Fuel 335 (2023) 127073

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Fuel
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A review on catalytic CO2 pyrolysis of organic wastes to

high-value products
Prakash Parthasarathy a, *, Shifa Zuhara a, Tareq Al-Ansari a, b, Gordon McKay a, *
a
Division of Sustainable Development, College of Science and Engineering, Hamad Bin Khalifa University, Qatar Foundation, Doha, Qatar
b
Division of Engineering Management and Decision Sciences, College of Science and Engineering, Hamad Bin Khalifa University, Qatar Foundation, Doha, Qatar

A R T I C L E I N F O A B S T R A C T

Keywords: As an alternative to conventional pyrolysis, CO2-assisted pyrolysis is ideal for treating organic waste materials
CO2 such as plant biomass, animal manure, domestic and municipal wastes as the usage of CO2 facilitates the
Catalysts decomposition of materials and inhibits the formation of many harmful chemical compounds. The application of
Pyrolysis
catalysts in CO2 pyrolysis has been viewed as a way to valorise waste on a large scale. This article provides
Organic wastes
Products characteristics
insight into the advantages of using CO2 and catalysts in pyrolysis and a list of catalysts currently used in CO2
pyrolysis. The main purpose of this review is to summarise the findings of recent analyses of catalytic CO2 py­
rolysis of wastes. The study also discusses the different procedures involved in catalyst preparation and provides
a broad review of the effects of catalytic CO2 pyrolysis on pyrolysis products’ quantity and quality. The article
concludes by evaluating the competency level of catalytic CO2 pyrolysis technology and providing an overview of
the technique’s current challenges and future recommendations. The review is in line with fostering the usage of
CO2 to meet CO2 emission regulations outlined by the 2015 Paris Agreement.

1. Introduction
Carbon dioxide (CO2) is the majorly greenhouse gas in the atmo­
sphere, and human-made activities including burning of conventional
fossil fuels, among others, are fast raising its emission to over 421 ppm
[1]. The International Energy Outlook (IEO) foresees that CO2 emission
will grow from 30.2 BMT (Billion metric ton) in 2008 to 43.2 BMT by
2035 [2]. But the encouraging fact is that it is feasible to reduce carbon
dioxide emissions to the atmosphere by developing CO2 utilization
routes, notably in energy production techniques, to help reduce the
anthropogenic influence on the climate. Therefore, it is imperative to
make efforts that use CO2 in many applications.
CO2 conversion and utilisation have recently become a key compo­
nent in research on sustainable development, as CO2 is plentiful and a
significant source of carbon. As a result, it has become an important raw
material in industries such as chemical (in the synthesis of urea, formic
acid, and specialty chemicals), fuel (in the production of pyrogas,
methanol, etc.), polymer (in the production of plastic, rubber, and fiber),
food (as an additive and acidity regulator), beverage (in the production
of carbonated soft drinks and soda water), construction (as a medium for
welding and to produce ready-mixed concrete), and so on.
In recent years, there has been a surge in the use of CO2 in thermo­
chemical processes like pyrolysis and gasification to valorise wastes like
biomass and plastics [3–6]. As CO2 is one of the main components of the
gases formed in the course of pyrolysis and gasification, its reuse as a
reactant will significantly reduce its release into the atmosphere [7]. A
further benefit of using CO2 is that it promotes the thermal breakdown of
volatile components and prevents the synthesis of many dreadful
chemical pollutants covering polycyclic aromatic hydrocarbons (PAHs)
and benzene derivatives [8]. Apart from that, recent research studies
have shown that pyrolysis/gasification of wastes in a CO2 environment
not only modifies the dissemination of products but also their compo­
sition, particularly bio-oil and pyrogas [9].
Catalysis is pivotal to most chemical processes, facilitating and
speeding up reaction kinetics and increasing the efficiency of desired
reaction paths. Catalysts are important in the synthesis of many bulk
chemicals including sulphuric acid, nitric acid, ammonia, and methanol,
as well as in a variety of process industries such as food, pharmaceutical,
textile, petroleum, fertilizer, polymer, and so on. Catalysts are used in
some form or another in over 90 % of the chemical manufacturing
processes used around the world today [10]. Catalyst demand is esti­
mated to be around $30 billion, and it is expected to grow over the next

* Corresponding authors.
E-mail addresses: pparthasarathy@hbku.edu.qa (P. Parthasarathy), gmckay@hbku.edu.qa (G. McKay).

https://doi.org/10.1016/j.fuel.2022.127073
Received 18 September 2022; Received in revised form 25 November 2022; Accepted 4 December 2022
Available online 13 December 2022
0016-2361/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
P. Parthasarathy et al.
decade as demand for all chemicals is rising, along with growing pres­
sure to reduce process costs, energy use, and emissions [11]. The need
for better catalysts is driven both by mass chemical production as well as
environmental demands as there is a growing demand for cleaner energy
and waste material utilization, including CO2.
The fundamental distinction between catalytic and thermal pyrolysis
is the application of a catalyst in pyrolysis process. Catalytic and thermal
pyrolysis are essentially comparable in process and most conditions.
Catalytic pyrolysis describes the method of using a catalyst to break
down wastes into products including biochar, bio-oil, and pyrogas. It has
a number of benefits over the non-catalytic method. First and foremost,
it significantly lowers the pyrolysis temperature by decreasing the re­
action activation energy [12]. In addition, the application of catalysts
has shown greater selectivity toward desired pyrolysis products
[13–16]. However, there are several limits to catalytic pyrolysis. The key
constraint is the decrease of catalyst performance over time. As a result,
catalyst durability and regeneration throughout the process should be
considered to optimise economic value. Catalysts can be used in situ as
well in ex situ pyrolysis systems [17]. Fig. 1 presents a simplified
schematic of the in situ and ex situ catalytic pyrolysis systems.
Pyrolysis can be made more efficient with the usage of CO2 as a
reactant. Using CO2 in the pyrolysis of organic feedstocks significantly
influences the selectivity and properties of pyrolysis products (biochar,
bio-oil, and pyrogas). It has been demonstrated experimentally that
using catalysts in CO2 pyrolysis improves the thermal efficiency of the
process [18,19]. In recent years, the concept of microwave heating and
vacuum pyrolysis have been introduced into catalytic CO2 pyrolysis.
Microwave pyrolysis is a thermal disintegration in an inert environment
that uses electromagnetic radiation as a heat source, whereas vacuum
pyrolysis is a thermal deterioration that occur in the absence of oxygen
and at low pressure. Microwave pyrolysis has received a lot of attention
because of its benefits over traditional methods, such as high heat
transfer efficiency, helps to save time, homogeneous internal heating,
and immediate response for fast start-up and shut down [20]. According
to a recent study, microwave pyrolysis yielded more pyrogas and less
bio-oil, but the pyrogas had higher H2 concentrations and lower CO2
concentrations than those produced by conventional pyrolysis [21]. For
the microwave process, the char had greater porosity and less oxygen.
Vacuum pyrolysis is also appealing because it allows for easier product
condensation and composition control (pyrogas, bio-oil, and biochar).
CO2-assisted catalytic pyrolysis is viewed as a possible remedy for
Fig. 1. A simplified schematic of the in situ and ex situ catalytic pyrolysis system.
2
Fuel 335 (2023) 127073
valorising organic waste, lowering CO2 emissions, and producing high-
quality biochar, bio-oil, and pyrogas [22]. It is the purpose of this review
article to provide researchers with a comprehensive understanding of
the function of CO2 in catalytic pyrolysis processes. A number of papers
have been published on CO2 used in the pyrolysis of organic wastes
[6,9,23–25], but there are only a few articles on catalytic CO2 pyrolysis
[26,27]. As a result, ample communication covering the essentials in this
area remains scarce. A review of recent studies conducted on catalytic
pyrolysis for the recovery of energy from a variety of waste feedstocks
such as agriculture (rice straw [28], pine bark [29]), animal (swine
manure [30], chicken manure [31], cow manure [32]), industrial
(textile waste [33], cellulose [34], cellulose acetate [35]), municipal
(fishing net waste [36], flood debris [37]), and domestic (food waste
[38], disposable diaper [39]) are summarized and discussed in this re­
view. This critique also includes research into the effect of CO2-assisted
catalytic pyrolysis on products yields and properties. It provides a list of
current catalysts used in CO2 pyrolysis and discusses the various pro­
cedures involved in catalyst preparation. Furthermore, the SWOT
(Strengths-Weaknesses-Opportunities-Threats) and Technology Readi­
ness Level (TRL) analyses are conducted to check the competency level
of the technology. A discussion of the process’s open challenges is also
provided, followed by recommendations for the future.
New information about recent scientific output may be particularly
valuable in this regard, given the importance of recent research. This
research article offers a novel approach to the production of value-added
products from organic waste materials through catalytic CO2 pyrolysis.
In the quest to provide sustainable energy as a product yield, this work
sheds light on the potential of CO2 assisted catalytic pyrolysis to valorise
organic wastes. The findings of this study are expected to make a sig­
nificant contribution to waste-to-energy research, organic waste treat­
ment and disposal, CO2 utilization, and catalytic CO2 pyrolysis
technology. The review is in line with encouraging the use of CO2 to
meet the Paris Agreement’s CO2 emission regulations made in 2015.
2. Pyrolysis mechanisms
Equation (1) is a generalized pyrolysis reaction
Cn Hm Op →CO2 + H2 O + CH4 + CO + H2 + (C2 − C5 ) (1)
The sequence of pyrolysis reactions is as follows. Below 300 ◦ C,
evaporation of water, formation of free radicals, and depolymerisation
P. Parthasarathy et al.
reactions occur resulting in the formation of carbonyl and carboxyl
compounds [40]. At this stage, the release of CO and CO2 also happens,
resulting in the formation of char. At 300–450 ◦ C, the glycosidic bonds
of polysaccharides are broken down by substitution reactions leading to
the formation of oligosaccharides, levoglucosan, and anhydrides. At
temperatures beyond 450 ◦ C, further evaporation, cracking, and rear­
rangement of sugar molecules occur leading to the release of compounds
such as glyoxal, acrolein, and acetaldehyde. All of the aforementioned
reactions occur above 500 ◦ C, resulting in the formation of a mixture of
all of the aforementioned products. During condensation, unsaturated
compounds condense resulting in the production of activated char
product.
2.1. CO2 impact on the pyrolysis behaviour and the distribution of
products
In CO2 pyrolysis, CO2 plays a multi-purpose role in the formation of
H2, CO2, CO, CH4, volatiles, char, and tar. The presence of CO2 enhances
CO2-char reactions, while it inhibits secondary char formation and
polymerization reactions by breaking down tar and volatile organic
compounds (VOCs) [41]. For example, tar cracking under CO2 condi­
tions significantly increases pyrogas production at the same time
reducing volatile compounds.
CO2 + Tar ↔ H2 + CO + CH 4 + Hydrocarbon(C2 , C4 ) (2)
Furthermore, CO2 is also utilised indirectly in gas-phase reactions
(GPRs) that result in the formation of CO through GPR between CO2 and
VOCs leading to a higher yield of pyrogas, and a lower yield of char and
volatiles than pyrolysis under N2 conditions. In addition to that, CO2
undergoes a dry reforming reaction with CH4 resulting in the increased
production of H2 and CO [8].
CH 4 + CO2 ↔ 2H2 + 2CO (3)
Also, CO2 undergoes a reverse water–gas shift reaction with H2,
enhancing the production of CO.
CO2 + H2 ↔ CO + H2 O (4)
In general, CO2 pyrolysis produces a higher yield of H2 and CO but a
lower yield of CH4, CO2, and other hydrocarbons than pyrolysis under
N2. Regardless, the extent of the above reactions are influenced by py­
rolysis conditions such as temperature, heating rate, and residence time.
This section contrasts the effect of CO2 on the thermolytic behaviour
of organic wastes and the distribution of pyrolysis products with the
effect of N2.The impact of CO2 on the Pt catalyst-induced pyrolysis of
food waste was investigated by Kim and Lee et al. [38]. To investigate
the impact of CO2, pyrolysis was performed in both N2 and CO2 atmo­
spheres. First, thermal degradation analysis using TGA revealed that no
change in TG-DTG patterns was observed under N2/CO2 mediums when
temperatures were below 820 ◦ C, but an obvious difference was
observed when temperatures were above 820 ◦ C. This difference in the
degradation pattern could be attributed to the production of CO due to
the Boudouard reaction as it is more favourable above 800 ◦ C. Under N2
and CO2 mediums, the experimental pyrolysis studies demonstrated that
the pattern of product distribution with respect to the temperature
change was the same under the Pt catalyst. According to the study, the
presence of CO2 in a catalytic pyrolysis process aids in the breakdown of
high molecular weight molecules (i.e., bio-oil) into low molecular
weight molecules (i.e., pyrogas).
In another study, Lee et al. (2020) studied the influence of CO2 on the
Ni/SiO2 catalyst-assisted pyrolysis of cow manure [32]. The CO2 atmo­
sphere produced 11.4 % more pyrogas yield than the N2 medium. This
improvement resulted in lower biochar and bio-oil yields. According to
the findings, CO2 plays an important role in the formation of pyrogas.
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Fuel 335 (2023) 127073
2.2. Role of catalysts in CO2 pyrolysis
During pyrolysis, many homogeneous and heterogeneous reactions
such as dehydration, cracking, polymerization, oxidation, reforming,
and condensation occur, which are classified into primary and second­
ary reactions. During primary reaction, H2 and CO are formed while the
production of aromatics including benzene derivatives occur during
secondary reactions. In general, at high pyrolysis temperatures, sec­
ondary reactions are suppressed due to short residence time of volatiles.
The slow removal of volatiles, on the other hand, simplifies the sec­
ondary pyrolysis reactions. However, the above phenomena can be
averted by employing catalysts. In addition to the above, the addition of
catalysts in pyrolysis speeds up reactions such as evaporation, cracking,
deoxygenation, decarboxylation, dehydrogenation, alkylation, decar­
bonylation, and so on [42]. At temperatures above 600 ◦ C, catalysts
induce the conversion of volatile compounds into non-condensable gas
components. As a result, higher yields of gaseous products and lower
yields of biochar and bio-oil are feasible due to catalytic activity.
Cho et al. (2021) confirmed the above findings by demonstrating that
there is increased pyrogas production when Ni/SiO2 is used as a catalyst
for deoxygenation and dehydrogenation reactions, which is due to the
mechanistic functions of Ni/SiO2 [35]. Furthermore, the use of Ni-based
catalysts enhances the functionality of CO2, thus increasing the pro­
duction of H2 and CO during pyrolysis. By simultaneously using Ni-
based catalysts and CO2, primary reactions are initiated, which lead to
the production of gases including H2 and CO2.
3. Catalysts in CO2 pyrolysis
A variety of parameters including the composition of feedstock
wastes, the kinds and qualities of the catalysts, and the process param­
eters govern catalytic pyrolysis processes, resulting in a diverse spec­
trum of product yields, compositions, and properties. Various types of
catalysts, including zeolites, alkaline, and alkaline earth metals,
calcium-based materials, etc. have been intensively researched for cat­
alytic pyrolysis of wastes [43]. Table 1 presents a list of catalysts that
have been employed in previous catalytic pyrolysis studies.
Although significant research has been conducted on catalytic py­
rolysis of wastes in the past, there are still challenges that need to
overcome before commercialisation of the process. The development
and design of catalysts and engineering processes for waste catalytic
pyrolysis products are underway in order to provide sustainable and
cost-effective energy and chemical uses.
3.1. Synthesis of catalysts
There are different methods to synthesize catalysts. A few methods of
catalyst synthesis followed by researchers are discussed below. Choi
et al. (2021) synthesized a biochar catalyst from livestock waste using
one-stage pyrolysis [52]. First, the feedstock was thermally decomposed
from ambient temperature to 650 ◦ C at 10 ◦ C/min under the influence of
a CO2 atmosphere. The biochar was then processed for roughly-one hour
at a uniform temperature of 650 ◦ C.
In another study, Lee et al. (2021) used a wetness incipient impreg­
nation approach to synthesize Ni/SiO2 catalyst [27]. First, deionized
water was used to dissolve nickel nitrate hexahydrate. Subsequent to
that, the nickel precursor solution was dropped onto the SiO2 support.
The impregnated sample was dried at 105 ◦ C overnight before being
calcined by heating to 500 ◦ C for nearly-one hour in a hot air oven. The
reduction process then involved heating the material from 30 to 550 ◦ C
(ramped at 2 ◦ C/min) while maintaining a 20 vol% H2 (N2 balance)
atmosphere.
Similar to the previous approach, Jung et al. (2020) prepared CO/
SiO2 catalyst [53]. Unlike previous approaches, Jiang et al. (2022) used
a high-temperature solid-state technique to produce a Ce-Co-Na ternary
composite catalyst [34]. Sodium carbonate (Na2CO3), cerium nitrate (Ce
P. Parthasarathy et al.
Table 1
Catalysts used in previous catalytic CO2 pyrolysis studies.
S. Pyrolysis Catalyst Catalyst features
no feedstock
1 Livestock Biochar In addition to its high
waste carbon-rich and porous
2 Hen manure nature, the
physicochemical
characteristics of biochar
can be easily altered by
acid/base treatment or
carbonization, making it
an excellent candidate for
catalytic activity.
3 Cellulose Ni-based Ni-based catalysts are
acetate often used as catalyst in
4 Plastic waste thermochemical processes
due to their proclivity to
rupture C–C bonds.
5 Pine bark Ni/SiO2 Because of their high
6 Cow manure reactivity and low cost,
7 Fishing net Ni/SiO2 catalysts are
waste utilized in the pyrolysis
8 Flood debris process.
9 Styrax
japonicus
10 Food waste Ni/Al2O3 Ni/Al2O3 are proven to
withstand extreme
reaction conditions.
11 Food waste Platinum Platinum catalysts have
high reactivity.
12 Food waste Platinum The Pt/AC catalyst is
loaded on commonly used because of
activated its remarkable thermal
carbon (Pt/ stability even under
AC) intense pyrolysis
conditions.
13 Polystyrene Steel slag Steel slag is a low-cost
14 Swine manure material. Furthermore, it
is inherently reactive due
to its composition of CaO,
SiO2, FeO, Fe2O3, and
Al2O3.
15 Synthetic Cobalt (CO) Cobalt-based catalysts are
textile waste viewed as an intriguing
alternative to noble metals
because to their lower
cost, abundant
availability, and improved
activity at low
temperatures.
16 Rice straw Co/SiO2 Because of its known
influence on diverse
C–H/C–O bond
scissions, Co/SiO2 are
normally employed as
catalyst.
17 Herb residue CaO CaO is widely employed as
it chemically active,
ecologically friendly,
plentiful, and inexpensive.
18 Fishing net Seashell Waste from seashells is
waste waste-derived abundant. There has been
catalysts widespread research into
the synthesis of solid base
catalysts from the waste
seashells for the catalytic
pyrolysis of polymeric
wastes.
19 Banner (made Cobalt oxide In addition to
of polyester) (Co3O4) decarboxylation, the
waste catalyst is also capable of
deoxygenation reactions.
Fuel 335 (2023) 127073
(NO3)3⋅6H2O), and cobalt carbonate (Ce (NO3)3⋅6H2O) were first
evenly blended in a ball mill. The powders were then heated in a tubular
References furnace from room temperature to 500 ◦ C at a ramp rate of 5 ◦ C/min
under the influence of N2. Following that, the powders were maintained
[31] isothermally for nearly 2 h and were eventually cooled down.
Yang et al. (2012) used co-precipitation to develop an Au/Al2O3
catalyst [54]. A 5 wt% Au loading was made by mixing K2CO3, HAuCl4,
and Al (NO3)3 solution in a water bath maintained at 60 ◦ C with a
constant pH of 8. The solution mixture was taken out from the bath after
an hour and allowed to cool down. The mixture was then screened
(using filter paper), centrifuged, and rinsed multiple times with deion­
ized water until the chloride presence vanished. The materials were
subsequently oven dried at 120 ◦ C for about 12 h before being calcined
[44]
at 250 ◦ C under the influence of air for nearly 2 h. Following that, the
catalysts were reduced in H2 atmosphere at 150 ◦ C for about 9 h.
3.2. Catalyst deactivation
[29]
Catalyst deactivation, also known as ageing, is the loss of activity of a
catalyst over time. This phenomenon can be chemical or physical, or
both at the same time in some cases. Deactivation of catalysts is un­
avoidable over time; however, it can be slowed down. Catalyst deacti­
[44] vation in pyrolysis is primarily caused by carbon/coke deposition on the
active sites of catalysts. Carbon deposition is a temperature–time phe­
nomenon, and it occurs at a relatively slow rate; however, deposition
[45] peaks over time and the catalysts become ineffective, necessitating
Settings
regeneration. The knowledge on catalyst deactivation is important as
[46] the reusability of catalysts is critical for commercial scale-up.
3.2.1. Catalyst deactivation control using CO2
Kwon et al. (2021) investigated the deactivation properties of a Co/
[47,30] SiO2 catalyst in the presence of CO2 [33]. The research also looked into
the deactivation characteristics of the catalyst in an N2 environment.
The quantity of carbon deposited onto Co/SiO2 catalyst was determined
using a temperature programmed oxidation (TPO) test employing TGA,
which compared the change in weight of a virgin cobalt catalyst to spent
[48] catalysts in the presence of both CO2 and N2 environments. In general,
decomposition of catalyst is attributed to the oxidation of carbon to form
CO2, whereas increase in weight of catalyst is ascribed to the oxidation
of metal-to-metal oxide. The weight difference between virgin and spent
cobalt catalysts represents the change in weight due to carbon deposi­
tion. Under CO2 and N2 ambience, the spent Co/SiO2 catalysts lost 1.2
and 5.1 wt% of their weight, respectively, when compared to the virgin
[28] cobalt catalyst. These findings demonstrated that CO2 substantially
suppressed deposition of carbon. A similar inference was also made by
Jung et al. (2020) and Lee et al. (2021), who investigated the deactiva­
tion property of Ni/SiO2 catalyst in the presence of CO2 [27,36].
[49]
3.3. Catalyst reactivation/regeneration
The reactivation of a catalyst heavily relies on the reversible nature
[50] of the deactivation phenomena. It is important to consider the rate at
which the catalyst is deactivating before deciding whether to regen­
erate/recycle or discard it altogether. Regeneration becomes economi­
cally necessary if deactivation occurs very quickly. Reclaiming precious
metals is almost always the best option when regeneration is impossible.
There are a number of economic and legal factors that must be consid­
ered before discarding catalysts. The removal of carbon/coke deposition
[51]
from catalysts in catalytic pyrolysis processes is normally accomplished
by gasifying it with oxygen, hydrogen, steam, and carbon dioxide as
gasification requires a gasifying agent. Although the above gasifying
agents produce the same pyrogas components such as CO, H2, CO2,
hydrocarbons, and tar, the composition of these components varies. The
gasifying agents also have an impact on the heating value of the pyrogas
produced. Steam and hydrogen, for example, produce a high heating
value pyrogas (15–20 MJ/kg), whereas CO2 and oxygen produce a
4
P. Parthasarathy et al.
medium heating value pyrogas (10–15 MJ/kg).
There are several factors that affect the gasification rate, including
the type of gasifying agent employed, catalyst activity, and the
complexity and reactivity of the carbon deposits on the catalysts [55]. At
moderate temperatures (e.g., 400–600 ◦ C), the catalytic removal of
carbon with oxygen occurs very rapidly, so industrial processes typically
regenerate catalytic materials that have been deactivated by carbon or
coke.
4. Experimental studies on catalytic CO2 pyrolysis of wastes
The pyrolysis operating conditions and findings of previous catalytic
CO2 pyrolysis studies is reviewed in Table 2. The table highlights the
influence of CO2 on organic waste pyrolysis using catalysts for energy
recovery. The effect of catalytic CO2 pyrolysis on the pyrolysis products
yields and characteristics are discussed in the subsequent sections.
4.1. Effect of catalytic CO2 pyrolysis on products yields
CO2-cofeed influences the carbon distribution of three pyrolysates
(pyrogas, bio-oil, and biochar) in accordance with the overall mass
balance. The pyrolytic product distribution in CO2-assisted pyrolysis
differs from that in N2-backed pyrolysis. The modification of pyrolytic
products is most likely due to the accelerated thermal cracking of vol­
atile matter produced during pyrolysis. Several studies have discovered
that adding CO2 results in less char, less bio-oil, and more pyrogas. This
result can be attributed to the reaction of char and CO2 at high tem­
peratures, which is further supported by an increase in CO yield in the
presence of CO2 [58].
The combined influence of catalyst and CO2 medium on the pyrolysis
products yields of some previous studies is illustrated in Fig. 2
[33–35,38,56,59]. Only the product yields obtained at high tempera­
tures (600–900 ◦ C) are shown here.
In all of the studies, the synergistic effect was observed to contribute
to the maximum yield of either pyrogas or bio-oil. Among the studies,
Cho et al. (2021) and Kwon et al. (2021b) reported the highest pyrogas
yields (85 % and 80 %, respectively) and the lowest bio-oil yields (0.3 %
and 1.5 %, respectively) [33,35]. This high pyrogas yield and low bio-oil
yield is attributed to the composition of cellulose acetate and synthetic
textile waste.
CO2 as a reaction atmosphere not only changes the distribution of
pyrolysis products, but also their compositions and characteristics. For
example, Ahmed et al. found that the CO2 reaction atmosphere increased
pyrogas yield by 15 % to 20 % when compared to the N2 reaction at­
mosphere [60]. Furthermore, the researchers reported increased pyro­
gas generation and decreased bio-oil production. This indicates that
when CO2 is used, the carbon distribution in the reaction products shifts
from condensable to non-condensable gases [38]. When both CO2 and
catalysts are used, condensable compounds decrease while non-
condensable gases increase. It is obvious that the presence of the cata­
lyst and CO2 aids in the cracking of heavy molecules (i.e., condensable
molecules) into light molecules (i.e., non-condensable gases).
4.2. Effect of catalytic CO2 pyrolysis on biochar characteristics
Kwon et al. (2019) compared the surface area characteristics of
biochar produced from chicken manure in CO2 and N2 environments
[61]. According to the researchers, the surface area of biochar made
from chicken manure feedstock under CO2 environment, is greater than
that from the N2 environment. It has been reported that the surface area
of biochar in CO2 and N2 is 13.59 and 3.37 m2g− 1, respectively. The
variance in surface areas could be ascribed to a heterogeneous reaction
between the feedstock particle surface and CO2, which alters the
composition and morphology of the char. The mean pore diameter of
CO2 and N2 biochar, on the other hand, is 9.29 and 10.93 nm, respec­
tively. The pore design or structure of biochar is more developed under
5
Fuel 335 (2023) 127073
the CO2 condition, according to the findings. Similar to the previous
study, Aljaziri et al. (2022) found that biochar produced by CO2 pyrol­
ysis of Salicornia bigelovii had a large surface area and great stability
[62].
Guizani et al. (2014) investigated the elemental composition prop­
erties of biochar made from CO2-produced beech wood chips [63]. Ac­
cording to the researchers, CO2 preferentially removes functional groups
containing oxygen and hydrogen. The amount of H2 was reduced by 60
%, and the amount of O2 was reduced by 18 %. The study concluded that
adding CO2 to the pyrolysis process increases hydrogen and oxygen loss
as well as residual char carbon enrichment. The elemental analysis of
peat biochar generated in CO2 and N2 conditions was compared by Lee et
al. (2017) [64]. It was noted that biochar synthesised under CO2 con­
ditions had higher O and N contents and lower C, H, and S compositions.
Yi et al. (2022) investigated the elemental analysis of cellulose biochar
generated in CO2 and N2 ambiences [65]. Biochar produced in a CO2
influence displayed a higher carbon composition and a lower oxygen
presence than biochar synthesised in a N2 condition.
4.3. Effect of catalytic CO2 pyrolysis on bio-oil characteristics
As a result of different pyrolysis/gasification reactions, the bio-oils
generated under CO2 and N2 conditions possess different chemical
compositions. In their study, Zhang et al. (2011) noticed that different
pyrolysing conditions affect bio-oil’s production and chemical compo­
sition [58]. It was noted that the bio-oil synthesised under a CO2
ambience exhibited a 3 % higher hydrocarbon composition and 5 %
lower oxygenate content than that synthesised under a N2 condition.
Under both CO2 and N2 atmospheres, Kwon et al. pyrolysed banana peels
[66]. In addition to increasing the aromaticity of pyrolytic oil, CO2-
assisted pyrolysis facilitated the dehydrogenation of liquid pyrolysates
without the need for catalysts.
According to He et al. (2020), bio-oil derived from CO2 has lower
toxicity than that derived from N2 [67]. In the study, it was found that
CO2 promotes the formation of phenolics and aromatics in bio-oils,
thereby producing a more stable bio-oil. The liquid produced by the
pyrolysis of food waste was analysed in N2 and CO2 by Ly et al. (2022)
[68]. The researchers reported that CO2-pyrolysis increases the pH of the
liquid. The bio-oil product produced from Salicornia bigelovii CO2 py­
rolysis was characterised by Aljaziri et al (2022) [62]. In the study, the
yield of bio-oil increased with greater amounts of acids, carbonyls, and
compounds containing nitrogen. By pyrolysing corncob using CO2,
Zhang et al. (2011) produced bio-oil with more acetic acid than when
using N2 [58]. According to Valizadeh et al. (2021), bio-oil obtained
with CO2 (17.1 %) had a lower cyclic content than bio-oil obtained with
N2 (22.4 %), demonstrating the combined influence of CO2 atmosphere
and catalyst [59].
4.4. Effect of catalytic CO2 pyrolysis on pyrogas composition
Jung et al. (2020) investigated catalytic pyrolysis using fishing net
waste and CO2 as feedstocks [36]. The study demonstrated that total
overall pyrogas generation (H2 and CO) was greater under CO2 condi­
tions than under N2 conditions and it indicated that the GPRs between
gaseous pyrolysates and CO2 happen at the same time as the reverse
water–gas shift reaction over Ni/SiO2 catalyst. Jung et al. (2020) used
cobalt to catalyse rice straw pyrolysis in a CO2 environment [53]. The
study clearly demonstrated that the cobalt metal catalyst accelerated
dehydrogenation and deoxygenation bond scissions on the volatile
organic compounds, resulting in increased pyrogas generation. Sur­
prisingly, the catalyst did not further activate CH4 and C2H4 formations.
Lee et al. (2020) used Ni/SiO2 catalyst to conduct CO2-assisted cat­
alytic pyrolysis of hen manure [57]. The study found that CO2-assisted
catalytic pyrolysis produced significantly more CO than non-catalytic
pyrolysis. Lee et al. (2020) investigated the influence of Ni/SiO2 cata­
lyst and CO2 on cow manure pyrolysis [32]. Similar to the previous
P. Parthasarathy et al. Fuel 335 (2023) 127073

Table 2
Summarizes the pyrolysis operating conditions and results of previous catalytic co2 pyrolysis studies.
Reactor type Feedstock Operating Catalyst and Specific results Comparison with N2 Inference Reference
and its and its conditions its pyrolysis
dimensions quantity composition

Tubular. Swine Temperature: Steel slag Catalytic CO2 pyrolysis Both N2 and CO2 pyrolysis This study experimentally [56]
Outer manure (1.0 20–900 ◦ C improved CO production. produced nearly the same demonstrated that CO2 could
diameter-2.5 g) Heating rate: The addition of catalyst amount of biochar. be promising for limiting the
cm, length- 10 ◦ C/min significantly improved the However, CO2 pyrolysis formation of toxic pollutants
120 cm. reaction kinetics yielded less bio-oil. in thermochemical
associated with the treatment because CO2
mechanistic role of CO2 provides an innovative and
(up to 80 %). strategic means of
controlling the C/H ratio.
Tubular. Fishing net Temperature: Ni/SiO2 (5 The formation of pyrogas The mass loss profiles of The CO2-mediated catalytic [36]
Outer waste (1.0 g) 35–600 ◦ C %). was accelerated by the fishing net waste under N2 pyrolysis produced a higher
diameter-2.5 Heating rate: application of the catalyst and CO2 mediums were H2 yield while maintaining
cm, Inner 10 ◦ C/min CO2 under CO2 ambience, same, according to TGA catalyst stability.
diameter-2.2 flow rate: 200 ml/ producing significant results. Due to catalyst
cm, Length- min amounts of H2 (770 mmol deactivation under N2
120 cm. g-1 − 1
cat h ) and CO (1157 influence, the rate of H2
mmol g-1 − 1
cat h ). synthesis considerably
decreased. Nonetheless,
an additional CO
formation was obtained
under CO2 conditions.
Tubular. Rice straw Temperature: Co/SiO2 (5 Relative to non-catalytic TGA clearly shows that, The combined influence of [53]
(1.5 g) Room-720 ◦ C %) pyrolysis, the use of the when compared to the N2 the CO2 feedstock and Co/
Heating rate: catalyst sped up the condition, rice straw SiO2 catalyst ensued in an
10 ◦ C/min CO2 kinetics of the CO and H2 underwent more increase in pyrogas
flow rate: 200 ml/ reactions by three and six thermolysis at a production, particularly in
min times, respectively. temperature of about the significant formations of
Significant amounts of H2 700 ◦ C. Under N2 and CO2 H2 and CO.
and CO were synthesized conditions, the final
as a result of the CO2 and weights of rice straw
catalyst’s synergistic samples were 32.0 wt%
effects. and 23.0 wt%,
respectively.
Tubular. Hen manure Temperature: Ni/SiO2 (5 Compared to non-catalytic In comparison to N2, CO2 CO2-assisted pyrolysis could [57]
Outer (1.0 g) Room-720 ◦ C %) pyrolysis, CO2-mediated promoted undue thermal be viewed as an
diameter-2.5 Heating rate: catalytic pyrolysis breakdown of volatile environmentally benign and
cm. 10 ◦ C/min CO2 substantially increased CO species into pyrogas. commercially feasible
flow rate: 100 ml/ production. method of producing
min pyrogas from biomass
materials.
Tubular. Cow manure Temperature: Ni/SiO2 (1.0 CO2 accelerated the CO2-cofeeding catalytic Cow manure pyrolysis using [32]
Outer (1.0 g) Room-720 ◦ C g) significant production of pyrolysis of cow manure CO2 is a practical method for
diameter-2.5 Heating rate: CO at 600 ◦ C through the produced 25 % more manure valorization in the
cm, Inner 10 ◦ C/min CO2 homogeneous reaction of pyrogas than catalytic livestock industry without
diameter-2.2 flow rate: 100 ml/ VOCs. pyrolysis in N2. the need for numerous pre-
cm, Length- min and post-treatment steps.
50 cm.
Tubular Food waste Temperature: Pt The CO2 reactant and Pt The TGA curves achieved A CO2-supported catalytic [38]
(1.0 g) Room-900 ◦ C catalyst and had zero effect under N2 and CO2 pyrolysis is as ecologically
Heating rate: on the quantity of biochar, ambiences at 820 ◦ C were benign disposal approach for
10 ◦ C/min CO2 but they did have an identical, there was a food waste.
flow rate: 300 ml/ impact on the generation noticeable variance at
min of bio-oil and pyrogas. At higher temperatures. The
700 ◦ C, with the catalyst quantity of cyclic species
presence, the CO2 in the catalytic reaction
atmosphere, produced diminished from 22 % in
roughly 67.3 % fewer N2 to 17 % in CO2.
cyclic compounds,
including derivatives of
benzene, than under non-
catalytic circumstances
without CO2.
Tubular Cellulose Temperature: Ni/SiO2 (1.0 Owing to the collective The TGA findings showed In contrast to N2, the study [35]
acetate (1.0 35–710 ◦ C Heating g) effects of CO2 reactant that CO2 degraded suggested that CO2 would be
g) rate: 10 ◦ C/min medium and the Ni-based cellulose acetate more a more advantageous
CO2 flow rate: 100 catalysts, a significant effectively than N2 did. In reactive co-feedstock for
ml/min enrichment of CO the N2 and CO2 pyrolysis from a technical
formation and pyrogas atmospheres, the residual and environmental
yield was obtained. weights of cellulose standpoint. As a result, this
Additionally, the CO2 acetate were 14.2 and study demonstrated a
helped to prevent biochar 13.2 wt%, respectively. straightforward and
adaptable technical
(continued on next page)

6
P. Parthasarathy et al. Fuel 335 (2023) 127073

Table 2 (continued )
Reactor type Feedstock Operating Catalyst and Specific results Comparison with N2 Inference Reference
and its and its conditions its pyrolysis
dimensions quantity composition

from depositing on the framework for converting

catalyst. cellulose acetate and CO2
into pyrogas.
Tubular. Flood debris Temperature: Ni/SiO2 (5 In comparison to pyrolysis Compared to pyrolysis The use of CO2 to aid [37]
Outer (5.0 g) 35–720 ◦ C Heating %) without catalyts, the under the N2 influence, pyrolysis of flood debris
diameter-2.5 rate: 10 ◦ C/min production of pyrogas CO production from the could maximize energy
cm, Inner CO2 flow rate: 200 increased by more than pyrolysis of debris waste production.
diameter-2.2 ml/min one order of magnitude was improved under the
cm, Length- when using a Ni/SiO2 CO2 reactant medium.
120 cm. catalyst. The synergistic
influence of CO2 reactant
and Ni catalyst produced
almost 50 % more pyrogas
than catalytic pyrolysis
under N2.
Tubular Livestock Temperature: Biochar The formations of H2 and The concentration profiles In comparison to pyrolysis [52]
waste (2.0 g) 35–720 ◦ C Heating (1.0–2.0 g) CO were improved by of the primary gaseous without catalysts, catalytic
rate: 10 ◦ C/min using biochar as a catalyst effluents from pyrolysis pyrolysis of livestock waste
CO2 flow rate: 200 material in the pyrolysis of under CO2 and N2 over biochar produced three
ml/min livestock waste, and the mediums were almost times as much pyrogas.
catalytic ability was same at 510 ◦ C. The
directly proportional to the evolution patterns of the
catalyst loading. main gaseous products
were, however, somewhat
different at 510 ◦ C. At
510 ◦ C, a greater amount
of CO was produced solely
from the CO2
environment.
Tubular. Pine bark Temperature: Ni/SiO2 (5 When the catalyst bed was The findings imply that The combined effect of CO2 [27]
Outer (1.0 g) Room-720 ◦ C %) at 500 ◦ C, each CO2 and Ni there is a greater amount medium and Ni/SiO2
diameter-2.5 Heating rate: catalyst independently of coke deposition on catalyst improved pyrogas
cm, Inner 10 ◦ C/min CO2 contributed to CO and H2 catalyst used in a N2 generation.
diameter-2.2 flow rate: 100 ml/ formation, respectively, medium than in a CO2
cm, Length- min whereas a synergistic ambience.
100 cm. influence of both CO2 and
Ni catalyst was
demonstrated at 600 ◦ C.
Tubular Disposable Temperature: Ni/SiO2 (5 Ni catalyst increased H2 CO2 provided a tactical way [39]
diaper (1.5 40–720 ◦ C Heating %) and CO formations at to create chemicals with
g) rate: 10 ◦ C/min higher temperature under added value and lessen the
CO2 flow rate: 200 CO2 by 4 and 15 times aromaticity of pyrogenic
ml/min more than pyrolysis products.
without catalyst.
Tubular Synthetic Temperature: Co/SiO2 (4 CO2-assisted catalytic In contrast to catalytic Waste synthetic textiles [33]
textile waste 40–720 ◦ C Heating %) pyrolysis produced three pyrolysis conducted under could be converted into
(1.0 g) rate: 10 ◦ C/min and eight times more H2 the N2 medium, which pyrogas using CO2-assisted
and CO than non-catalytic produced 7 wt% of catalytic pyrolysis, which
pyrolysis, respectively. condensable gases, only 1 would minimize the
Over 80 % of the textile wt% of volatiles were left production of polycyclic
waste was transformed over from the CO2-assisted aromatic hydrocarbons and
into pyrogas and CH4 method. benzene derivatives.
thanks to this process,
which also inhibited
catalyst deactivation.
Tubular Cellulose Temperature: Ce-Co-Na (5 CO2 increased ketone yield The study offers an [34]
(20.0 g) Room-600 ◦ C %) in bio-oil and CO yield in alternative method for
pyrogas. pyrolyzing biomass to
produce pyrogas and ketone
platform compounds.

study, the researchers noted an increase in CO and H2 yield in the
pyrogas composition. The total amount of gas products obtained in a
CO2 environment was 25 % greater than in a N2 environment. The
findings strongly suggest that both CO2 and Ni/SiO2 promoted pyrogas
generation during cow manure pyrolysis.
Kim and Lee (2020) investigated pyrolysis decomposition of food
waste under a CO2 atmosphere using a platinum catalyst [38]. The
combined influence of platinum catalyst and CO2 contributed to a
considerable increase in the production of non-condensable gases but
only a slight increase in the formation of less condensable species. The
study found that when CO2 was used, the distribution of carbon in the
reactants changed from volatiles to permanent (non-condensable) gas
species.
Cho et al. (2021) investigated catalytic pyrolysis of cellulose acetate
under the influence of NiSiO2 in a CO2 environment [35]. The combined
effect of CO2 and catalyst increased H2 and CO production. The
increased CO production was attributed to GPRs between volatile py­
rolysates and CO2 gas. It was also observed that increasing the Ni metal
loading boosted H2 generation. Furthermore, the overall quantity of
pyrogas in the CO2 environment was found to be 47 % greater than that

7
P. Parthasarathy et al.
Fig. 2. Effect of catalytic CO2 pyrolysis on products yields.
in the N2 medium. Furthermore, the catalytic influence of Ni/SiO2 on
GPRs was found to be proportional to pyrolysis reaction temperature
and Ni loading.
Choi et al. (2021) catalysed flood debris pyrolysis in a CO2 envi­
ronment using a Ni/SiO2 catalyst [37]. The study inferred that the
synchronised employment of Ni/SiO2 and CO2 aided in the enhance­
ment of CO. Choi et al. (2021) investigated the pyrolytic effects of CO2
and cattle waste biochar as a catalyst on the pyrolysis product behaviour
of cattle manure [52]. It was reported that the presence of biochar
significantly increased the formation of all gaseous emissions. The
generation of H2 and CO in particular were augmented, and the obser­
vations clearly demonstrated that the kinetics of GPRs are catalytically
positively influenced. Lee et al. (2021) utilized pine bark to examine the
influence of Ni/SiO2 catalyst and CO2 [27]. The researchers found an
increase in CO and H2 yield in the pyrogas composition. It was inferred
that the Ni/SiO2 catalyst accelerated gas phase reactions (GPR) for
increased CO production, possibly through the reverse CO-shift reaction
(H2 + CO2 ↔ H2 O + CO). Both GPRs and reverse water-gas shift re­
actions were found to contribute to the increased CO generation. When
compared to catalytic pyrolysis under an N2 ambience, CO2-supported
pyrolysis under the catalyst influence produced 23 % undue pyrogas.
Kwon et al. (2021) investigated the degradation of disposable diapers
in a CO2-mediated medium using a Ni/SiO2 catalyst [39]. In the pyrogas
composition, the researchers noticed an increase in CO and H2 yield. The
results indicate that CO2 speeds up thermal breakdown liberating H2O.
Kwon et al. (2021) used Co/SiO2 catalyst to investigate the degradation
of synthetic textile waste in a CO2-assisted medium [33]. According to
the researchers, CO2-supported catalytic pyrolysis bettered CO and H2
yields. However, the concentration of CH4 in both CO2 and N2 atmo­
spheres was almost the same with and without the catalyst.
Jiang et al. (2022) used Ce-Co-Na ternary catalyst to perform CO2-
supported pyrolysis decomposition of cellulose material [34]. The re­
sults showed that the synergistic influence of the CO2 medium and the
ternary catalyst had a positive effect on increasing ketones (bio-oil) and
pyrogas production. Using steel slag as catalyst, Lee et al. (2020) studied
the pyrolysis of polystyrene under CO2 medium [47]. The improved
generation of CO2 indicates that CO2 is catalytically developed and
controlling its aromaticity might be feasible. The results of the study
indicate that CO2 can be converted into fuel in CO2-to-fuel processes.
8
Fuel 335 (2023) 127073
4.5. Selectivity of products in CO2 assisted pyrolysis using catalysts
In catalytic pyrolysis of organic wastes, H2 and CO are the main
gaseous effluents. During pyrolysis, the ratio of H2/CO in feed is
extremely important for selecting desired products from chemical re­
actions of pyrogas [27]. Commonly, CO2-assisted pyrolysis enhances CO
production through GPRs. In general, diffused catalytically active
compounds such as Ni, Pt, Fe, and Co produce a high number of catalytic
activities, recyclability, H2 selectivity, and pyrolysis efficiency when
they are used on porous pellet supports [69]. Catalysts based on Ni are
more cost-effective, gum-resistant, and possess the appropriate catalytic
activity as compared to others [70]. On the other hand, the addition of
catalysts such as calcium oxide, nickel, etc., in conjunction with the
selection of appropriate operating parameters, enhances methane
selectivity [71]. The following is a review of a few studies on CO2-
assisted pyrolysis selectivity using catalysts.
Lee et al. (2019) used steel slag as a catalyst to catalytically pyrolyse
swine manure in a CO2 medium [56]. The results showed that CO2
increased the generation of CO while suppressing the formation of H2.
Researchers reported that using steel slag as a catalyst, the kinetics of the
reaction related to the mechanistic role of CO2 were significantly
improved (up to 80 %). Choi et al. (2021) used biochar as a catalyst to
pyrolyse livestock waste in a CO2 atmosphere [52]. The catalyst accel­
erated the GPR kinetics and increased the formation of H2 and CO. The
catalytic capability was found to be directly proportional to the amount
of catalyst loaded.
Kim and Lee investigated the pyrolytic degradation of food waste in a
CO2 medium using a platinum catalyst. Both the platinum catalyst and
CO2 slowed the synthesis of bio-oil molecules while increasing the
production of pyrogas. The use of the catalyst and CO2 simultaneously
was most effective in reducing the content of condensable cyclic com­
pounds, including benzene derivatives. The combined effect of the
catalyst and CO2 reduced the harmful chemical species produced by
food waste pyrolysis. The findings indicate that CO2-assisted catalytic
pyrolysis is an environmentally friendly method of disposing food waste.
Jiang et al. (2022) used CO2-supported pyrolysis to decompose cellulose
using a Ce-Co-Na ternary catalyst [34]. The addition of CO2 and a
catalyst improved the liquid product’s selectivity for ketones. Further­
more, the production of CO in the pyrogas was encouraged. This
P. Parthasarathy et al.
research suggests an alternative method for pyrolysing biomass to pro­
duce ketone platform compounds and pyrogas.
Kwon et al. (2021) catalytically pyrolysed synthetic textile waste in a
CO2 medium using a Co-supported on SiO2 catalyst [33]. The combi­
nation of catalyst and CO2 accelerated the GPR kinetics for the pro­
duction of pyrogas. CO2-assisted catalytic pyrolysis produced three and
eight times more H2 and CO than non-catalytic pyrolysis, respectively.
Over 80 % of textile waste can also be converted into pyrogas and CH4
using this method, thereby reducing catalyst deactivation. In an exper­
iment published in 2020, Jung et al. (2020) generated pyrogas through
CO2-mediated catalytic pyrolysis of rice straw [53]. SiO2-supported Co
(Co/SiO2) catalysts produced three folds more CO and six folds more H2
when compared to non-catalytic pyrolysis. As a result of the synergistic
effects of the Co/SiO2 catalyst and CO2, significant amounts of H2 and
CO were produced.
Jung et al. (2020) used a CO2 medium and a Ni/SiO2 catalyst to
catalyse the pyrolysis of fishing net waste [36]. The combined effect of
CO2 and catalyst improved the kinetics of the H2 reaction and the gen­
eration of CO. According to the findings, CO2-mediated catalytic py­
rolysis is very effective in the synthesis of H2 while maintaining catalyst
stability. Lee et al. (2020) used a Co-supported on SiO2 catalyst to
catalytically pyrolyse hen manure in a CO2 medium [57]. Relative to
non-catalytic pyrolysis, CO2-assisted catalytic pyrolysis produced more
CO significantly. Lee et al. (2020) examined catalytic pyrolysis of cow
manure using CO2 over a Ni/SiO2 catalyst [32]. CO2-assisted catalytic
pyrolysis of cow manure produced 25 % more gas production than cow
manure catalytic pyrolysis under an N2 atmosphere.
Cho et al. (2021) used a Ni-based catalyst to catalytically pyrolyse
cellulose acetate in a CO2 medium [35]. The presence of CO2 and a
catalyst aided in the formation of CO and the generation of pyrogas. The
study proposed an innovative and environmentally friendly method of
converting cellulose acetate waste into energy in the form of pyrogas. A
study by Choi et al. (2021) investigated the process of thermally
Fig. 3. Effect of catalytic CO2 pyrolysis on pyrolysis products characteristics.
9
Fuel 335 (2023) 127073
converting flood debris into pyrogas with CO2-assisted pyrolysis [37].
Ni/SiO2 catalysts significantly enhanced pyrogas production when
compared with non-catalytic pyrolysis. Nearly 50 % more pyrogas was
produced through the synergistic effect of CO2 and Ni catalysts than by
catalytic pyrolysis under N2.
Kim and Lee (2021) investigated the pyrolysis of pine bark under a
CO2 atmosphere using a Ni/SiO2 catalyst [27]. CO2 and Ni/SiO2 syn­
ergistically promoted pyrogas formation while delaying catalyst deac­
tivation. Kwon et al. (2021) used a Ni/SiO2 catalyst to study the
degradation of disposable diapers in a CO2-mediated medium [39]. At
700 ◦ C, pyrolysis with CO2 and catalyst produced 4 and 15 times more
H2 and CO, respectively, than pyrolysis without catalyst.
The effect of eggshell (EG)- and homo-type (HO) Ni/Al2O3 catalysts
on the pyrolysis of food waste under a CO2 atmosphere was studied by
Valizadeh et al. (2021) [59]. Compared to Ni–HO catalyst, Ni-EG cata­
lytic pyrolysis was more selective in producing H2 and CO, especially
under CO2 rather than N2 conditions. Results indicated that Ni-EG cat­
alysed bio-oils had higher selectivity for H2 and CO, lower levels of
cyclic and detrimental compounds in bio-oil, and greater stability than
Ni–HO catalysed bio-oils. According to this study, metallic Ni loaded on
EG catalysts (in collaboration with CO2) produced more H2 and CO
while suppressing unwanted reactions compared with uniformly
diffused Ni on HO catalysts.
4.6. Key outcomes of the CO2 catalytic pyrolysis studies
The influence of CO2 on pyrolysis of organic wastes is shown in
Fig. 3. Pyrolysis involves many homogeneous and heterogeneous re­
actions (e.g., evaporation, cracking, oxidation, reforming, polymeriza­
tion, condensation, etc.), which can be categorized into primary and
secondary reactions [72]. Primary reactions produce pyrogas containing
H2 and CO, while secondary reactions produce aromatics (e.g., benzene
derivatives). In the presence of CO2, the active centre of biochar first
P. Parthasarathy et al.
reacts with CO2, followed by thermal cracking of tar, resulting in an
increase in char production and a decrease in pyrogas production. At
high temperatures, secondary primary reactions predominate over pri­
mary pyrolysis reactions. By employing catalysts, undesired reactions
such as aromatics that might increase tar content can be effectively
mitigated. Furthermore, the presence of catalysts speeds up dehydra­
tion, cracking, dehydrogenation, decarboxylation, deoxygenation,
alkylation, and decarbonylation, eventually leading to catalytic
decomposition of bio-oil into pyrogas at temperatures above 600 ◦ C
[73]. However, at medium temperatures around 500 ◦ C, CO2-assisted
catalytic pyrolysis likely affects homogeneous reaction with VOCs.
Overall, the use of catalysts in CO2 pyrolysis improves the functionality
of CO2 to increase the generation of H2 and CO.
It is evident that the results reported by the researchers differ
significantly and sometimes show inconsistency, making comparisons
between them difficult. It is because pyrolysis product yields and their
compositions are influenced by a wide variety of parameters, including
waste composition, operating temperature, heating rate, pressure, solid
residence time, apparent vapor residence time, flow dynamics, etc. [74].
There are several factors that influence the rate of heating, including the
temperature distribution, the conditions of convection and radiative
heat transfer inside the reactor, as well as the particles’ size, shape, and
mass. However, the key outcomes of the CO2 catalytic pyrolysis studies
discussed above are outlined in Fig. 3.
5. Technology competency
The five key elements of an organic waste source of energy are sus­
tainability, low price, good quality, sufficient quantity, and low emis­
sions. There have been many developments in renewable energy
technology in recent decades, including gasification, liquefaction, etc.;
most of them have proven to be successful in achieving initially set goals
and are suitable for producing high amounts of energy under certain
conditions [75]. There are, however, some flaws associated with the five
key elements mentioned earlier. As a result, in this study the competency
level of catalytic CO2 pyrolysis of organic wastes is thoroughly assessed
Fig. 4a. SWOT analysis of the conventional N2 pyrolysis process for wastes valorisation.
10
Fuel 335 (2023) 127073
with regard to its Strengths, Weaknesses, Opportunities, and Threats
(SWOT) and Technology Readiness Level (TRL).
5.1. SWOT analysis of catalytic CO2 pyrolysis
Analysis of SWOT is vital for determining a project’s, process’,
product’s, or service’s current state. An assessment of strengths, weak­
nesses, opportunities, and threats is a simple and effective way to
identify potential problems and critical issues, and it provides a foun­
dation for making decisions [76]. As a general rule, strengths refer to the
qualities and resources that contribute to success, while weaknesses are
the traits and resources that impede success. Threats are external factors
that threaten the success of a process, whereas opportunities can be
leveraged to its advantage. The conventional N2 pyrolysis and CO2
catalytic pyrolysis have been analysed by a SWOT analysis (Figs. 4a and
4b.) to gain insight into business strengths, weaknesses, opportunities,
and threats.
A major strength of these two processes pyrolysis is their high flex­
ibility of their operations. Different yields and quality of solid, liquid,
and gaseous products can be controlled by changing parameters such as
temperature or heating rate. An unquestionable advantage of these
techniques is their possibility of thermal treatment of various types of
waste, both industrial and household.
Although there is not much difference between the two processes,
the SWOT analysis demonstrates that there are more strengths and op­
portunities than weaknesses and threats in the waste valorisation pro­
cess specifically in catalytic CO2 pyrolysis. The main strength of this
process is the use of greenhouse gases such as CO2 for waste manage­
ment and the production of valuable commodities. The energy and
products produced by CO2 catalytic pyrolysis would be much cleaner
than those produced by conventional N2 pyrolysis. Furthermore, the
process is applicable to the treatment of all types of solid waste. Finally,
as a robust and versatile process, pyrolysis provides numerous
opportunities.
P. Parthasarathy et al. Fuel 335 (2023) 127073

Fig. 4b. SWOT analysis of the CO2 catalytic pyrolysis process for wastes valorisation.

5.2. TRL of catalytic CO2 pyrolysis
Identifying the challenges and perspectives of a new concept or
technology can be accomplished through the assessment of TRL. In
addition to measuring the maturity of a technology, TRL provides a
comparison tool for different techniques considering their requirements,
capabilities, and concepts of the program. A TRL consists of nine phases:
progress lab-scale (phases 1–4) for obtaining basic data, development of
pilot-scale (phases 5–7) for obtaining the most optimal process param­
eters and overcoming technical obstacles before the new technology is
applied to an industrial setting, and finally development of industrial-
scale (phases 8–9) for the production of the final output/product [77].

Fig. 5. . Compares catalytic pyrolysis, co2 pyrolysis, and CO2 catalytic pyrolysis technologies TRL assessments.

11
P. Parthasarathy et al.
Industries around the world have used the TRL assessment. Industrial
processes evolve from a conceptual concept to a fully developed appli­
cation as they progress from lower to higher TRLs. Pyrolysis is an
effective way of treating agricultural and municipal wastes. Pyrolysis is
a relatively simple process that has been commercialized and used on an
industrial scale with a TRL of 7–9. Nevertheless, this method faces
challenges due to the high emissions of GHGs like CO2. A TRL appraisal
comparing catalytic pyrolysis, CO2 pyrolysis, and CO2 catalytic pyrolysis
is exemplified in Fig. 5.
A TRL of 7 to 9 for catalytic pyrolysis indicates that the technique is
in the commercialization stage. A TRL value for CO2 pyrolysis between 4
and 6 indicates that the method has been prototyped and the relevant
system is competent. The score also indicates that the facility is run for
profit and that the products are marketed. A TRL score of 4 or 5 for
catalytic CO2 pyrolysis indicates that the technique has been corrobo­
rated but has yet to be prototyped.
The TRL metrics were used by Beims et al. (2019) to track the
development of biomass pyrolysis. The researchers claimed that
although the technology has nearly reached its pinnacle, there are still
some obstacles to be overcome. Further research is required on issues
like kinetics mechanism, efficient heat integration, and the creation of
cost-effective upgrading techniques [78]. Pyrolysis is anticipated to
reach up to a TRL of 9 in the following two decades, according to Lepage
et al [79].
Even if a TRL evaluation is crucial for evaluating technology, it
cannot be relied upon entirely because it considers numerous techno­
logical and financial factors. However, the appraisal helps all parties
(investigators, legislators, businesses, etc.) understand the state of the
technique, technology, system, and maturity level.
5.3. Challenges and future recommendations
While CO2-assisted pyrolysis has received a lot of attention, the
technology is yet to be used on a commercial-scale because the use of
either compressed or high purity CO2 gas which increases the operating
cost of the pyrolysis process. Future research should look into using
unpurified CO2 to cut costs for practical applications. The optimisation
of the N2 and CO2 gas mixture for pyrolysis of various wastes would also
help to optimise the economics of industrial-scale processes. The life
cycle analysis of CO2-assisted pyrolysis for waste treatment and energy
recovery will help determine its effectiveness in reducing global carbon
emissions and reducing climate change. In spite of the fact that CO2 is
clearly an effective agent in pyrolysis of waste materials, the mecha­
nisms by which it works are largely unknown. Investigating these
mechanisms is therefore crucial.
Process simulation can be useful in developing CO2 pyrolysis pro­
cesses as feedstock types, temperature, heating rate, reactor configura­
tion, feedstock size, and CO2 flow rate, all have a significant impact on
the process. Multiple operating conditions can be analysed and opti­
mised using simulation studies. Another important facet of CO2 pyrol­
ysis that necessitates more research is the application of microwave
heating rather than traditional heating methods. There has been evi­
dence showing that microwaves produce better physicochemical prop­
erties in biochar than conventional heating methods under N2 inerting
conditions. The life cycle assessment of microwaves must be evaluated,
thermodynamic parameters must be considered, and economics must be
appraised in order to benefit from comparing microwave heating to
conventional heating.
6. Conclusion
This paper reviews the CO2-assisted catalytic pyrolysis of organic
waste in order to develop a sustainable framework for waste manage­
ment and energy recovery. The primary goal of this review is to high­
light the findings of the latest research studies on catalytic CO2 pyrolysis
of wastes. The study also includes an extensive investigation of the
12
Fuel 335 (2023) 127073
effects of CO2 on catalytic pyrolysis products and the article concludes
by assessing the capability of catalytic CO2 pyrolysis technology con­
ducting the SWOT (Strengths-Weaknesses-Opportunities-Threats) and
technology readiness level (TRL) analyses. The article summaries the
current challenges and future recommendations for catalytic CO2
pyrolysis.
Based on previous studies, it can be concluded that using CO2-
assisted catalytic pyrolysis increases thermal efficiency, resulting in a
more efficient valorisation of the waste materials than using N2. It is
most likely since CO2 breaks down tar and polymerises volatile com­
pounds to inhibit secondary char formation.
The application of CO2 in the catalytic pyrolysis process has been
shown to have a significant positive effect on product compositions and
properties. The utilisation of CO2 in catalytic pyrolysis improves biochar
properties such as porosity and surface area, produces more stable bio-
oil, and generates higher quality pyrogas. Aside from modifying the
compositions and properties of pyrolysis products, the CO2-supported
catalytic pyrolysis is effective for valorising organic wastes such as plant
biomass, animal manure, algae, food, textiles, plastics, and other ma­
terials. Another major benefit of CO2 pyrolysis is its ability to mitigate
the release of harmful chemical species such as polycyclic aromatic
hydrocarbons (PAHs) and benzene derivatives. The SWOT and TRL
analyses confirm that catalytic CO2 pyrolysis has a high potential for
waste valorisation in the near future.
While CO2-assisted catalytic pyrolysis has received a lot of attention,
it has yet to be used commercially. For practical applications, future
research should investigate the utilisation of impure/spent CO2. Opti­
mization of N2 and CO2 can be one of the ways for commercialisation by
using impure CO2. Previous research has shown that using mixed at­
mospheres (CO2 and N2) results in higher quality pyrogas with higher
CO yields. Another important aspect of CO2 pyrolysis that requires
additional research is the use of microwave heating rather than tradi­
tional heating methods. The review is unquestionably in line with
encouraging the use of CO2 to meet the Paris Agreement’s CO2 emission
regulations made in 2015.
CRediT authorship contribution statement
Prakash Parthasarathy: Conceptualization, Investigation, Writing –
original draft. Shifa Zuhara: Writing – original draft. Tareq Al-Ansari:
Funding acquisition, Resources, Project administration, Writing – re­
view & editing. Gordon McKay: Funding acquisition, Resources, Project
administration, Supervision, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
Open Access funding provided by the Qatar National Library. The
authors would like to thank Qatar National Research Fund (QNRF) for
their support of this research through NPRP-11S-0117-180328, the Su­
preme Committee for Delivery and Legacy (SCDL) and to Hamad Bin
Khalifa University (HBKU) and Qatar Foundation (QF).
P. Parthasarathy et al. Fuel 335 (2023) 127073

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