.
Cu and Ag catalyze mainly CH3OH [12]. Supported Ni catalyst are the most promising catalysts for COx
(x = 1, 2) methanation due to their good catalytic performance and relatively low price. Oxides such as
Al2O3, TiO2, ZrO2 and CeO2 are the most commonly used supports for nickel catalysts. Among them,
Ni/SiO2 and Ni/Al2O3 have been widely studied due to their good initial activities, which however often
suffers from sintering and serious carbon deposition at high temperatures [13]. Ni/Al2O3 based catalysts
seem to be mostly supplied by catalyst manufacturers, e.g., by Johnson Matthey, Topsøe and Clariant-Süd
Chemie [14]. Additionally, Ru based catalysts are also offered for the methanation processes [5, 14].
Recently, most of the attention on catalyst development for CO2 methanation has been support and
promoter improvement for Ni based catalyst. Composite support consists of two or more typical oxides
has been found to improve catalytic properties such as reducibility, active metal dispersion and stability.
A study by Cai et al. [15] investigated the effect of ZrO2 in a ZrO2-Al2O3 composite, where the support
was prepared by different methods before Ni impregnation. The improvements observed in dispersion
and reducibility was mainly attributed to ZrO2 inhibiting the incorporation of Ni species in the lattice of
γ-Al2O3. Improvement in CO2 conversion and CH4 selectivity were observed for all the ZrO2 promoted
catalysts, where the preparation method of the composite support had a high impact on the catalyst’s
performance.
Abate et al. [10] investigated a multi-composite support of γ-Al2O3-ZrO2-TiO2-CeO2, which was
synthesized by impregnating the γ-Al2O3 with the other metal oxides followed by precipitation.
Subsequently the synthesized support was impregnated with Ni precursor solution. Activity test showed
higher activity for the catalysts with the composite support, where the support containing the highest
fraction of TiO2, ZrO2 and CeO2 was superior.
Hydrotalcite (HT) has received much attention recently for Ni based catalyst. In HT-derived catalyst,
Ni species are found commonly in the form of mixed oxides solid solutions with the other added metals.
2026 Kristian Stangeland et al. / Energy Procedia 105 (2017) 2022 – 2027

Lei et al. [16] found that Ni-Al2O3-HT derived catalyst exhibited well-dispersed Ni nanoparticles, which
improved the CO2 conversion and CH4 selectivity compared to an impregnated Ni/Al2O3 catalyst. Large
amounts of strong basic sites existed on the Ni-Al2O3-HT catalyst, which facilitated the activation of CO2
and consequently promoted the activity.
Promoters can further enhance the performance of catalysts. Fe as a promoter for Ni based catalysts
has been extensively studied. The H2 adsorption on polycrystalline Fe is better than that of Ni and can
thereby enhance the activity [17]. Modification with alkaline earth metals could be used to enhance CO2
activation and increase the stability of the HT structure, where Mg has commonly been used in HT-
derived catalysts [18, 19]. Wang et al. [17] investigated the effect of Fe and Mg as promoters for Ni-
Al2O3-HT, where a pure Ni-Al2O3-HT catalyst was synthesized for comparison. Incorporation of Fe and
Mg was found to increase Ni dispersion and prevent crystalline growth of NiO particles. Fe was proposed
to inhibit the growth of the HT structure, and thus mainly cause the improvement in reducibility. On the
other hand, high Mg loading reduced the catalyst’s reducibility, and Mg can therefore enhance the
interaction of nickel with the support. In the activity tests, low amounts of Fe and Mg was found to
increase the activity of the catalyst, where Fe modification was superior at low temperatures.
Interestingly, ethane was observed at 200-300 oC with Fe, which increased at higher Fe loading.
Wierzbicki et al. [19] investigated the effect of La promoted Ni-Mg-Al2O3-HT catalysts. The addition
of La improved the reducibility of Ni species by weakening the interaction between Ni and the HT
matrix. Additionally, La affected the CO2 adsorption capacity through the introduction of medium
strength basic sites. The higher activity at lower temperatures was attributed to both the improved
reducibility and the increase in basicity. The loading of La was of importance, where an optimum was
found at a Ni/La ratio of 15/2.

4. Conclusion

CO2 methanation could have a wide range of important industrial applications, where power-to-gas for
intermittent renewable energy storage has been mostly investigated. Biogas upgrading through direct
methanation of the CO2 and CH4 gas mixture could be a competitive option instead of CO2 removal,
which is the main technique in biogas upgrading today.
In this short review, we emphasized that Catalyst development should focus on improving the reaction
rate at lower temperatures, while maintaining high activity and stability in an operating window up to ca
500 oC. Nanosized nickel particles appears to be the most promising non-precious metal catalyst to
achieve high conversion at low temperatures. Promoters can further enhance the catalyst by improving H 2
and CO2 activation, as well as the catalyst’s reducibility, active metal dispersion and stability. HT derived
Ni based catalysts are very interesting in terms of increased activity at lower temperatures, in addition to
high selectivity for CH4 and great stability.

Acknowledgements

The authors would like to thank the Department of Petroleum Engineering, University of Stavanger for
the financial support of this project.
 Kristian Stangeland et al. / Energy Procedia 105 (2017) 2022 – 2027 2027

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Biography
Zhixin Yu is Professor at Department of Petroleum Engineering, University of Stavanger,
Norway. He received his doctorate in Chemical Engineering from Norwegian University
of Science and Technology (2005). He has then worked as research scientist at SINTEF,
IRIS and Statoil. His main research interests are energy production by nanotechnology.