Fuel 166 (2016) 276–296

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Review on methanation – From fundamentals to current projects

Stefan Rönsch a,⇑, Jens Schneider a, Steffi Matthischke a, Michael Schlüter a, Manuel Götz b,
Jonathan Lefebvre c, Praseeth Prabhakaran b, Siegfried Bajohr c
a
DBFZ – Deutsches Biomasseforschungszentrum gGmbH, Torgauer Straße 116, 04347 Leipzig, Germany
b
DVGW Research Center at the Engler-Bunte-Institute of the Karlsruhe Institute of Technology, Engler-Bunte-Ring 1, 76131 Karlsruhe, Germany
c
Karlsruhe Institute of Technology, Engler-Bunte-Institute, Fuel Technology, Engler-Bunte-Ring 1, 76131 Karlsruhe, Germany

h i g h l i g h t s

Comprehensive overview of CO and CO2 methanation technology.

Survey of methanation fundamentals, catalysts, and mechanisms.

Up-to-date overview of methanation research and projects.

a r t i c l e i n f o a b s t r a c t

Article history: Methane production from syngas goes back to more than 100 years of research and process development.
Received 21 August 2015 Early developments (1970–1980) using syngas from coal gasification plants primarily focused on fixed-
Received in revised form 22 October 2015 bed and fluidized-bed methanation technologies. Temperature control and catalyst deactivation, e.g.
Accepted 27 October 2015
caused by fouling and mechanical stress, were key issues of investigation.
Available online 31 October 2015
Due to the debate about a sustainable energy supply, research on methanation has been intensified
during the last ten years. Novel reactor developments comprise e.g. micro reactors and three-phase reac-
Keywords:
tors aiming at an advanced temperature control and a reduced complexity of future methanation plants.
Catalytic methanation
Substitute Natural Gas (SNG)
The developments are supported by detailed modeling and simulation work to optimize the design and
Power-to-gas dynamic behavior.
Biomass-to-gas To accompany and facilitate new methanation developments, the present work is aimed at giving
Reactor modeling researchers a comprehensive overview of methanation research conducted during the last century. On
Sabatier reaction one hand, application-orientated research focusing on reactor developments, reactor modeling, and pilot
plant investigation is reviewed. On the other hand, fundamentals such as reaction mechanisms and
catalyst deactivation are presented.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
2. Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
3. Methanation concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
3.1. History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
3.2. Established methanation concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
3.2.1. Adiabatic fixed-bed methanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 279
3.2.2. Cooled fixed-bed methanation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.2.3. Fluidized-bed methanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.2.4. Three-phase methanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.2.5. Market availability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

⇑ Corresponding author at: Deutsches Biomasseforschungszentrum gemeinnützige GmbH, Torgauer Str. 116, 04347 Leipzig, Germany. Tel.: +49 341 2434 451.
E-mail address: stefan.roensch@dbfz.de (S. Rönsch).

http://dx.doi.org/10.1016/j.fuel.2015.10.111
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
 S. Rönsch et al. / Fuel 166 (2016) 276–296 277

3.3. Research activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

3.3.1. Fixed-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
3.3.2. Fluidized-bed reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
3.3.3. Three-phase reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
3.4. Comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4. Demo projects and commercial plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4.1. CO methanation projects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4.2. CO2 methanation projects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
5. Catalysts, activation, and deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.1. Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.1.1. Active compound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.1.2. Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.1.3. Promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.2. Reduction and activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5.3. Deactivation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.3.1. Poisoning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
5.3.2. Vapor–solid reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
5.3.3. Thermal degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
5.3.4. Fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
5.3.5. Attrition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
5.3.6. Crushing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
6. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
6.1. CO methanation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
6.2. CO2 methanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
6.3. A consistent mechanism for CO and CO2 methanation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
7. Modeling and simulation of methanation reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
7.1. Modeling and simulation scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.2. Reactor modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.2.1. Time resolution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.2.2. Reactor dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
7.2.3. Phase modeling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.2.4. Temperature characteristic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.2.5. Kinetics approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
7.2.6. Software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
7.3. Plant modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
8. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
8.1. Methanation concepts and research. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
8.2. Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
8.3. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
8.4. Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
9. Abbreviations and symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293

1. Introduction

Methane is an energy carrier of significant importance to the Electricity grid

industry, energy, and transportation sectors worldwide. Its existing
distribution infrastructure in many countries makes it a constitu- Biomass/Coal
tive element of modern economies. The major share of industrially
used methane comes from fossil natural gas resources. However, O2 Gasification
the debate of the finiteness of fossil resources and climate change
caused the research expenditures relating to catalytic and biologi-
cal methane production from carbon oxide-rich gases (methana- Gas cleaning CO2
tion) to increase over the last years. Biological methanation Electric Syngas
proceeds at low temperatures (<70 °C) in stirred tank reactors or energy
CO methanation
trickle-bed reactors (e.g. [1–4]). In contrast, catalytic methanation
Raw SNG
is operated at temperatures above 250 °C, predominantly in fixed-
bed reactors. Research into catalytic methanation processes Power generation Raw SNG upgrading
focuses on two options, CO methanation and CO2 methanation.
SNG SNG

CO methanation (Eq. (1)) is an exothermic process using carbon
monoxide and hydrogen as educts for the catalytic production
Natural gas grid
of methane and water [5]. Educt gases mainly come from coal
or biomass gasification at synthetic fuel production plants
(Fig. 1) [6–8]. Fig. 1. Exemplary biomass/coal-to-SNG plant setup with CO methanation.
278
Electricity grid
Electric
energy
Electrolysis
H 2O
O2
Hydrogen
CO2 Gas mixing
Syngas
CO2 methanation
Raw SNG
Raw SNG upgrading Power generation
SNG
Natural gas grid
Fig. 2. Exemplary PtG plant setup with CO2 methanation.

CO2 methanation processes (Eq. (2)) use carbon dioxide and
hydrogen as educts. If electrolysis hydrogen is supplied as an
educt (PtG – Power-to-Gas), CO2 methanation allows for the
chemical storage of electricity (Fig. 2) [9–11,4].
Current research efforts relating to CO and CO2 methanation
primarily focus on the optimization of processes developed in the
1970s and 1980s and pick up on a multitude of findings from that
time. However, new methods (e.g. micro reactor manufacturing
[12–14]) and material properties (e.g. advanced heat transfer fluids
[15]) unleash a potential for the adaptation and optimization of
state-of-the-art technologies from the last century to meet new
requirements of a more and more decentralized energy system.
To accompany and facilitate new methanation developments, this
work is aimed at giving researchers a comprehensive overview of
methanation research in the last century and of new developments
against the background of a changing energy system. The overview
focuses on methanation fundamentals, concepts, projects, cata-
lysts, mechanisms, and modeling.
2. Fundamentals
Methanation processes aim to produce methane from hydrogen
and carbon oxides. The conversion of carbon monoxide is referred
Fig. 3. Pressure and temperature influence on the equilibrium composition of CO methanation and water–gas shift reaction (left: 300 °C, right: 1 bar). Educt gas composition:
yCO = 0.25, yH2 = 0.75.
S. Rönsch et al. / Fuel 166 (2016) 276–296
to as CO methanation (Eq. (1)), the conversion of carbon dioxide as
CO2 methanation, respectively (Eq. (2)).
1
CO þ 3H2
CH4 þ H2 O ðgÞ  206 kJ mol ðat 298 KÞ ð1Þ
1
CO2 þ 4H2
CH4 þ 2H2 O ðgÞ  164 kJ mol ðat 298 KÞ ð2Þ
Both reactions are basically exothermic. While the stoichiomet-
ric methanation of carbon monoxide releases 206 kJ heat per mole
(Eq. (1)), the conversion of carbon dioxide releases 164 kJ per mole
Electric
energy (Eq. (2)). For each 1 m3 methane (STP) produced per hour this cor-
responds to 2.3 and 1.8 kW heat, respectively. In addition, the reac-
tion is characterized by a significant volume contraction of the
reacting gases, which is stronger for CO methanation (volume
reduction by 50%) than for CO2 methanation (volume reduction
by 40%).
SNG CO2 methanation (Eq. (2)) is a linear combination of CO metha-
nation and reverse water–gas shift reaction (Eq. (3)), which always
accompanies the CO methanation reaction using nickel catalysts in
practical operation (see Section 6.2). However, conversion of CO2 is
inhibited, if the CO concentration exceeds a certain threshold
[16,17].
1
CO2 þ H2
CO þ H2 O ðgÞ 41 kJ mol ðat 298 KÞ ð3Þ
The equilibrium of both reactions is influenced by pressure and
temperature. Detailed studies regarding the pressure and temper-
ature dependence of methanation and water–gas shift reaction can
be found in literature (e.g. [18–21]). Basically, these studies rely on
thermodynamic equilibrium models available from commercial
process simulation software, such as Aspen Plus or Chemcad.
In thermodynamic equilibrium, high pressures favor the pro-
duction of methane. High temperatures, by contrast, limit methane
formation. The influence of pressure and temperature on the
chemical equilibrium of CO methanation and water–gas shift reac-
tion is shown in Fig. 3 by way of example. The equilibrium compo-
sition was calculated based on a simplified equilibrium model
described in [8] with equilibrium constants for CO methanation
and water–gas shift reaction taken from [22].
The influence of pressure and temperature on the equilibrium
composition of CO2 methanation and water–gas shift reaction is
presented in Fig. 4.
3. Methanation concepts
A high heat of reaction and sensitive catalysts make methana-
tion a challenging process with a long history of process develop-
ment and research. This development, the methanation concepts
developed, and current research activities are presented in the fol-
lowing chapter.
 S. Rönsch et al. / Fuel 166 (2016) 276–296
Fig. 4. Pressure and temperature influence on equilibrium composition of CO2 methanation and water–gas shift reaction (left: 300 °C, right: 1 bar). Educt gas composition:
yH2 = 0.8, yCO2 = 0.2.
3.1. History
CO and CO2 methanation processes were first discovered by
Sabatier and Senderens in 1902 [5] and have now been investi-
gated and developed for more than 100 years (Fig. 5).
The original and most important application of CO methanation
is the removal of carbon monoxide from syngases, e.g. in ammonia
production processes [23] and later upstream proton-exchange
membrane fuel cells [24]. CO methanation gained importance for
the production of SNG during the oil crisis in the late 1970s. The
aim was to produce a natural gas substitute using syngas from coal
gasification [25]. At that time, several methanation concepts were
developed. Comprehensive overviews of CO methanation develop-
ments of the 1970s and 1980s are given by Kopyscinski et al. [25]
and Rönsch and Ortwein [26].
CO2 methanation process developments primarily rely on CO
methanation research, but they were driven by the wish of using
alternative educt gases. Basic studies covering CO2 methanation
processes were performed in the 1980s (e.g. [27,28]). These studies
focused on the use of coke oven gas or blast furnace gas for down-
stream methanation. However, due to high efforts required for the
cleaning of these gases [29], only a few of those concepts reached
the commercial scale.
As a result of a growing environmental consciousness and the
urgent task of reducing anthropogenic greenhouse gas emissions,
research into CO methanation processes was reanimated at the
beginning of the 21st century. At that time, methanation projects
predominantly revived developments from the 1970s and 1980s.
In parallel, CO2 methanation processes gained new attention at
research institutions and in industry due to an increasing demand
Methanation for gas cleaning (ammonia synthesis, later proton-exchange membrane fuel cells)
1902 1910 1925
Fischer-
Haber-Bosch
Patent
Sabatier
Tropsch
Fig. 5. History of methanation; Abbreviations: Jap – Japan, Ger – Germany.
279
for electricity storage, which was caused by increasing shares of
wind and solar power (Power-to-Gas). Already in the 1980–
1990s did Hashimoto et al. [9] propose a combination of sea-
water electrolysis and CO2 methanation as a possibility to recycle
CO2 and prevent global warming. In 2009, this idea was revived
by Sterner [30], again for the prevention of climate change and
the storage of electric energy.
Over the last 50 years, several methanation concepts have been
developed. An overview is shown in Fig. 6.
3.2. Established methanation concepts
An overview about established methanation concepts is given
in the following.
3.2.1. Adiabatic fixed-bed methanation
3.2.1.1. Air Liquide (formerly Lurgi). In the 1970s, the Lurgi company
developed a methanation process based on two fixed-bed reactors
with intermediate cooling and gas recycling. This technology still is
commercially available from Air Liquide. Experience was gained
through many applications – for example, in crude oil refineries
(Schwechat, Austria [31]) or coal gasification plants (Beulah, North
Dakota, USA [32]).
3.2.1.2. Haldor Topsøe. Another methanation concept, which still is
commercially available, comes from the Danish company of Haldor
Topsøe. The so-called TREMP (Topsøe Recycle Energy-efficient
Methanation) process is similar to Lurgi methanation, but consists
of 3–4 instead of two adiabatic fixed-bed reactors (see Fig. 7) and
Biomass-to-Gas
PtG Jap PtG Ger
Coke oven gas (CO2-meth.)
Coal-to-Gas
1950 1973 1979 1984 2000 2014
Great Plains
Oil crisis
Oil crisis
Werlte
280 S. Rönsch et al. / Fuel 166 (2016) 276–296

Catalytic methanation concepts

Two-phase Three-phase
(gas/solid) (gas/liquid/solid)

Fluidized- Slurry
Fixed-bed reactorsc Structured reactorsr Fluidized-bed reactorsd
bed reactorsd reactorsr

Micro- Honey- Sorption-

Adiabatic Polytropic
channel comb enhanced

High Thotspot Low

Fig. 6. Overview of different methanation concepts; State of development: c – commercial, d – demonstration scale, r – research.

Syngas Reactor 1 Reactor 2 Reactor 3

Steam Boiler
Steam
super- feedwater
generator
heater preheater
Steam SNG
Recycle-gas cooler generator

Heat exchanger Low-temperature

heat recovery
Recycle-gas
compressor Condensate

Fig. 7. Exemplary fixed-bed methanation with intermediate cooling and gas recycle (TREMP adapted from Haldor Topsøe [35]).

focuses on high-temperature methanation (<700 °C). Since 1978,
several thousand hours of operation have been gathered from the
ADAM I project together with the Forschungszentrum Jülich and
the Rheinische Braunkohlewerke AG [33,34]. Recently, the TREMP
technology started operation at the GoBiGas plant in Gothenburg
(Sweden).
3.2.1.3. British Gas and Conoco. A similar methanation process with
three adiabatic fixed-bed reactors, intermediate cooling, and gas
recycling was developed by British Gas (BTG) and Conoco. In
1973, the process was tested for several hundred hours at the coal
gasification plant in Westfield (Scotland) [36]. Now, this technol-
ogy – named HICOM (High Combined Shift Methanation) – is avail-
able from the company of Johnson Matthey (Davy Technologies).
3.2.1.4. Ralph M. Parsons (RMP). To avoid gas recycling and internal
reactor cooling, the Ralph M. Parsons company suggested a reactor
concept with 4–7 adiabatic fixed-bed reactors in series. Tempera-
ture control of the exothermic methanation reaction was accom-
plished by intermediate gas coolers and a staged gas feed into
the reactors [36]. Nevertheless, a commercial plant of this technol-
ogy was not realized.
3.2.1.5. Imperial Chemical Industries (ICI) and Koppers. Another
once-through methanation process was developed by Imperial
Chemicals Industries and Koppers for syngas from the Koppers-
Totzek gasifier. The process used several fixed-bed reactors in ser-
ies with intermediate cooling. To limit catalyst temperature
increase inside the reactors, steam was added between the reactors
[25].
3.2.1.6. Clariant and Foster Wheeler. A further example of a com-
mercially available methanation process is the Vesta methanation
by Clariant and Foster Wheeler. This process – consisting of three
fixed-bed reactors in series with steam addition for temperature
control [37] – conceptually relies on the technology from Imperial
Chemical Industries (ICI) developed in the 1970s. However, adap-
tations to state-of-the-art syngases and catalysts have been made.
3.2.1.7. Johnson Matthey (Davy Technologies). The methanation
technology from Johnson Matthey (Davy Technologies) is based
on developments from the last century, namely, on HICOM metha-
nation from British Gas and Conoco. The concept is characterized
by the use of three adiabatic fixed-bed reactors with intermediate
gas cooling and gas recycling.
 S. Rönsch et al. / Fuel 166 (2016) 276–296
3.2.2. Cooled fixed-bed methanation
3.2.2.1. Linde. The Linde company developed another fixed-bed
methanation process. The process consists of a cooled reactor with
an integrated contorted heat exchanger and a second adiabatic
reactor. To control the carbon monoxide conversion and heating
rate inside the reactors, the educt gas is added in a flexible way
between both reactors [38]. The methanation concept was not
brought into commercial application. However, the developers
from Linde continued their work on isothermal reactors, which
nowadays are in operation for methanol synthesis worldwide.
3.2.3. Fluidized-bed methanation
3.2.3.1. Bituminous Coal Research Inc.. Due to the sophisticated pro-
cess control, fluidized-bed methanation processes were primarily
investigated by research institutions (e.g. the Synthane process of
the Bureau of Mines’s Fuel Technology Division). One of the first
fluidized-bed methanation processes developed by industry was
the Bi-Gas-Process of Bituminous Coal Research Inc. The reactor
contained two internal heat exchangers in the bed. The develop-
ment started in 1963 and the reactor was tested at the laboratory
for several thousand hours [39,40].
3.2.3.2. Thyssengas. Another fluidized-bed reactor concept with
internal heat exchanger was developed by Thyssengas GmbH,
Didier Engineering GmbH, and the DVGW-Forschungsstelle in
Karlsruhe (Germany). A first test plant of this COMFLUX process
was constructed in 1977 and a pilot plant was commercially
operated at the Ruhrchemie plant site in Oberhausen (Germany)
[41–43].
3.2.4. Three-phase methanation
3.2.4.1. Chem Systems Inc.. The Liquid-Phase Methanation (LPM)
concept was developed by Chem Systems Inc. in the 1970s and
was based on a single three-phase reactor operated up to 70 bar
[42]. The catalyst was suspended in an inert liquid phase (mineral
oil) enabling simple heat removal and temperature control. Besides
other reactors, a pilot plant producing 2000 m3 h1 was built. A Gas
Hourly Space Velocity GHSV of 4000 h1 (Eq. (4)) was aimed for
[44].
F V;STP
GHSV ¼
VR
Beside the different methanation concepts, there are several
options concerning the integration of the methanation unit in an
overall plant concept. A key decision for CO methanation plants
is, whether carbon dioxide should be removed upstream or down-
stream the methanation. On the one side, a carbon dioxide diluted
syngas limits the reactor heating due to the exothermal reaction.
On the other side, a diluted syngas stream is related to a higher
energy effort in case of an upstream gas compression.
3.2.5. Market availability
Not all methanation processes developed in the past currently
are commercially available. An overview of commercially available
CO methanation technologies is given in Table 1.
Table 1
CO methanation technologies available on the market.
Supplier Concept
Air Liquide (formerly Lurgi) 2 adiabatic fixed-bed reactors with gas recycling and intermediate cooling
Haldor Topsøe 3–4 adiabatic fixed-bed reactors with gas recycling and intermediate cooling
Clariant and Foster Wheeler 3 fixed-bed reactors with steam addition and without gas recycle
Johnson Matthey (Davy Technologies) 3 adiabatic fixed-bed reactors with gas recycling and intermediate cooling
Linde 1 isothermal fixed-bed reactor with internal contorted heat exchanger
281
Several CO2 methanation projects and process developments
were initiated in the last years. Similar to the CO methanation of
biomass-derived syngas, most of the recent CO2 methanation pro-
cess developments are based on methanation processes from the
1970s and 1980s. Nevertheless, essential adaptations regarding
e.g. reactor cooling and dynamic operation behavior had to be
made. Companies providing commercial technologies tailor-made
for CO2 methanation are summarized in Table 2. In addition, the
technologies listed in Table 1 can be basically applied in commer-
cial CO2 methanation plants.
3.3. Research activities
Even though methanation has been applied by industry for
many years, the demands of a changing energy system call for a
continuous optimization of state-of-the-art methanation technolo-
gies. Optimization approaches focus primarily on an enhancement
of temperature control, cost efficiency and methanation process
flexibility depending on the fluctuating availability of renewable
syngases.
3.3.1. Fixed-bed reactors
The main concern of fixed-bed reactor research for methanation
applications is reactor temperature control. It is important to meet
the SNG quality requirements for injection into the gas grid. More-
over, temperature control contributes to a cost-efficient process
design by reduction of equipment (e.g. recycle compressors, heat
exchangers). Investigation also focuses on process flexibility, i.e.
dynamic operation, of fixed-bed reactors. In this area, detailed sim-
ulation work is performed (e.g. [45,46,11]).
Several research groups focus on fixed-bed methanation devel-
opment and optimization. They primarily use cascades of adiabatic
or cooled fixed-bed reactors similar to the concepts developed in
the 70–80s (e.g. [47,45,48–51]).
To overcome the drawbacks of adiabatic fixed-bed reactors,
namely, temperature hot spots and high pressure drops, structured
reactors are under development. Due to their internal structure,
these reactors feature better heat transfer capacities and lower
pressure drops compared to adiabatic fixed-bed reactors
[52,53,14,13]. The structure improves radial heat transport by
ð4Þ
two or three orders of magnitude [54]. Examples of such reactors
are honeycomb reactors with catalyst coating and thermo-oil cool-
ing envisaged for small-scale methanation applications (see
Table 4) [55].
Table 2
CO2 methanation technologies available on the market.
Supplier Concept Technology name
Outotec Staged fixed-bed reactor Outotec methanation
with intermediate cooling
Etogas Fixed-bed reactor or plate Etogas methanation
reactor with steam cooling
MAN 1 isothermal fixed-bed reactor MAN methanation
with molten salt cooling
Technology name
Lurgi methanation
TREMP
Vesta
HICOM
Linde isothermal reactor
282 S. Rönsch et al. / Fuel 166 (2016) 276–296

Micro-structured reactors represent a further development of
structured reactors. They are characterized by a high surface-to-
volume ratio. However, it is more difficult to place the catalyst
onto the metallic structure and to replace it when it is deactivated.
The sorption-enhanced methanation reactor concept is another
further development of structured fixed-bed reactors [56,57]. In
this concept, the water produced during the methanation reaction
is adsorbed on the catalyst support. In this way, the thermody-
namic limitation of CO or CO2 conversion is reduced. Once the
adsorbent is fully loaded with water, the catalyst support can be
regenerated by applying temperature and/or pressure swing
methods.
3.3.2. Fluidized-bed reactors
Other research groups focus on the development of fluidized-
bed reactors. The Paul Scherrer Institute (PSI) built a fluidized-
bed methanation reactor with an SNG output power of 1 MW to
investigate and demonstrate the methanation of CO derived from
biomass gasification [19,58]. To further improve this process, a
pilot plant with an output power of 160 kW SNG is planned to be
constructed in Villingen (Switzerland) by PSI [59]. In addition,
the Engie gas company (former GDF SUEZ) recently started to com-
mission a Power-to-Gas demonstration facility with biomass gasi-
fication and methanation in fluidized-bed reactors. Fluidized-bed
reactors ensure effective heat removal, as a result of which one sin-
gle reactor can be used instead of a reactor cascade. Nevertheless,
this reactor concept also has drawbacks: fluidization of catalyst
particles results in high mechanical stress of the particles and reac-
tor walls, leading to catalyst loss and shorter reactor life. To tackle
this issue, the Chinese Academy of Sciences focuses on the devel-
opment of catalysts specially designed for fluidized-bed reactor
conditions [60,61].
3.3.3. Three-phase reactors
Götz et al. concentrate on three-phase methanation by investi-
gating hydrodynamics and heat transfer fluid stability [62,20]. The
Key Laboratory of Coal Science and Technology of Taiyuan (China)
focuses on the development of optimized catalysts for three-phase
methanation processes [63,64]. In three-phase methanation, the
liquid phase is characterized by a high heat capacity which allows
for effective and accurate reactor temperature control. The reactor
can be operated under isothermal process conditions even at high
load variations [11]. Drawbacks of this reactor concept are related
to the additional gas–liquid mass transfer resistance as well as to
the decomposition and evaporation of the heat transfer fluid.
three types of temperature profiles: adiabatic, isothermal, and
polytropic (Table 3). Kiewidt and Thöming [65] used the Seminov
number (Eq. (5)) to distinguish methanation reactors by the heat-
ing and cooling rate.
DaI  B Heat production rate
Se ¼ ¼ ð5Þ
St Cooling rate

Adiabatic fixed-bed reactors (Se ? 1)
Fixed-bed reactors without external or integrated cooling typi-
cally exhibit an almost adiabatic temperature profile with a dis-
tinct hot spot in the bed and high reactor exit temperatures.
Since methanation catalysts cannot withstand temperatures above
550–700 °C, gas recirculation or steam addition may be necessary
[34,35]. Main advantages are the high reaction rate (leading to a
high GHSV (Eq. (4))) and the possibility to produce steam at high
temperatures. However, the process setup is relatively complex.

Isothermal reactors (Se ? 0)
Fluidized-bed reactors and three-phase reactors ideally are
isothermal reactors. The process takes place at a temperature
ensuring total CO or CO2 conversion. This leads to a simple process
setup and a simple reactor. Furthermore, thermal load acting on
the catalyst is low. The limited reaction rates caused by isothermal
operation at moderate temperatures are a drawback of such reac-
tors. Another drawback, especially with regard to fluidized-bed
reactors, is a significant catalyst consumption due to attrition.

Polytropic reactors (0 < Se < 1)
Cooled fixed-bed and structured reactors (e.g. microchannel,
honeycomb) usually have a hot spot close to the inlet of the reac-
tor. In comparison to adiabatic reactors, however, the hot spot
temperature is significantly lower and the product gas leaves the
reactor at moderate temperatures (commonly about 300 °C). Such
polytropic reactors combine the advantages of isothermal and adi-
abatic reactors. The moderate hot spot leads to increased reaction
rates, whereas the lower outlet temperature enables high conver-
sion rates with respect to thermodynamic limitations. In general,
polytropic reactors are the most expensive ones.
4. Demo projects and commercial plants

3.4. Comparison A number of methanation projects were initiated in the last

years. Usually, these projects were associated with large research
The main difference between the methanation technologies is expenditures. Current projects at pilot or commercial scale are pre-
the temperature profile inside the reactor. In principle, there are sented in the following chapter.

Table 3
Comparison of different methanation concepts.

Concept Adiabatic FB reactors Cooled FB reactors Micro-reactors Fluidized-bed reactors Three-phase reactors
Operation mode Adiabatic Polytropic Polytropic Isothermal Isothermal
Reactor stages 2–7 1–2 1–2 1–2 1–2
Gas recycling Usually Sometimes No Sometimes No
Temperature range 250–700 250–500 250–500 300–400 300–350
Arrangement/State of cat. Packing Packing Coated Fluidized Fluidized or suspended
Particle size Millimeters Millimeters <200 lm 100–500 lm <100 lm
Mechanical stress of cat. Low Low Low High Moderate
Thermal stress of cat. High Moderate Moderate Low Low
Complexity of process setup High Low Low Low Low
Reactor costs Medium High Very high Low Low–medium
GHSV (Eq. (4)) Medium–high High High Medium–high Low–medium
Technology readiness level 9 7 4–5 7 4–5

FB: fixed-bed, cat.: catalyst.

 S. Rönsch et al. / Fuel 166 (2016) 276–296 283

Table 4
Current CO methanation projects at pilot and commercial scale.

Project name Location Capacity Methanation Status

a
GAYA Saint Fons 400 kW n.s. Pilot plant
(Engie) (France) SNG output (under construction)
GOBIGASa Gothenburg 20 MW TREMP Commercial plant
(Göteborg Energi) (Sweden) SNG output (in operation)
BioSNGa Güssing 1 MW PSIc Pilot plant
(EU project) (Austria) SNG output (not in operation)
Great Plains Synfuels Plantb Beulah 1500 MW Lurgi methanation Commercial plant
(Dakota Gasification Company) (North Dakota, USA) fuel input (in operation)
DemoSNGa Köping 50 kW KITc Pilot plant
(EU project) (Sweden) SNG output (honeycomb) (not in operation)
CPI projectb Yili City 6 billion m3 a1 TREMP Commercial plant
(CPI Xingjiang Energy Co.) (Xingjiang, China) SNG output (in operation)
Keqi projectb Chifeng 4 billion m3 a1 HICOM Commercial plant
(Datang) (Inner Mongolia, China) SNG output (in operation)
Fuxin projectb Fuxin 4 billion m3 a1 HICOM Commercial plant
(Datang) (Liaoning, China) SNG output (under construction)
Huineng projectb Ordos 1.6 billion m3 a1 TREMP Commercial plant
(Huineng Coal Electricity Group) (Inner Mongolia, China) SNG output (in operation)
Xinwen projectb Yili City 4 billion m3 a1 HICOM Commercial plant
(Xinwen Mining Group) (Xingjiang, China) SNG output (under construction)
Qinghua projectb Yili City 5.5 billion m3 a1 TREMP Commercial plant
(Qinghua Group) (Xingjiang, China) SNG output (in operation)
POSCO Projectb Gwangyang 0.7 billion m3 a1 TREMP Commercial plant
(POSCO) (South Korea) SNG output (under construction)

n.s.: not specified.

a
Biomass as fuel.
b
Coal as fuel.
c
Research institute.

4.1. CO methanation projects
An overview of CO methanation projects at pilot or commercial
scale is given in Table 4.
In 1984, the Great Plains Synfuels Plant in Beulah (North
Dakota, USA) started operation. It was the first large-scale
(>1000 MW fuel input) coal-to-SNG facility. The plant is based on
process developments from the 1970s (oil crisis) and is equipped
with Lurgi fixed-bed gasifiers, Rectisol gas scrubbing and Lurgi
fixed-bed methanation. It produces approximately 1500 MW SNG
from lignite [32].
The first pilot plant converting biomass (wood chips) into SNG
was the BioSNG plant in Güssing (Austria). The plant started oper-
ation in 2008 with a pilot-scale capacity of 1 MW SNG [66]. In
Güssing, syngas is produced by an allothermal fluidized-twin-bed
gasifier combined with sophisticated gas cleaning (filter, oil scrub-
bing, adsorption) [67] upstream of a fluidized-bed methanation
reactor designed by PSI [19].
In the last years, various other methanation projects using bio-
genic syngases were brought to pilot-scale (GAYA project [68],
DemoSNG project [55]; see Table 4) or commercial maturity
(GOBIGAS project [69]; see Table 4) in Europe. Climate change con-
cerns were the main drivers of those biomass-based projects and
continue to drive currently planned projects. An example of a pro-
ject planned is the Bio2G project of E.ON that is to be built in Land-
skrona or Malmö (Sweden) with an SNG output of 200 MW [70].
Another example is a project of the Energy Research Centre of
the Netherlands (ECN). The ECN scientists focus on the fixed-bed
methanation ESME (ECN System for Methanation), which is similar
to Lurgi methanation with several fixed-bed reactors, intermediate
cooling, and gas recycling. Together with the companies of Gasunie
and Dahlman, a first pilot plant with a fuel input of 4 MW is
planned to be built in Alkmar or Delfzijl (Netherlands). Here, ESME
will be combined with the ECN gasification technology MILENA
[71] and the oil-based gas cleaning device OLGA [72].
In recent times, further methanation projects were triggered by
Chinese investments for methane production from coal gasification
[73,74]. For these projects, primarily large-scale entrained-flow
gasification units are combined with methanation systems. Due
to the plant size, commercial, large-scale gas cleaning technology
(e.g. Rectisol scrubbing) and commercially proven methanation
processes (mainly TREMP, HICOM) are applied.
4.2. CO2 methanation projects
An overview of current CO2 methanation projects at pilot and
commercial scale is given in Table 5.
CO2 methanation projects mostly take place in Germany. This is
due to the transformation of the German energy system towards a
system that is 100% based on renewable energies which is associ-
ated by an increasing demand for chemical storage of electric

Table 5
Current CO2 methanation projects at pilot and commercial scale (without plants using coke oven gas).

Project name Location Capacity Methanation Status

Hashimoto CO2 recycling plant (IMR) Sendai (Japan) n.s. IMR Pilot plant 1996 (not in operation)
PtG ALPHA plant Bad Hersfeld (ZSW, IWES) Bad Hersfeld (Germany) 25 kW power input Etogas/ZSW Pilot plant 2012a
PtG ALPHA plant Morbach (Juwi AG, ZSW, Etogas, Etogas) Morbach (Germany) 25 kW power input Etogas/ZSW Pilot plant 2011a
PtG ALPHA plant Stuttgart (ZSW, Etogas) Stuttgart (Germany) 25 kW power input Etogas/ZSW Pilot plant 2009a
PtG test plant Stuttgart (ZSW, IWES, Etogas) Stuttgart (Germany) 250 kW power input Etogas/ZSW Pilot plant 2012
PtG test plant Rapperswil (Erdgas Obersee AG, Etogas, HSR) Rapperswil (Switzerland) 25 kW power input Etogas/ZSW Pilot plant 2014a
E-Gas/PtG BETA plant (ZSW, Audi, Etogas, EWE, IWES) Werlte (Germany) 6300 kW power input MAN Commercial operation 2013

n.s.: not specified.

a
Using the same portable methanation reactor (no simultaneous operation possible).
284 S. Rönsch et al. / Fuel 166 (2016) 276–296

energy and the compensation of fluctuating wind and solar energy about 120 times more expensive than Ni (mass basis) in 2015
provision. [81], however, it is not used for industrial-scale SNG production.
Between 2009 and 2012, different CO2 methanation plants Neglecting the price per gram, ruthenium is the catalyst of
reached pilot and in 2013 finally commercial scale (E-Gas project choice especially at low temperatures [82].
[75]; see Table 5). Educt hydrogen is basically produced by elec-
Nickel (Ni). Following the activity order defined by Mills and
trolysis units and mixed with CO2 from different sources (e.g. gas Steffgen [16], nickel is the most selective methanation catalyst.
bottles, biogas). The methanation technology of most of these pro- Because of this and because nickel still has a high activity and a
jects was delivered by the Etogas company. Either tube reactors comparatively low price, it is the most commonly applied active
with gas recycling or steam-cooled plate reactors are applied metal for commercial methanation applications.
[76]. The methanation technology of the PtG plant in Werlte was
Cobalt (Co). Cobalt catalysts exhibit a methanation activity sim-
supplied by MAN [77]. ilar to that of nickel, but cobalt is more expensive. Hence, they
are not that widely used for commercial applications as nickel
5. Catalysts, activation, and deactivation catalysts [83].

Iron (Fe). Iron catalysts are known to have a high reactivity, but
Besides the methanation reactor concepts, catalysts are crucial a very low selectivity towards methane. Thus, they are more
for methanation processes. Not only is the reactor design clearly often used in ammonia synthesis or in the Fischer–Tropsch pro-
influenced by the catalyst applied, its activity, and selectivity, but cess [84–86].
also are up- and downstream processes. An overview of methana-
Molybdenum (Mo). Compared to ruthenium and the iron group
tion catalysts, the reduction procedure, and its deactivation is metals (Fe, Co, Ni), molybdenum has a low methanation activ-
given below. ity. Another drawback is that molybdenum catalysts exhibit a
higher selectivity towards C2+ hydrocarbons than nickel [87],
5.1. Catalysts
which influences the maximum possible methane yield.
However, molybdenum catalysts have the highest known sulfur
5.1.1. Active compound
tolerance of all active metals described above [16]. In operation
In their early work, Sabatier and Senderens discovered that
they are usually in a sulfidic state.
nickel was able to catalyze the reaction between carbon monoxide
and hydrogen to form methane and water (Eq. (1)) [5]. Now, more
5.1.2. Support
than 100 years later, many metals mainly in groups 8–10 have
Not only does the active metal influence the activity of metha-
been found to be active for methanation reaction (Fig. 8).
nation catalysts, also supports, promotors, and preparation
Fischer et al. [78] studied these metals as unsupported metal
conditions are important to obtain a catalyst that guarantees high
catalysts under methanation conditions and found that their activ-
selectivity and activity [16]. Common supports for methanation
ity varies as follows:
catalysts are metal oxides of large surface area, e.g. Al2O3 (alu-
mina), SiO2 (silica), or TiO2 (titania). Among which Al2O3, especially
Activity: Ru > Ir > Rh > Ni > Co > Os > Pt > Fe > Mo > Pd > Ag
the c-modification, being used most frequently [88]. The supports
also influence the activity order of the catalytic metals mentioned
However, Fischer et al. were not able to consider differences
above [82]. Besides supported catalysts, there are also unsupported
regarding the metal surface area. Therefore, Vannice et al. [79]
kinds of methanation catalysts, such as Raney-Nickel [89], but they
published another order for the specific activity and selectivity of
also require large surface areas to reach a sufficient methanation
the respective metals:
activity. MoS2 is used as methanation catalyst in supported [90]
and unsupported [91] form. In recent years, quite a few results
Activity: Ru > Fe > Ni > Co > Rh > Pd > Pt > Ir
obtained for new kinds of catalyst supports were published, e.g.
Selectivity: Pd > Pt > Ir > Ni > Rh > Co > Fe > Ru
zeolites [92,93], foams [94,95], or biochar [96]. In general, the
active metal is supported to enlarge the catalyst surface area. A
According to Mills and Steffgen [16], the activity order can be
large surface area of a catalyst is obtained by supporting small par-
shortened to the metals that are ‘‘. . .important for methanation
ticles of active metals on large surface-area supports [97].
catalysts. . .”, namely Ru, Ni, Co, Fe, and Mo:

5.1.3. Promoters
Activity: Ru > Fe > Ni > Co > Mo
Sometimes, promoters are used for improving the supported
Selectivity: Ni > Co > Fe > Ru
catalysts. The promoter MgO is able to increase carbon resistance
[98] and thermal stability [99] of Ni/Al2O3 catalysts. Cobalt pro-

Ruthenium (Ru). Ruthenium is known to be the most active
moters may modify the surface structure of molybdenum catalysts
metal for methanation of CO, CO2, or mixtures [80]. As Ru is
such that catalytic activity for sulfur-resistant methanation is
6 7 8 9 10 11 improved [100]. La2O3 is found to increase the activity of an
24 25 26 27 28 29
Ni/Al2O3 catalyst by increasing Ni dispersion and H2 uptake
Cr Mn Fe Co Ni Cu [101]. V2O3 improves the activity, thermal stability, and coke resis-
Chromium Manganese Iron Cobalt Nickel Copper tance of a nickel catalyst [102]. An Ni/Al2O3 catalyst doped with
42 43 44 45 46 47 CeO2 reaches a higher reducibility and long-term stability than
an unpromoted one [103]. However, promotional effects are not
Mo Tc Ru Rh Pd Ag always positive. Potassium, for example, may increase the selectiv-
Molybdenum Technetium Ruthenium Rhodium Palladium Silver
ity of Ni catalysts towards higher hydrocarbons [104], which
74 75 76 77 78 79 certainly is an undesired effect for methane production plants.
W Re Os Ir Pt Au
Tungsten Rhenium Osmium Iridium Platinum Gold
5.2. Reduction and activation

Fig. 8. Excerpt from the periodic system of elements (active metals for methanation Before application, methanation catalysts have to be reduced. In
are marked in gray). contrast to many other catalytic processes (e.g. Fischer–Tropsch-
 S. Rönsch et al. / Fuel 166 (2016) 276–296 285

Table 6
Exemplary overview of Ni/Al2O3 reduction conditions.

Catalyst Catalyst mass in g Gas composition Gas flow in ml g1 min1 Temp. in °C Reduction time in h Ref.
10 wt.% Ni/Al2O3 0.2 100% H2 250 600 2 [107]
15 wt.% Ni/Al2O3 n.s. 100% H2 80 400 n.s. [108]
20 wt.% Ni/Al2O3 36.2 6% H2 in N2 14.3 320 5 [47]
5–40 wt.% Ni/Al2O3 0.5 100% H2 60 600 4 [98]
40 wt.% Ni/Al2O3 2.0 100% H2 50 600 4 [109]

n.s.: not specified.

Reduction procedures with different Ni/Al2O3 catalysts are

listed in Table 6. For all studies, H2 is the reducing agent of choice.
The reduction temperature and duration depend on the nature
of the catalyst (e.g. metal loading, surface area), i.e. on the active
metal and support. According to Doesburg et al. [105], reduction
of an Ni/Al2O3 catalyst at comparatively low temperatures favors
the formation of higher hydrocarbons in subsequent catalyst appli-
cations. An increasing reduction temperature, by contrast, causes a
higher reduction rate of the catalyst and, hence, a higher selectivity
towards methane and a higher activity. Still, it has to be considered
that an excessively high reduction temperature may cause sintering
of metal particles on the catalyst surface and, thereby, deactivation
of the catalyst itself [110]. Moreover, long-term stability may be
influenced negatively by increasing reduction temperatures.
Additionally, it is possible to re-reduce the catalyst by periodi-
cally alternating reaction and reduction conditions, called hydro-
gen bracketing technique [108]. This reactivation technique may
extend the long-term stability of a catalyst and decelerate catalyst
Fig. 9. Exemplary TPR profile of an Ni/Al2O3 methanation catalyst (own data).
deactivation.

Synthesis) nickel-based methanation catalysts do not require any

5.3. Deactivation
separate activation in addition to reduction. The reduction of
nickel-based methanation catalysts usually takes place in an atmo-
In general, the methanation reaction is catalyzed by the metals
sphere of hydrogen at temperatures ranging from 300 to 600 °C
of group 8–10 of the periodic table. Due to good selectivity, sulfur
(Table 6). The reduction process has a significant impact on the
tolerance, and price, nickel is preferably used in commercial
activity of the catalyst [105]. Detailed information on the behavior
methanation plants.
of a methanation catalyst under reductive conditions (increased
The deactivation of nickel-based methanation catalysts can be
temperature and hydrogen atmosphere) can be obtained by TPR
classified according to Bartholomew [111]. Bartholomew distin-
measurements (TPR – temperature-programmed reduction)
guished chemical, thermal, and mechanical catalyst deactivation.
[106]. A TPR-profile of an Ni/Al2O3 catalyst is given exemplarily
For commercial, nickel-based methanation processes, primarily
in Fig. 9. The temperature regions with considerable H2 consump-
two chemical, one thermal, and three mechanical kinds of catalyst
tion are the regions where the main reduction processes take place.
deactivation have to be considered (Table 7).
Each maxima of the profile may be linked to a component of the
catalyst that is reduced at the specific temperature. Taking into
account the component active in the methanation reaction, the 5.3.1. Poisoning
TPR profile may provide important information on optimum acti- Methanation catalysts react sensitively to a multitude of gas
vation conditions. impurities as chlorine compounds, tars, particles, ammonia, sulfur

Table 7
Mechanism of catalyst deactivation ([111] adapted).

Mechanism Description Relevance to methanation

Poisoning (chemical) Chemisorption of species on catalytic sites Chemisorption of sulfur (e.g. H2S, thiophenes)
(cf. [112])

Vapor–solid reactions(chemical) Reaction of fluid, support or promoter with catalytic Formation of nickel carbonyls at temperatures below 230 °C in the
phase presence of carbon monoxide
(cf. [34])

Thermal degradation (thermal) Thermally induced loss of active surface area Thermal sintering of active nickel especially in quasi adiabatic fixed-bed
reactors
(cf. [113])

Fouling (mechanical) Physical deposition of species from fluid phase onto the Carbon or coke deposition on nickel surface caused by the Boudouard
catalytic surface and into catalyst pores reaction or decomposition of higher hydrocarbons (e.g. tars)
(cf. [19])

Attrition (mechanical) Loss of catalytic material due to abrasion Attrition of active material in fluidized-bed reactors
Crushing (mechanical) Breakup of catalyst particles due to thermal or Thermal stress caused by reactor startup/shutdown; mechanical stress
mechanical stress caused by pressure fluctuations
286 S. Rönsch et al. / Fuel 166 (2016) 276–296
compounds or alkalis. Catalyst poisoning by sulfur compounds is
one of the main issues to be considered when planning and oper-
ating methanation plants [49,114]. Especially CO methanation
plants operating with syngases from coal or biomass gasification,
but also CO2 methanation plants using sulfur-containing carbon
dioxide streams from anaerobic biogas plants have to be equipped
with an appropriate sulfur removal system. Therefore, in general,
commercial technology such as absorptive Rectisol washing with
low-temperature methanol or adsorption with zinc oxide are
applied [8,115,116]. State-of-the-art nickel catalysts require sulfur
contents in the range of several parts per billion to maintain activ-
ity over hundreds of hours [6]. Catalyst poisoning by sulfur com-
pounds probably follows the chemical reaction equation (6). By
this reaction, hydrogen sulfide reacts with nickel oxide resulting
in nickel sulfide and water, with nickel sulfide losing its activity
for the methanation reaction.
H2 SðgÞ þ NiOðsÞ
NiSðsÞ þ H2 OðgÞ ð6Þ
In case organic sulfur compounds are present in the educt gas
(e.g. thiophenes from biomass gasification [112]), those com-
pounds are first hydrogenated to H2S and carbon hydrates (Eq.
(7)) and then react with Ni according to Eq. (6).
2H2 ðgÞ þ C4 H4 SðgÞ
H2 SðgÞ þ C4 H10 ðgÞ ð7Þ
5.3.2. Vapor–solid reactions
For methanation plants in stationary applications, catalyst-
deactivating vapor–solid reactions are of minor importance. With
typical gas compositions in methanation reactors, formation of
nickel carbonyls with carbon monoxide occurs at temperatures
below approximately 230 °C [34]. Due to the low methanation
activity of commercial catalysts below 250 °C, these temperatures
are generally avoided. Exceptions, of course, are startup and shut-
down phases of the methanation plant, where any contact between
catalyst and carbon monoxide has to be prevented. The
vapor–solid reaction leading to nickel carbonyls can be described
by Eq. (8). According to this equation, solid nickel enters the vapor
phase by forming nickel tetracarbonyl.
NiðsÞ þ 4COðgÞ
NiðCOÞ4 ðgÞ ð8Þ
At methanation plants that are operated dynamically or even
intermittently, vapor–solid reactions can occur during stand-by
operation under a pure CO2 atmosphere. According to Mutz et al.
[117], methanation catalysts undergo fast bulk-like oxidation in
this atmosphere.
5.3.3. Thermal degradation
Thermal degradation, i.e. nickel sintering, is a problem espe-
cially in adiabatic fixed-bed methanation reactors with a distinc-
tive hot spot. Its risk increases particularly under dynamic
operation conditions without appropriate countermeasures [45].
Sintering of the active catalyst leads to a loss of surface area and,
hence, a reduction of catalyst activity [118]. Depending on the cat-
alyst, temperatures above 500 °C have to be avoided. However, cat-
alysts for high-temperature methanation between 600 and 700 °C
are available on the market [113].
5.3.4. Fouling
In particular for CO methanation, prevention of fouling caused
by carbon deposition is one of the major challenges [19]. Carbon
deposition is no problem in CO2 methanation [20].
Catalyst fouling is the physical deposition of species from the
gas phase onto active catalyst material. In methanation processes,
especially the deposition of carbon and coke has to be prevented.
Carbon deposits are formed by the Boudouard reaction (Eq. (9)).
By this reaction, carbon monoxide is converted into carbon dioxide
and solid carbon, which deposits on the active nickel surface [19].
To avoid carbon deposits, steam can be added or the H2/CO-ratio
can be increased, as water and hydrogen react with the carbon
and inhibit the formation of stable carbon [20].
2COðgÞ
CO2 ðgÞ þ CðsÞ ð9Þ
Coke deposits originate from higher hydrocarbons (e.g. tars) at
temperatures between approximately 500 and 600 °C. Thereby,
hydrocarbons adsorb on the catalyst surface and release H2. Simul-
taneously, coke precursors are formed that finally turn into coke by
polymerization [19].
5.3.5. Attrition
The attrition of active catalyst material by abrasion is a problem
known in heterogeneous catalysis in moving-bed, fluidized-bed
such as (less importantly) slurry-bed reactors [111]. It is associated
with financial expenditures for make-up catalysts. To prevent any
destruction of downstream equipment, it is also important to
separate the abraded catalyst from the product gas [19]. For
methanation in fixed-bed reactors, attrition is no problem.
5.3.6. Crushing
Besides attrition, crushing of catalyst particles is another
mechanical deactivation mechanism. Crushing can be caused
either by thermal stresses (due to fast catalyst heating or cooling)
or by mechanical stresses (due to pressure fluctuations in the reac-
tor) [111]. Both situations may be associated with a startup and
shutdown of the methanation. Also load fluctuation by flexible
methanation operation of PtG or polygeneration plants, i.e. varia-
tions of the syngas flow rate, may lead to mechanical catalyst
stressing and crushing.
6. Mechanism
For further improvements of the methanation process and in
particular of the catalyst (e.g. sulfur resistance, thermal stability),
understanding of the reaction mechanism is of crucial importance.
For this reason, the mechanism of CO and CO2 methanation on
nickel-containing catalysts will be discussed below.
6.1. CO methanation
In the past, several reviews (e.g. [16,79,119–121,107]) and stud-
ies (e.g. [122–128]) were made with respect to CO methanation
using different catalytic materials. In addition, some mechanistic
studies of the hydrogenation of CO on Ni were published (e.g.
[122,129–136]). A selection of mechanisms suggested in literature
is given in Table 8.
Van Meerten et al. [129] studied kinetics and the mechanisms
of methanation of CO on a 5% Ni/SiO2 catalyst in a differential flow
microreactor at 187 6 T 6 567 °C, 133 6 pCO 6 8.7  104 Pa, and
7.3  103 6 pH2 6 9.3  104 Pa. They reported that the reaction
order in pCO increased with temperature, decreased with pCO , and
increased with pH2 while the reaction order in pH2 decreased with
temperature, decreased with pH2 , and increased with pCO . Van
Meerten et al. assumed that CO and H2 compete for the adsorption
on the same sites, since their reaction orders mutually interact.
Only less than 1% of the Ni surface is expected to be active for
the rate-determining step (RDS) of this suggested mechanism.
Hayes et al. [132] used a tubular microreactor with a sample
mass of up to 1 g at a pressure of 1.3 bar and temperatures
of 270 6 T 6 380 °C for dynamic response studies of
alumina-supported Ni catalysts prepared by impregnation and
co-precipitation. Furthermore, scanning electron microscopy,
X-ray photoelectron spectroscopy, and computer-enhanced
 S. Rönsch et al. / Fuel 166 (2016) 276–296 287

Table 8 Sehested et al. [136] investigated the methanation activity and

Mechanistic schemes for the catalytic hydrogenation of carbon monoxide. The adsorption of CO and H2 on a supported Ni catalyst and
symbols ⁄ and # represent ordinary (type 1) and 5-fold coordinated reaction sites
(type 2) [136], respectively.
micrometer-sized Ni threads with a mass of up to 0.4 g at low CO
partial pressures (pCO < 25 mbar) in single-pass and recirculation
Reaction step Description reactors at a total pressure of 1.4 bar (mostly H2) and temperatures
van Meerten et al.
 of 225 6 T 6 400 °C. Two different reactive sites were suggested:
CO þ 2  ¢ CO   Non-dissociative adsorption Type 2 sites (depicted by # in Table 8) are connected to 5-fold coor-
at low temperature
CO   ¢ C  þ O  and subsequent dissociation,
equilibrium
dinated sites that are energetically favorable for C adsorption only,
CO þ 2  ¢ C  þ O gat high temperature Dissociative adsorption, while type 1 sites are related to step edges (depicted by ⁄ in Table 8),
equilibrium where all other species can adsorb. It was found that CO and H2
H2 þ 2  ¢ 2H  Dissociative adsorption, compete for adsorption at low CO pressures, while the surface is
equilibrium
nearly completely covered by CO at higher CO pressures. The sug-
O  þ H  ¢ OH  þ  LH surface reaction, equilibrium
OH  þ H  ! H2 O þ 2  LH surface reaction, rate- gested mechanism (see Table 8) includes non-dissociative adsorp-
determining tion of CO and dissociative adsorption of H2 at type 1 sites. The
C  þ H  ¢ CH  þ  LH surface reaction, equilibrium dissociation of CO at type 2 sites, which might amount to 5% of all
CH  þ H  ! CH2  þ  LH surface reaction, rate- surface nickel atoms only [137,136], is defined as the RDS. This is
determining
supported by experimental findings of Dalmon et al. [130]. All
CH2  þ H  ! CH3  þ  LH surface reaction, fast
CH3  þ H  ! CH4 þ 2  LH surface reaction and hydrogenation reactions are expected to proceed with non-
desorption, fast adsorbed hydrogen (Eley–Rideal mechanism). Sehested et al. com-
Hayes et al. ment that the hydrogenation mechanism might be different at
CO þ 2  ¢ C  þ O  Dissociative adsorption, lower H2/CO ratios, where more than one RDS may be active. Since
equilibrium adsorbed CO is inactive relative to the active surface carbon, nega-
H2 þ 2  ¢ 2H  Dissociative adsorption,
tive reaction orders with respect to pCO result at moderate to high
equilibrium
C  þ H  ! CH  þ  LH surface reaction, rate- CO partial pressures and were observed by van Meerten, Dalmon,
determining and Sehested et al. [129,130,136].
O  þ H  ! CO  þ  LH surface reaction, fast Fujita et al. [133] calculated CO and C coverages in transient
CHj  þ H  ! CHjþ1  þ ; 16j62 LH surface reaction, fast response experiments during CO and CO2 methanation at atmo-
CH3  þ H  ! CH4 þ 2  LH surface reaction and
spheric pressure, 200 °C, and varying H2/COx ratios in a differential
desorption, fast
OH  þ H  ! H2 O þ 2  LH surface reaction and flow reactor containing 1.0 g of Ni catalyst. The Ni catalyst was
desorption, fast unsupported and made of commercial NiCO3. By reducing pH2 , C
Sehested et al. (low CO pressures) coverage increased, while the change in CO coverage was less pro-
CO þ  ¢ CO  Non-dissociative adsorption, nounced. Dissociation of adsorbed CO seemed to be independent of
equilibrium pH2 , while hydrogenation of adsorbed C (generating CH4) followed
H2 þ 2  ¢ 2H  Dissociative adsorption,
equilibrium a power law with p0:39 H2 . An appreciable amount of reversibly
CO  þ # ! O  þ C # Dissociation at type 2 sites, adsorbed CO seemed to be present during CO methanation, while
rate-determining it was practically negligible during CO2 methanation. The coverage
C # þ 2H2 ! CH4 þ # ER surface reaction and
of the surface with CO was typically higher than with C. Formation
desorption, fast
O  þ H2 ! H2 O þ  ER surface reaction and of CH4 was expected to take place via the formation of adsorbed C
desorption, fast by CO dissociation and subsequent addition of adsorbed H atoms
during CO and CO2 methanation.
multiple reflectance infrared spectroscopy were applied to investi-
gate the adsorption and desorption of CO, CO2, CH4, and H2 on the 6.2. CO2 methanation
catalysts prepared. The effects of different promoters (Ag, K, La, Pt,
Ru) were studied as well. The dynamic response studies of Hayes There are several studies focusing on CO2 methanation (e.g. [1
et al. suggested that the surface reaction of C and H is the RDS, 24,138,28,126,133,139–141]), while the mechanism is examined
while CO and H2 compete for dissociative adsorption (Table 8). Dif- in [142,17,134,143–149,128].
ferent forms of surface carbon were found as a function of temper- Falconer and Zagli [142] made temperature-programmed
ature, gas composition, and duration of exposure to the educt gas. desorption and reaction experiments with CO and CO2 on a 6.9%
They varied in hydrogenation activity and could be hydrogenated Ni/SiO2 catalyst. Silica was preferred to alumina, since the latter
easily or not at all. easily adsorbs CO2. Only 0.5 lmol g1 of CO2 adsorbed on the Ni/
Kammler and Küppers [135] directed H and D atom beams at SiO2 catalyst at room temperature and desorbed at 127 °C without
carbon-covered Ni surfaces in an ultra-high vacuum system decomposition. In contrast to this, 79.7 lmol g1 of CO adsorbed at
(p < 1012 bar) with Auger electron spectroscopy and thermal des- room temperature. 56% of the previously adsorbed CO desorbed as
orption spectroscopy instrumentation at temperatures of CO, while 21% desorbed as CO2 when heating the catalyst to tem-
153 6 T 6 23 °C. The complete mechanism of CO hydrogenation peratures above 527 °C. When the catalyst, on which CO2 had
(including CO adsorption and dissociation) was not analyzed by adsorbed at elevated temperatures, got into contact with H2 in a
them and, hence, is not included in Table 8. However, the mecha- temperature-programmed reaction experiment, water formed at
nism of C hydrogenation by gaseous H and D atoms was studied in room temperature already. Its amount was close to the amount
detail. Methane was found to be the only product in the gas phase, of CO2 adsorbed at elevated temperatures. No water formed in a
while the adsorbed intermediates CDiH4i (1 6 i 6 3) where proven comparable experiment with CO. It followed that CO2 dissociated
to be stable in the absence of H beams. Consequently, Kammler into adsorbed CO and O species at elevated temperatures, while
and Küppers concluded that C⁄ + H ? CH⁄ is the RDS and that the the latter reacted with H2 at room temperature. In both cases of
stepwise hydrogenation of adsorbed carbon takes place by the CO or CO2 adsorption on the catalyst at different temperatures,
Eley–Rideal (ER) instead of the Langmuir–Hinshelwood (LH) mech- CH4 and H2O formed in single peaks at a temperature of 200 °C.
anism under the conditions studied. The rates of CH4 and H2O formation were of first order as a function
288 S. Rönsch et al. / Fuel 166 (2016) 276–296
of CO coverage during CO2 hydrogenation. It is suggested that CO
bond breaking is the RDS in CO and CO2 hydrogenation. The slow
adsorption of CO2 may result in higher H2/CO surface ratios in com-
parison to those existing for CO adsorption. The formation of CH4 is
favored compared to higher hydrocarbons in case of the CO2
methanation. The slow adsorption of CO2 relative to CO explains
the inhibiting effect of CO on the hydrogenation of CO2.
Weatherbee and Bartholomew [17] studied CO2 hydrogenation
with a 3% Ni/SiO2 catalyst at temperatures between 227 and
327 °C, total pressures between 140 and 175 kPa, and space veloci-
ties between 30 000 and 90 000 h1 with a maximum CO2 conver-
sion of 10% in an isothermal, one-pass differential reactor. H2 and
CO partial pressures varied between 2% and 10% and 0.2% and 2%
of total pressure, respectively. The rate of CO2 hydrogenation was
sensitive to pH2 and pCO at low values (<14 and <3 kPa, respectively)
and insensitive at higher values. The reaction orders for pH2 and pCO
in CO2 hydrogenation were also dependent on temperature. A sim-
ple power law for the rate could not be fitted to the experimental
data. Instead, an LH rate equation was used for data fitting. A mech-
anism was suggested, with CO2 being adsorbed dissociatively on Ni,
thus forming adsorbed CO and O species. Further conversion of
adsorbed CO into CH4 was expected as in the case of CO hydrogena-
tion. Based on this, it was tried to fit the experimental data with LH
rate equations. The assumption of the dissociation of adsorbed CO
being the RDS was the only one that resulted in physically meaning-
ful rate and adsorption equilibrium constants. This is also supported
by the observation of comparable specific reaction rates in CO2 and
CO methanation on Ni/SiO2. The mentioned RDS is applicable at
moderate temperatures between 252 and 302 °C. At higher temper-
atures (>302 °C), hydrogenation of carbon might be rate-controlling.
An inhibition of the CO2 hydrogenation is expected to be present at
CO concentrations of 30 ppm at 227 °C and 1200 ppm at 327 °C.
Tada and Kikuchi [128] reviewed numerous studies of CO and
CO2 methanation. They suggested locations of active sites in CO2
methanation and influences of supporting materials, promoters,
and crystallite size of the active metal. Conversion of CO2 into CO
was proposed to take place at the metal-support interface, since
CO2 adsorbs preferably at the supporting material, while CO disso-
ciation is expected to take place at the metal surface. Hence, it is
possible to manufacture catalysts that are active for CO, but not
for CO2 methanation in a defined temperature range. A Ru-based
catalyst having such a feature was presented by Dagle et al.
[150]. Besides the loading of the active metal, its crystallite size
also influenced the CO conversion performance. The CO conversion
activity was shifted to lower temperatures (DT  20 K) by decreas-
ing the crystallite size (from 34 to 11 nm). Full CO conversion at a
low CO2 conversion (<5%) was reached between 220 and 230 °C
[150]. The promoter materials La, K, and Na are reported to
increase CO2 methanation activity under CO and CO2 co-existing
conditions [128]. Furthermore, Ni/Al2O3 catalysts promoted with
V seem to enhance CO and CO2 methanation activities [102,151].
Miyao et al. [148] prepared Ni/AlxOy catalysts, impregnated them
with different Cl-containing solutions, and studied their perfor-
mance under CO and CO2 co-existing conditions. Activities for CO2
methanation and reverse water–gas shift reaction were reduced sig-
nificantly due to the addition of Cl on the catalyst surface by sup-
pressing the dissociation of CO2. Simple NH4Cl solutions for the
impregnation of the catalyst were more effective than RuCl3 and
HCl solutions.
6.3. A consistent mechanism for CO and CO2 methanation
The review of numerous literature sources reveals that mecha-
nisms suggested for CO and CO2 methanation do not include
sorbed oxygenated species (e.g. CHO, HCOH, HCOO) as reaction
intermediates contrary to suggestions by some authors (e.g.
[152,139,143,146]). The mechanism proceeding via the formation
of surface carbon seems to be more likely, since this species forms
typically on industrial methanation catalysts and reacts very
slowly with hydrogen [122,131,135]. Oxygenated intermediates
might be important in the formation of higher hydrocarbons in Fis-
cher–Tropsch synthesis [122].
As discussed above, it is likely that CO2 hydrogenation proceeds
by CO2 adsorption and dissociation and subsequent hydrogenation
of adsorbed CO [122,17,133,141]. CO2 adsorption takes place
preferably on the metal-support interface (if present), while CO2
dissociation takes place on the active metal surface [128]. CO2 con-
version can be enhanced by a supporting material that fosters high
CO2 coverages (e.g. Al2O3) or promoters on the catalyst surface,
which improve the conversion of CO (e.g. La, K, Na, V) [128]. It
can be decreased by an additive that suppresses CO2 dissociation
(e.g. Cl) [128]. Furthermore, small amounts of CO suppress the
methanation of CO2, since the Ni surface is preferably covered by
CO rather than by CO2 [142,17].
CO methanation (see Table 8) starts with CO adsorption on step
edges of the active metal surface [136]. Adsorbed CO, CO2, H2, H2O,
and CH4 species seem to be in equilibrium with the surrounding gas
phase and to be located on these edges. The active metal and the
catalyst support, together with temperature and pressure, deter-
mine the equilibrium concentrations of these species on the cata-
lyst surface. The dissociation of CO into adsorbed C and O seems
to take place on 5-fold coordinated sites of the active metal [136],
where carbon atoms can form several bonds. 5-fold coordinated
sites are rare in comparison to step edges and amount to a few per-
cent of the active metal surface only [137,136]. Their ratio may be
increased by decreasing the crystallite size of the active metal or
applying a combination of materials that improve formation (e.g.
Ni/AlVOx, Ru–Ni/Al2O3). High CO conversions at temperatures
below 220 °C were reported [153,151] and might result from an
increase in the amount of 5-fold coordinated sites. Adsorbed C
and O undergo stepwise hydrogenation reactions forming sorbed
CH and OH species or inclusion reactions forming sorbed CH2 and
desorbed H2O species [131], with gas-phase hydrogen in Eley–
Rideal rather than in Langmuir–Hinshelwood surface reactions
[135,136]. A hydrogenation mechanism that involves Eley–Rideal
surface reactions is assumed especially under conditions in com-
mercial methanation facilities (high partial pressures of H2 and
CO), where the Ni surface lacks adsorbed hydrogen atoms [136].
The rate-determining steps in CO and CO2 methanation are the
dissociation of adsorbed CO and the hydrogenation reaction of sur-
face C depending on reaction conditions [122,17,135,136]. Subse-
quent hydrogenation reactions of CHi species (1 6 i 6 3) are
faster than the first formation of a C–H bond [135]. Unfortunately,
it is not clear which of the two suggested RDS is rate-limiting
under a certain condition. CO dissociation might be the RDS at
T < 300 °C, while the hydrogenation of C might become the RDS
at higher temperatures according to Weatherbee and Bartholomew
[17]. This contradicts Klose et al. who excluded the dissociation of
CO to be the RDS at T < 284 °C [131]. On the other hand, Sehested
et al. suggested CO dissociation to be the RDS between 270 and
400 °C [136].
7. Modeling and simulation of methanation reactors
Modeling and simulation work is an inherent part of the analy-
sis, optimization, and engineering of methanation reactors and
concepts. An overview is given in the following sections. The first
part focuses on the scope of methanation modeling and simulation.
A second part deals with modeling fundamentals and summarizes
literature articles on the modeling of single methanation reactors.
 S. Rönsch et al. / Fuel 166 (2016) 276–296
Finally, a brief overview of methanation modeling as an integrated
part of SNG plant concept analysis is given.
7.1. Modeling and simulation scope
Basically, modeling and simulation work pursues the four tar-
gets process design, process evaluation, process optimization, and
process adaptation.

Process design. The design of processes is a major task of
computer-aided work in chemical engineering. Regarding
methanation reactors key design parameters are the reactor
dimensions and the location of gas injectors or cooling devices.
Due to the exothermal character of the methanation reactions,
the reactor temperature is of special interest. It can be influ-
enced by reactor design (e.g. diameter, length, cooling and insu-
lation), process design (residence time, composition of the feed
gas), and the catalyst (activity, dilution).
A parameter directly related to the reactor dimensions is the
catalyst inventory or space velocity (e.g. [154,155]). For
fluidized-bed and three phase reactors with gas injectors,
design studies often are aimed at optimizing hydrodynamics
(e.g. fluidization) as well as heat and mass transfer inside the
reactor (e.g. [156,157,20]). In contrast to this, the computer-
aided design of structured fixed-bed reactors predominantly
focuses on the geometrical configuration of the heat transfer
structure (e.g. [158]) for reactor cooling.

Process evaluation. The performance (e.g. efficiency, steam pro-
duction, carbon conversion, selectivity, and methane yield) of
methanation reactors or whole process chains can be evaluated
by means of simulation-based process parameters such as tem-
perature, product composition, and heat of reaction. For eco-
nomic evaluations, these data are complemented by design
specifications, such as reactor dimensions and further economic
parameters (e.g. material costs). For example, Kao et al. [159]
calculated the capital and operating costs and El Sibai et al.
[160] minimized the SNG production cost to determine the low-
est price process configuration. In addition, Sudiro et al. [158]
calculated the amount of CO2 emission to assess the process
with respect to ecological aspects.

Process optimization. Simulation-based process optimization in
many cases relies on parameter variations with steady-state
simulation models. Parameters of the feed gas (e.g. composition,
temperature or flow rate) and/or the fluids (e.g. pressure, tem-
perature of gas and cooling media) are varied [155,13,161–163].
Due to an increasing demand for flexibly operating methana-
tion concepts, recent simulation studies focused on an opti-
mization of the reactor dynamics. In that case, simulation
models are applied to predict the behavior caused by load
changes (e.g. [164–166,51,167,45,46]) and to develop control
strategies (e.g. [164,167,168,159]).

Process adaptation. As mentioned before, current process devel-
opments are primarily based on CO methanation concepts from
the 1970s and 1980s. This is in particular true for modern CO2
methanation processes applied in PtG plants. For this purpose,
knowledge of reactor design and operation is adapted to the
modern CO2 methanation processes and investigated by model-
ing and simulation (e.g. [169,161,170,171]).
7.2. Reactor modeling
In the past, predominantly fixed-bed, fluidized-bed, and special
designs (e.g. fixed-bed tube-bundle or structured fixed-bed reac-
tors) were modeled as methanation reactors. The characteristics
of those reactor models differ significantly and strongly depend
on the objective of modeling and simulation. Main characteristics
289
are the time resolution of the model, the reactor dimension, the
phase modeling, the temperature characteristics, the kinetic
approach, and the software.
7.2.1. Time resolution
Depending on the objective, either stationary or dynamic
reactor models are developed. In addition to spatial derivatives of
stationary models, the differential equations of dynamic reactor
models include derivations of time. The models are used to analyze
the methanation reaction over time and pay e.g. attention to the
design and optimization of methanation reactors in PtG plants
under fluctuating operation conditions.
Recent approaches also include the possibility to simulate dis-
crete events [173,174] where the dynamic simulations are
designed to adapt in real time to instantaneous changes or events.
These are especially relevant in processes where instantaneous
temperature dependent changes may or may not occur during
the reactions. Studies have already focused on the use of discrete
event modeling in a general simulation environment [175] and it
has been used to control the operation of chemical plants [174].
Due to the challenges involved in the stochastic dynamic control
of methanation, discrete event modeling based simulations could
potentially make reactor modeling easier. But further analysis
needs more studies where methanation models are simulated
specifically using event handling capabilities.
7.2.2. Reactor dimensions
Reactor models consider zero to three spatial dimensions. If
reactors are modeled zero-dimensionally, they operate like contin-
uous stirred tank reactors being perfectly mixed. Several
zero-dimensional models can be arranged in series to obtain a
one-dimensional (axial) profile, as done by Kang and Lee [162]
and Cobb and Streeter [40].
Most commonly and especially for fixed-bed reactors, the reac-
tor models are one-dimensional. They consider the axial distribu-
tion of gas species and temperature. The radial profiles are often
neglected, because plug flow and a constant radial temperature
are assumed.
Two-dimensional models additionally include radial distribu-
tions and temperature profiles. However, these models are charac-
terized by a significantly higher computational effort needed for
solving the differential equations. Schlereth and Hinrichsen [169]
compared a one-dimensional model and a two-dimensional,
pseudo-homogeneous fixed-bed reactor model. They concluded that
the one-dimensional model can be used to evaluate qualitative
trends and to screen possible process conditions. The two-
dimensional model gives more detailed information for a quantita-
tive evaluation and the comparison with experimental results.
An even higher computational effort is needed to solve the
equations of three-dimensional models. They are indispensable
in particular for detailed optimization and design. Liu and Hinrich-
sen [157] compared a 2D and a 3D fluidized-bed reactor model.
Both led to similar results. Due to the lower computational effort,
Liu et al. preferred the 2D model.
The process temperature obtained from these models is always
a result of various factors like cooling mechanisms, variations in
feed-gas flow and concentrations. However, the components con-
trolling these parameters are typically outside the purview of the
equations representing the reaction process. This means that con-
trolling the above mentioned factors involves simulating the reac-
tion process happening in the reactor together with the physical
processes in other components that typically lie outside the reactor
(e.g. valves, heat exchangers, pipes). This requires the use of block
based (e.g. Matlab Simulink) or Object Oriented (e.g. Modelica)
simulation approaches that help in the so called ‘‘system” concept
of simulation where various components are aggregated together
290 S. Rönsch et al. / Fuel 166 (2016) 276–296

as a system which in turn is simulated dynamically. The tradeoff is reactors. Despite sophisticated efforts regarding heat removal from
that the specific intra component details and multi-dimensional the reaction zone, there generally is a temperature peak in the
representation and post processing of results inside individual reactor, which leads to a typically polytropic temperature profile
components are mostly not possible. However, up to a tenfold (see Section 3). For methanation modeling, the temperature profile
decrease in the overall effort required for modeling as well as pro- often is approximated by an ideal temperature profile. While ideal
totyping has been reported when using such models as opposed to fixed-bed reactors without cooling typically show adiabatic tem-
conventional methods [176]. perature profiles, ideal fluidized-bed, liquid-phase or fixed-bed
tube-bundle reactors with cooling are characterized by isothermal
temperature profiles [8].
7.2.3. Phase modeling
Methanation reactors are heterogeneous reactors. Besides the
reactor wall, they consist of a gaseous phase (reactants and prod-
7.2.5. Kinetics approach
ucts) and a solid phase (catalyst). Three-phase methanation reac-
In the last decades, different methanation catalysts were
tors consist of a gaseous phase (educts and products), a solid
developed and investigated. Consequently, various kinetic
phase (catalyst), and a liquid phase (usually inert heat transfer flu-
approaches of the methanation reaction can be found in litera-
ids). In contrast to this, fluidized-bed reactors are modeled with a
ture. Overviews of kinetic approaches are given by Kopyscinski
gas phase describing the bubble and a dense phase containing cat-
[180], Klose [181], Mills and Steffgen [16], and Vannice [79]. Sim-
alyst and less gas. More detailed fluidized-bed models additionally
ulation models most frequently apply the Langmuir–Hinshelwood
incorporate a third phase (cloud phase) [8].
kinetics published by Xu and Froment [182] and Kopyscinski
Heterogeneous reactors can be simplified by pseudo-homogeneous
[180] (see Tables 9–11). However, the validity of this kinetics is
reactor models, if the effect of external mass transfer and pore diffusion
limited and depends on the applied catalyst and reaction condi-
limitations are negligible. In a pseudo-homogeneous model, the
tions. While Xu measured the kinetics for steam reforming on
multi-phase mixture is treated as a single homogeneous continuum
nickel catalysts with temperatures above 500 °C, the kinetics of
[177]. To find out whether the phase limitations are insignificant, the
Kopyscinski is to model quasi-isothermal fluidized-bed reactors
criteria of Mears [178,179] are commonly used.
around 300 °C. Parlikkad et al. [155] renewed the kinetics of Xu
Schlereth and Hinrichsen [169] and Parlikkad et al. [155] com-
with own experimental data. Kang and Lee [162] multiplied the
pared the simulation results of a heterogeneous and a pseudo-
rate constant of Xu by a constant factor to adapt the simulation
homogeneous fixed-bed model. Schlereth and Hinrichsen [169]
to experimental results. An adaptation of kinetics of Xu as well
stated that the heterogeneous model should be employed, when
as of Klose and Baerns [131] for state-of-the-art catalysts was also
the catalyst particles are large and have small pore radii or the
made by Zhang et al. [183]. An overview of rate equations for CO
methanation reactor operates with low Reynolds numbers. They
and CO2 methanation and their validity is given by Rönsch et al.
suggested using the heterogeneous model for temperature control
[184]. Especially for the dynamic simulation of methanation pro-
and optimization on pellet level [169]. Parlikkad et al. [155] recom-
cesses with wide temperature and pressure ranges, Rönsch et al.
mended using the heterogeneous model especially for a precise
recommend the rates given by Klose or Zhang, complemented by
reactor dimensioning (catalyst inventory, reactor volume, etc.).
a term for the reverse reaction (Eq. (10)). This is important, to
take the methane reforming at higher temperatures into account.
7.2.4. Temperature characteristic In case of CO2 methanation, the rate for CO methanation can be
As the methanation reaction is strongly exothermal, the control complemented by a rate for the reverse water–gas shift reaction
of the heat of reaction is a key task when designing methanation (Eq. (11)) [184]:

Table 9
Model characteristics of fixed-bed methanation reactors.

Time Reactor Phase modeling Temperature Kinetic approach Software Authors

resolution dimensions characteristic
dyn. 1D Heterogeneous (therm.) Adiabatic (supposed) – (equilibrium) Modelica Fluid Bader et al. [164]
stat. 3D Pseudo-homogeneous Polytropic Measured (1st order) Femlab Cao et al. [154]
dyn. 1D Pseudo-homogeneous Adiabatic n.s. Fortran Dissinger et al. [168]
dyn. 1D Pseudo-homogeneous Adiabatic van Herwijnen et al. [187] n.s. van Doesburg et al. [165,166]
stat. 1D Pseudo-homogeneous Isothermal Kopyscinski [180] Aspen Plus Er-rbib et al. [170–172]
dyn. 1D Pseudo-homogeneous Isothermal Kopyscinski [180] ACM Güttel [51]
stat. 1D Heterogeneous (cat. Adiabatic Xu and Froment [182] Matlab Khorsand et al. [185]
isoth.)
dyn. 1D Pseudo-homogeneous Polytropic Xu and Froment [182] Aspen Li et al. [167]
Dynamics
dyn. 1D Heterogeneous (therm.) Polytropic Measured n.s. Lunde [163]
dyn. 1D Heterogeneous (therm.) Adiabatic Xu and Froment [182] Matlab Matthischke and Rönsch [46]
stat. 1D Heterogeneousa Adiabatic Xu and Froment (refit) n.s. Parlikkad et al. [155]
[182]
dyn. 0D Heterogeneous (therm.) Adiabatic – (equilibrium) Matlab Rönsch et al. [45]
stat. 1D Heterogeneousa Polytropic Xu and Froment [182] Matlab Schlereth and Hinrichsen
[169]
stat. 2D Pseudo-homogeneous Polytropic Xu and Froment [182] Matlab Schlereth and Hinrichsen
[169]
stat. 1D Pseudo-homogeneous Adiabatic van Doesburg. (refit) [188] – Wedel and Luss [186]

n.s.: not specified.

Abbreviations time resolution – stat.: stationary, dyn.: dynamic.
Abbreviations phase modeling – therm.: thermal (catalyst and reactor wall as heat storages), cat.: catalyst, isoth.: isothermal.
Abbreviations software - ACM: Aspen Custom Modeler.
a
Comparison of different model complexities including pseudo-homogeneous models.
 S. Rönsch et al. / Fuel 166 (2016) 276–296 291

Table 10
Model characteristics of three-phase (Götz [20]) and fluidized-bed (Cobb and Streeter [40], Kopyscinski et al. [58], Liu and Hinrichsen [157]) methanation reactors.

Time Reactor Phase modeling Temperature Kinetic approach Software Authors

resolution dimensions characteristic
stat. 1D Three phases, pseudo-homogeneous Isothermal Measured Matlab Götz [20]
(1st order)
stat. 1D (0D i.s.) Two phases, pseudo-homogeneous dense phase Isothermal (supposed) Measured n.s. Cobb and Streeter [40]
(1st order)
stat. 1D Two phases, pseudo-homogeneous dense phase Defined profile Kopyscinski [180] Athena Kopyscinski et al.
package [58,156]
dyn. 2D/3Da Two phases, heterogeneous dense phase Isothermal Kopyscinski [180] Open FOAM Liu and Hinrichsen
[157]

n.s.: not specified.

Abbreviations time resolution – stat.: stationary, dyn.: dynamic.
Abbreviations reactor dimensions – i.s.: in series.
a
Comparison of different model complexities.

Table 11
Model characteristics of fixed-bed tube bundle and structured methanation reactors.

Time Reactor Phase modeling Temperature Kinetic approach Software Authors

resolution dimensions characteristic
stat. 1D Pseudo-homogeneous Polytropic Xu and Froment [182] AMPL El Sibai et al. [160]
stat./dyn. 1D Pseudo-homogeneous Polytropic Kopyscinski [180] Aspen Jürgensen et al. [161]
Dynamics
dyn. 1D (0D i.s.) Pseudo-homogeneous Polytropic Xu and Froment [182] Matlab Kang and Lee [162]a
dyn. 1D Heterogeneous (cat. Defined profile Lunde (refit) [163] LIMEX Brooks et al. [13]
isoth.)
dyn. 1D Heterogeneous Polytropic Sughrue and Bartholomew [189] gProms Sudiro et al. [158]
and Weatherbee and Bartholo-
mew [17]

Abbreviations time resolution – stat.: stationary, dyn.: dynamic.

Abbreviations reactor dimensions – i.s.: in series.
Abbreviations phase modeling – cat.: catalyst, isoth.: isothermal.
a
Comparison of different model complexities.

k1  K C  K 2H  p0:5
CO  pH2
7.3. Plant modeling
r METH ¼   3
1 þ K C  p0:5
CO þ K H  pH2
0:5
Methanation modeling is an inherent part of simulation-based
  studies of SNG production plants (biomass/coal-to-SNG or PtG
K 2H
k1  K C   pCH4  pH2 O  p0:5

CO p2 1
H2 K METH
þ ð10Þ plants; see Figs. 1 and 2). Concept comparison, process integration,
 3
1 þ K C  p0:5 heat integration, efficiency estimation, and data generation for eco-
CO þ K H  pH2
0:5
nomic and ecological assessments are primary objectives of those
studies. An overview of selected studies is given in Table 12.
 pH pCO

k2
pCO  pH2 O  K2WGS 2 The commercial flow sheet simulation program Aspen Plus is
pH
r WGS ¼  2
2 ð11Þ most frequently used for SNG plant analysis. Methanation reactor
KH pH
1 þ K CO  pCO þ K H2  pH2 þ K CH4  pCH4 þ 2O 2O models are significantly simplified, i.e. all methanation concepts
pH
2 were modeled in a stationary way and except for the simulation
Measurements at pilot- or lab-scale plants confirm that apart of De Saint Jean et al. [190], zero-dimensional equilibrium reactor
from using kinetics, basic investigations can be conducted with models were included (e.g. RGibbs model from Aspen Plus).
equilibrium models (cf. [66,19]). This is possible especially for The studies listed in Table 12 predominantly focus on concept
the analysis of the product gas composition, the heat of reaction comparisons for different gasification systems based on efficiency
(e.g. [19]), the influence of varying syngas characteristics, and the calculations. Overall efficiencies (fraction of SNG output power to
dynamic reactor behavior (e.g. [45]). fuel input power) in the range of 60–65% are estimated (e.g.
[191,50]), which agree with the efficiency reported for the pilot
plant in Güssing (Austria) [66]. Few studies additionally take SNG
7.2.6. Software production costs (e.g. [192,191,50]) or greenhouse gas emissions
A multitude of simulation programs are available to set up and (e.g. [191,193]) into account. The production costs are estimated
solve partial or ordinary differential equations used for methana- to be around 9 €ct/kWh SNG.
tion reactor modeling. Matlab is the most common software for
that purpose (cf. Tables 9–11). Due to the extremely fast methana-
tion reaction especially in adiabatic fixed-bed reactors, the avail- 8. Summary
ability of efficient solvers able to handle stiff differential
equations (e.g. based on BDF – backwards differentiation formulas) Methanation research looks back on a history of more than
is a crucial criterion for the choice of the software. 100 years and is presently attracting new attention because of cli-
An overview of different fixed-bed methanation models mate change, finiteness of fossil fuels, and a changing energy system
reported in literature is listed in Table 9. In Tables 10 and 11, an with a high share of renewables. Two different methanation pro-
overview of characteristics of fluidized-bed reactor models and cesses are discussed: CO methanation for the production of natural
special designs (fixed-bed tube bundle and structured methanation gas substitutes in combination with coal or biomass gasification and
reactors) is given, respectively. CO2 methanation for the chemical storage of electric energy.
292 S. Rönsch et al. / Fuel 166 (2016) 276–296

Table 12
Selected simulation studies for SNG plant simulation.

Authors Plant concept Focus Methanation reactor Software

De Saint Jean et al. [190] Power to gas Process assessment: efficiency 1D fixed-bed, kinetic ProSimPlus
Fendt et al. [192] Biomass to SNG Concept comparison: efficiency, costs 0D n.s., equilibrium Aspen Plus
Heyne et al. [194,195] Biomass to SNG Process optimization and concept comparison 0D, fixed-bed, equilibrium Aspen Plus
Koytsoumpa et al. [196] Coal to SNG Technology assessment: acid gas removal 0D n.s., equilibrium Aspen Plus
Nagumo et al. [197] Biomass to SNG Process optimization: process integration 0D n.s. equilibrium Aspen Plus
Rehling et al. [66] Biomass to SNG Process optimization: heat integration 0D fluidized-bed, equilibrium IPSEPro
Rönsch et al. [198] Biomass to SNG Concept comparison: efficiency 0D fixed-bed, equilibrium Aspen Plus
Rönsch and Kaltschmitt [191] Biomass to SNG Concept comparison: efficiency, costs, GHG emissions 0D fluidized-bed equilibrium Matlab Simulink
Swedish Gas Centre [199] Biomass to SNG Concept comparison: efficiency 0D fixed-bed, equilibrium Aspen Plus
Tremel et al. [200] Biomass to SNG Process optimization: process integration 0D fluidized-bed, equilibrium Aspen Plus
van der Meijden et al. [71] Biomass to SNG Concept comparison: efficiency 0D fixed-bed, equilibrium Aspen Plus
Zwart et al. [50] Biomass to SNG Concept comparison: efficiency, costs 0D fixed-bed, equilibrium Aspen Plus

n.s.: not specified.

GHG: Greenhouse gas.

CO methanation projects in Europe primarily focus on the use of
gases from biomass gasification and subsequent methanation.
Additionally, a significant increase in methanation activities in Asia
(mainly China) can be reported. These activities basically concen-
trate on large-scale (>500 MW fuel input) coal-to-SNG plants to
complement China’s limited natural gas resources.
CO2 methanation projects generally focus on Europe and espe-
cially Germany, the objective being to contribute to a flexible
energy system. For this reason, they are combined with electrolysis
units for the production of hydrogen.
ried out. It is distinguished between methanation reactor modeling
and methanation modeling as part of SNG plant modeling. Single
reactor models are primarily one-dimensional, pseudo-
homogeneous models focusing on fixed-bed methanation. For
methanation modeling as part of an SNG plant, predominantly
the software Aspen Plus is used. Concept comparisons based on effi-
ciency calculations are dominating in the published literature.
9. Abbreviations and symbols

8.1. Methanation concepts and research See Tables 13 and 14.

For both, CO and CO2 methanation processes, the management of

the heat of reaction is a difficult task. A multitude of methanation
concepts were brought to pilot and commercial scale in the past. Only Table 13
Abbreviations.
a few of them are currently available on the market. All of those com-
mercially available concepts are fixed-bed reactor concepts that are Abbreviation Denotation
predominantly equipped with gas recycling and intermediate cooling ACM Aspen Custom Modeler
(TREMP, HICOM, Lurgi methanation). However, to reduce investment AG Aktiengesellschaft
and operational efforts, there is the trend to avoid recycle-gas com- BDF Backwards Differentiation Formula
cat. Catalyst
pressors in future applications (e.g. Vesta, TREMP modified).
DBFZ Deutsches Biomasseforschungszentrum
Although methanation processes are commercially available DVGW Deutsche Vereinigung des Gas- und Wasserfaches
already, there is still research demand to understand the mecha- dyn. Dynamic
nism of reaction for new catalysts and varying educt gas composi- ECN Energy Research Centre of the Netherlands
tions, to improve methanation catalysts and to develop reactor as ER Eley-Rideal
ESME ECN System for Methanation
well as process models. This is in particular true for future metha- EWE Ems-Weser-Elbe Netz GmbH
nation concepts with dynamic operation conditions. Process tem- FB Fixed-bed
perature control, enhancements of cost efficiency and flexibility, Ger Germany
i.e. dynamic operation behavior, are in the focus of research. GHG Greenhouse Gas
HICOM High Combined Shift Methanation
8.2. Catalysts HSR Hochschule für Technik Rapperswil
i.s. In series
isoth. Isothermal
Basically all metals located in groups 8–10 of the periodic table ICI Imperial Chemical Industries
are suited for catalyzing the methanation reaction. Due to a good IMR Institute for Material Research
combination of price, activity, and selectivity, however, nickel cat- IWES Fraunhofer-Institut für Windenergie und
alysts are predominantly applied in commercial methanation Energiesystemtechnik
Jap Japan
plants. Current investigations focus on an improvement of the
KIT Karlsruhe Institute of Technology
thermal stability and sulfur resistance of methanation catalysts. LH Langmuir-Hinshelwood
n.s. Not specified
8.3. Mechanism PSI Paul Scherrer Institut
PtG Power-to-gas
Surface carbon seems to be the most important reaction inter- RDS Rate-Determining Step
SGC Swedish Gas Centre
mediate in CO and CO2 methanation, its formation (due to the dis-
SNG Synthetic Natural Gas
sociation of adsorbed CO) and its hydrogenation to adsorbed CH or stat. Stationary
CH2 are the rate-determining steps of the catalyzed reaction. STP Standard Temperature Pressure
therm. Thermal
8.4. Modeling TPR Temperature Programmed Reduction
TREMP Topsøe Recycle Energy-efficient Methanation
For methanation process design, evaluation, optimization and ZSW Zentrum für Sonnenenergie- und Wasserstoff-Forschung
Baden-Württemberg
adaptation, intensive process modeling and simulation work is car-
 S. Rönsch et al. / Fuel 166 (2016) 276–296 293

Table 14 [18] Gao J, Wang Y, Ping Y, Hu D, Xu G, Gu F, et al. A thermodynamic analysis of

Symbols. methanation reactions of carbon oxides for the production of synthetic
natural gas. RSC Adv 2012;2:2358–68.
Symbol Unit Denotation [19] Seemann M. Methanation of biosyngas in a fluidized bed reactor –
development of a one-step synthesis process, featuring simultaneous
AC m2 Surface area catalyst
methanation, watergas shift and low temperature tar reforming. PhD
B – Heat production potential thesis. ETH Zurich; 2006.
DaI – Damköhler number (first order) [20] Götz M. Methanisierung im Dreiphasen-Reaktor. PhD thesis. Karlsruher
FV,STP m3 h1 Volume flow at standard temperature Institut für Technologie (KIT); 2014.
and pressure [21] Sahebdelfar S, Ravanchi MT. Carbon dioxide utilization for methane
GHSV h1 Gas Hourly Space Velocity production: a thermodynamic analysis. J Petrol Sci Eng 2015;134:14–22.
k1 mol kg1 cat. s1 Rate coefficient CO methanation [22] Hiller H, Reimert R. Physicochemical basis for gas production. In: Ullmann’s
k2 mol kg1 cat. s1 bar1 Rate coefficient water–gas shift reaction encyclopedia of industrial chemistry. Weinheim: Wiley-VCH Verlag GmbH &
K METH bar2 Equilibrium constant CO methanation Co. KGaA; 2006. p. 15.
K WGS – Equilibrium constant water–gas shift [23] Hiller H, Reimert R, Stönner H-M. Product gas treatment. In: Ullmann’s
reaction encyclopedia of industrial chemistry. Weinheim: Wiley-VCH Verlag GmbH &
Co. KGaA; 2006. p. 20.
KC bar0.5 Adsorption constant C
[24] Wolf MP. Minimierung des Druckverlusts durch Optimierung der CO-
K CH4 bar1 Adsorption constant CH4
Entfernungsstufe für ein stationäres PEM-Brennstoffzellenheizgerät. PhD
K CO bar1 Adsorption constant CO thesis. Karlsruhe Institute of Technology; 2010.
KH bar0.5 Adsorption constant H [25] Kopyscinski J, Schildhauer TJ, Biollaz SMA. Production of synthetic natural gas
K H2 bar1 Adsorption constant H2 (SNG) from coal and dry biomass – a technology review from 1950 to 2009.
K H2 O – Adsorption constant H2O Fuel 2010;89:1763–83.
p Pa Pressure [26] Rönsch S, Ortwein A. Methanisierung von Synthesegasen – Grundlagen und
pi bar Partial pressure of gas component i Verfahrensentwicklungen. Chem Ing Tech 2011;83:1200–8.
rj mol kg1 cat. s1 Rate of reaction j [27] Kaltenmaier K. Untersuchungen zur Kinetik der Methanisierung von CO2-
Se – Seminov number reichen Gasen bei höheren Drücken. PhD thesis. Universität Karlsruhe (TH);
St – Stanton number 1988.
[28] Weatherbee GD, Bartholomew CH. Hydrogenation of CO2 on group VIII
T K Temperature
metals: I. Specific activity of Ni/SiO2. J Catal 1981;68:67–76.
VR m3 Reactor volume
[29] Hiller H, Reimert R. Types of gases. In: Ullmann’s encyclopedia of industrial
y – Molar fraction chemistry. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA; 2006. p. 10.
[30] Sterner M. Bioenergy and renewable power methane in integrated 100%
renewable energy systems – limiting global warming by transforming energy
systems. PhD thesis. University of Kassel; 2009.
[31] Strakey JP, Forney AJ, Haynes WP. Methanation in coal gasification processes,
report. Pittsburgh Energy Research Center; 1975.
References [32] U.S. Department of Energy (USDE). Practical experience gained during the
first twenty years of operation of the Great Plains Gasification Plant and
[1] Söhngen NL. Het ontstaan en verdwijnen av waterstof en methan. PhD thesis. implications of future projects, report. Office of Fossil Energy; 2006.
Delft University of Technology; 1906. [33] Höhlein B. Methanation – Pilot Plant ADAM I (NFE Project) and other
[2] Thauer RK, Kaster A-K, Seedorf H, Buckel W, Hedderich R. Methanogenic methanation pilot plants, report. Kernforschungsanlage Jülich GmbH, Institut
archaea: ecologically relevant differences in energy conservation. Nat Rev für Reaktorbauelemente; 1978
Micro 2008;6:579–91. [34] Harms H, Höhlein B, Skov A. Methanisierung kohlenmonoxidreicher Gase
[3] Seifert AH, Rittmann S, Herwig C. Analysis of process related factors to beim Energie-Transport. Chem Ing Tech 1980;52:504–15.
increase volumetric productivity and quality of biomethane with [35] Haldor Topsoe: From solid fuels to substitute natural gas (SNG)
Methanothermobacter marburgensis. Appl Energy 2014;132:155–62. using TREMPTM, <http://topsoe.ru/business_areas/gasification_based/
[4] Götz M, Lefebvre J, Mörs F, McDaniel Koch A, Graf F, Bajohr S, et al. Renewable Processes/Substitute_Natural_Gas.aspx> [download: 23.07.2015].
power-to-gas: a technological and economic review. Renew Energy; 2015 [in [36] Haynes WP, Forney AJ. High BTU gas from coal: status and prospects, report.
press]. Pittsburgh Energy Research Center; 1976.
[5] Sabatier P, Senderens J-B. Comptes Rendus Des Séances De L‘Académie Des [37] Eckle S. SNG technologies at Clariant, presentation. In: 2nd Nuremberg
Sciences, Section VI – Chimie. Paris: Imprimerie Gauthier-Villars; 1902. workshop methanation and second generation fuels. Nuremberg; 2014.
[6] Boll W, Hochgesand G, Müller W-D. Methanation and methane synthesis. In: [38] Lohmüller R. Methansynthese mit kombinierten isothermen und adiabaten
Ullmann’s encyclopedia of industrial chemistry. Weinheim: Wiley-VCH Reaktoren. Berichte aus Technik und Wissenschaft, report. Linde; 1977.
Verlag GmbH & Co. KGaA; 2006. p. 85. [39] Blazek CF, Baker NR, Tison RR. High-Btu coal gasification processes, report.
[7] Rönsch S. Optimierung und Bewertung von Anlagen zur Erzeugung von Institute of Gas Technology; 1979.
Methan. Strom und Wärme aus biogenen Festbrennstoffen. PhD thesis. TU [40] Cobb Jr JT, Streeter RC. Evaluation of fluidized-bed methanation catalysts and
Hamburg-Harburg; 2011. reactor modeling. Ind Eng Chem Proc Des Dev 1979;18:672–9.
[8] Rönsch S. Anlagenbilanzierung in der Energietechnik – Grundlagen, [41] Friedrichs G, Proplesch P, Wismann G, Lommerzheim W. Methanisierung von
Gleichungen und Modelle für die Ingenieurpraxis. 1st ed. Wiesbaden: Springer Kohlevergasungsgasen im Wirbelbett Pilot-Entwicklungsstufe, report.
Vieweg; 2015. Thyssengas GmbH; 1985.
[9] Hashimoto K, Yamasaki M, Fujimura K, Matsui T, Izumiya K, Komori M, et al. [42] Hedden K, et al. Gleichzeitige Konvertierung und Methanisierung CO-reicher
Global CO2 recycling – novel materials and prospect for prevention of global Gase, report. DVGW-Forschungsstelle am Engler-Bunte-Institut der
warming and abundant energy supply. Mater Sci Eng A 1999;267:200–6. Universität Karlsruhe; 1986.
[10] Götz M, Bajohr S, Buchholz D. Speicherung elektrischer Energie aus [43] Friedrichs G, Wismann G. Untersuchung über die Einsatzmöglichkeiten
regenerativen Quellen im Erdgasnetz. Energie|wasser-praxis 2011;62:72–6. gekühlter Gas/Feststoff-Druckwirbelschichten, insbesondere der COMFLUX-
[11] Lefebvre J, Götz M, Bajohr S, Reimert R, Kolb T. Improvement of three-phase Technik für chemische Prozesse, report. Thyssengas GmbH; 1987.
methanation reactor performance for steady-state and transient operation. [44] Martin JW. Liquid-phase methanation/shift process development, report.
Fuel Process Technol 2015;132:83–90. Chem Systems, Inc.; 1982.
[12] Schubert K, Brandner J, Fichtner M, Linder G, Schygulla U, Wenka A. [45] Rönsch S, Matthischke S, Müller M, Eichler P. Dynamische simulation von
Microstructure devices for application in thermal and chemical process Reaktoren zur Festbettmethanisierung. Chem Ing Tech 2014;86:1198–204.
engineering. Microscale Thermophys Eng 2001;5:17–39. [46] Matthischke S, Rönsch S. Lastflexibilität der Festbettmethanisierung am
[13] Brooks KP, Hu J, Zhu H, Kee RJ. Methanation of carbon dioxide by hydrogen Beispiel der kombinierten SNG-Produktion. In: Proceedings DGMK-
reduction using the Sabatier process in microchannel reactors. Chem Eng Sci Fachbereichstagung, Konversion von Biomassen, Rotenburg a.d. Fulda; 2014.
2007;62:1161–70. [47] Kiendl I, Klemm M, Clemens A, Herrmann A. Dilute gas methanation of
[14] Liu Z, Chu B, Zhai X, Jin Y, Cheng Y. Total methanation of syngas to synthetic synthesis gas from biomass gasification. Fuel 2014;123:211–7.
natural gas over Ni catalyst in a micro-channel reactor. Fuel [48] Köchermann J, Schneider J, Matthischke S, Rönsch S. Sorptive H2S removal by
2012;95:599–605. impregnated activated carbons for the production of SNG. Fuel Process
[15] Götz M, Ortloff F, Reimert R, Basha O, Morsi BI, Kolb T. Evaluation of organic Technol 2015;138:37–48.
and ionic liquids for three-phase methanation and biogas purification [49] Baumhakl C. Substitute natural gas production with direct conversion of
processes. Energy Fuels 2013;27:4705–16. higher Hydrocarbons. PhD thesis. Friedrich-Alexander-Universität Erlangen-
[16] Mills GA, Steffgen FW. Catalytic methanation. Catal Rev 1974;8:159–210. Nürnberg; 2014.
[17] Weatherbee GD, Bartholomew CH. Hydrogenation of CO2 on group VIII [50] Zwart RWR, Boerrigter H, Deurwaarder EP, van der Meijden CM, van Paasen
metals: II. Kinetics and mechanism of CO2 hydrogenation on nickel. J Catal SVB. Production of synthetic natural gas (SNG) from biomass, ECN-E-06-018,
1982;77:460–72. report. Energy research Centre of the Netherlands; 2006.
294 S. Rönsch et al. / Fuel 166 (2016) 276–296
[51] Güttel R. Study of unsteady-state operation of methanation by modeling and
simulation. Chem Eng Tech 2013;36:1675–82.
[52] Müller K, Städter M, Rachow F, Hoffmannbeck D, Schmeißer D. Sabatier-
based CO2-methanation by catalytic conversion. Environ Earth Sci
2013;70:3771–8.
[53] Görke O, Pfeifer P, Schubert K. Highly selective methanation by the use of a
microchannel reactor. Catal Today 2005;110:132–9.
[54] Janke C, Duyar MS, Hoskins M, Farrauto R. Catalytic and adsorption studies
for the hydrogenation of CO2 to methane. Appl Catal B 2014;152–153:
184–91.
[55] Bajohr S, Schollenberger D. Kopplung der PtG-Technologie mit
thermochemischer Biomassevergasung: Das KIC-Projekt ‘‘DemoSNG”. GWF
– Gas|Erdgas 2014;155:470–5.
[56] Borgschulte A, Gallandat N, Probst B, Suter R, Callini E, Ferri D, et al. Sorption
enhanced CO2 methanation. Phys Chem Chem Phys 2013;15:9620–5.
[57] Walspurger S, Elzinga GD, Dijkstra JW, Sarić M, Haije WG. Sorption enhanced
methanation for substitute natural gas production: experimental results and
thermodynamic considerations. Chem Eng J 2014;242:379–86.
[58] Kopyscinski J, Schildhauer TJ, Biollaz SMA. Methanation in a fluidized bed
reactor with high initial CO partial pressure: Part II – Modeling and sensitivity
study. Chem Eng Sci 2011;66:1612–21.
[59] Biollaz S. Forschung & Entwicklung zum Thema SNG/PtG am PSI, presentation.
TUM-Workshop: SNG als Schlüssel für künftige Energiesysteme, Garching;
2014.
[60] Liu B, Ji S. Comparative study of fluidized-bed and fixed-bed reactor for
syngas methanation over Ni–W/TiO2–SiO2 catalyst. J Energy Chem
2013;22:740–6.
[61] Liu J, Cui D, Yu J, Su F, Xu G. Performance characteristics of fluidized bed syngas
methanation over Ni–Mg/Al2O3 catalyst. Chin J Chem Eng 2015;23:86–92.
[62] Götz M, Bajohr S, Graf F, Reimert R, Kolb T. Einsatz eines Blasensäulenreaktors
zur Methansynthese. Chem Ing Tech 2013;85:1146–51.
[63] Zhang J, Bai Y, Zhang Q, Wang X, Zhang T, Tan Y, et al. Low-temperature
methanation of syngas in slurry phase over Zr-doped Ni/c-Al2O3 catalysts
prepared using different methods. Fuel 2014;132:211–8.
[64] Meng F, Li Z, Liu J, Cui X, Zheng H. Effect of promoter Ce on the structure and
catalytic performance of Ni/Al2O3 catalyst for CO methanation in slurry-bed
reactor. J Nat Gas Sci Eng 2015;23:250–8.
[65] Kiewidt L, Thöming J. Predicting optimal temperature profiles in single-stage
fixed-bed reactors for CO2-methanation. Chem Eng Sci 2015;132:59–71.
[66] Rehling B, Hofbauer H, Rauch R, Aichernig C. BioSNG – process simulation and
comparison with first results from a 1-MW demonstration plant. Biomass
Conv Bioref 2011;1:111–9.
[67] Rauch R. 2nd Generation Biofuels from Biomass by steam gasification,
presentation. In: 2nd Nuremberg workshop methanation and second
generation fuels. Nuremberg; 2014.
[68] Galnares A. The Gaya Project and GDF SUEZ’s activities in the field of BioSNG,
presentation. In: 2nd Nuremberg workshop methanation and second
generation fuels. Nuremberg; 2014.
[69] Hedenskog M. The GoBiGas-project, presentation. In: SGC international
seminar on gasification. Malmö; 2014.
[70] Möller BF. Status of Bio2G and gasification testing at GTI, presentation. In:
SGC international seminar on gasification. Malmö; 2014.
[71] van der Meijden CM, Veringa HJ, Rabou LPLM. The production of synthetic
natural gas (SNG): a comparison of three wood gasification systems
for energy balance and overall efficiency. Biomass Bioenergy 2010;34:
302–11.
[72] van der Meijden CM. The MILENA gasification technology for the production
of Bio-Methane, presentation. In: 2nd Nuremberg workshop methanation
and second generation fuels. Nuremberg; 2014.
[73] Yang C-J, Jackson RB. China’s synthetic natural gas revolution. Nat Clim
Change 2013;3:852–4.
[74] C. Li, Current development situation of Coal to SNG in China, presentation,
IEA-MOST Workshop: Advances in deployment of fossil fuel technologies,
Beijing 2014.
[75] Rieke S. Erste industrielle power-to-gas-anlage mit 6 megawatt. GWF – Gas|
Erdgas 2013:660–4.
[76] Etogas GmbH: project references. <http://www.etogas.com/en/references/>
[download: 16.07.2015].
[77] MAN: Wir sind Zukunft – Geschäftsbericht; 2013. <http://www.entry.man.
eu/man/media/de/content_medien/doc/global_corporate_website_1/investor_
relations_1/gb/2013_4/man_q4_gbd_2013.pdf> [download: 12.08.2015].
[78] Fischer F, Tropsch H, Dilthey P. Reduction of carbon monoxide to methane in
the presence of various metals. Brennst-Chem 1925;6:265–71.
[79] Vannice MA. The catalytic synthesis of hydrocarbons from carbon monoxide
and hydrogen. Catal Rev 1976;14:153–91.
[80] Panagiotopoulou P, Kondarides DI, Verykios XE. Selective methanation of CO
over supported Ru catalysts. Appl Catal B 2009;88:470–8.
[81] InfoMine: Mining Intelligence & Technology. <http://www.infomine.com/
investment/nickel/> <http://www.infomine.com/investment/ruthenium/>
[download: 04.06.2015].
[82] Powell JB, Langer SH. Low-temperature methanation and Fischer–Tropsch
activity over supported ruthenium, nickel, and cobalt catalysts. J Catal
1985;94:566–9.
[83] Kok E, Scott J, Cant N, Trimm D. The impact of ruthenium, lanthanum and
activation conditions on the methanation activity of alumina-supported
cobalt catalysts. Catal Today 2011;164:297–301.
[84] Watson GH. Methanation catalysts. ICTIS/TR 09, report. IEA Coal Research;
1980.
[85] van der Laan GP, Beenackers AACM. Kinetics and selectivity of Fischer–
Tropsch synthesis: a literature review. Catal Rev – Sci Eng 1999;41:255–318.
[86] Iglesias G M, de Vries C, Claeys M, Schaub G. Chemical energy storage in
gaseous hydrocarbons via iron Fischer–Tropsch synthesis from H2/CO2 –
kinetics, selectivity and process considerations. Catal Today
2015;242A:184–92.
[87] Saito M, Anderson RB. The activity of several molybdenum compounds for the
methanation of CO. J Catal 1980;63:438–46.
[88] Gao J, Liu Q, Gu F, Liu B, Zhong Z, Su F. Recent advances in methanation
catalysts for the production of synthetic natural gas. RSC Adv
2015;5:22759–76.
[89] Lee GD, Moon MJ, Park JH, Park SS, Hong SS. Raney Ni catalysts derived from
different alloy precursors, Part II. CO and CO2 methanation activity. Korean J
Chem Eng 2005;22:541–6.
[90] Wang B, Ding G, Shang Y, Lv J, Wang H, Wang E, et al. Effects of MoO3 loading
and calcination temperature on the activity of the sulphur-resistant
methanation catalyst MoO3/c-Al2O3. Appl Catal A 2012;431–432:144–50.
[91] Liu J, Wang E, Lv J, Li Z, Wang B, Ma X, et al. Investigation of sulfur-resistant,
highly active unsupported MoS2 catalysts for synthetic natural gas
production from CO methanation. Fuel Process Technol 2013;110:249–57.
[92] Westermann A, Azambre B, Bacariza MC, Graca I, Ribeiro MF, Lopes JM, et al.
Insights into CO2 methanation mechanism over NiUSY zeolites: an operando
IR study. Appl Catal B 2015;174–175:120–5.
[93] Teh LP, Triwahyono S, Jalil AA, Mukti RR, Aziz MAA, Shishido T. Mesoporous
ZSM5 having both intrinsic acidic and basic sites for cracking and
methanation. Chem Eng J 2015;270:196–204.
[94] Li Y, Zhang Q, Chai R, Zhao G, Liu Y, Lu Y. Structured Ni–CeO2–Al2O3/Ni-foam
catalyst with enhanced heat transfer for substitute natural gas production by
syngas methanation. ChemCatChem 2015;9:1427–31.
[95] Frey M, Édouard D, Roger A-C. Optimization of structured cellular foam-based
catalysts for low-temperature carbon dioxide methanation in a platelet milli-
reactor. CR Chim 2015;18:283–92.
[96] Zhu L, Yin S, Yin Q, Wang H, Wang S. Biochar: a new promising catalyst
support using methanation as a probe reaction. Energy Sci Eng
2015;3:126–34.
[97] Cusumano JA, Dalla Betta RA, Levy RB. Scientific resources relevant to the
catalytic problem in the conversion of coal, FE-2017-1, report. Energy
Research and Development Administration; 1976.
[98] Hu D, Gao J, Ping Y, Jia L, Gunawan P, Zhong Z, et al. Enhanced investigation of
CO methanation over Ni/Al2O3 catalysts for synthetic natural gas production.
Ind Eng Chem Res 2012;51:4875–86.
[99] Fan M-T, Miao K-P, Lin J-D, Zhang H-B, Liao D-W. Mg–Al oxide supported Ni
catalysts with enhanced stability for efficient synthetic natural gas from
syngas. Appl Surf Sci 2014;307:682–8.
[100] Wang B, Yao Y, Jiang M, Li Z, Ma X, Qin S, et al. Effect of cobalt and its adding
sequence on the catalytic performance of MoO3/Al2O3 toward sulfur-resistant
methanation. J Energy Chem 2014;23:35–42.
[101] Qin H, Guo C, Wu Y, Zhang J. Effect of La2O3 promoter on NiO/Al2O3 catalyst in
CO methanation. Korean J Chem Eng 2014;31:1168–73.
[102] Liu Q, Gu F, Lu X, Liu Y, Li H, Zhong Z, et al. Enhanced catalytic performances
of Ni/Al2O3 catalyst via addition of V2O3 for CO methanation. Appl Catal A
2014;488:37–47.
[103] Liu H, Zou X, Wang X, Lu X, Ding W. Effect of CeO2 addition on Ni/Al2O3
catalysts for methanation of carbon dioxide with hydrogen. J Nat Gas Chem
2012;21:703–7.
[104] Campbell CT, Goodman DW. A surface science investigation of the role of
potassium promoters in nickel catalysts for CO hydrogenation. Surf Sci
1982;123:413–26.
[105] Doesburg EBM, Orr S, Ross JRH, van Reijen LL. Effect of temperature of
reduction on the activity and selectivity of a coprecipitated Ni–Al2O3 catalyst
for the Fischer–Tropsch and methanation reactions. J Chem Soc Chem
Commun 1977:734–5.
[106] Robertson SD, McNicol BD, De Baas JH, Kloet SC, Jenkins JW. Determination of
reducibility and identification of alloying in copper–nickel-on-silica catalysts
by temperature-programmed reduction. J Catal 1975;37:424–31.
[107] Gao J, Jia C, Li J, Zhang M, Gu F, Xu G, et al. Ni/Al2O3 catalysts for CO
methanation: effect of Al2O3 supports calcined at different temperatures. J
Energy Chem 2013;22:919–27.
[108] Cehn Y-W. The kinetics of methanation on nickel catalysts. J Eng
1988;1:7–18.
[109] Li J, Zhou L, Li P, Zhu Q, Gao J, Gu F, et al. Enhanced fluidized bed methanation
over Ni/Al2O3 catalyst for production of synthetic natural gas. Chem Eng J
2013;219:183–9.
[110] Nguyen TTM, Wissing L, Skjøth-Rasmussen MS. High temperature
methanation: catalyst considerations. Catal Today 2013;215:233–8.
[111] Bartholomew CH. Mechanisms of catalyst deactivation. Appl Catal A
2001;212:17–60.
[112] Struis RPWJ, Schildhauer TJ, Czekaj I, Janousch M, Biollaz SMA, Ludwig C.
Sulphur poisoning of Ni catalysts in the SNG production from biomass: a TPO/
XPS/XAS study. Appl Catal A 2009;362:121–8.
[113] Rostrup-Nielsen JR, Pedersen K, Sehested J. High temperature methanation –
sintering and structure sensitivity. Appl Catal A 2007;330:134–8.
[114] Argyle MD, Bartholomew CH. Heterogeneous catalyst deactivation and
regeneration: a review. Catalysts 2015;5:145–269.
 S. Rönsch et al. / Fuel 166 (2016) 276–296
[115] Hochgesand G, Kriebel M, Schlichting H. Absorption processes. In: Ullmann’s
encyclopedia of industrial chemistry. Weinheim: Wiley-VCH Verlag GmbH &
Co. KGaA; 2006. p. 95.
[116] Higman C, van der Burgt M. Gasification. 1st ed. Burlington: Gulf Professional
Publishing, Elsevier Science; 2003.
[117] Mutz B, Carvalho HWP, Mangold S, Kleist W, Grunwaldt J-D. Methanation of
CO2: structural response of a Ni-based catalyst under fluctuating reaction
conditions unraveled by operando spectroscopy. J Catal 2015;327:48–53.
[118] Zhang G, Sun T, Peng J, Wang S, Wang S. Comparison of Ni/SiC and Ni/Al2O3
catalyzed total methanation for production of synthetic natural gas. Appl
Catal A 2013;462–463:75–81.
[119] Ponec V. Some aspects of the mechanism of methanation and Fischer–
Tropsch synthesis. Catal Rev 1978;18:151–71.
[120] Bell AT. Catalytic synthesis of hydrocarbons over group VIII metals. A
discussion of the reaction mechanism. Catal Rev 1981;23:203–32.
[121] Biloen P, Sachtler WMH. Mechanism of hydrocarbon synthesis over Fischer–
Tropsch catalysts. In: Eley DD, Pines H, Weisz PB, editors. Advances in
catalysis. New York: Academic Press; 1981. p. 165–216.
[122] Araki M, Ponec V. Methanation of carbon monoxide on nickel and nickel–
copper alloys. J Catal 1976;44:439–48.
[123] McCarty JG, Wise H. Hydrogenation of surface carbon on alumina supported
nickel. J Catal 1979;57:406–16.
[124] Solymosi F, Erdohelyi A. Hydrogenation of CO2 and CO over alumina-
supported nobel metals. J Mol Catal 1980;6:471–4.
[125] Watson PR, Somorjai GA. The hydrogenation of carbon monoxide over
rhodium oxide surfaces. J Catal 1981;72:347–63.
[126] Iizuka T, Tanaka Y, Tanabe K. Hydrogenation of CO and CO2 over rhodium
catalysts supported on various metal oxides. J Catal 1982;76:1–8.
[127] Frennet A, de Bocarmé TV, Bastin J-M, Kruse N. Mechanism and kinetics of the
catalytic CO–H2 reaction: an approach by chemical transients and surface
relaxation spectroscopy. J Phys Chem B 2005;109:2350–9.
[128] Tada S, Kikuchi R. Mechanistic study and catalyst development for selective
carbon monoxide methanation. Catal Sci Technol 2015;5:3061–70.
[129] van Meerten RZC, Vollenbroek JG, de Croon MHJM, van Nisselrooy PFMT,
Coenen JWE. The kinetics and mechanism of the methanation of carbon
monoxide on a nickel–silica catalyst. Appl Catal 1982;3:29–56.
[130] Dalmon JA, Martin GA. The kinetics and mechanism of carbon monoxide
methanation over silica-supported nickel catalysts. J Catal 1983;84:45–54.
[131] Klose J, Baerns M. Kinetics of the methanation of carbon monoxide on an
alumina-supported nickel catalyst. J Catal 1984;85:105–16.
[132] Hayes RE, Thomas WJ, Hayes KE. A study of the nickel-catalyzed methanation
reaction. J Catal 1985;92:312–26.
[133] Fujita S-I, Terunuma H, Nakamura M, Doi T, Takezawa N. Mechanisms of
methanation of CO and CO2 over Ni. Ind Eng Chem Res 1991;30:
1146–51.
[134] Fujita S-I, Nakamura M, Doi T, Takezawa N. Mechanisms of methanation of
carbon dioxide and carbon monoxide over nickel/alumina catalysts. Appl
Catal A 1993;104:87–100.
[135] Kammler T, Küppers J. Methanation of carbon on Ni(1 0 0) surfaces at 120 K
with gaseous H atoms. Chem Phys Lett 1997;267:391–6.
[136] Sehested J, Dahl S, Jacobsen J, Rostrup-Nielsen JR. Methanation of CO over
nickel: mechanism and kinetics at high H2/CO ratios. J Phys Chem B
2005;109:2432–8.
[137] Dahl S, Törnqvist E, Jacobsen CJH. Dissociative adsorption of dinitrogen on a
multipromoted iron-based ammonia synthesis catalyst: linking properties of
catalysts and single-crystal surfaces. J Catal 2001;198:97–102.
[138] Solymosi F, Erdohelyi A, Bansagi T. Methanation of CO2 on supported
rhodium catalyst. J Catal 1981;68:371–82.
[139] Fujita S-I, Takezawa N. Difference in the selectivity of CO and CO2
methanation reactions. Chem Eng J 1997;68:63–8.
[140] Abe T, Tanizawa M, Watanabe K, Taguchi A. CO2 methanation property of Ru
nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method.
Energy Environ Sci 2009;2:315–21.
[141] Eckle S, Anfang H-G, Behm RJ. Reaction intermediates and side products in
the methanation of CO and CO2 over supported Ru catalysts in H2-rich
reformate gases. J Phys Chem C 2011;115:1361–7.
[142] Falconer JL, Zagli AE. Adsorption and methanation of carbon dioxide on a
nickel/silica catalyst. J Catal 1980;62:280–5.
[143] Marwood M, Doeppner R, Renken A. In-situ surface and gas phase analysis for
kinetic studies under transient conditions. The catalytic hydrogenation of
CO2. Appl Catal A – Gen 1997;151:223–46.
[144] Lapidus AL, Gaidai NA, Nekrasov NV, Tishkova LA, Agafonov YA, Myshenkova
TN. The mechanism of carbon dioxide hydrogenation on copper and nickel
catalysts. Petrol Chem 2007;47:75–82.
[145] Kim HY, Lee HM, Park J-N. Bifunctional mechanism of CO2 methanation on
Pd–MgO/SiO2 catalyst: independent roles of MgO and Pd on CO2
methanation. J Phys Chem C 2010;114:7128–31.
[146] Wei W, Jilong G. Methanation of carbon dioxide: an overview. Front Chem Sci
Eng 2011;5:2–10.
[147] Garbarino G, Riani P, Magistri L, Busca G. A study of the methanation of
carbon dioxide on Ni/Al2O3 catalysts at atmospheric pressure. Int J Hydrogen
Energy 2014;39:11557–65.
[148] Miyao T, Shen W, Chen A, Higashiyama K, Watanabe M. Mechanistic study of
the effect of chlorine on selective CO methanation over Ni alumina-based
catalysts. Appl Catal A – Gen 2014;486:187–92.
295
[149] Pan Q, Peng J, Sun T, Wang S, Wang S. Insight into the reaction route of CO2
methanation: promotion effect of medium basic sites. Catal Commun
2014;45:74–8.
[150] Dagle RA, Wang Y, Xia G-G, Strohm JJ, Holladay J, Palo DR. Selective CO
methanation catalysts for fuel processing applications. Appl Catal A
2007;326:213–8.
[151] Miyao T, Sakurabayashi S, Shen W, Higashiyama K, Watanabe M. Preparation
and catalytic activity of a mesoporous silica-coated Ni-alumina-based
catalyst for selective CO methanation. Catal Commun 2015;58:93–6.
[152] Schild C, Wokaun A, Koeppel RA, Baiker A. CO2 hydrogenation over nickel/
zirconia catalysts from amorphous precursors: on the mechanism of
methane formation. J Phys Chem 1991;95:6341–6.
[153] Chen A, Miyao T, Higashiyama K, Yamashita H, Watanabe M. High catalytic
performance of ruthenium-doped mesoporous nickel–aluminum oxides for
selective CO methanation. Angew Chem Int Edit 2010;49:9895–8.
[154] Cao C, Wang Y, Holladay JD, Jones EO, Palo DR. Design of micro-scale fuel
processors assisted by numerical modeling. AIChE J 2005;51:982–8.
[155] Parlikkad NR, Chambrey S, Fongarland P, Fatah N, Khodakov A, Capela S, et al.
Modeling of fixed bed methanation reactor for syngas production: operating
window and performance characteristics. Fuel 2013;107:254–60.
[156] Kopyscinski J, Schildhauer TJ, Biollaz SMA. Fluidized-bed methanation:
interaction between kinetics and mass transfer. Ind Eng Chem Res
2010;50:2781–90.
[157] Liu Y, Hinrichsen O. CFD simulation of hydrodynamic and methanation
reactions in a fluidized-bed reactor for the production of synthetic natural
gas. Ind Eng Chem Res 2014;53:9348–56.
[158] Sudiro M, Bertucco A, Groppi G, Tronconi E. Simulation of a structured
catalytic reactor for exothermic methanation reactions producing synthetic
natural gas. In: Proceedings. 20th European symposium on computer aided
process engineering – ESCAPE20, Ischia; 2010.
[159] Kao YL, Lee PH, Tseng YT, Chien IL, Ward JD. Design, control and comparison
of fixed-bed methanation reactor systems for the production of substitute
natural gas. J Taiwan Inst Chem Eng 2014;45:2346–57.
[160] El Sibai A, Rhiko-Struckmann L, Sundmacher K. Synthetic methane from CO2:
dynamic optimization of the Sabatier process for power-to-gas applications.
In: Proceedings, 12th International symposium on process system
engineering and 25th European symposium on computer aided process
engineering, Copenhagen; 2015.
[161] Jürgensen L, Ehimen EA, Born J, Holm-Nielsen JB. Dynamic biogas upgrading
based on the Sabatier process: thermodynamic and dynamic process
simulation. Bioresour Technol 2015;178:323–9.
[162] Kang WR, Lee KB. Effect of operating parameters on methanation reaction for
the production of synthetic natural gas. Korean J Chem Eng
2013;30:1386–94.
[163] Lunde PJ. Modeling, simulation, and operation of a Sabatier reactor. Ind Eng
Chem 1974;13:226–33.
[164] Bader A, Bauersfeld S, Brunhuber C, Pardemann R, Meyer B. Modelling of a
chemical reactor for simulation of a methanisation plant. In: Proceedings, 8th
International modelica conference, Dresden; 2011.
[165] van Doesburg H, De Jong WA. Transient behaviour of an adiabatic fixed-bed
methanator – I: experiments with binary feeds of CO or CO2 in hydrogen.
Chem Eng Sci 1976;31:45–51.
[166] van Doesburg H, De Jong WA. Transient behaviour of an adiabatic fixed-bed
methanator – II: methanation of mixtures of carbon monoxide and carbon
dioxide. Chem Eng Sci 1976;31:53–8.
[167] Li X, Yang B, Zhang Y. Dynamics and control study on low temperature
methanation reactor with mass and heat recycle. J Process Control
2013;23:1360–70.
[168] Dissinger GR, Johnson SH, Stein FP. Dynamic simulation of methanation
reactors, interstage heat exchanger, and controllers. Chem Eng Commun
2007;4:577–91.
[169] Schlereth D, Hinrichsen O. A fixed-bed reactor modeling study on the
methanation of CO2. Chem Eng Res Des 2014;92:702–12.
[170] Er-rbib H, Bouallou C. Modelling and simulation of methanation catalytic
reactor for renewable electricity storage. Chem Eng Trans 2013;35:541–6.
[171] Er-rbib H, Bouallou C. Methanation catalytic reactor. CR Chim
2014;17:701–6.
[172] Er-rbib H, Bouallou C. Modeling and simulation of CO methanation process
for renewable electricity storage. Energy 2014;75:81–8.
[173] Fritzson P, Bunus P. Modelica – a general object-oriented language for
continuous and discrete-event system modeling and simulation. In:
Proceedings. 35th Annual simulation symposium, San Diego; 2002.
[174] Jung SH, Kim TG, Park KH. Event-based intelligent control of saturated
chemical plant using an endomorphic neural network model. J Intell Manuf
1995;6:365–76.
[175] Remelhe MAP. Combining discrete event models and modelica – general
thoughts and a special modeling environment. In: Proceedings, 2nd
International modelica conference, Oberpfaffenhofen; 2002.
[176] Wetter M, Haugstetter C. Modelica versus TRNSYS – a comparison between
an equation-based and a procedural modeling language for building energy
simulation. In: Proceedings, 2nd SimBuild conference, Cambridge; 2006.
[177] Jakobsen HA. Chemical reactor modeling – multiphase reactive flows. 2nd
ed. Cham: Springer; 2014. p. 1061.
[178] Mears DE. Tests for transport limitations in experimental catalytic reactors.
Ind Eng Chem Process Des Dev 1971;10:541–7.
296 S. Rönsch et al. / Fuel 166 (2016) 276–296
[179] Mears DE. On criteria for axial dispersion in nonisothermal packed-bed
catalytic reactors. Ind Eng Chem Fund 1976;15:20–3.
[180] Kopyscinski J. Production of synthetic natural gas in a fluidized bed reactor.
PhD thesis. ETH Zurich; 2010.
[181] Klose J. Reaktionskinetische Untersuchungen zur Methanisierung von
Kohlenmonoxid. PhD thesis. Ruhr-Universität Bochum; 1982.
[182] Xu J, Froment GF. Methane steam reforming, methanation and water–gas
shift: 1. Intrinsic kinetics. AIChE J 1989;35:88–96.
[183] Zhang J, Fatah N, Capela S, Kara Y, Guerrini O, Khodakov AY. Kinetic
investigation of carbon monoxide hydrogenation under realistic
conditions of methanation of biomass derived syngas. Fuel 2013;111:
845–54.
[184] Rönsch S, Köchermann J, Schneider J, Matthischke S. Global reaction kinetics
of CO and CO2 methanation for dynamic process modeling – review,
selection, empirical adaption and application to a one-dimensional
dynamic model with commercial Ni/Al2O3 catalysts. Chem Eng Technol;
2015 [submitted for publication].
[185] Khorsand K, Marvast MA, Pooladian N, Kakavand M. Modeling and simulation
of methanation catalytic reactor in ammonia unit. Petrol Coal 2007;49:
46–53.
[186] Wedel S, Luss D. Steady-state multiplicity features of an adiabatic fixed-bed
reactor with Langmuir–Hinshelwood kinetics; carbon monoxide or carbon
dioxide methanation. Ind Eng Chem Fund 1984;23:280–8.
[187] van Herwijnen T, van Doesburg H, De Jong WA. Kinetics of the methanation of
CO and CO2 on a nickel catalyst. J Catal 1973;28:391–402.
[188] van Doesburg H. Transient behaviour of an adiabatic fixed-bed methanator.
PhD thesis. Technische Hogeschool Delft; 1974.
[189] Sughrue EL, Bartholomew CH. Kinetics of carbon monoxide methanation on
nickel monolithic catalysts. Appl Catal 1982;2:239–56.
[190] De Saint Jean M, Baurens P, Bouallou C. Parametric study of an efficient
renewable power-to-substitute-natural-gas process including high-
temperature steam electrolysis. Int J Hydrogen Energy 2014;39:17024–39.
[191] Rönsch S, Kaltschmitt M. Bio-SNG – concepts and their assessment. Biomass
Conv Bioref 2012;2:285.
[192] Fendt S, Tremel A, Gaderer M, Spliethoff H. The potential of small-scale SNG
production from biomass gasification. Biomass Conv Bioref 2012;2:275–83.
[193] Rönsch S, Zeymer M, Majer S. Treibhausgasvermeidungskosten von
synthetischem Methan und Methanol aus Biomasse und Kohle. Chem Ing
Tech 2014;86:1678–89.
[194] Heyne S, Harvey S. Methane from biomass: process-integration aspects. Proc
Inst Civil Eng Energy 2009;162:13–22.
[195] Heyne S, Thunman H, Seemann M, Harvey S. Bio-SNG production via
gasification-process integration – aspects for improving process
performance. In: Proceedings, 21st European biomass conference and
exhibition, Copenhagen; 2013.
[196] Koytsoumpa EI, Atsonios K, Panopoulos KD, Karellas S, Kakaras E, Karl J.
Modelling and assessment of acid gas removal processes in coal-derived SNG
production. Appl Therm Eng 2015;74:128–35.
[197] Nagumo R, Iwata S, Mori H. Simulated process evaluation of synthetic natural
gas production based on biomass gasification and potential of CO2 capture
using membrane separation technology. J Jpn Petrol Inst 2013;56:395–400.
[198] Rönsch S, Dreher M, Vogel A, Kaltschmitt M. Erdgassubstitut aus biogenen
Festbrennstoffen – Eine technische analyse. VGB PowerTech 2008;88:110–6.
[199] Swedish Gas Centre (SGC) (Ed.). Substitute natural gas from biomass
gasification. Rapport SGC 187, ISRN SGC-R-187-SE, report. Swedish Gas
Centre; 2008.
[200] Tremel A, Gaderer M, Spliethoff H. Small-scale production of synthetic natural
gas by allothermal biomass gasification. Int J Energy Res 2013;37:1318–30.