Process Safety and Environmental Protection 145 (2021) 172–194

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Catalytic conversions of CO2 to help mitigate climate change:

Recent process developments
Maryam Takht Ravanchi ∗ , Saeed Sahebdelfar
Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company, P.O. Box 14358-84711, Tehran, Iran

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

Article history: Despite its bad reputation as a greenhouse gas and pollutant, carbon dioxide can be viewed as a renewable,
Received 8 June 2020 non-toxic and cheap feedstock for chemical synthesis. The chemical utilization of CO2 not only could
Received in revised form 20 July 2020 reduce greenhouse gas emissions, but also saves the fossil fuels resources. In this work, the chemical
Accepted 3 August 2020
conversions relevant to large-scale utilization of CO2 including use of CO2 as an oxidant, conversion of
Available online 7 August 2020
CO2 to energy materials and synthesis of CO2 -based polymers are reviewed with emphasis on catalysis
and reaction engineering as well as technology readiness and processes. Environmental metrics such as
Keywords:
atom economy, life cycle analysis and exergy efficiency are also considered. A circular economy based on
Carbon dioxide
Catalytic conversion
CO2 is possible if renewable energies, catalyst development and separation technologies are integrated
Renewable sources and further developed.
Sustainable development © 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Circular economy
CO2 value chain

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2. Utilization technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3. Catalytic conversion processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
3.1. CO2 as mild oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
3.1.1. Dry reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
3.1.2. Oxidative dehydrogenation of alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
3.1.3. Oxidative dehydrogenation of ethylbenzene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
3.1.4. Oxidative coupling of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
3.2. CO2 hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.2.1. Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180

Abbreviations: A2F, Air-to-Fuels; ASU, Air separation unit; ATR, autothermal reforming; bpd, barrel per day; CAMERE, carbon dioxide hydrogenation to form methanol via
reverse water gas shift; CE, Carbon Engineering; CHO, cyclohexene oxide; CRI, Carbon Recycling International; CCS, carbon capture and sequestration; CCU, carbon capture
and utilization; CNT, carbon nanotube; DAC, direct air capture; DEA, diethanolamine; DGA, diglycolamine® ; DIPA, diisopropanolamine; DMC, dimethyl carbonate; DME,
dimethyl ether; DMR, dry-methane reforming; EB, ethylbenzene; EBDH, ethylbenzene dehydrogenation; ECBM, enhanced coal-bed methane; ECH, epichlorohydrin; EGR,
enhanced gas recovery; EGS, enhanced geothermal systems; EO, ethylene oxide; EOR, enhanced oil recovery; ETL, Emissions to Liquids; FDI, fossil depletion index; FT, Fischer-
Tropsch; GHG, greenhouse gas; GTL, gas to liquid; GWI, global warming impact; GWP, global warming potential; ICI, Imperial Chemical Industries; IPCC, Intergovernmental
Panel on Climate Change; KIER, Korean Institute of Energy and Research; KIST, Korea Institute of Science and Technology; KOGAS, Korea Gas Corporation; LCA, life cycle
assessment; LPG, liquefied petroleum gas; MDEA, methyldiethanolamine; MEA, monoethanolamine; MEK, methyl ethyl ketone; MF, melamine-formaldehyde; MMA, methyl-
methacrylate; MtBE, methyl tert-butyl ether; MTG, methanol to gasoline; MTO, methanol to olefins; OCM, oxidative coupling of methane; ODH, oxidative dehydrogenation;
PHA, polyhydroxyalkanoate; PMMA, polymethylmethacrylate; PO, propylene oxide; POM, Polyoxymethylene; POX, partial oxidation; PSA, pressure swing adsorption; PPC,
poly(propylene carbonate); PPP, polyether carbonates polyols; PtG, power-to-gas; PtL, power-to-liquid; PU, polyurethane; RITE, Research Institute of Innovative Technology
for the Earth; RWGS, reverse water gas shift; SABIC, Saudi Basic Industry Corporation; SGC, Samsung General Chemicals; SMR, steam-methane reforming; SNG, synthetic
natural gas; SODECO2 , Styrene production via Oxidative Dehydrogenation of Ethylbenzene with CO2 as soft oxidant; SOEC, solid oxide electrolysis cells; STY, space-time
yield; TEA, triethanolamine; TRL, technology readiness level; TSA, temperature swing adsorption; UF, urea-formaldehyde.
∗ Corresponding author.
E-mail addresses: m.ravanchi@npc-rt.ir, maryamravanchi@gmail.com (M. Takht Ravanchi).

https://doi.org/10.1016/j.psep.2020.08.003
0957-5820/© 2020 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194 173

3.2.2. Dimethyl ether . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182

3.2.3. C1 hydrocarbon (Methane) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
3.2.4. C2+ hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
3.3. CO2 to polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.3.1. Polymers from CO2 as a co-monomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
3.3.2. Polymers from CO2 -derived compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
3.3.3. Industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
3.4. CO2 to fine chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
4. Technical and scientific challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
5. Environmental impacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
6. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191

1. Introduction duction (Saeidi et al., 2014). For the first strategy, new capturing
and sequestration technologies must be developed. For the second
Any human being is responsible for climate change. If the level strategy, it is confirmed that CO2 chemical reactions that produce
of greenhouse gases (GHGs) in the atmosphere is not controlled, valuable chemicals and fuels are good candidates. For the third
ecosystem destruction, powerful and destructive storms and hur- strategy, improvements in energy efficiency and switching from
ricanes, melting of polar ice caps and consequent flooding will fossil fuels to hydrogen and renewable energy as less carbon inten-
increase which is a high threat to our security and prosperity sive energy source is required (Sahebdelfar and Takht Ravanchi,
(Mebrahtu et al., 2019). Water vapor, CO2 , CH4 and ozone are main 2017).
atmospheric greenhouse gases. Due to their high greenhouse effect, As different processes generate CO2 , a one-size-fit-all technol-
utilization routes for CO2 and CH4 are of high interest (Artz et al., ogy cannot be used for its capture. There are various capturing
2018). methods with different maturity levels. Pre-combustion capture,
Generally, CO2 is emitted from oil refineries, power plants, post-combustion capture and oxy-fuel combustion are common
ammonia and ethylene oxide processes, cement production, and CO2 capture technologies. As the detailed explanation of this topic is
steel and iron industries (Cuellar-Franca and Azapagic, 2015). By out of the scope of this manuscript, the interested reader if referred
burning fossil fuels, stored CO2 is released. Deforestation and to Cuellar-Franca and Azapagic (2015).
human activities in chemical processing are other sources of CO2 Generally, for CO2 separation from a process stream, different
release to atmosphere (Yu et al., 2008). methods are evaluated; the most common ones are physical or
Tursunov et al. (2017) reported the global annual CO2 emis- chemical absorption, membrane separation, adsorption and cryo-
sion in the period of 1990−2019. It was announced that until 2002 genic distillation (Takht Ravanchi and Soleimani, 2020).
(approximately), CO2 emissions are quite stable or slowly increas- Absorption is the common method for CO2 separation. In
ing, but since 2003 a sharp increase is observed that has overlap the absorption column, CO2 is scrubbed from the flue gas; in
with increasing global temperatures. Friedlingstein et al. (2014) the subsequent regeneration column, solvent is regenerated and
reported that in 2014, the global greenhouse gas concentration by heat addition and/or pressure reduction, CO2 is released.
was 65 % above its emissions in 1990. In 2015, at United Nations Absorption systems are available as physical or chemical pro-
Climate Change Conference in Paris, it was decided to limit the cesses. In the physical process, absorption occurs at high CO2
increase of global average temperature not higher than 2 ◦ C above partial pressure and low temperature. Selexol® (dimethylether
pre-industrial level. A report published by IPCC (Intergovernmen- of polyethylene glycol) and Rectisol® (cold methanol) are com-
tal Panel on Climate Change) announced that, in the near future, mercial solvents used for physical absorption. Main advantage of
CO2 levels would range from 541 to 970 ppm till 2100 (Houghton physical absorption is its low energy requirement and less sensi-
et al., 2001). Moreover, it was decided that over the next 100 tivity of solvent to feed impurities. Chemical absorption is suitable
years, CO2 emission must be controlled effectively in order to main- for lean streams of CO2 that have low partial pressures of car-
tain atmospheric CO2 concentration below 550 ppm. The European bon dioxide. In this process, a chemical reaction occurs between
Commission decided to reduce GHG emissions from 1990 to 2050 CO2 and chemical solvent and a weakly-bond intermediate com-
by 80–95 %. Consequently, different companies around the world pound is formed which is dissociated by heat after which CO2
decided to control their emissions; for instance, TOTAL oil Com- is released and original solvent is regenerated. Alkanolamines
pany decided to limit its CO2 emissions to approximately 15 Gt/y and alkaline salts are commercial solvents used for chemical
in 2050 (Li et al., 2018). Kyoto Protocol, Copenhagen Accord and absorption. MEA (monoethanolamine), DEA (diethanolamine), TEA
Cancún Agreements are examples of international actions done (triethanolamine), MDEA (methyldiethanolamine), DIPA (diiso-
to decrease CO2 emission. In order to obtain this goal, renewable propanolamine) and DGA (diglycolamine® ) are examples of
energy sources must be used and low carbon economy must be commercial alkanolamines and potassium carbonate is an example
developed (Fernandez Bertos et al., 2004). of commercial alkaline salt. In the case of low CO2 partial pres-
Scholes et al. (2009) reported that rate of increase in atmo- sures, alkanolamines are best chemical solvents for CO2 recovery.
spheric CO2 concentration is 4.2 Gt/y. On the other hand, Aresta Main disadvantage of chemical absorption process is its high energy
et al. (2016) predicted that for the next 20 years, fossil fuels would demand for solvent recovery (Mohammad et al., 2020).
be the dominant energy source all around the world. The CO2 val- Based upon molecular size, membrane separates CO2 from flue
orization is a potential route by which CO2 emission would be gases. Zeolite, carbon nanotube (CNT), polyimides, polyether sul-
reduced at least 3.7 Gt annually which is approximately 10 % of the fone, polysulfone and polydimethyl phenylene oxide are different
world’s annual emissions (Takht Ravanchi and Sahebdelfar, 2014). materials that can be used as membrane for CO2 separation. The
In order to reduce CO2 emissions, three different strategical main advantage of membrane separation process is its lower capi-
routes can be used; CO2 storage, CO2 use and reduction in CO2 pro- tal cost and lower space requirement. On the other hand, due to high
174 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
membrane cost and its short life time, its large scale application is
hindered (Leung et al., 2014).
In the adsorption process, CO2 is adsorbed on the solid adsor-
bent, which is regenerated in the next step by PSA (pressure
swing adsorption) or TSA (temperature swing adsorption) process
by which CO2 is released. In the adsorption process, a physi-
cal or chemical attraction occurs between adsorbent site and gas
molecule. This process is an expensive energy-intensive one and is
suitable for the removal of CO2 with low concentration. Zeolites,
activated carbon, lithium orthosilicate (Li4 SiO4 ), lithium zirconate
(Li2 ZrO3 ) and molecular sieve are adsorbents evaluated for CO2
separation (Eldardiry and Habib, 2018).
In the cryogenic distillation, CO2 is condensed, separated and
purified from flue gases at low temperatures. In this method, liq-
uid CO2 is produced directly with high purity. In the case of feed
gas with high pressure, cryogenic distillation is the most cost-
effective process. The main drawback of this process is high energy
required for refrigeration and the subsequent necessary removal
of components that have freezing points above normal operating
temperatures (in order to avoid freezing and blockage of process
equipment) (Kargari and Takht Ravanchi, 2012).
The main goal of CCS (carbon capture and sequestration) and
CCU (carbon capture and utilization) is capturing carbon diox-
ide which was emitted from different sources (such as power
plants and industrial processes) and preventing its emission to
atmosphere. The main difference between CCS and CCU is final des-
tination of the captured CO2 ; in CCS it is sent to a suitable place for
long-term storage while in CCU it is changed into different prod-
ucts. Different choices of CCS and CCU are presented in Fig. 1. CCU is
the heart of a circular economy, by which CO2 as a waste emission
is economically and ecologically converted into a resource (Takht
Ravanchi et al., 2011). If it is decided to consider the obtained profit
by selling a product, CCU is advantageous over CCS. On the other
hand, CO2 is a cheap, non-toxic and renewable resource. Although
carbon dioxide is thermodynamically stable and its conversion to
different products is energy-intensive; but the main privilege of
CCU is providing different fuels and chemicals (Yu et al., 2008).
In the present work, a thorough review of catalytic conversions
of carbon dioxide to valuable products emphasizing on recent pro-
cess developments is provided.
2. Utilization technologies
Generally, the valorization of CO2 can be categorized into the
following subsections (Huang and Tan, 2014):
1 Direct (physical) use of concentrated CO2 (e.g. CO2 used as a
reactive solvent).
2 CO2 conversion into chemicals / fuels (e.g. mineralization, cat-
alytic reduction and biological fixation).
Since the Industrial Revolution, carbon dioxide has found appli-
cations in different industries; the most notable and earliest one
was in beverage industries for carbonated drinks. Besides carbon-
ated drinks (as an example of physical utilization of CO2 ), there
are other applications such as fire extinguisher, refrigerant, dry
ice, solvent, process fluid and welding medium. These are, how-
ever, small-scale direct application of CO2 that has little impact on
overall CO2 abatement (Muradov, 2014). EOR (enhanced oil recov-
ery), ECBM (enhanced coal-bed methane) recovery, EGS (enhanced
geothermal systems) and EGR (enhanced gas recovery) are large-
scale industrial examples for direct utilization of CO2 . EOR is not a
low-carbon route as it enhances fossil fuel use that was applied for
oil displacement and due to soil porosity, part of the applied CO2
is re-emitted. It is worth mentioning that in physical utilization
methods, CO2 molecules remains intact or dissolved in a mixture
and do not crack or react.
A schematic diagram of CO2 conversion routes to different prod-
ucts is depicted in Fig. 2. For chemical or fuel syntheses, CO2 is used
as a feedstock. In these chemical processes, under specific operating
conditions, CO2 molecules crack down to CO or pure C or react with
other components to form the desired product. In these processes,
CO2 helps to enhance the synthesis process, add value or cut the
withdrawal of raw materials. A carbon-free route must be used for
H2 production; such as biological production from algae or water
electrolysis using carbon-free electricity. Renewable energy can be
used directly or indirectly by production of renewable hydrogen
or by generation of electrons or protons in electrochemical routes.
Process integration for the production of fuels and chemicals from
carbon dioxide is another viable choice. When processes are inte-
grated, waste hydrogen from one process can be applied to another
one for CO2 reduction (Aresta and Nocito, 2019; Centi et al., 2013;
Demirci and Miele, 2013).
There is a large anthropogenic CO2 emission and its potential
sources must be investigated. Currently, total global CO2 utiliza-
tion is less than 200 Mt/y which is negligible in comparison to its
emission (that is more than 13,000 Mt/y) (Rafiee et al., 2019).
3. Catalytic conversion processes
Carbon dioxide is an abundant C1 building block that can be used
for the synthesis of different categories of chemicals. It can also be
used as a source of carbon in producing other more versatile C1
building blocks, as for example, in dry reforming.
CO2 is thermodynamically a very stable molecule (Gf o =-394
kJ/mol). There are large thermodynamic and kinetic barriers for
its conversion. These difficulties can be overcome by using high-
energy co-reactants (such as hydrogen and epoxides) and suitable
catalysts, respectively (Nocitoa and Dibenedetto, 2020).
As CO2 has highest oxidation state of carbon (+4), it can be con-
verted by reduction reactions (to a negative-going oxidation state)
(Wang et al., 2014) or mineralization (to a lower Gibbs free energy)
(Duan et al., 2014).
A number of chemicals are commercially produced from carbon
dioxide. By far, urea production consumes the largest amount of
CO2 (about 120 Mt/y), followed by methanol synthesis (about 2–3
Mt/y). However, the current chemical fixation capacity is not sig-
nificant compared to CO2 emissions. If hydrogen from a non-fossil
source (such as water electrolysis performed by solar and wind as
renewable energy source) is used, CO2 emission can be decreased
(Tahriri Zangeneh et al., 2011).
Based upon oxidation state of the carbon atom in the product
molecule, CO2 conversions can be classified into two groups (Aresta
and Dibenedetto, 2003):
• Reactions in which the entire CO2 molecule is fixed onto an
organic substrates. The oxidation state of carbon (+4) does not
change during reaction; therefore, the heat of reaction is small
and denoted by the substrate. These reactions typically occur at
lower temperatures (-30 to 150 ◦ C).
• Reactions that convert CO2 to another C1 or Cn valued as fuels.
The large amount of energy required for reduction of carbon is
provided by hydrogen, electrons or heat. These reactions typically
occur at higher temperatures (300 to 700 ◦ C).
The former group of reactions are encountered in chemical
industry for the production of fine and commodity chemicals
including ureas (RRNCONRR), carbonates (ROC(O)OR), carboxy-
lates and lactones (RCOOR), isocyanates (RNCO) and carbamates
(R1 R2 NCOOR3 ).
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194 175

Fig. 1. Different choices of CCS and CCU.

Fig. 2. Schematic route of CO2 conversions.

The latter group is encountered in energy and chemical indus-

tries and the products have potentially much larger market. Main
products of this category are hydrocarbons, formaldehyde (H2 CO),
methanol (CH3 OH), formates (HCOO− ), oxylates [(C(O)O)2 2- ] and
carbon monoxide (CO).
The market potential and the amount of CO2 consumed have
influence on the selection of a CO2 conversion pathway. In Fig. 3,
the status of some chemicals according to their market and their
CO2 use is provided. It is obvious that, currently, methane has the
highest market whilst it uses high amount of CO2 .
The effective catalytic activation and conversion of carbon diox-
ide into value-added products is an active and challenging research
topic in C1 chemistry (Sahebdelfar and Takht Ravanchi, 2020).
In below sections, different applications of carbon dioxide in
catalytic conversions are provided.

3.1. CO2 as mild oxidant Fig. 3. Market potential as a function of the amount of CO2 used for some chemicals
(data adapted from Chauvy et al. (2019) and Pan et al. (2010)).

The dissociation of CO2 on catalyst surfaces can produce active

oxygen species. Therefore, some heterogeneous catalyzed reactions
can benefit from CO2 as a mild oxidant or a source of “oxygen”
176 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
atoms. In catalytic transformation processes, carbon dioxide can
act as a soft oxidant, H-transfer agent and surface modifier (Ansari
and Park, 2012).
Carbon dioxide has low oxidizing ability and high heat capac-
ity. Therefore, its application can minimize hot-spot risk inside
the reactor due to which catalyst deactivation, temperature run-
away and undesirable side reactions and products oxidation might
occur. N2 O, O2 and SO2 are alternative oxidants being evaluated, for
example, in ODH (oxidative dehydrogenation) reaction. The main
disadvantage of the application of N2 O is its safety hazards. For
O2 , its main drawback is over-oxidizing valuable hydrocarbons and
generation of undesirable carbon oxides. SO2 is also an unfavorable
oxidizing agent due to the formation of CS2 , COS and benzoth-
iophene which are all corrosive and toxic by-products. Hence, in
oxidative dehydrogenation reaction, CO2 would be a promising
oxidant.
3.1.1. Dry reforming
Synthesis gas (or syngas, a mixture of CO and H2 , and sometimes
CO2 , with varying proportions) has a central role in indirect conver-
sion of carbon sources (natural gas, coal, biomass, organic wastes)
into valuable products via syngas chemistry. Therefore, many
hydrogenation reactions of carbon monoxide such as methanol and
hydrocarbon syntheses are well-established commercial technolo-
gies.
For the production of syngas from natural gas (and other hydro-
carbons) by reforming process, methane is partially oxidized and
according to the oxidant used, the processes are known as SMR
(steam-methane reforming, Eq. (1)), DMR (dry-methane reforming,
Eq. (2)), and POX (partial oxidation, Eq. (3)).
CH4 + H2 O ⇔ CO + 3H2 0
H298 = 206 kJ/mol
CH4 + CO2 ⇔ 2CO + 2H2 0
H298 = 248 kJ/mol
0 which CO2 is utilized as well. Dry reforming of methane can be
CH4 + 0.5O2 ⇔ CO + 2H2 H298 = −35.6 kJ/mol
RWGS (reverse water-gas shift) is also an accompanying reac-
tion (Eq. (4)):
0
H2 + CO2 ⇔ CO + H2 O H298 = 41.2 kJ/mol
This reaction can alter the stoichiometric H2 /CO ratio of the
respective reforming reactions. The endothermic reactions (1), (2)
and (4) are favorable at high temperatures (above 640, 620 and 815
◦ C, respectively).
These basic reformings differ in heat requirement and obtained
H2 /CO ratios. Dry reforming, for instance, is much more endother-
mic than steam reforming and produces a lower H2 /CO than the
latter. Combined reformings are also used for adjusting H2 /CO
ratio and heat integration (Nematollahi et al., 2011). Autothermal
reforming (ATR), for example, is a combination of exothermic POX
and endothermic SMR for achieving a H2 /CO ratio of about 2, suit-
able for methanol and Fischer-Tropsch syntheses. Another choice
is tri-reforming process which is the combination of methane oxi-
dation (Eq. (3)), steam reforming (Eq. (1)) and dry reforming (Eq.
(2)) that can directly be used for flue gases (Halmann and Steinfeld,
2009).
The final application of syngas, the economy and location of the
plant determines the selection of the process for syngas production.
Side reactions resulting in coke formation include CO dispropor-
tionation or Boudouard reaction (Eq. (5)), methane decomposition
(Eq. (6)) and CO reduction (Eq. (7)).
2CO ⇔ C + CO2 0
H298 = −172kJ/mol
CH4 ⇔ C + 2H2 0
H298 = 75kJ/mol
CO + H2 ⇔ C + H2 O 0
H298 = −131kJ/mol
Coke deposition, through CO disproportionation (Eq. (5)) and
methane decomposition (Eq. (6)), is the main challenge of DMR
reaction as it causes catalyst deactivation.
Thermodynamic equilibrium calculations show that lower pres-
sures, higher temperatures and higher CO2 /CH4 ratios in the feed
increase equilibrium conversion of methane and reduce coke for-
mation tendency (Jafarbegloo et al., 2015). Under typical test
conditions of 700−850 ◦ C and CH4 /CO2 = 1, methane conversions
(XCH4 ) and CO selectivites (SCO ) of ∼100 and 95 %, respectively, has
been reported.
Dry reforming of methane is an attractive reaction, due to the
below advantages (Fan et al., 2009):
• CO2 and natural gas utilization and their transformation to syngas
as a valuable product.
• The production of a high CO/H2 ratio syngas.
• The utilization of low-graded natural gas resources that have CO2
impurities.
In POX and ATR processes, an ASU (air separation unit) is
required as these processes need oxygen feed; but the produced
syngas of these processes has H2 :CO≈2 which is perfect for GTL (gas
to liquid) and FT (Fischer-Tropsch) processes (Rafiee et al., 2018). If
air is used in POX process, a nitrogen-diluted syngas is obtained.
In auto-thermal technology, new concepts of simultaneous CO2
reforming and CH4 partial oxidation could be future perspectives
to overcome drawbacks of present processes. SMR is a process with
less capital cost as it does not need ASU; but the resulting syngas
has H2 :CO≈3 which needs to pass a separation unit before entering
GTL process in order to balance its H2 content. Adiabatic, tubular
(1) and heat-exchange reformers are different types of reactors that
can be used for SMR reaction. By combining SMR and DMR reac-
(2) tions, a syngas with desirable H2 /CO ratio can be obtained through
(3)
used directly for flue gases, but other reforming processes need a
CO2 separation unit in advance (Lim et al., 2012).
In some regions, there are limitations in water usage for steam
reforming reaction for syngas production. In this case, dry reform-
(4)
ing can be used (Pakhare and Spivey, 2014).
Dry reforming of methane (Eq. (2)) is an endothermic reaction.
As its thermodynamics is unfavorable at temperatures lower than
600 ◦ C, proposing a system operatable at lower temperatures is
equivalent to lower energy consumption. One possible choice is the
integration of DMR with FT reaction (as a highly exothermic reac-
tion using syngas as feed). The coupling of DMR with FT reaction at
natural gas wells produces liquid hydrocarbons that can easily be
transported (Centi et al., 2013).
3.1.1.1. Catalysts. Different catalyst types used in this process are
metal oxides, supported metal catalysts and mono- and bi-metallic
catalysts. Generally, these catalysts are metals (such as Co, Ni, Rh,
Ru, Pd, Pt and Ir) on oxide supports (such as La2 O3 , SiO2 , CaO,
MgO, Al2 O3 , ZrO2 , TiO2 and CeO2 ) (Wittich et al., 2020). Noble
metals exhibit the best activity and stability in DMR (Rezaei et al.,
2006). Ni-based catalysts showed similar activity with lower price
than noble metals; hence, they are other alternate catalysts. It was
reported (Bouarab et al., 2004) that Co-based catalysts had better
performance than Ni-based ones. It was found that Ru and Rh had
high activity and stability while Ir, Pt and Pd have lower activity
and susceptible to deactivation (Ma et al., 2009).
(5) Oxide supports are categorized as acidic and basic supports
that have different behavior towards carbon deposition. In order
(6) to retard carbon deposition on catalyst, metal oxides with basic
sites were used as catalyst support. Supports with Lewis basic sites
(7) (such as CaO, Al2 O3 and MgO) promote CO2 adsorption capacity
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
and enhances deactivation resistance of the catalyst (Bradford and
Vannice, 1999).
The application of zirconia (Li and Wang, 2004) and ceria (Lima
et al., 2006) as catalyst promoters, significantly reduced coke for-
mation. Ni supported on nanocrystalline zirconia resulted in high
stability even at relatively low temperatures (700 ◦ C) and low
CO2 /CH4 ratios (1 mol/mol), which otherwise catalyst deactivation
would be rapid (Rezaei et al., 2009).
CeO2 has been widely used as support material mostly due to
its high oxygen storage capacity (linked to the redox transforma-
tion between Ce3+ and Ce4+ ) which has crucial contributing to the
removal of the carbonaceous species from support surface by oxi-
dation. The addition of ceria as promoter to alumina in Ni/Al2 O3
catalyst further modifies metal support interaction and increase
active metal dispersion and alumina thermal stability (Stroud et al.,
2018). The active metal can be electronically promoted by addition
of a second metal (e.g., Co, Fe, Cu, or Mn) (Zhang et al., 2007).
It was reported that alumina and/or silica-based catalysts pre-
coated with CaO or MgO had better performance. For Ni-based
catalysts, deactivation and methanation of catalyst are the major
problems. However, a stable performance of 55 h was reported for
Ni supported on Mg aluminate spinel. A detailed description of dif-
ferent catalysts evaluated for DMR reaction is provided in Fan et al.
(2009).
Active metal, metal particle size, support surface area and metal-
support interactions are the critical points in catalyst that has
influence on catalytic performance of DMR process.
3.1.1.2. Mechanism. In the process of dry reforming of methane,
adsorption and dissociation, as main reactive steps between
methane and catalyst, can be direct or precursor-mediated.
Methane adsorption on metal part of the catalyst occurs in a dis-
sociated form after which hydrogen (H2 ) and hydrocarbon species
(CHx , x = 0−4) are produced. Metal substrate and reaction tem-
perature determines the x value. CHx and H atoms are attached to
metal active sites. Subsequently, most of hydrogen species (that
were adsorbed) are re-combined to form H2 molecules that des-
orb into the gaseous phase. Metal-support interaction has critical
role and CO2 dissociation proceed via H2 spillover mechanism. By
CO2 dissociation, oxygen species are produced by which oxidation
of CHx to CHx O species on active metal sites occurs. Afterwards,
further decomposition reaction occurs and CO and H2 are formed
(Cheng et al., 2001).
Due to the presence of different supports, various reaction
mechanisms were reported. For silica-supported catalysts, as the
case of acidic supports, metal active sites activate CH4 and CO2 .
For Al2 O3 , MgO, TiO2 and La2 O3 supports, bi-functional reaction
mechanism was proposed in which CO2 activation occurs on sup-
port surface. As carbon dioxide is readily adsorbed on basic sites,
this kind of support enhances CO2 activation (Fan et al., 2009).
Over Ni/MgO catalyst, the dissociation of CH4 on Ni sites,
often considered as rate-determining step, is structure-sensitive.
It occurs preferentially on low coordinated sites such as steps
and edges which are more abundant on small Ni particles
(Serrano-Lotina and Daza, 2014). Coke formation is similarly
structure-sensitive and smaller particles are more resistant to coke
formation. Consequently, metal cluster size and support type play
an important role in catalyst performance.
3.1.1.3. Catalyst deactivation. A major problem in commercializa-
tion of DMR is rapid catalyst deactivation by coke formation
although other deactivation mechanisms such as metal oxidation
and sintering may play a role. Coke formation is more noticeable on
larger nickel particles and with acidic supports. It has been shown
that in dry reforming of methane, the carbon nucleates are formed
177
on step sites of nickel crystallites followed by formation of filamen-
tous whisker type carbon (Bengaard et al., 2002).
Basic supports not only increase CO2 adsorption, but also pro-
mote dissociation of the adsorbed CO2 and water to active oxygen
species which remove coke by oxidation. CeO2 plays an impor-
tant role in formation of active oxygen species owing to its high
oxygen capacity and therefore in coke removal. The addition of
small amount of water to the feed suppressed coke formation and
increased the lifetime of Ni-based catalysts (Eltejaei et al., 2012).
3.1.1.4. Processes. Unlike steam reforming of methane which has
been used over a century, dry reforming is still under research and
development.
In Hokkaido, Japan, Yufutsu GTL pilot plant using bi-reforming
was in operation at capacity of 7 bpd (barrel per day) (Yagi et al.,
2005). During 2001–2004, the process was stable for more than
6000 h with 1300 g/(kgcat .h) productivity.
In April 2009, by a joint venture between Chiyoda, JAPEX, Nip-
pon Oil, INPEX and JOGMEC, Niigata Demonstration Plant was
completed with capacity of 500 bpd using tri-reforming for syngas
production (Quadrelli et al., 2011).
SPARG and CALCOR processes are two available technologies for
CH4 −CO2 reforming. These two processes have different markets;
CALCOR targeted the production of very pure CO and SPARG tar-
geted retrofitting of steam reforming plants. These two processes
operate at high temperatures (>900 ◦ C) at which carbon formation
is less favorable. For these processes, methane slip is very low; for
SPARG process it is lower than 2.7 vol.% and for CALCOR process it is
lower than 0.1 vol.%. In 1987, SPARG process (Fig. 4) was first com-
merciallized at Sterling Chemical Inc. in Texas, USA. In this process,
sulfur-passivated Ni catalysts are used to minimize carbon forma-
tion and subsequent catalyst deactivation. If CO2 is available with
no cost, SPARG process is an economical choice for syngas produc-
tion with H2 /CO = 1. The operating temperature of this process is
915−945 ◦ C (Song and Guo, 2006). In CALCOR process, CO with high
purity is produced from LPG or natural gas. Membrane technology
and pressure swing adsorption are two methods used for the purifi-
cation of CO product; first option gives CO purity of ∼ 98.9 vol.% and
second one gives 99.4 vol.% CO purity (Seshan and Lercher, 1994).
3.1.2. Oxidative dehydrogenation of alkanes
Light alkenes (C2 -C4 ) are important petrochemical and refining
building block being used for the production of polyolefins and fuel
(additives). They are mostly by-products of steam and fluid crack-
ers. Due to ever-increasing demand, on-purpose methods such as
dehydrogenation of the corresponding alkane (Eq. (8)) has received
attention.
0
C3 H8 ⇔ C3 H6 + H2 H298 = 124 kJ/mol (8)
Industrial implementation of the reaction is complicated due to
thermodynamic limitation and rapid catalyst deactivation by coke
deposition (Tahriri Zangeneh et al., 2013). Consequently, catalyst
regeneration is an integral part of the commercial processes. Oxida-
tive dehydrogenation (ODH) reduces thermodynamic limitation by
removing hydrogen, but oxidation of the product by oxygen is a
problem. A mild oxidant such as CO2 could relive this problem.
The CO2 -ODH of light alkanes is an endothermic reaction in
which by formation of water (Eq. (9)), thermodynamic constraints
are reduced. On the other hand, the reverse Boudouard reaction
(Eq. (5)) eliminates carbon deposition during ODH reaction and a
stable catalytic activity is obtained.
C3 H8 + CO2 ⇔ C3 H6 + CO + H2 O 0
H298 = 164 kJ/mol (9)
Thermodynamic equilibrium calculations show that the
replacement of an inert diluent with equimolal amount of CO2 can
178 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 4. SPARG process for CO2 reforming of methane (re-drawn from Song and Guo, 2006).
reduce the required operating temperature for a given conversion
(Tahriri Zangeneh et al., 2016).
The main advantage of ODH reaction is that it is a feasible
process at small volumes of alkanes. Moreover, catalytic CO2 dehy-
drogenation process, saves energy, lowers GHG emissions and
reduces operating and capital costs (Ansari and Park, 2012).
3.1.2.1. Catalysts. Most of the oxide catalysts active in simple dehy-
drogenation of lower alkanes are also active in CO2 -ODH. Many bulk
and supported oxides have been evaluated as catalysts for CO2 -
ODH. Among the investigated catalysts, those containing Cr or Ga
were found to be the most active and selective ones (de Oliveira
et al., 2018).
3.1.2.2. Reaction mechanism. A one-step mechanism has been pro-
posed for redox oxides (Cr2 O3 , Cr2 O5 , ZnO and V2 O5 ), in which CO2
can participate as an oxidizing agent in the following redox cycle
(Eqs. (10) and (11)) (Michorczyk et al., 2008).
C3 H8 + MOx ⇔ C3 H6 + MOx-1 + H2 O
CO2 + MOx-1 ⇔ CO + MOx
in which M is the metal.
Over non–redox oxides such as Ga2 O3 , the two-step pathway
has been proposed, that is simple hydrogenation (Eq. (8)) followed
by RWGS reaction.
3.1.3. Oxidative dehydrogenation of ethylbenzene
Styrene, an important monomer for synthetic polymers, is
produced by vapor-phase ethylbenzene dehydrogenation (EBDH)
which is among ten most important industrial processes (Eq. (12)).
In commercial practice, EBDH reaction occurs over bulk Fe-Cr-K
catalyst at 600−650 ◦ C in the vapor phase in the presence of excess
superheated steam (molar ratio of H2 O/EB >10:1) in an adiabatic
reactor. Steam provides the required heat of the endothermic reac-
tion; increases equilibrium conversion by diluting ethylbenzene
and prevents coke deposition. Its main disadvantage is losing the
large latent heat of vaporization (Saito et al., 2010).
0 VOx /Al2 O3 showed high activity and selectivity in CO2 -EBDH
C6 H5 − CH2 CH3 ⇔ C6 H5 − CH = CH2 + H2 H298 = 118kJ/mol
This is an energy-consuming process with thermodynamic lim-
itations.
Oxidative dehydrogenation of ethylbenzene is an alternative
route for styrene manufacture. This reaction is an exothermic one
without thermodynamic limitations. The main drawback of oxi-
dation process is its need to oxygen (which is a strong oxidant)
by which oxygenates and carbon oxides are produced and styrene
selectivity is reduced.
As a substitute to oxygen, carbon dioxide can play its roles.
Furthermore, the application of CO2 -EBDH reaction (Eq. (13)) can
overcome some of the disadvantages of steam.
C6 H5 − CH2 CH3 + CO2 ⇔ C6 H5 − CH = CH2 + CO + H2 O
(13)
0
H298 = 159kJ/mol
Side reactions include dealkylation of EB and coke formation.
3.1.3.1. Catalysts. In the pioneering researches on the application
(10) of CO2 in the oxidative dehydrogenation of EB (ethylbenzene) to
(11) styrene, zeolite-supported iron oxide catalyst was evaluated that
showed better conversion than that of simple dehydrogenation
in N2 environment. It was observed that besides styrene; water,
hydrogen and carbon monoxide were produced such that the ratio
of hydrogen to carbon monoxide was ¼. It was concluded that reac-
tion proceeded in an oxidative pathway in which CO2 molecule was
dissociated to CO and surface oxygen which abstract hydrogen and
water was formed (Ansari and Park, 2012).
The iron oxide catalyst optimized for traditional EB dehydro-
genation process exhibits poor performance in CO2 -EBDH. Many
oxides have been tested as the catalyst but the best results have
been obtained for Fe, Cr and V oxides (Reddy et al., 2008). Most of
these are supported on oxides (Al2 O3 , MgO, ZnO, WO3 , SiO2 and
ZrO2 ), carbons and zeolites. The support can have impact on acidic
or basic properties of dispersed active site; the oxide support has
acidic properties while surface oxygen atoms are electron-poor and
in case of being electron-rich, they have basic properties. Alkali and
alkali earth metals have been used as promoters.
(Xiang et al., 2008). The reduction of active species V5+ to less active
(12) V4+ and V3+ during reaction has found to be the main cause of cata-
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
lyst deactivation, while coke deposition has a secondary role (Chen
et al., 2020). Mixed oxides such as TiO2 -ZrO2 are also active in the
reaction (Sun et al., 2004).
For ODH reactions, acid-base bi-functionality has a crucial role.
In catalyst, for the activation of substrate, acidic properties are
important; whereas for CO2 activation and hydrogen atoms, basic
sites are critical.
3.1.3.2. Reaction mechanism. In simple dehydrogenation pathway,
basic sites of the catalyst abstract ␣-hydrogen atom of ethylben-
zene and carbanions are formed, which in turn loses another “H”
and styrene and H2 are formed. In oxidative dehydrogenation,
strong basic sites of the catalyst activate carbon dioxide and ␣-
hydrogen atom of EB is abstracted. In the next step, activated CO2
and generated hydrogen react and CO, H2 O and styrene are formed.
There is a distinct difference between basic sites participating in
CO2 activation and those abstracting ␣-hydrogen atoms (Ansari and
Prk, 2012).
At first, researchers studied CO2 -ODH reaction of ethylbenzene
to styrene over ZSM-5-supported iron oxide catalyst. Reduced and
isolated magnetite (Fe3 O4 )-like phase was found to be the active
phase of the catalyst that has oxygen vacancy in zeolite structure
(Ansari and Park, 2012).
The oxygen atom of a CO2 molecule acts as the oxidant to
abstract hydrogen atom, as C–H bond dissociation through hydro-
gen abstraction with oxygen species is the rate-determining step
in hydrocarbon dehydrogenation. Hence, over catalysts that are
able to activate CO2 for the generation of atomic surface oxygen,
hydrogen is abstracted from the ethyl group of ethylbenzene.
On an acid-base catalyst, an ODH reaction might proceed by
simple dehydrogenation (Eq. (12)) and oxidative dehydrogenation
(Eq. (13)), partially (Ansari and Park, 2012). In ODH reaction, redox
properties of catalyst have the main role in transferring oxygen
from carbon dioxide to hydrocarbon. At first, the hydrocarbon is
contacted with metal oxide due to which partial reduction of metal
oxide and oxidative dehydrogenation of hydrocarbon occurs, simi-
lar to ODH of lower alkanes over reducible oxides (Eq. (10)). In the
next step, in vicinity of CO2 , the reduced metal oxide is changed
to a fully oxidized state (Eq. (11)). ODH reaction, in comparison
to conventional method (in which steam is used for hydrocarbon
dehydrogenation) gives a higher selectivity.
3.1.3.3. Industrial processes. Among the mentioned CO2 -ODH pro-
cesses, ethylbenzene oxidative dehydrogenation was evaluated at
pilot-scale plants. Ansari and Park (2012) presented an ODH process
for ethylbenzene to styrene in the presence of CO2 . This process is
operated at 560 ◦ C on zeolite-supported iron oxide catalyst. In this
process, carbon dioxide can be used directly from a reforming plant
or a by-product of a petrochemical oxidation process. Due to the
high styrene selectivity of this process, for 0.6 Mtstyrene /y, $2.7 mil-
lion saving was obtained. The commercial process required much
higher energy; most of which is consumed in reactor and separator.
In the commercial process, 63 × 105 kJ/tonstyrene energy is required
while that of CO2 -ODH is 26 × 105 kJ/tonstyrene ; which is equiva-
lent to 33 % energy saving and $6.5 million for 0.6 Mtstyrene /y. In
the commercial process, energy loss at the separator is 63 × 105
kJ/tonstyrene while that of CO2 -ODH is 14 × 105 kJ/tonstyrene . In the
commercial process, 63 × 105 kJ/tonstyrene energy is required for
reactor while CO2 -ODH needs 7.9 × 105 kJ/tonstyrene . An example
of this mini-pilot is at Samsung General Chemicals Co. (SGC) with
100 kgstyrene /day (Ansari and Park, 2012).
ISOCO2 process, a joint project of SABIC (Saudi Basic Industry
Corporation) at Inha University, is another example of CO2 -ODH of
ethylbenzene (Park et al., 2010).
SODECO2 (Styrene production via Oxidative Dehydrogenation
of Ethylbenzene with CO2 as soft oxidant) is a novel process for
179
styrene production by oxidative dehydrogenation of ethylbenzene
using carbon dioxide (Park and Chang, 2004). A schematic dia-
gram of this process is depicted in Fig. 5. An advantage of SODECO2
process is that it uses CO2 obtained from reforming or oxidation
process without further purification. In comparison to the conven-
tional dehydrogenation process, SODECO2 process obtained high
selectivity for styrene (>97 %) and improved activity (>30 %) and
a decrease in reaction temperature (40−50 ◦ C). Moreover, energy
consumption for ethylbenzene dehydrogenation was 30 % lower
than conventional process (Park and Chang, 2004).
3.1.4. Oxidative coupling of methane
The conventional conversion of methane to higher hydrocar-
bons via reforming reaction is highly energy and capital intensive.
Therefore, direct conversion routes such as coupling of methane
(Eq. (14)) would be highly desirable.
2CH4 ⇔ C2 H6 + H2 0
H298 = 64.4kJ/mol (14)
The reaction is endothermic and strongly equilibrium limited
(G1000 = 71 kJ/mol). However, in the presence of oxygen, that is
oxidative coupling of methane (Eq. (15)), it is thermodynamically
favorable.
0
2CH4 + 0.5O2 ⇔ C2 H6 + H2 O H298 = −176 kJ/mol (15)
Ethane is the primary product, while the more valuable ethylene
is the secondary product being produced by (oxidative) dehydro-
genation of ethane.
CO and CO2 are produced as undesirable by-products through
deep oxidation of methane and/or C2 products. As the C2+ products
are more reactive than methane towards oxidation, the single-
pass yield is limited to about 25 % as formulated by rule of 100
% which states that the conversion and selectivity roughly sum up
to 100 (Sahebdelfar et al., 2012). Unlike oxygen, CO2 as oxidant does
not induce gas-phase deep oxidation reactions which consume the
products at higher conversions.
Oxidative coupling of methane (OCM) in the presence of CO2
can be explained by Eqs. (16) and (17):
2CH4 + CO2 ⇔ C2 H6 + CO + H2 O 0
H298 = 106kJ/mol (16)
2CH4 + 2CO2 ⇔ C2 H4 + 2CO + 2H2 O 0
H298 = 284kJ/mol (17)
At 800 ◦ C, the equilibrium yields of ethane and ethylene are suf-
ficiently high (13 % and 57 %, respectively) in the CO2 −OCM (Krylov
and Mamedov, 1995). However, the experimental yield of C2 hydro-
carbons over a metal oxide catalyst is <9% under typical reaction
conditions of 850 ◦ C and CO2 /CH4 = 2 (Nishiyama and Aika, 1990)
due to kinetic limitations. Such results highlight the importance of
development of effective catalysts to approach the thermodynamic
boundary of the reaction.
3.1.4.1. Catalysts. A number of single, binary and ternary oxides
such as MgO, CeO2 , CaO-CeO2 , CaO-ZnO, Na2 WO4 /Mn/SiO2 and
CaO-MnO/CeO2 have been tested for CO2 −OCM reaction (Ansari
and Park, 2012 and references therein). It has been suggested
that on CaO-CeO2 catalyst, CO2 is activated by CeO2 due to its
Ce3+ /Ce4+ redox properties and produces CO and active oxygen
species responsible for CH4 oxidation while CaO enhance the selec-
tivity. CaO-ZnO exhibited higher C2 selectivity than binary oxide
CaO-CrOx and CaO-CeO2 catalysts under the same C2 yield opera-
tion, possibly due to lower reactivity of lattice oxygen in the former
(Wang and Ohtsuka, 2000).
In case of application of CO2 as oxidant, the selectivity toward
ethane and ethylene are increased, but as the sites responsible for
methane activation are poisoned, conversion decreases.
180 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 5. Schematic diagram of SODECO2 process for styrene production by oxidative dehydrogenation of ethylbenzene using carbon dioxide (re-drawn from Park and Chang,
2004).
3.1.4.2. Reaction mechanism. Two mechanisms were proposed for
reactions (16) and (17). In the first approach, carbon dioxide is
adsorbed on metal oxide, and decomposed, active oxygen species is
formed and CO is released (Eq. (18)). Methane is oxidized by active
oxygen species and by coupling of methyl radicals ethane is formed
(Eqs. (19) and (20), respectively) as the primary product (Wang and
Zhu, 2004).
CO2 + ∗ → CO + O∗
CH4 + O∗ → CH3(radical) + OH
2CH3(radical) → C2 H6
In the second approach, methane reacts with lattice oxygen of
metal oxides and methyl radical is formed (Eq. (21)) which in turn is
converted to C2 hydrocarbons (Eq. (22)), and the partially reduced
oxides are re-oxidized by CO2 (Eq. (23)) (Ansari and Park, 2012).
2CH4 + O(surface) → 2CH3(radical) + H2 O + 䊐(vacant site)
2CH3(radical) → C2 H6
䊐(vacant site) + CO2 → CO + O(surface)
3.1.4.3. Industrial processes. The application of carbon dioxide in
oxidative coupling of methane reaction has positive impact on
the thermodynamics of this reaction; nevertheless, state-of-the-art
catalysts do not show satisfactory performance. KIER and KRICT in
collaboration with Samsung Total Corp. had successful pilot plant
test for this process with oxygen as oxidant (Choi and Cho, 2008).
3.2. CO2 hydrogenation
The portfolio of heterogeneous CO2 hydrogenation products is
limited; however, they have the largest potential market, as they
include fuels and basic chemicals. The reactions are strongly equi-
librium limited and complete conversion of CO2 is rarely achieved.
Unlike CO hydrogenation, the technologies for CO2 hydrogenation
are, for the most part, under research and development (Zhou et al.,
(18) 2019). Over most of CO2 hydrogenation catalysts RWGS reaction
(19) can also occur, therefore, strict differentiation between CO2 and
CO is rather arbitrary. Consequently, the effective hydrogen/carbon
(20) ratio in the feed is commonly characterized by a modulus value, M,
defined as:
[H2 ] − [CO2 ]
M= (24)
[CO] + [CO2 ]
(21)
The desirable value of M is, for instance, about 2 for methanol
(22) synthesis (Sec. 3.2.1) and about 3 for methanation (Sec 3.2.3).
The above concept has been applied for the development of tan-
(23) dem catalysts and processes which use consecutive RWGS reaction
and syngas chemistry for a particular hydrogenation product (Hu
et al., 2013).
The main products of CO2 hydrogenation are oxygenates and
hydrocarbons. Methanol and hydrocarbons, as typical products of
CO2 hydrogenation, are valuable clean fuels for internal combustion
engines. Splitting water by electrolysis is one renewable source of
H2 production for CO2 hydrogenation (Yang et al., 2006).
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 6. Conversion routes of methanol.
3.2.1. Methanol
Methanol is a multi-source, multi-purpose chemical that can
be used as fuel, blending component for gasoline, reactant of MTO
(methanol to olefins) or MTG (methanol to gasoline) process, feed
for fuel cells, solvent, building block of the chemical industry (for
the production of formaldehyde, MtBE (methyl tert-butyl ether)
and acetic acid) and energy storage material (Fig. 6). In comparison
to gasoline, methanol has half energy density and excellent com-
bustion properties that can be used as vehicle fuel. Moreover, in
comparison to conventional fossil fuels, it is less polluting (Ashok
et al., 2019).
Currently, the largest worldwide methanol demand is for
formaldehyde production (≈30 %) and methanol to olefins,
amounting about 20 % of total consumption, which is a rapidly
growing sector for on-purpose production of light olefins from non-
petroleum sources.
The “Methanol Economy” proposed by Nobel Laureate George
Olah emphasizes on the production of methanol (or dimethyl ether
(DME)) by chemical recycling of CO2 and their subsequent conver-
sion to varied products including hydrocarbons (Goeppert et al.,
2018).
Nowadays, methanol is industrially produced by catalytic con-
version of synthesis gas (Eq. (25)); which in turn is produced
from natural gas or coal. For methanol production from syngas,
Cu/ZnO/Al2 O3 is the commercial catalyst. Relatively “soft” condi-
tion of 210−270 ◦ C and 50−100 bar is used as industrial operating
conditions, by which 99 % selectivity to methanol is obtained
(Ullmann’s Encyclopedia of Industrial Chemistry, 2002).
0 CO2 hydrogenation catalyst mainly contains Cu and Zn as main
CO + 2H2 ⇔ CH3 OH H298 = −90.6 kJ/mol
Generally, methane, DME, methyl formate and higher alcohols
are obtained as by-products (Van-Dal and Bouallou, 2013).
The main challenge of CO2 to methanol process (Eq. (26)) is
lower reactivity of CO2 in comparison to CO, hence under the same
operating conditions, methanol yield from CO2 is much lower than
that from CO and, consequently, a more expensive and larger reac-
tor is required. In the process of methanol production from CO2 ,
more water is produced and crude methanol contains approxi-
mately 30−40 wt.% water that inhibits process kinetics and requires
large reactors. On the other hand, this process is less exothermic
which simplifies its reactor design; tube-cooled reactors are appro-
priate (Marlin et al., 2018).
CO2 + 3H2 ⇔ CH3 OH + H2 O 0
H298 = −49.4 kJ/mol
181
Methanol synthesis from CO2 is an exothermic reaction with
decreasing molecule number. From thermodynamic viewpoint,
decreasing temperature and increasing pressure is in favor of this
reaction. Under typical reaction conditions of T = 240−280 ◦ C, P =
40 bar and H2 /CO2 = 3, the reported methanol yields are limited to
about 15 % (corresponding to XCO2 = 20 % and SCH3OH = 80 %). The
main by-product is CO from RWGS reaction that can be recycled.
Methanol production from pure CO2 limits the production
of various types of by-products such as higher alcohols (mostly
ethanol), ethers (mostly DME), esters and ketones (such as ace-
tone and MEK (methyl ethyl ketone)). Saito et al. (1996) reported
that the obtained methanol is extremely pure with 5-times lower
by-products. Hence, purification step is simplified and number of
distillation columns and energy consumption is reduced.
3.2.1.1. Catalysts. Although isotope labeling studies showed that
the primary source of methanol is carbon dioxide, also when H2 /CO
mixture is used as feed (CO2 is formed by RWGS reaction), the tradi-
tional three-component Cu-based catalysts exhibit low conversion
and selectivity in methanol synthesis from pure CO2 (Olah et al.,
2018).
Researchers developed various kinds of metal-based catalysts
for methanol synthesis among which Cu was the main active phase
with different promoters (Zn, Zr, Ce, Al, Si, V, Ti, Ga, B and Cr). The
selection of the suitable supports helps the formation and stabi-
lization of the active phase, tuning the interaction between active
phase and promoter, and determining the acidity/basicity of the
catalyst (Liu et al., 2003a).
(25)
components and Zr, Ga, Si, Al, B, Cr, Ce, V and Ti as various modifiers
(Arena et al., 2007). Saeidi et al. (2014) reported the performance of
different catalysts for CO2 hydrogenation to methanol. They con-
cluded that in traditional fixed-bed tubular reactor using different
catalysts, CO2 conversion is usually low, but in recycle reactors its
conversion is very high which is favorable. Tursunov et al. (2017)
and Porosoff et al. (2016) presented a detailed comparison for the
effect of operating parameters (such as catalyst type, pressure and
temperature) on the performance of conversion of H2 /CO2 mixture
to methanol.
3.2.1.2. Reaction mechanism. Methanol synthesis reaction occurs
at the interface of cupper and oxides. CO2 could be adsorbed on
bare oxides and H2 could be dissociated on Cu species. The nature
(26) of Cu (at the interface) as active phase is still ambiguous.
182 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
In literature, for methanol synthesis, two categories of reaction
routes are discussed. The first route is formate pathway in which
rate-determining step is intermediate HCOO formation. Monoden-
tate formate is the intermediate formed on ZnO and bidentate
formate is the intermediate formed on Cu. The second route is
CO formation through RWGS reaction and subsequent syngas to
methanol conversion. In the formate mechanism, CO is formed
from methanol decomposition and in the RWGS mechanism, CO
is formed as a major by-product (Lim et al., 2009).
3.2.1.3. Methanol production process. Two different routes can be
used for methanol production from CO2 ; namely one-step (Eq. (26))
and two-step (Eqs. (4) and (25)) conversions. Direct hydrogenation
of CO2 to methanol is one step conversion. In two-step conver-
sion, CO2 is first transformed to CO by RWGS reaction and then
hydrogenated to methanol (Van-Dal and Bouallou, 2013).
Both routes of methanol production generated large amount of
H2 O as by-product that caused catalyst deactivation and conse-
quently had inhibitory effect on active phase (Ma et al., 2009).
Joo et al. (1999) reported that two-step conversion process has
higher yield than one-step. Oil barrel price, CO2 price, electricity
price and by-products use determined economic viability of com-
mercial plants.
In modern syngas-based methanol production plants, addition
of CO2 to syngas (up to 8%) is practiced to increase the methanol
yield and to consume carbon dioxide as a source of carbon.
3.2.1.4. Industrial advances. According to CO2 mitigation concept,
several processes were developed. In 1994, Lurgi built first demon-
stration plant for methanol production from CO2 . In 1996, first pilot
plant (capacity: 50 kg/h) was constructed for methanol production
from CO2 and H2 over SiO2 -modified CuO/ZnO catalyst. Operating
at 250 ◦ C and 5 MPa and recycling the product, over 8000 h oper-
ation, 99.9 % selectivity with STY (space-time yield) of 600 g/(L.h)
for methanol was obtained (Ashok et al., 2019).
Mitsui Chemicals Inc. in collaboration with RITE (Research Insti-
tute of Innovative Technology for the Earth) constructed another
pilot plant (capacity: 100 t/y) in Japan for methanol production
from CO2 and H2 . In this plant, H2 was produced by photochemical
water splitting using solar energy. An ethylene production plant of
Osaka Works Petrochemical Complex supplied CO2 feed. This plant
has been in operation since 2010; a schematic diagram of which is
provided in Fig. 7 (Tremblay, 2008; Samiee and Gandzha, 2020).
At the end of 2010, CRI (Carbon Recycling International)
installed a methanol production plant that produced 3000 t/y
methanol in Iceland. From 18 ton carbon dioxide, this unit pro-
duced 10 ton methanol. CO2 feed is obtained from an aluminum
production plant and Svartsengi geothermal power plant and H2 is
produced from alkaline water electrolysis using Iceland’s entirely
renewable grid electricity. The obtained methanol was branded as
VulcanolTM (CRI, 2020) that is consumed as a blend component
of gasoline. By this plant, 5500 t/y CO2 is recycled. Icelandic grid
supplied all the required energy of the CRI plant. This plant was
patented as ETL (Emissions to Liquids) technology. Carbon dioxide
passes a gas-conditioning system in which impurities are omit-
ted and suitable CO2 feedstock for downstream methanol plant is
obtained. Afterwards, CO2 and H2 (with ratio of 1:3) are mixed,
compressed and reacted. Increasing the number of electrolysis cells
is one method of unit scale-up. Methanol synthesis reaction is
highly exothermic; the generated heat is used in downstream distil-
lation unit in which the produced methanol is purified to fuel-grade
product to be blended with gasoline (Stefansson, 2015).
BSE Engineering developed a flexible process for methanol pro-
duction from CO2 and H2 . In this process, an alkaline electrolyzer
and excess renewable electricity are used for hydrogen produc-
tion. Carbon dioxide is captured, purified and fed with hydrogen
(at a specific ratio) to the methanol synthesis reactor. The heat of
reaction is recovered as steam and used in the methanol purifica-
tion step. The raw product contains 64 % methanol and 36 % H2 O
that is purified in the distillation tower to obtain the final methanol
product with purity >99.85 wt.%. The methanol synthesis process
and H2 O electrolysis are highly flexible. The first plant of 10-MW
power to methanol was envisioned in 2019–2020 by BSE Engineer-
ing (Schweitzer, 2017).
CAMERE (carbon dioxide hydrogenation to form methanol via
reverse water gas shift) process was developed by KIST (Korea Insti-
tute of Science and Technology) on bench-scale (50−100 kg/d) and
operated by KIER (Korean Institute of Energy and Research) and
KOGAS (Korea Gas Corporation) (Choi and Cho, 2008). In CAMERE
process (Fig. 8), methanol is produced from CO2 and H2 at 75 Mt/y
capacity. In this process, at first, RWGS reaction occurs on ZnAl2 O4
catalyst; then after water removal, methanol is synthesized on
Cu/ZnO/ZrO2 /Ga2 O3 catalyst. The main disadvantage of this process
is the need to two different catalysts and reactors. In the CAMERE
process, due to the intermediate water removal, three times higher
productivity was obtained (Centi et al., 2013; Joo et al., 2004).
In Iran, Fanavaran Petrochemical plant produces 1 million t/y of
methanol by CO2 utilization. In this plant, natural gas and CO2 enter
with flow rates of 610 kt/y and 268 kt/y, respectively. These feed
streams along with steam (generated on site) are fed to SMR sys-
tem and the produced syngas, after pressurizing, fed to methanol
reactor (Powell and Qiao, 2006).
3.2.2. Dimethyl ether
Dimethyl ether (DME, CH3 OCH3 ) has received much attention as
a chemical intermediate for the production of a variety of chemicals
such as olefins. It is also a potential environmental-friendly energy
carrier and LPG (liquefied petroleum gas) or diesel substitute.
DME can be produced from CO2 by two reaction routes. In the
indirect or two-step route, methanol is first synthesized by hydro-
genation of CO2 followed by dehydration to DME (Eq. (27)) (Rafiee
et al., 2019).
2CH3 OH ⇔ CH3 OCH3 + H2 O 0
H298 = −24.0 kJ/mol (27)
The reaction is exothermic and thermodynamically favorable
(equilibrium conversion = 86.5 % at 300 ◦ C).
Solid acids such as alumina and zeolites catalyze the reaction.
Conversions close to equilibrium (>85 %) can be achieved. Alumina
shows good catalytic performance in methanol dehydration to DME
(Mollavali et al., 2008).
In the direct route (Eq. (28)), DME is produced directly from CO2
hydrogenation in a single reactor over multi-functional catalysts
containing methanol synthesis and dehydration functionalities
(Azizi et al., 2014).
2CO2 + 6H2 ⇔ CH3 OCH3 + 3H2 O 0
H298 = −122.8 kJ/mol (28)
In single-step route, the product of CO2 hydrogenation
(methanol) is used by the tandem methanol dehydration to DME
reaction, thereby resulting in lower thermodynamic limitation
compared to methanol synthesis and, thus, two-step route. How-
ever, multi-step routes have the advantage of the possibility of
inter-stage removal of the produced water, to avoid its adverse
effects on catalyst components.
CuO-ZnO-Al2 O3 /␥-Al2 O3 , CuO-ZnO-Al2 O3 /HZSM-5 and CuO-
ZnO-Al2 O3 -ZrO2 +HZSM-5 were examples of bi-functional catalysts
(Centi et al., 2013). Despites its good performance in methanol
dehydration, alumina is not suitable as a component of bi-
functional catalysts for direct hydrogenation of CO2 to DME due to
its hydrophilic nature. The large amount of water produced com-
petes with methanol for active sites leading to its reduced catalytic
performance as a dehydration component of the catalyst.
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 7. Schematic diagram of Mitsui process for methanol production (re-drawn from Tremblay, 2008 and Samiee and Gandzha, 2020).
Fig. 8. CAMERE process for methanol production (re-drawn from Joo et al., 2004 and Tahriri Zangeneh et al., 2011).
3.2.3. C1 hydrocarbon (Methane)
Synthetic natural gas (SNG) production is an emerging process
for CO2 conversion into solar fuels by which storage and transporta-
tion of renewable energy is possible. Many researchers focused on
CO2 methanation (Abe et al., 2009; Eckle et al., 2011).
In methanation process, methane is produced from the reac-
tion of hydrogen and carbon oxides. If carbon monoxide is used, it
is called CO methanation (Eq. (29)) and if carbon dioxide is used,
it is called CO2 methanation or Sabatier reaction (Eq. (30)). Both
reactions are highly exothermic (Rönsch et al., 2016).
CO + 3H2 ⇔ CH4 + H2 O 0
H298 = −206 kJ/mol
0
CO2 + 4H2 ⇔ CH4 + 2H2 O H298 = −165 kJ/mol
The methanation of CO2 is thermodynamically highly favorable
and nearly complete equilibrium conversions are possible at lower
temperature (Sahebdelfar and Takht Ravanchi, 2015). Under typical
reaction conditions of T = 300−400 ◦ C, P = 1 bar, XCO2 and SCH4 of
90 and ∼100 %, respectively, have been reported in the literature.
In view of thermodynamics, CO2 methanation is a combination
of CO methanation (an exothermic reaction) and RWGS reaction (an
endothermic one). Different thermodynamic studies were reported
in literature (Su et al., 2016).
Due to the exothermic nature of the reaction, lower tempera-
ture is favored for CO2 methanation reaction. At ambient pressure,
in order to have conversions higher than 90 % and high selectivity
to CH4 , temperatures lower than 300 ◦ C is required. The favorable
operating condition for CO2 methanation is temperatures lower
than 300−350 ◦ C, elevated pressure and stoichiometric ratio of
H2 /CO2 = 4. For favorable equilibrium composition, a specific reac-
tor configuration is needed in which careful heat management
could be done and activation energy barrier could be overcome
(Mebrahtu et al., 2019).
183
In 1980–1990s, Hashimoto et al. (1999) proposed a new process
that is a combination of CO2 methanation and water electrolysis.
Sterner (2009) evaluated this process in details.
3.2.3.1. Catalysts. Despite its thermodynamic favorability, CO2
methanation reaction is kinetically limited because the fully oxi-
dized carbon is to be reduced to methane in an 8-electron process.
Consequently, a suitable catalyst that has adequate activity and
selectivity toward methane is necessary (Park and McFarland,
2009).
For methanation reaction, all metals of groups 8–10 of periodic
(29) table are active. Transition metals such as Ni, Pd, Co, Ru and Rh can
be used as catalysts of CO2 methanation reaction. It was reported
that activity performance of these catalysts was decreased in order
(30) Ru > Rh > Ni > Co > Pt > Pd. In comparison to noble metals (Ru, Rh
and Pd), Co and Ni-based catalysts are the best ones due to their low
cost. A detailed explanation of different catalysts evaluated for CO2
methanation is provided in Li et al. (2018) and references therein.
Ni-supported on various metal oxides (mainly ␥-Al2 O3 ) is the
most common catalyst for this reaction (Rahmani et al., 2014).
Despite its low cost, it has high activity and methane selectiv-
ity. Zeolites, SiO2 , carbon nanotubes, TiO2 , hydrotalcites, CeO2 and
ZrO2 are different supports used for catalysts of CO2 methanation
process (Abate et al., 2016; Zhou et al., 2016).
In methanation plants at pilot scale, nickel catalysts are used as
they have high activity at low temperature, high methane selectiv-
ity, good redox properties and price, and easy availability. Sintering,
fouling, mechanical straining and poisoning are main causes of cat-
alyst deactivation (Rönsch et al., 2016). There is a need to improve
sulfur resistance and thermal stability of methanation catalysts. In
order to enhance both activity and stability of Ni-based catalysts,
the implication of a second metal and a hydrotalcite-like material
are recommended.
For commercial applications, dual-functional catalyst with the
ability of adsorption and hydrogenation of CO2 to methane is of
184 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
high importance. For instance, combining Ru/␥-Al2 O3 with CaO,
the obtained catalyst can adsorb carbon dioxide from flue gas and
hydrogenate it to methane. In the practical application, this catalyst
can directly be used in a flue gas stream without any need to purify
and transport the gas (Duyar et al., 2015).
3.2.3.2. Reaction mechanism. Some examples of evaluated mecha-
nisms for CO2 methanation is provided in Tada and Kikuchi (2015)
and Wei and Jilong (2011). Miao et al. (2016) published a review
paper for kinetic studies and mechanisms proposed for CO2 metha-
nation. Generally, these mechanisms can be divided to associative
and dissociative ones. In the associative configuration, after asso-
ciative adsorption of CO2 , it reacts with adsorbed hydrogen atom to
form oxygenates and in the subsequent step, they are hydrogenated
to methane. In this sequence, no distinctive CO intermediate is
formed. In the dissociative configuration, firstly carbon dioxide
dissociates to carbonyl (CO) and oxygen (O) atom. During CO
methanation, step-wise hydrogenation of CO occurs and methane
is formed (Aldana et al., 2013).
3.2.3.3. Processes. Various reactor configurations were evaluated
for CO methanation. Air Liquide (Lurgi methanation technology),
Haldor Topsøe (TREMP technology), British Gas (BTG) and Conco,
Ralph M. Parsons (RMP), Imperial Chemical Industries (ICI) and
Koppers, Clariant and Foster Wheeler (Vesta technology), Johnson
Matthey (Davy Technologies) used adiabatic fixed-bed reactors;
Linde used cooled fixed-bed reactor; Bituminous Coal Research Inc.
and Thyssengas used fluidized bed reactor. Recently, different CO2
methanation processes were started and developed from 1970s and
1980s. Most of CO2 methanation projects are in Germany. The main
reason is that Germany decided to shift its energy system towards
a system that is 100 % based on renewable energies.
The PtG (power-to-gas) process is a 3-step one which comprises
renewable electricity generation, renewable hydrogen production
and thermo-chemical carbon dioxide conversion to methane by
renewable hydrogen through Sabatier reaction. In this process,
hydrogen is generated by water electrolysis (with the renewable
energy of sun or wind) and reacts with CO2 to produce methane.
The obtained methane can be used for natural gas infrastructure or
storage services. PtG ALPHA plants in Bad Hersfield, Morbach and
Stuttgart (in Germany) are examples of pilot plants each with 25
kW power input capacity (Rönsch et al., 2016).
During 2009–2012, some CO2 methanation plants were at pilot
scale and in 2013, E-Gas project was at commercial scale. In this
plant, hydrogen was produced by electrolysis. In most of these pro-
cesses, methanation technology of Etogas Company was used and
tube reactor with gas recycling or steam-cooled plate reactors were
used (Etogas, 2020).
ETOGAS (a German Co.) designed and built multi-megawatt
turn-key systems, that consists of methanation systems and
high pressure alkaline electrolyzers. In Wertle, Germany, ETOGAS
designed and installed a 6.3 MW power-to-SNG system for Audi
AG (as a customer) that has been in operation since 2013. This
plant consists of three 2 MW units and produced synthetic methane
(namely Audi e-gas). The plant operated with wind power, its CO2
came from a biogas plant and produced 1000 t/y Audi e-gas with
chemically binding of 2800 tons of CO2 . The methane content of
the end product was higher than 96 %. The main method for scale-
up of this plant is increasing the number of electrolyzer units. In
Germany, from 2009 to 2013, five projects of PtG process was in
operation with different capacities of 25 kW–6300 kW. In 2016,
in Copenhagen, Denmark, a commercial scale PtG process was in
operation with 1.0 MW capacity (Agarwal et al., 2015; Rönsch et al.,
2016; Younas et al., 2016).
Both CO and CO2 methanation processes have difficulty in man-
aging heat of reaction. Fixed-bed reactors with gas recycling and
intermediate cooling, e.g. in TREMP, HICOM and Lurgi processes,
are commercially available cases. In order to reduce operational
and investment costs, in future applications, recycle gas compres-
sors can be avoided (e.g. in modified TREMP and Vesta processes)
(Rönsch et al., 2016; Samiee and Gandzha, 2020). Schematic dia-
grams of Lurgi, TREMP and Linde processes are provided in Fig. 9.
In Denmark, Haldor Topsøe, developed TREMPTM that is a
methanation process which consists of three adiabatic fixed-bed
reactors. The heat of methanation reaction is used for the pro-
duction of high-temperature steam that is required for solid oxide
electrolysis cells (SOEC) unit. A 40 kW SOEC unit was built by Haldor
Topsøe in Foulum, Denmark (Zhu, 2019).
In Sendai Technology Institute, a process was developed in
which methane was produced from CO2 over catalysts based on
zirconia-samarium ceramic with an amorphous layer of Ni as active
phase. In this process, hydrogen was produced from electrolysis of
seawater. Due to a joint-venture project between PTTEP, Hitachi
Zosen Corp and Daiki Ataka Engineering Corp., this operation was
transferred to Thailand to develop a new process based on solar
energy in which methane was synthesized from CO2 , sea water
and solar energy (Habazaki et al., 1998).
In Norway, a pilot-plant was developed by RCO2 AS in which
CO2 was recovered from flue gas and by renewable hydrogen, it
was transformed to methane. In this plant, CO2 sequestration costs
were in the range of 60−100 US $/Mt of CO2 . In order to lower the
carbon footprint, this renewable methane can be used in chemical
industry (Centi et al., 2013).
3.2.4. C2+ hydrocarbons
Fischer-Tropsch reaction (Eq. (31)) is known for more than a
century:
2nCO + (3n + 2) H2 → 2Cn H2n+2 + 2nH2 O n = 1, 2,... (31)
The reaction is exothermic and thermodynamically favorable.
Commercially, iron- and cobalt-based catalysts are employed. Iron,
due to its RWGS activity, can be used over a wider H2 /CO ratio range
of the syngas feed, especially with coal- and biomass-based syngas
which have a low H2 /CO ratio.
In traditional Fischer-Tropsch (FT) synthesis reaction, CO is used
as carbon source for the synthesis of hydrocarbons. By substituting
CO with CO2 (Eqs. (32) and (33)), the reaction would be thermody-
namically more difficult (Muleja et al., 2017).
CO2 + 3H2 → − (CH2 ) − +2H2 O
(32)
H500 = -119 kJ/mol,G500 = -16.9 kJ/mol
CO2 + 2H2 → − (CH2 ) − +H2 O + CO
(33)
H500 = -79.6 kJ/mol,G500 = 3.4 kJ/mol
The reported experimental yield of the hydrocarbon products
(<40 %) is much smaller than that of methanation reaction under
similar reaction conditions.
The chain-growth probability (˛) for CO2 -FT is typically smaller
than that for conventional FT, because CO acts as the chain growth
agent in FT reaction. This results in lower molecular weight of the
hydrocarbon product (<C5+ ) in CO2 -FT.
CO2 -FT is a direct process for the production of alkanes and
olefins from carbon dioxide. Due to the higher energy density of
long-chain hydrocarbons, their production from CO2 hydrogena-
tion is of importance.
3.2.4.1. Catalysts. The catalyst of CO2 -FT process is specific as it
should be active for both FT and RWGS reactions. If Fisher-Tropsch
step is fast enough to overcome thermodynamic limitations of
RWGS step (as the main challenge of CO2 -FT), high CO2 conversions
can be obtained.
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194 185

Fig. 9. Different CO2 methanation configurations; (a) Lurgi process, (b) TREMP process, (c) Linde process (re-drawn from Rönsch et al., 2016; Samiee and Gandzha, 2020).
186 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Li et al. (2018) reported the performance of different catalysts for
C2+ hydrocarbons production from CO2 hydrogenation. Fe-based
catalysts are mainly used for CO2 -FT reaction; as Fe can improve
the coupling of C C bond, which is the rate-determining step (Nie
et al., 2017).
Two main difficulties in designing new catalysts for CO2 -FT pro-
cess are the presence of water (as an unavoidable by-product of
CO2 -FT process) that is a catalyst poison regarding its activity and
selectivity; and the presence of CO2 that is a poison for CO hydro-
genation catalyst. Researchers must be focused on synthesizing a
catalyst with high activity and selectivity being resistant to water
in temperature range of 100−300 ◦ C (Pan et al., 2010).
Recently, it was reported that for CO2 -FT process, the appli-
cation of Fe-based catalysts in comparison to Co-based catalysts,
produced more olefins. Fe/␥-Al2 O3 catalyst produced C2+ hydro-
carbons (Dorner et al., 2010).
Alternatively, methanol can be used as a bridge and building
unit for the synthesis of C2+ hydrocarbons by CO2 hydrogena-
tion; that is, the indirect methanol-mediated pathway (Wang et al.,
2016). Methanol is synthesized and dehydrated to hydrocarbons
over shape-selective acidic component of a composite catalyst (e.g.,
Cu-ZnO-Al2 O3 /HB zeolite, (Fujiwara et al., 2015)).
3.2.4.2. Mechanism. For the mechanism of CO2 -FT process, two
routes were proposed. In the first one, C O bond cleavage of CO2
molecule occurs and CO is formed and converted to methane. The
possible key intermediate is the adsorbed surface carbon (Cads ).
In the second one, at first, CO2 is activated into carbonates, and
hydrogenated into formate and methoxy species. According to
this mechanism, for CO2 adsorption, weak basic sites are needed
(Aldana et al., 2013).
For the production of CH4 , CH3 OH, CO and other hydrocarbons
from carbon dioxide, different pathways were proposed (Behrens,
2014; Das and Deo, 2011; Uzunova et al., 2015).
The main difference between CO2 methanation and CO2 hydro-
genation to C2+ hydrocarbons is C C coupling barrier for the
formation of C2+ hydrocarbons. If H/C ratio can be controlled on
a suitable ratio, long-chain hydrocarbons can be produced; due
to excess hydrogenation, too much surface H* will cause methane
formation and the opposite condition reduce activity of CO2 con-
version. C C bond formation and C O bond cleavage are main steps
of hydrocarbon synthesis by CO2 hydrogenation. Fe- and Co-based
catalysts are used for catalyzing CO/CO2 hydrogenation to hydro-
carbons. As Cu is able to cleavage C O bond, it usually converted
CO/CO2 to C2+ hydrocarbons or alcohols (Gnanamani et al., 2016;
Helden et al., 2017; Landau et al., 2017).
In CO2 -FT process, when CO and CO2 were simultaneously used
as feedstock, due to competitive adsorption, CO hydrogenation is
the primary route while CO2 hydrogenation is the secondary path-
way (Visconti et al., 2009).
3.2.4.3. Processes. In Inner Mongolia, China, Shenhua group started
Erdos program in which 1 million t/y diesel was produced. Yitai
plant and Luan plant with capacity 160 kt/y are in successful run-
ning for ammonia, diesel and urea (Amouroux et al., 2014).
Sunfire process is one for conversion of syngas to long−Chain
hydrocarbons (−CH2 -) by Fischer-Tropsch process for the pro-
duction of chemicals or fuels. The syngas is resulted from
co-electrolysis (syntrolysis) of H2 O and CO2 in solid oxide elec-
trolysis cells. Fisher-Tropsch reaction is an exothermic one and the
released heat of reaction is used for water vaporization for the elec-
trolysis of steam and a high level of efficiency of approximately 70
% was obtained (Zhu, 2019).
In Dresden, Germany, in April 2015, Sunfire GmbH constructed
a pilot plant that produced diesel fuel with high quality (Sunfire,
2020). The electrolyzer with 10 kW capacity operated at 1.5 MPa.
This pilot plant was in operation for more than 1500 h with carbon
conversion efficiency of 90 %. The end product of this plant was a
synthetic fuel namely “Audi-e-diesel” with high cetane value and
excellent combustion properties. Sunfire GmbH started scale-up of
a power-to-liquid (PtL) production plant in July 2017, in Norway.
A Norweigian Cleantech Company, namely Nordic Blue Crude AS,
operate 20 MWe PtL plant with production capacity of 800 t/y Blue
Crude (Sherrard, 2020).
Carbon Engineering (CE), as a Canadian Company, commercial-
ized its Air-to-Fuels (A2F) system. This system is a combination of
direct air capture (DAC) technology with H2 O electrolysis and fuel
synthesis and the obtained product was liquid hydrocarbon fuels.
In this plant, at first, CO2 is captured from atmospheric air, purified
and compressed into a liquid. Then water is electrolyzed by clean
electricity and H2 is generated. At last, H2 and CO2 are thermo-
catalytically reacted and syngas is generated and converted into
hydrocarbons (e.g. Jet fuel and diesel) (Carbon Engineering, 2020).
In 2015, a DAC pilot plant was commissioned by CE. This plant
captured and purified 1 t/d CO2 from atmosphere. In 2017, a water
electrolysis and a Greyrock M-Class fuel production plant with a
capacity of synthesizing 1 bpd of fuel were installed. In Dec. 2017, a
small amount of liquid fuels was produced by A2F system. Although
A2F process was a proven technology, but its large footprint and
high costs are its main disadvantages (Carbon Engineering, 2020).
3.3. CO2 to polymers
Interestingly, CO2 shows high activity in polymerization reac-
tions and can be converted with high yields. For the chemical
fixation of CO2 , polymers with annual production of more than
200 million tons worldwide are good candidates (Alper and Orhan,
2017).
There are two approaches for the synthesis of polymers from
CO2 . In direct route, CO2 is used directly as a co-monomer in poly-
merization reaction (e.g., synthesis of polycarbonates, polyurea and
polyurethanes from CO2 ). In indirect routes, CO2 is first converted
to a monomer (e.g., (a)cyclic carbonates, urea, carbomates) from
which a large variety of polymers are produced (Langanke et al.,
2015). This approach is compatible with current technologies and
can be more rapidly developed.
The favorable reaction is copolymerization of epoxides and
CO2 for the production of polycarbonates. Cyclohexene oxide
(CHO), propylene oxide (PO) and epichlorohydrin (ECH) were the
commonly used epoxides. Poly(propylene carbonate) (PPC), as
the product of copolymerization of PO and CO2 and a low-cost
eco-friendly polymer, is very common in academia and indus-
try (Klaus et al., 2011; Ree et al., 2006). Urea-formaldehyde (UF)
and melamine-formaldehyde (MF) resins are preferred polymers in
which CO2 derivatives are used to construct the macromolecules.
In the polymerization reaction, the application of CO2 as a sol-
vent is troublesome which is a consequence of weak CO2 solvating
power that caused low dissolution for polymers (Brunner, 2005).
3.3.1. Polymers from CO2 as a co-monomer
Carbon dioxide can copolymerized with different reactive
monomers such as strained heterocyclic molecules (epoxides,
azidirines, episulfides) and dienes to form a variety of polymers.
In late 1960s, Inoue pioneered the copolymerization of epox-
ide and CO2 (Inoue et al. (1969)). During the past four decades,
researchers were focused on developing new catalysts for these
processes (Liu and Wang, 2017). Based upon the applied catalyst,
polycarbonate, polyethercarbonate or cyclic carbonate can be pro-
duced (Fig. 10). Thus, Cr- or Co-salen complexes and zinc salts
catalyze polycarbonate formation, while double metal cyanides and
dinuclear zinc complexes promote polyethercarbonate formation.
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 10. Different products obtained from CO2 -epoxide reaction.
Fig. 11. Direct carboxylation of CO2 -glycerol.
The cyclic carbonate is the thermodynamically favored prod-
uct whereas polycarbonate formation exhibits lower activation
energy. Therefore, higher temperatures favor cyclic carbonate for-
mation whereas lower temperatures shift the selectivity towards
the polymer. Higher pressures accelerate the reactions and favor
polycarbonate formation by enhancing CO2 insertion (Kamphuis
et al., 2019). The cyclic carbonate by-product is also valuable as
aprotic solvents and precursors of polycarbonates.
Linear and cyclic organic carbonates are used for the synthe-
sis of various chemicals from CO2 , such as phosgene-free aromatic
polycarbonates or aliphatic polycarbonates like polypropylene
carbonate, polyimonene carbonate, polyethylene carbonate and
polyurethanes (Dibenedetto et al., 2012; Zhao et al., 2019).
Aliphatic polycarbonates can be used as packaging materials and
polyethercarbonates can be used as raw material in the structure
of polyurethanes. In several countries and specifically in China, PPC
commercialization is in process. Based upon utilization, the product
of the copolymerization reaction of CO2 and PO can be catego-
rized to two groups; one is PPC that has good biodegradability, high
molecular weight and carbonates contents and used in packaging
materials and gas barrier films, the other is low molecular weight
polycarbonate polyols that is used as raw material in polyurethane
industry. Currently, most of the polyols are petroleum-based. New
CO2 -based polyols are novel products for polyurethane industry
(Qin et al., 2015).
The synthesis of polyethercarbonate polyols from epoxides and
CO2 is also reported. Based upon low viscosity and favorable glass
transition temperature, the obtained polyethercarbonate polyols
can be used for the production of polyurethane (PU) foams. Theo-
retically, by the production of polyethercarbonate polyols, 1.6 Mt/y
CO2 was used as feedstock. For the production of polyethercarbon-
ate polyols, CO2 can be used as monomeric C1 building block by
which the cleavage of C O bond (which is an energy-intensive one)
is avoided (Assen and Bardow, 2014a).
During the production of biodiesel from natural triglycerides, a
large amount of glycerol is produced; hence, the direct coupling of
187
glycerol and carbon dioxide is of industrial interest by which glyc-
erol carbonate was obtained (Fig. 11) that can be used as a monomer
for the synthesis of functionalized polymers (Yu et al., 2008).
By copolymerization of aziridines and azetidines with car-
bon dioxide, poly(urethane)s are obtained (Lermusieau and Collin,
2001). Aziridine form simple structured polyurethanes with carbon
dioxide (Eq. (34)):
(34)
Polyurethanes have –NHCOO– group, but other groups can also
occur in their repeating chain. Currently, they are produced by reac-
tion of isocynates (R N C O) and diols. The product of Eq. (34) (as
shown) has urethane and amine linkages because homopolymer-
ization of aziridines occur competitively with a rate comparable to
that of copolymerization of aziridines and CO2 (Darensbourg et al.,
2010). Although the copolymerization reaction proceeds without
a catalyst or inititator (supercritical CO2 as solvent at 100 ◦ C and
100 bar), alkali metal salts, salts of quaternary amines and salen
complex of chromium catalyze the reaction. To date, little progress
in this area has been achieved in general.
Polyureas have –NHCO-NH- groups in their backbone. The tra-
ditional route is based on isocynate. The alternative routes are
CO2 -diamine or acyclyic carbonates with urea systems.
In the commercial processes for the production of cyclic and
polymeric carbonates based on CO2 , the epoxide starting mate-
rials (such as ethylene oxide and propylene oxide) are produced
from fossil feedstock. Substituting petroleum-based epoxides with
bio-based ones is a crucial challenge. It is worth mentioning that
polycarbonates based on carbon dioxide are biodegradable and
from economic point of view, their recycle is preferable (Kamphuis
et al., 2019).
3.3.1.1. Catalysts. ZnEt2 -active hydrogen containing systems, dou-
ble metal cyanide complexes, zinc dicarboxylates and rare-earth
188 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
metal coordination ternary catalysts are examples of heteroge-
neous catalysts used in CO2 copolymerization (Allen et al., 2002;
Dong et al., 2012; Wu et al., 2013; Zhang et al., 2011).
For CO2 -epoxide copolymerization, Moore et al. (2002) used
metal tetraphenylporphyrin complex as a homogeneous catalyst.
Other examples of homogeneous catalysts are metal-porphyrin,
discrete ␤-diiminate zinc, zinc phenolate, metal-salen or –salen
complexes (Cohen and Coates, 2006; Kember et al., 2012; Ren et al.,
2009; Saini et al., 2014; Wu et al., 2011).
Transition metal compounds are mostly toxic and colored, thus
are not favorable in catalyst formulation because of producing col-
ored products and also complex production. Zhang et al. (2016)
synthesized the first metal-free Et3 B/PPNCl catalyst for ethylene
oxide (EO) and cyclohexane oxide copolymerization with CO2 . The
triethyl borane was used as the Lewis acid to activate the epox-
ides, while onium alkoxides or onium halides involving either
ammonium, phosphonium, or phosphazenium cations were cho-
sen to initiate the copolymerization. Triethyl borate, however, is
pyrophoric and sensitive to water which imposes limitation for
its application. Later, Andrea and Kerton (2019) used triarylborane
with a co-catalyst or as a Lewis acid/base adduct to prepare either
the cyclic organic carbonate as metal-free catalyst.
Due to cheapness and recoverability, metal or mixed oxides are
helpful heterogeneous catalysts. For the production of dimethyl
carbonate from methanol and carbon dioxide, catalysts based on
CeO2 are active ones; they are good candidates for the production
of polycarbonates from polyols and carbon dioxide. The reaction
between propylene oxide and CO2 for the production of propy-
lene carbonate can be catalyzed by polyhedral MgO (Arbeláez et al.,
2019; Solmi et al., 2019).
3.3.1.2. Reaction mechanism. A two-step consequtive
coordination-insertion mechansim has been proposed for copoly-
merization of CO2 and epoxides by metal complexes, that is, ring
opening of epoxide by metal halide or carboxylate to give metal
alkoxide followed by CO2 insertion (Fig. 12) (Trott et al., 2016).
If an alkoxide is used as the catalyst, the insertion of CO2 is the
initiating step and ring opening occurs afterwards.
The metal complex coodrinates with epoxide and attacks it with
nucleophile group X (halide or carboxylate) which leads to ring
opening of epoxide and the resulting metal alkoxide initiates the
reaction. The resulting metal alkoxide intermediate is converted to
a metal carbonate by formal insertion of CO2 . In the propagation
step, the resulting carbonate serves as an initiator for ring-opening
of another coordinated epoxide to form a new metal alkoxide,
followed by CO2 insertion to generate a carbonate, which contin-
ues the polymerization process. The propagation step, therefore,
involves the cycling between metal alkoxide and carbonate inter-
mediates.
3.3.2. Polymers from CO2 -derived compounds
Certain CO2 -based molecules such as urea, organic carbon-
ates and unsaturated carboxylic acids can act as intermediates
or building blocks for the production of polymers by homo- and
co-polymerization (Langanke et al., 2015). Cyclic carbonates, as
substitute to toxic phosgene, can participate in ring opening co-
polymerization reactions.
Nowadays, large amount of CO2 is used in the formation of C N
bonds for industrial production of urea. Phosgene-free routes are
based on CO2 and amines (urea); and CO2 , amines and alcohols
(carbonates, Eq. (35)) in which by the removal of products, reac-
tion is shifted and thermodynamic limits are overcome. Carbamic
acids are produced from the interaction between CO2 and primary
amines which is dehydrated in-situ (under Mitsunobu conditions)
to intermediate isocyanates which are condensed with the same
amines to ureas (Grignard et al., 2019).
RNH2 + CO2 + R OH → RNHC(O)OR + H2 O (35)
The direct reaction of CO2 and amines for the production of urea
derivatives needs 14−140 atm pressure and 130−170 ◦ C temper-
ature but N,N-́diaryl, dialkyl and alkyl-aryl ureas are produced as
well (Nocitoa and Dibenedetto, 2020).
Urea and formaldehyde are both produced from CO2 and ther-
mosetting UF resin is produced according to below two-step
reaction (Eqs. (36) and (37)):
(36)
(37)
Based upon Eq. (38), melamine is obtained from urea:
(38)
From the reaction of melamine and formic acid, hexamethylol
melamine is obtained by the polymerization of which thermoset-
ting MF resins are obtained. From the reaction of carbon dioxide
with epoxides or diols, transesterification with dimethyl carbonate,
polyalkylene carbonates are produced which are good candidates
to be substituted with polyethers in polyurethane production.
Polyoxymethylene (POM) as another polycondensation poly-
mer is produced from CO2 via 1,3,5-trioxane and formic acid (Eq.
(39)) (Alper and Orhan, 2017):
(39)
Despite its high price, due to better mechanical properties, POM
could replace polyethylene and polypropylene. Methylmethacry-
late (MMA) is another product of methanol that can be polymerized
by which CO2 will be fixed in polymethylmethacrylate (PMMA)
(Alper and Orhan, 2017).
In polymerization processes, CO2 can be used as an anti-solvent.
For the preparation of macro-porous polymer beads by suspension-
polymerization method, Lermusieau et al. (2001) used supercritical
CO2 . These polymers have versatile applications such as ion-
exchange resins, solid-supported reagents and chromatography
separation media. By changing CO2 density, the porosity of polymer
beads can be controlled. By changing temperature and pressure,
CO2 can easily be separated and disposed (Hunt et al., 2010).
3.3.3. Industrial processes
For the production of CO2 -based polycarbonates (without using
CH2 Cl2 and phosgene), Asahi Kasei Corporation (Japan) developed
a process which uses bisphenol-A, ethylene oxide and CO2 . This
process produces polycarbonate and monoethylene glycol. In this
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Fig. 12. Catalytic cycle of CO2 /epoxide polymerization (M: active metal site; X: halide or carboxylate; OR: growing chain (e.g. OCHR1 CH2 X); R2 OH = alcohol or water).
process, due to high activity and selectivity of the catalyst, prod-
ucts have high yield and purity and no separation or purification is
needed. On the other hand, no waste is produced to be treated or
disposed. It has been claimed (Fukuoka et al., 2007) that the Asahi
Kasei process has lower capital cost compared to the commercial
phosgene-based processes. The first commercial Asahi Kasei pro-
cess for the production of polycarbonate was started in 2002 in
Taiwan and after that several plants were constructed in Russia,
South Korea and Saudi Arabia under license. Six companies have
purchased this license with a total capacity of 1.07 Mt/y for polycar-
bonate production by 2019, which is equivalent to 0.185 Mt CO2 /y
fixation (Zhu, 2019). The first plant was a joint plant of Asahi Kasei
and Chi Mei, named as Chimei Asai plant in Taiwan with production
capacity of 50 kt polycarbonate in 2002 to 150 kt in 2007. In Yeosu,
Korea Cheil Industries and Honam Petrochemical used Asahi Kasei
process with a capacity of 65 kt/y. In 2009, Asahi Kasei process was
licensed to Saudi Kayan Petrochemical Co. (in Jubail, Saudi Arabia)
for the production of polycarbonate in a plant with capacity 260
kt/y. In the traditional plants of polycarbonate production, CH2 Cl2
and water are used in large amount and the final product contains
huge amount of Cl− impurities. In Asahi Kasei process, on the other
hand, the CO2 feedstock is the by-product of ethylene oxidation
to epoxide. Due to the low cost of CO2 and avoiding the applica-
tion of toxic phosgene, the new environmentally friendly process
is successfully industrialized (Aresta et al., 2002).
For the production of polyether carbonates polyols (PPP) from
carbon dioxide, a process (namely “Dream Production”) was
developed jointly by Bayer Material Science and Bayer Technol-
ogy Service, the RWTH University of Applied Science (Aachen,
Germany) and RWE power. Their pilot plant produced PPP on kilo-
189
gram scale. In 2003, this pilot consumed 6 Mt/y polyols (Quadrelli
et al., 2011).
Covestro (Germany) and its partners developed a process
(namely Production Dreams) which utilizes up to 20 % of
carbon dioxide as a feed stock for the production of polyether-
polycarbonate polyols (CardyonTM polyols). The developed catalyst
of this process has high selectivity and no undesirable by-product is
produced. Since June 2016, in Dormagen (Germany) Covestro oper-
ated a production plant; CardyonTM polyols were produced which
were used, in turn, for the production of flexible polyurethane
foams. This plant is in operation with 5000 t/y capacity and $17
million investment (Convestro, 2020).
The commercialization of CO2 to polyolefin carbonate technol-
ogy was started in late 1980s/ early 1990s and Arco, Mitsui and Air
Products were involved in. As a result of Coates’ research at Cornell
University, in 2004, Novomer Co. was founded and a catalytic pro-
cess for the production of polypropylene carbonate polyols with
up to 50 wt.% carbon dioxide was developed by them with trade-
mark of Converge® polyols. 1000 and 2000 MW grade diols were
the first products obtained commercially in Houston (USA). Praxair
supplied CO2 of an ethanol fermentation plant to Novomer pilot
plant and polyethylene and polypropylene carbonate were devel-
oped. At commercial scale, as CO2 is cheaper than conventional
petroleum-based raw materials, Converge® polyols were cheaper
than conventional polyols. The commercial application of Novomer
Binder 180 ◦ C (NB-180) (as the first commercial polypropylene car-
bonate of Novomer Co.) is as binders that decompose clearly and
fast. These coating resins are potentially cost-reduced and have
environmentally and technically well performance (Aresta et al.,
2002; Novomer, 2020).
190 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Nanyang Zhongju Tianguan Low Carbon Technology Co. (China)
announced the copolymerization of CO2 and propylene oxide for
the production of biodegradable polypropylene carbonate. In this
process, supported zinc glutarate catalyst was used for the copoly-
merization of CO2 and propylene oxide. In 2015, this plant had 25
kt/y capacity. Of course, PPC glass transition temperature is 37 ◦ C
which limits its special application (Quadrelli et al., 2011; Tianguan,
2020).
Jinlong Green Chemical Co. used CO2 and ethylene oxide over
a polymer-supported bimetallic compound (as a catalyst) and pro-
duced aliphatic polycarbonate polyols (Zhu, 2019).
In USA, aliphatic polycarbonates that were produced by the
copolymerization of EO and CO2 were sold by PC Corporation. In
2002, in Taiwan, a commercial plant was built by Chimei-Asahi
Corp. for polycarbonate production with initial 50 kt/y capacity
which was raised to 150 kt/y in 2006 (Brunner, 2005).
The synthesis of polyhydroxyalkanoate (PHA) from epoxides
and carbon dioxide was performed by Novomer Co. Their pilot
plant was constructed near a sugar-based ethylene oxide plant. In
2009, in Dongfang Chemical City (Hainan Province of China), China
National Offshore Oil Corporation started a plant that produced
degradable chlorinated polypropylene carbonate based on carbon
dioxide with production capacity of 3 kt/y and CO2 consumption of
2.1 kt/y (Quadrelli et al., 2011).
In Nantong (Jiangsu, China) a 10 kt/y production line of CO2 -
polyols was constructed in Huasheng Polymer Co. (Liu and Wang,
2017).
A main obstacle for commercial development of epoxide-based
polymers and cyclic carbonate is limited availability to epoxides,
the production of which is associated with pollution.
3.4. CO2 to fine chemicals
Fine chemicals are produced industrially with a high or well-
defined purity in relatively small quantities and are thus expensive.
Due to their low production capacity, their impact on global CO2
mitigation is not significant. In this section, salicylic acid was
selected as a well-established CO2 -based fine chemical which is
commercialized for many years.
The process for the synthesis of salicylic acid was developed in
the 2nd half of 1800s. The Kolbe-Schmitt reaction (Eq. (40)) is an
old one in organic synthesis for the production of salicylic acid. In
this reaction, CO2 is used as feedstock which reacts with phenolate
anion (by electrophilic substitution) and salicylic acid is produced.
According to Eq. (40), difficulty in selectivity toward p- or o-isomers
persists. These two products have different applications. Approxi-
mately, 170 kt/y of salicylic acid is produced worldwide. The main
disadvantage of this reaction is the need to stoichiometric amounts
of strong bases by which stoichiometric amount of salts are pro-
duced as by-products (Aresta et al., 2014; Dabral and Schaub, 2019;
Markovic et al., 2007).
4. Technical and scientific challenges
Despite its high stability and low reactivity, carbon dioxide can
be transformed into a wide variety of products ranging from fine
chemicals to bulk chemicals and fuels by thermo-catalytic conver-
sion. Only limited numbers of reactions are in commercial use with
relatively low capacity. There are several barriers for using CO2 as
a C1 feedstock in chemical industries.
The most important is, perhaps, the availability of carbon
dioxide and the co-reactants, especially hydrogen, in large scale.
Technologies should be developed to produce these compounds
cost-effectively and sustainably with minimum environmental
impact (e.g., water electrolysis with renewable electricity).
Another important challenge is catalyst development. CO2 -
based reactions typically show high kinetic barriers which should
be overcome by the catalyst. Tandem catalysts based on syn-
gas chemistry and RWGS reaction are not often straight forward
for hydrogenation reactions because of adverse effect of large
amount of water produced on catalyst components. Therefore,
the active species might necessarily change. There are technical
challenges associated with RWGS catalyst development for higher
temperature operation in cascade reactions including sintering
and coke deposition which leads to rapid deactivation of catalysts
(Sahebdelfar and Takht Ravanchi, 2020).
As a consequence, many of the CO2 -based technologies are not
mature with industrial references. Further research and devel-
opment in scientific and technology issues are necessary. The
socio-economical driving forces should be set forward to make the
application of the alternative technologies more attractive.
CO2 utilization technologies were tabulated in Table 1, accord-
ing to their maturity level and expected time for commercialization
(Chauvy et al., 2019). For CO2 utilization, main challenges are cost
of CO2 capture and the required external energy for carbon dioxide
conversion (Javaid Zaidi, 2010).
5. Environmental impacts
In general, the comprehensiveness of the metrics used for envi-
ronmental assessments in chemistry increases as they move from
assessments of single stoichiometric reactions (e.g. atom economy)
towards multistep-reaction assessments considering the actual
mass balances (e.g. E-factor), that is, by considering the entire life
cycle (Assen et al., 2014b).
Although, the chemical conversions mentioned above consume
CO2 , the overall CO2 -based production could even increase CO2
emission considering CO2 emitted from power plants for electricity
and fossil fuels combustion for heat supply. This would be the case
for CO2 -based fuels today. A holistic metric for comparative eval-
uation can be obtained by life cycle assessment (LCA) using global
warming impact (GWI) and fossil depletion index (FDI), quantifying
overall effect on CO2 emission and resource consumption, respec-
tively. Relatively few LCA has been published on CO2 chemical
utilization.
According to Artz et al. (2018), the GWI for H2 supply could be
greatly decreased in best case scenarios for 2020 (from current 10.6
kg of CO2 equiv/kg for H2 based on SMR down to 0.43 for water elec-
trolysis with wind energy). The GWI for heat and electricity supply
(40)
can also show significant decrease by increasing share of renewable
electricity, whereas those for CO2 and natural gas would not show
significant changes. This will improve the GWI of the hydrogen con-
suming CO2 conversion processes, e.g. RWGS reaction versus DMR
reaction for syngas production.
Thonemann and Pizzole (2019) performed a thorough research
on life cycle assessment of CCU technologies in chemical industry.
In their analysis, the environmental impact for the production of
 M. Takht Ravanchi, S. Sahebdelfar / Process Safety and Environmental Protection 145 (2021) 172–194
Table 1
Technology readiness level (TRL) for main CO2 utilization technologies (adapted data from (Ampelli et al., 2014; Chauvy et al., 2019; Quadrelli et al., 2011)).
Reaction
Dimethyl carbonate synthesized from methanol and CO2
Dimethyl carbonate synthesized from EO and CO2 (two-step)
DME synthesis by CO2 hydrogenation
Methane synthesis by CO2 hydrogenation or CO2 methanation
Methanol synthesis by CO2 hydrogenation
Polyurethanes synthesis from CO2 (two-step)
Salicylic acid synthesis from phenol and CO2
Syngas synthesis by DMR
(1)
TRL = 1−3: R&D stage; 4−6: development scale; 7−9: demonstration scale.
(2)
N.R.: not-reported.
different chemicals (such as CO, CH3 OH, syngas, CH4 , formic acid,
DME, dimethyl carbonate (DMC) and polymers) were evaluated.
It was concluded that by chemical production via CCU and using
electricity from a renewable resource, GHG emissions would be
reduced. It was reported (Hoppe et al., 2018) that by the production
of formic acid and methane, the highest reduction in environmen-
tal impact could be obtained. Main findings of the environmental
assessments obtained by CCU technologies have been reviewed
(Cuellar-Franca and Azapagic, 2015). Artz et al. (2018) reported
that production of chemicals by CCU technologies reduced GWI.
The production of formic acid and CO2 -based polyol are examples.
It was reported (Cuellar-Franca and Azapagic, 2015) that dimethyl
carbonate production by CO2 , in comparison to conventional pro-
duction routes, lowered GWI by 4.3 times. A specific guideline for
performing LCA on CCU technology has been reported (Assen et al.,
2013).
A contribution analysis for the global warming impact of differ-
ent CO2 conversion technologies are provided in Thonemann and
Pizzol (2019). The technologies are mainly producing polyols, DMC
and formic acid. For each technology, CO2 supply has the 2nd and
heat generation and electricity has the 3rd largest contribution to
the total GWI. H2 supply has a lower impact as its short-term sup-
ply was considered to be by the market and that of long-term was
considered by electrolysis that has low GHG emissions.
In the urea-based process, the application of carbon dioxide cap-
tured by MEA for the production of DMC reduced global warming
potential (GWP) by 4.3 times in comparison to conventional route
of DMC production from phosgene (31 vs 132 kg CO2 /kg DMC ). In
all CCS options, average GWP is approximately 276 kgCO2 per ton
of the removed CO2 . This value is considerably lower than GWP of
any CCU option. For instance, in CCU via chemical product (such
as DMC), average GWP is approximately 59.4 tCO2 per ton of the
removed CO2 ; which is 216 times that of CCS. From an economic
viewpoint, CCU is a better choice than CCS. Based upon a life cycle
analysis, cost effectiveness and environmental impacts of CCU must
be evaluated carefully (Cuellar-Franca and Azapagic, 2015).
Assen and Bardow (2014a) used a real industrial pilot plant for
LCA, considering cradle-to-gate system boundaries, and showed
that CO2 -based polycarbonate polyol containing 20 wt.% CO2 could
reduce GHG emissions by 11–19 % and fossil fuel resource con-
sumption by 13–16 %. This route allows substitution of part of the
petrochemical product epoxy with renewable CO2 .
Another issue for evaluating processes for environmental
impacts is exergy. The exergy is a measure of useful power accord-
ing to the Second Law of Thermodynamics, such that maximizing
exergy efficiency promotes sustainability. A high rate of exergy loss
corresponds to higher environmental impact. Therefore, exergy
analysis is useful for assessment of energy conversion systems and
sustainable development.
Kamphuis et al. (2019) evaluated the performance of two
methanol production routes from CO2 captured from power plant
flue-gas, namely, direct hydrogenation and the indirect conversion
through natural gas bi-reforming (combined DMR and SMR reac-
191
TRL(1) Expected commercialization time (years)
4−5 0−4
8−9 N.R.(2)
1−3 0−10
7 0−4
8−9 0−4
8−9 N.R.(2)
9 0
6 0−7
tions) for syngas production. Exergy efficiency of the direct route
was obtained as 66.3 %, against 55.8 % for the indirect one, indi-
cating the lower sustainability of the latter. Such an assessment is
irrespective of GWI of hydrogen or natural gas. Therefore, it would
be more meaningful when used in combination with LCA.
6. Concluding remarks
The worldwide attention to carbon dioxide capture and utiliza-
tion is growing both in academic and industrial communities. These
are mostly ecological and social driven which are ever-increasing.
The fixation of CO2 by chemical routes into chemicals and espe-
cially fuels is cyclic in nature, that is, the CO2 avoided is released
subsequently. Therefore, net CO2 removal is not achieved over their
whole life cycle. However, they can reduce CO2 emissions via indus-
trial capture that displaces fossil fuel use. According to the intense
research and development efforts worldwide, such process will
acquire larger share in chemical industry in the near future.
In energy sector, compared to competitive technologies such as
battery or fuel cell driven vehicles, despite their potential higher
efficiencies, the CO2 -based fuels are more compatible with the
existing infrastructure. In fact, they can supply the feed of certain
fuel cells such as direct methanol fuel cells in the future.
The production of biodegradable PPC with high molecular
weight and poly(carbonate-ether) diol with low molecular weight
for polyurethane industry are recent topics in the field of CO2
utilization for polymer synthesis and they can partially or totally
substitute the polymers.
At any rate, the development of efficient and viable processes
for chemical valorization of CO2 is essential to achieve a circular
economy. To achieve carbon dioxide-based chemical industry, the
challenges mentioned in the previous section should be resolved
to make these technologies more competitive and attractive.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
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