Journal of Cleaner Production 242 (2020) 118409

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Journal of Cleaner Production

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

Review

Recent advances in carbon-based renewable adsorbent for selective

carbon dioxide capture and separation-A review
Rafay Ahmed a, Guijian Liu a, b, *, Balal Yousaf a, b, Qumber Abbas a, Habib Ullah a,
Muhammad Ubaid Ali a
a
CAS-Key Laboratory of Crust-Mantle Materials and the Environments, School of Earth and Space Sciences, University of Science and Technology of China,
Hefei, 230026, PR China
b
State Key Laboratory of Loess and Quaternary Geology, Institute of Earth Environment, The Chinese Academy of Sciences, Xi'an, Shaanxi, 710075, China

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

Article history: In terms of net intensification in the greenhouse effect ie., rise of global temperature which has triggered
Received 29 March 2019 melting of glacier thus increasing sea level and acidification of sea, carbon dioxide alone contributes
Received in revised form approximately three-fourth of the net greenhouse radiative forcing by man-made (anthropogenic)
10 September 2019
greenhouse gases emissions. Carbon dioxide capture and storage (CCS) technology; a promising strategy
Accepted 11 September 2019
Available online 12 September 2019
for capturing of carbon dioxide from point sources before its release to atmosphere by using various
sorbents is gaining global interest. In this study, the established carbon capture technologies with
^ as de
Handling editor; Cecilia Maria Villas Bo methods of carbon dioxide separation along there pros and cons are discussed. Carbon-based adsorbents
Almeida are considered as the most versatile adsorbents for carbon dioxide due to their extraordinary physical
and chemical properties. In this manuscript, recent developments on carbonaceous adsorbents (biochar,
Keywords: activated carbons, and graphene-based adsorbents) and their role in carbon dioxide capture during
Carbon dioxide emissions different combustion processes and conditions have been comprehensively focused.
Capture and storage © 2019 Elsevier Ltd. All rights reserved.
Biochar
Activated carbons
Graphene

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Technologies used for capture of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. CO2 capture before combustion process (pre-combustion) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Oxy-fuel combustion capture process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.3. Post-combustion capture process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. CO2 separation methods from flue gas in combustion capture process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1. Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.2. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.3. Membrane separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.4. Calcium looping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Use of solid sorbents for CO2 capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1. Carbonaceous adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1.1. Biochar production and CO2 capturing performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
5.1.2. Physicochemical activation of carbons and their capture performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5.1.3. Graphene-based adsorbents, their production and CO2 capture performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

* Corresponding author. CAS-Key Laboratory of Crust-Mantle Materials and the

Environments, School of Earth and Space Sciences, University of Science and
Technology of China, Hefei, 230026, PR China.
E-mail address: lgj@ustc.edu.cn (G. Liu).

https://doi.org/10.1016/j.jclepro.2019.118409
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

6. Conclusions and future recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Acknowledgment: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

1. Introduction achieved if CO2 capture and storage technologies are adopted

immediately (Zhao et al., 2018). Researchers have designed
Global emission of greenhouse gases especially carbon dioxide different methods including absorption and adsorption in CCS for
(CO2) is rising at an alarming rate and creating many serious separation of CO2 gas from other exhaust gases produced at power
environmental issues such as global warming and climate change pants (Keller et al., 2018).
(Sumida et al., 2012). As a consequence of continuous rise in earth's Absorption of CO2 from flue gas by amine scrubbing with high
temperature glaciers are melting, depleting ice lands and rising sea efficiency in fossil fuels fired power plants is a traditional method
level (Yousaf et al., 2017). The major cause of CO2 emission in the and currently in operation. However, due to some drawbacks of
atmosphere is human activities in which combustion of fossil fuel, amine scrubbing method such as, corrosion of mechanical parts,
agricultural practices, and industries play the dominant role release of toxic chemicals and gases, and requirement of high en-
(Hussain et al., 2018). Since the era of industrialization, fossil fuels ergy for regeneration, has limit the application of this technology
utilization in power generation sector is a major production source (Parshetti et al., 2015; Tian et al., 2018). Adsorption is more efficient
of CO2 and other harmful gases. Moreover, the atmospheric CO2 alternative method for CO2 capturing and could replace amine-
emission from developing countries will rise continuously due to based absorption technique (Babu et al., 2017). In adsorption,
ever increasing energy demand with rapid economic growth (Luu solid porous sorbents including metal-organic frameworks (MOF),
et al., 2015; Waqas et al., 2018; Chundong Zhang et al., 2016a). It porous carbons, zeolites, etc. are used. These adsorbents are cost-
is estimated that in the year 2050; oil requirement for energy effective, environment-friendly, having high surface area and
production will reach up to 44,600 Mt (Waqas et al., 2018). In his- resistant to water and chemicals (Ben-Mansour et al., 2016; Zhao
tory, the highest amount of CO2 was released into environment et al., 2018).
during the period of 2000e2010 (~49 Gt); 78% of this CO2 emission To fulfill the world's present energy demand, fossil fuels are the
came from industrial processes and combustion of fossil fuels and major source of energy production. Thus emission of CO2 through
out of which 25.9% CO2 produced only from combustion process fossil fuels combustion and other anthropogenic activities resulted
(Luu et al., 2015; Norahim et al., 2018). Meanwhile, in 2014 only in higher CO2 concentration in atmosphere, creating a change in
from the burning of coal about 16 Gt CO2 was released to atmo- world's climate and making it hotter than the preindustrial period
sphere (Keller et al., 2018). (Ben-Mansour et al., 2016; Vinoba et al., 2017). Emission of CO2
As the concentration of CO2 increases in atmosphere, it warms through fossil fuel burning have significantly increased from nearly
earth climate by enhancing the natural greenhouse effect. The zero in 1870 to 33 Gt in 2015 (IEA, 2017). Flue gas, a mixture of
mechanism behind this rise in global temperature due to increasing different gasses (CO2, NOx, Sox etc.) from coal-based power units
level of CO2 is that, when solar radiation enters in atmosphere and are considered as the main source of anthropogenic. The excessive
strike with earth's surface, it reflects back to the atmosphere while emission of greenhouse gases in the form of flue gas produced by
re-emitting energy in the form of infrared or ultraviolet rays which industries has created serious concerns in form of climate change
are absorbed by greenhouse gases especially CO2 when escaping (Treut et al., 2007).
the atmosphere. These gases again reflect light energy in all di- Intergovernmental Panel on Clime Change (IPCC) in a report has
rections which results in heating the earth's atmosphere (Anderson mentioned that atmospheric level of CO2 will rise to ~450 ppm in
et al., 2016). Increase in CO2 concentration also enhance the radi- the year 2035 resulting 2
C rise in global temperature (Vinoba
ative force, which as a result increase sea surface temperature (Joos et al., 2017). However climate modeling studies have shown that
et al., 1999). In order to mitigate the challenges of greenhouse gases CO2 concentration below 350 ppm is safe (Rahman et al., 2017).
emission at an alarming rate and their deleterious effects on During the period of 2000e2014, the average increasing rate of CO2
environment have encouraged the researchers to develop advanced content in atmosphere by anthropogenic activities was 2.6% per
technologies (Norahim et al., 2018). According to Mouna Loa year as compared to the pre-industrial period (1970e2000). The
Observatory's latest update on September 5, 2019; the CO2 con- ever increasing amount of CO2 and its properties similar to that of
centration in atmospheric environment was reached up-to greenhouse gases are considered to be the main reason of increase
409.95 ppm in August 2019, which is 3.04 ppm more from the in earth's surface temperature resulting in severe heat waves,
concentration recorded in August 2018 (USDC, 2019). Thus, it is droughts, temperature shifting, rise in sea level, melting of glaciers
necessary for all countries to adopt certain preventive measures (Chu et al., 2016). Hence creating dangers for human health, forest
and develop alternate means of energy production that can help in species and overall ecosystem safety (Rahman et al., 2017).
decreasing dangerous level of atmospheric CO2 (Ben-Mansour Emission of CO2 from point sources including industries and
et al., 2016). In recent years, various agreements such as Paris thermoelectric power plants should be reduced urgently in order to
Agreement and Kyoto Protocol are signed among nations in order to eliminate or minimize its negative impact on climate (Rochelle,
regulate and reduce CO2 emissions from different regions of the 2009). Knowing the severity of global warming issue, if required
world. Scientific community have also proposed certain strategies actions are not taken immediately, then unsurprisingly our next
including carbon capture, utilization and storage (CCUS) techniques generations will face the adverse effects of climate (Yu et al., 2017).
through which excess amount of CO2 in atmosphere can be For the reduction of CO2 emission from atmosphere, different clean
captured, stored and utilized for sustainable energy production energy approaches should be considered and adopted (Leung et al.,
(Qaroush et al., 2018; Szima and Cormos, 2018; Chundong Zhang 2014). These projects or approaches included the use of low carbon
et al., 2016a). A report of International Energy Agency (IEA) fuels (nuclear power, hydrogen fuel), utilization of renewable en-
mentioned that global temperature rise below 2
C can only be ergy sources (solar, wind and bioenergy) and capture, storage and
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 3

utilization of CO2 from their emission sources (Song et al., 2018; are shown in Fig. 1 (Blomen et al., 2009; Haszeldine, 2009). The
Yaumi et al., 2017). working conditions (pressure, temperature, and material) are
CO2 capture, storage or utilization (CCS/U) are promising ap- different for each type. Hence, customization in infrastructure and
proaches for mitigating or reducing the emission of human additional energy is required in these combustion processes. These
generated greenhouse gasses. It has been recognized that CCS conditions make the capture techniques economically feasible only
approach is capable of reducing up to 20% emission of CO2 (Abass A. in large scale plants (Yu et al., 2017).
Olajire, 2010). This technique is also considered an important
component of different climate change mitigation plans and acts as 3.1. CO2 capture before combustion process (pre-combustion)
a bridge between future renewable energy and current fossil fuel
based economy (Bains et al., 2017). Like CCS, CO2 capture and uti- Fossils fuels most importantly (coal) are low-cost source of en-
lization (CCU) is also getting more interest. The process of CO2 ergy and extensively present on earth. Low-efficient pulverized coal
capture and storage (CCS) refers to direct removal of CO2 from the used in coal fired power generation system and other industries has
sources, its compression and transportation to a storage site where caused several environmental concerns including the production of
it is deposited in the ground or ocean bedrock securely without greenhouse gases especially CO2 (Ho et al., 2015). Pre-combustion
releasing back into atmosphere (Li et al., 2013; Mack and capture is the technique used for the capturing of CO2 before
Endemann, 2010). The storage process included pre and post combustion process (Theo et al., 2016). Integrated gasification
management of storage site to observe and predict the effect on the combined cycle (IGCC) power plants mostly use this technique to
environment (Hellevang and Aagaard, 2013). Selection of an capture CO2. These IGCC power plant systems first convert biomass
appropriate technique for CO2 capture/adsorption mainly relies on or fossil fuel into synthesis gas through partial oxidation or gasifi-
the type of fuel burning system and the amount of CO2 produced cation process, which is a mixture of carbon monoxide and
during combustion process (Blomen et al., 2009). Key points that hydrogen gas (Babu et al., 2015). Particulate matter is removed from
needs to be considered in CCS techniques are: the cost should be synthesis gas using cyclone separator and gas is transferred to
minimum for the entire process including transportation and water gas shift (WGS) reformer for reaction with water to convert
storage from point source to the site of storage, storage must be for CO into CO2. At later stage after removal of sulfur, liquid or solid
long time, minimum environmental impact of storage and acci- sorbents are applied for CO2 sequestration as illustrated in Fig. 2 (a).
dental leakage risk should be reduced or eliminated (Fu and Hydrogen fuel is usually produced from this type of carbon
Gundersen, 2011; Rahman et al., 2017). capture technique which can be used in different industries for
The major contribution of this review is to provide the infor- power generation purpose with less CO2 emissions (Theo et al.,
mation regarding techniques and methods being used in capturing 2016). Pre-combustion capture process is commonly used in the
of CO2 during different combustion stages by using carbon based production of fertilizers and hydrogen (Babu et al., 2013). The
adsorbents; Furthermore, recent advances in these carbon based concentration of CO2 produced in this process ranges from 15 to 60
adsorbents and their CO2 adsorption performance are also dis- percent which makes it easy to capture; however, the process of
cussed in this manuscript. gasification and water gas shift reaction are expensive and chal-
lenging (Pires et al., 2011).
2. Methodology
3.2. Oxy-fuel combustion capture process
The main purpose of this review of literature was to summarize
the performance of recent carbon based porous adsorbents for the Sequestration of CO2 by oxy-fuel combustion technique has
adsorption of CO2, while finding the challenges and issues for attracted attention in recent years due to low separation and
future directions. The methodology section of the manuscript en- capturing cost of CCS considerably (Yin and Yan, 2016). According to
compasses how the literature was searched, collected and then a technology roadmap of International Energy Agency (IEA), by the
sorted by finding the knowledge gaps present in the previous year 2020, oxy-fuel combustion capture technique can be
research. For the detailed review of literature and article search commercialized in coal-powered power plants because of its low
from peer-reviewed journals was done by using the scientific da- cost as compare to other CCS technologies (Wu et al., 2018). In this
tabases and various search engines including Web of Science, Sci- process, air is replaced with pure O2 for burning of fuel as a result
ence Direct, Scopus, Google Scholar, NCBI and major publishers. For concentration of N2 in flue gas reduced significantly compared to
the drafting of this manuscript, the search for literature was limited H2O and CO2. The CO2 and H2O enriched flue gas is further purified
and mainly focused to studies from the year 2000e2018. Several from particulates by drying and liquefaction process. The liquefied
appropriate key words with respect to the main theme of this paper carbon enriched product is transported safely to storage site via
were used for the search of literature. These key words include ships and pipelines (Carrasco-Maldonado et al., 2016).
carbonaceous adsorbents, renewable, porous adsorbent, CO2 cap- In order to acquire the moderate temperature of furnace, opti-
ture, biochar, activated carbons, graphene and carbon capture mum flame temperature is required which is managed by recycling
technique. Articles were selected after reading the information flue gas with O2 at 27e35% molar fraction. Moreover, optimum
from abstracts and research articles with most relevant information level of O2 required for combustion process is calculated at boiler
were preferred. Articles published in no-English language were inlet and depends upon boiler design and properties of fuel used
excluded to avoid translating difficulty. A total of 264 articles were (Yin and Yan, 2016). Schematic process of oxy-fuel combustion
considered to be reviewed for this manuscript and most of the process is shown in Fig. 2 (b). Efficiency losses of oxy-fuel com-
literature is from chemistry, materials science and engineering bustion systems working in coal power plant can be decreased up
search areas. to 7e11% by upgrading processes (Cau et al., 2018). The drawback of
this technology is separation of oxygen from the air which requires
3. Technologies used for capture of CO2 additional energy (Leung et al., 2014; Yu et al., 2017).

The process of CO2 capture and separation is classified into three 3.3. Post-combustion capture process
types depending on the combustion method and the amount of CO2
generated during that process. Different CO2 capture technologies The main goal in post-combustion capture processes is to
4 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

Fig. 1. Carbon dioxide capture and storage techniques (a) pre-combustion, (b) oxy-fuel combustion, (c) post-combustion capture system. Modified by permission from (Teir et al.,
2018).

separate and capture CO2 from N2 present in flue gas generated in natural gas-fired and 13e15 vol % in coal-fired system) (Zhang
after burning of fossil fuel (Zou et al., 2017). Recently, this technique et al., 2017). This process is suitable for all the existing power
is getting more attention because various materials and methods plants with only a slight modification in infrastructure (Bui et al.,
for CO2 separation and capture can be used in this technique 2014).
(Adderley et al., 2016; Bui et al., 2014). When fossil fuel is burned in
coal-fired power plants, it generates exhaust gases mainly N2 and 4. CO2 separation methods from flue gas in combustion
CO2 with a small portion of water vapors, particulate matter, SO2, capture process
and NO2. The gas stream is then transferred to CO2 capturing sys-
tem at ~1 atm pressure and 40e120
C temperature. Temperature There are different advanced separation methods that are used
of the system is maintained by steam released from power gener- during combustion process for the separation of CO2 from flue gas
ating units to make the process more efficient (Gardarsdo ttir et al., (Leung et al., 2014). These methods are absorption, adsorption,
2015), as illustrated in Fig. 2 (c). Among various techniques, post- membrane separation and cryogenics (Lee et al., 2013; Pires et al.,
combustion capture process is the most widely used method at 2011; Samanta et al., 2012).
industrial scale. Examples of this technique can be found in Sask-
Power (Canada) and TMC Mongstad (Norway) capable of capturing 4.1. Absorption
1,000,000 tonnes and 300,000 tonnes of CO2 per year, respectively
(Henry et al., 2015). Separation of impurities from captured CO2 in Absorption is widely used method, has received a lot of atten-
post-combustion capturing process is the main hurdle at ambient tion for absorbing large emission volumes from power plants and
conditions because of low amount of CO2 in flue gas (about 4 vol % chemical industries. Chemical absorption is a major method used in
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 5

Fig. 2. (a) absorption. reprinted with permission from (Dutcher et al., 2015), (b) adsorption. reprinted with permission from (Sumida et al., 2012), (c) membrane separation.
reprinted with permission from (Zaman and Lee, 2013): showing separation methods during combustion processes.

coal fired powered plants for separation of CO2 because of its energy requirement for regeneration of some solvents, solvent
suitability to existing power plants with low infrastructure as well degradation due to the occurrence of O2, NOx, and SOx in the flue
as operating cost (Liu et al., 2016). Chemical CO2 absorption tech- gas, production of volatile compounds and erosion of equipment
nology is favorable at commercial scale due to several advantages (Conway et al., 2015).
such as technique maturity, capacity of handling, and efficiency (Liu
et al., 2014). Solvents having good adsorption capacity and low
regeneration energy are preferred to be used in this process (Kim 4.2. Adsorption
et al., 2016). Typical amine sorbents used in this method includes
diethanolamine (DEA), monoethanolamine (MEA) and potassium Aqueous solvents are highly selective for CO2 absorption but
carbonate. Monoethanolamine (MEA) is found to be the most effi- major drawback of using chemical absorbents is high-energy con-
cient sorbent as its efficiency for CO2 is over 90% (Aaron and Tsouris, sumption during regeneration process, uses almost 30% of the total
2005; Knudsen et al., 2009). In absorption, for the separation of CO2 energy produced by power plant. So there is need to develop such
from flue gas with the use of liquid sorbent (MEA) different reaction methods for CO2 capture which are economical, more efficient,
mechanisms are proposed. One of the most accepted reaction environmental friendly and easily installable in the existing power
mechanism is zwitterion mechanism. In this mechanism zwitter- plants (Bahamon and Vega, 2016). Researchers have found that
ions are first produced upon CO2 reaction with alkanolamines separation and capturing of CO2 from other gases by adsorption is
(primary and secondary) that converts into carbamate after im- the most promising technique. Adsorption process requires a good
mediate neutralization by amines or base such as OH or H2O (Lv adsorbent, regeneration process and adsorption cycle time to carry
et al., 2015; Shakerian et al., 2015). Reaction mechanism of CO2 out efficient removal of adsorbate from the system. Operating
absorption on MEA surface and their end products according to conditions like pressure and temperature of reactor, and gas used
zwitterions are shown in the following equations: within the reactor determine the adsorption performance (Kacem
et al., 2015). In adsorption, CO2 is selectively captured on the sur-
CO2 þ RNH2 # RNHþ  face of adsorbent by different mechanisms such as chemical
2 COO (1)
adsorption (chemisorption) or physical adsorption (physisorption)
RNHþ   þ (Bhown and Freeman, 2011). In physical adsorption, the adsorbate
2 COO þ RNH2 # RNHCOO þ RNH3 (2)
is attracted on the surface of sorbent having high specific surface
Moreover, absorption process of CO2 with other solvents such as area and porous structure with the help of electrostatic and Van der
modified ionic liquids and mixed amines are well explained by Waals forces, while in case of chemisorption, adsorbate is attached
zwitterions mechanism. MEA has shown good results for a long on binding sites present on surface of sorbent via covalent bonding
time in purification processes of the acid-gas mixture. It is still used (Berger and Bhown, 2011). Different materials show different
in industries because of its easy handling during operation and fast chemisorption mechanisms, for-example: in metal-organic frame-
CO2 adsorption capacity (Rochelle, 2009). In order to regenerate the works, the chemical interaction of CO2 in MOFs occurs through
liquid solvent for next cycle, heating or depressurizing of liquid uncoordinated metal sites and also from the functional groups that
sorbent is done (Bhown and Freeman, 2011). Separation of CO2 by are present on the surface of MOFs; while in carbonaceous mate-
absorption method is shown in Fig. 2 (a). Despite the high efficiency rials, chemisorption of CO2 usually takes place by functional groups
of absorption, this method has major drawbacks including high that are naturally produced or can be introduced by chemical
modification (Bui et al., 2018). Previous studies indicated that
6 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

chemical adsorption of CO2 can be enhanced by introducing basic types of membranes for the separation of CO2, some of them are,
organic groups and inorganic metal oxides such as amine and alkali mixed matrix membranes (MMMs), microporous organic polymers
metals respectively. Chemical adsorption of CO2 with materials is (MOPs), carbon molecular sieve membranes (CMSMs), and inor-
achieved by two methods; carbonates and carbamates, carbonates ganic membranes and polymers (He et al., 2015). Membrane sep-
can be organic or inorganic and have 1:1 and 1:2 mechanisms for aration technology can also be used for gas separation in different
chemisorption (Qaroush et al., 2017). Different theories showed CCS such as pre-combustion and post-combustion capture pro-
that physical adsorption of gas molecules on the adsorbent surface cesses. Polymeric membranes are usually considered more effi-
occur through mass transfer process and selective adsorption is cient, durable and flexible for cost-effective capture of CO2 from
carried out via electrostatic and Van der Waals forces (Sarker et al., industries. Correlation between selectivity and permeability for
2017). CO2 having high values of polarizability and quadruple capturing of CO2 by polymeric membranes is described by an ‘upper
movement 29.1 1025 cm3 and e 13.71  1040 cm2, respectively, bond’ relationship analysis (Turi et al., 2017). Synthesis of poly-
which favor its adsorption electrostatically on the adsorbent sur- meric membranes for better results can be achieved by using glassy
face as compared to N2 and CH4. Moreover, thermodynamic equi- and rubbery materials having different separation principle
librium and compound diffusional velocities also determine CO2 depending on size and diffuse ability. It has been found that sep-
selective adsorption on adsorbent surface (Kacem et al., 2015). aration of gas by glassy and rubbery polymers is mediated by
Regeneration of adsorbent after adsorbing CO2 from flue gas for condensability and difference in kinetic or size of gas molecules
cyclic adsorption process was studied extensively and showed high (Vinoba et al., 2017). Normally working capacity of membranes
purity results. Cyclic adsorption of adsorbents was accomplished by used in gas separation system are calculated numerically by using
using following three different regeneration processes: i.e. (i) models, as it is difficult to examine operation conditions for quick
temperature swing adsorption (TSA), (ii) pressure swing adsorption performance (Lee et al., 2017). To achieve better results on an in-
(PSA), and (iii) vacuum swing adsorption (VSA) (Krishnamurthy dustrial scale, it is recommended that the performance of mem-
et al., 2014). During PSA and VSA, the captured gas is desorbed by branes should not be affected by impurities present in flue gas (He
decreasing the pressure of adsorbent fixed column. The difference et al., 2015). Researches have achieved an efficiency of 82e88% for
between PSA and VSA is that, in PSA the column is first filled with separation of CO2 from other gases (Brunetti et al., 2010; Favre,
gas till saturation after which column pressure is decreased to 2011). However, the main limitations in the commercialization of
ambient pressure which results in desorption. While in VSA, this separation method are membrane materials have low selec-
desorption of gas saturated adsorbent took place by applying vac- tivity and permeability (Bernardo et al., 2009), poor performance
uum in the column (Siqueira et al., 2017; Sumida et al., 2012). TSA is under severe operating conditions and low selectivity for CO2 in
gaining more interest as compared to PSA and VSA because of its flue gas conditions where the pressure and concentration of CO2 is
potential in utilizing low grade thermal energy for regeneration low (Wang et al., 2017).
produced from power plant, also it is considered promising for
capturing CO2. In TSA adsorbent placed column is filled with flue
gas and is then heated till material desorption temperature. Thus
this rise in temperature tends gas molecules to leave adsorbent 4.4. Calcium looping
surface, while increase in pressure and gas purging helps in moving
the desorbed gas out from the column as displayed in Fig. 2 (b) (Joss Capturing of CO2 by using calcium in the form of lime is an old
et al., 2015; Ntiamoah et al., 2016; Sreedhar et al., 2017). Main method however its use in reversible capturing of CO2 from waste
criteria for the selection of an appropriate adsorbent includes its flue gas is relatively new, second generation low cost technique
specific surface area, adsorption capacity, pore size and volume, known as calcium looping technology. Application of calcium
density, regeneration ability, production method, selectivity for the looping technology shows same working principles in pre and post
target material (adsorbate) and sustainability (Deanna M. et al., combustion systems (Blamey et al., 2010). In this technique a cheap
2010; Mara and Mercedes, 2012; Sumida et al., 2012). Some regenerable source of CaO such as limestone is used as sorbent to
typical examples of adsorbents used for the CO2 adsorption are capture CO2 through carbonation and calcination cycles. The gas is
zeolites, activated carbon, metal organic frameworks and silica captured by CaO sorbent in a carbonator reactor at high tempera-
material. Recently, research in development of novel sorbent from ture (650e850
C) under atmospheric pressure; the sorbent is then
renewable sources is getting more interest. transferred or circulated to calciner reactor where calcination of
CaCO3 is done at temperature higher than 930
C to collect
4.3. Membrane separation concentrated stream of CO2 that is transferred to storage site
 n et al., 2016). The regenerated CaO is again recycled to
(Perejo
Membrane separation is an innovative method for physical carbonator reactor and the carbonation/calcination cycle continues
separation of CO2 from other flue gases through a semipermeable (Bosoaga et al., 2009). The reversible reaction of CO2 with CaO is as
membrane or barrier (Khalilpour et al., 2015). Membrane separa- following:
tion technology is an inexpensive process due to low energy
requirement as compared to traditional solvent absorption method CaO þ CO2 # CaCO3 DH ¼ 178 kJ/mol (3)
(Ansaloni et al., 2017). Membrane separation technique has been
applied successfully since last two decades in various fields for Calcium looping technology can be distinguished from other
selective gas separation such as, upgrading of biogas, hydrogen carbon capture and storage technologies by the following main
production, separation of air and natural gas sweetening. Nowa- features: it utilizes cheap sorbents such as limestone which is
days researchers have started extensive work on the development abundantly available on the earth; it can produce additional energy
of membrane-based material that can be used for the separation of from the steam produced from carbonator/calciner reactors thus
CO2 released during the operation of different industries. In- reducing energy penalties; the used sorbent can be further used in
addition, from environmental and economic perspective this industries like cement industry (Bui et al., 2018). However, the main
technique has shown excellent results (Li et al., 2015). Fig. 2 (c) challenge in calcium looping technology is high decay rate of the
represents the separation of CO2 from flue gas with membranes sorbent which reduces the efficiency of sorbent after 20e30 cycles,
separation method. Different scientists have fabricated various due to attrition and sintering (Erans et al., 2016).
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 7

5. Use of solid sorbents for CO2 capture groups (Wang et al., 2011). In carbon matrix, these surface moieties
increase acidity/basicity results change in surface charge distribu-
High demand of energy for regeneration process and corrosion tion and enhancement of adsorbent adsorption capacity (Abass A
of current CO2 scrubbers (aqueous alkanolamine solutions) have Olajire, 2010). Carbonaceous adsorbents can be pyrogenic carbon
motivated the researchers to develop solid adsorbents. These are materials (biochar, charcoal, carbonized biomass), activated car-
environmental friendly and require low heat for regeneration Car- bons, carbon fibers and ordered carbon nano-materials (graphene,
bon Dioxide Capture in MetaleOrganic Frameworks (Sumida et al., nano-tubes) (Bui et al., 2018).
2012). Solid sorbents are classified into physisorption (physical)
and chemisorption (chemical) based on mode of interaction be- 5.1.1. Biochar production and CO2 capturing performance
tween material and molecule of CO2. Physical interaction (phys- Pyrogenic carbonaceous adsorbents such as carbonized
isorption) occur mainly due to electrostatic forces and bonding biomass, charcoal, and other low-cost carbon materials have been
such as hydrogen bonding etc., In chemisorption process (chemical extensively investigated as a tool for carbon sequestration and soil
interaction) different acidic or basic functional groups incorporated conditioners. These are gaining attention among scientific com-
on adsorbent surface are involved (Raganati et al., 2018). These munity due to their remediation ability of many environmental
solid adsorbents are classified into carbonaceous materials pollutants (Barrow, 2012; Chih-Hung et al., 2014; Jeffery et al.,
including activated carbons (Titirici et al., 2015), ordered porous 2011). Highly stable aromatic structure, carbon-rich material ‘bio-
carbon, graphene, and activated carbon fibers and non- char’ can be produced by biomass thermal treatment process at
carbonaceous like zeolite, modified porous silica, metal organic elevated temperature under inert conditions (Yousaf et al., 2018).
frameworks and covalent organic frameworks (Ding and Wang, Biochar is eco-friendly and cost effective material compared to
2013; Yaumi et al., 2017). Solid sorbents having capacity of other carbonaceous sorbents (activated carbon, graphene, carbon
capturing CO2 from flue gas at high temperature is also attaining fibers etc.). It can be produced from easily available, cheap biomass
interest of researchers. Temperature of flue gas released after feedstock and wastes from different industries such as agricultural,
burning of fossil fuels usually ranges from 400 to 700
C, which is forestry, dairy manure and many other solid biowastes (Lehmann
needed to be cooled before adsorption process (Seggiani et al., et al., 2006; Norah et al., 2015; Sevilla and Fuertes, 2011). There
2013). Lithium based sorbents are can sorb CO2 at relatively high are numerous methods (gasification, torrefaction, hydrothermal
temperature and are more stable as compared to CaO. Lithium carbonization, and pyrolysis) for the production of biochar from
ceramics have the tendency to sorb CO2 gas from 25
C to 700
C biomass. Operating conditions, yield and end products vary from
and shows higher capture efficiencies (Izquierdo et al., 2018). method to method.
Lithium ceramics including lithium cuprate (Li2CuO2), lithium In gasification, solid or liquid biomass is thermo-chemically
aluminate (Li5AlO4), lithium orthosilicate (Li4SiO4) and lithium converted into useful products icluding gaseous fuel (synthesis
ferrites (Li5FeO4 and LiFeO2) showed good results. However, studies gas), biochar and tar (oil). These products can be used for the
showed that lithium zirconate (Li2ZrO3) and lithium orthosilicate generation of energy or manufacturing of many chemicals (Ciferno
(Li4SiO4) are promising high temperature (500e700
C) sorbents and Marano, 2002; Rapagna  et al., 2000). Biomass gasification is
(Ham-liu et al., 2018). When CO2 reacts with lithium ceramics complex process involves biomass conversion through various
(lithium orthosilicate), lithium oxide reversibly reacts with CO2 chemicals reactions at elevated temperature (500e1400
C) and
molecule and converts into lithium carbonate and lithium meta- pressure (~33 atm) in presence of a gasifying agent (O2, air, water
silicate as expressed in the reaction: vapors and CO2) to change the molecular structure of biomass (high
H/C ratio) (Baruah and Baruah, 2014; Laird et al., 2009; Loha et al.,
Li4SiO4 þ CO2 # Li2CO3 þ Li2SiO3 (4) 2014). This complex process of gasification generally involves four
consecutive steps viz. drying of feedstock, pyrolysis, partial com-
Lithium orthosilicate as compared to lithium zirconate adsorb bustion (oxidation) and reduction (gasification of charred products)
CO2 more rapidly and is lower in cost due to cheaper SiO2 (Ochoa- (Luo et al., 2009; Parthasarathy and Narayanan, 2014; Srirangan
Fernandez et al., 2006). Selective capturing of CO2 through et al., 2012). The production quality of end-products depends on
adsorption process can be achieved by modification of physical the type of feedstock, gasification reactor, gasifying agent as well as
structure (number of pores, pores size) (Haoran et al., 2012) or with operational conditions (temperature and pressure). Gasifier re-
the addition of various functionalities (amine, etc.) on adsorbent actors are further divided into three types ie. fixed bed, fluidized
surface (Prenzel et al., 2014). Different solid adsorbents have been bed and entertained flow; depending on the gas-solid contact
used developed and used for the capture of CO2 from different (Go mez-Barea and Leckner, 2010; Wongsiriamnuay et al., 2013).
emission sources. In the below section, adsorption of CO2 using The yield of biochar produced by gasification is generally low
carbonaceous sorbents is discussed. (<10%) compared to other biochar production methods. This is
because of partial oxidation condition that produces carbon mon-
5.1. Carbonaceous adsorbents oxide from carbon. The main disadvantage of gasification process is
the production of tar (a viscous black liquid containing high
Carbonaceous adsorbents represent the class of materials that amount of aromatic hydrocarbons and heavy metals) which causes
are chiefly composed of carbon atoms in their structure. These degradation of biochar and also creates some operational issues
materials are widely used for the purification of industrial emis- (Laird et al., 2009; Li and Suzuki, 2009; Mohan et al., 2014).
sions containing mixture of different gases. Carbon-based materials Recently, research on biochar production by torrefaction process
can be prepared easily with low cost. These also have numerous is gaining momentum. In torrefaction, biomass is thermally treated
advantages over non-carbonaceous materials as carbonaceous for short time period generally from few minutes to couple of hours
materials are chemically and thermally stable, having very high at low or mild temperature (200e300
C) at atmospheric pressure
pore volume and specific surface area and can be regenerated easily under inert conditions (Guizani et al., 2016; Rousset et al., 2012;
(Zhang et al., 2014a). Moreover, these materials are hydrophobic in Ullah et al., 2017). Properties of raw biomass such as low calorific
nature and their adsorption efficiency is not affected in the pres- value, low oxygen to carbon and hydrogen to carbon ratios and
ence of moisture. The surface chemistry of these adsorbents can hygroscopicity can be enhanced by torrefaction process (van der
also be modified through incorporation of different functional Stelt et al., 2011). As a result of torrefaction, biomass is converted
8 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

into solid (chars and ashes), liquid (water, alcohols, acetic acid, and yield of bio-oil than biochar (Tripathi et al., 2016; Wang et al.,
ketones) and gaseous (CO2, CO, CH4, and H2) states (Chen et al., 2005). The main disadvantage of this pyrolysis process is the low
2015, 2011; Huang et al., 2012). Moisture content of torrefied quality and stability of oil due to the presence of ash and biochar
biomass is also reduced to a significant level as compared to the raw (Canabarro et al., 2013). It was found that biochar produced from
biomass. About 60e80% of the original mass of feedstock is retained fast or flash pyrolysis have macro-pores structure and slow pyrol-
during the process of torrefaction thus product have high energy ysis produced biochar possess micro-porous structure (Abbas et al.,
contents (Guizani et al., 2016; Toptas et al., 2015). Operating con- 2018; Laird et al., 2009).
ditions (temperature and retention time) are the main parameters It is necessary to get inside knowledge about the physio-
which determine the quantity and nature of by-products. Solid chemical mechanism involved in the formation of biochar under
torrefied product has properties of both biochar and raw biomass as distinctive environments. Quality and quantity of biochar depend
it is not fully carbonized and still contains some amount of volatile on several parameters including operational conditions and feed-
nature organic compounds (Pala et al., 2014). Moreover, the process stock material. To understand the thermo-chemical changes take
of torrefaction is highly insignificant for biomass with higher place in feedstock during biochar formation, physical and chemical
moisture content (Kambo and Dutta, 2015; Liu and Han, 2015). characterization of produced biochar is performed. Cellulose,
Hydrothermal carbonization (HTC) was first discovered in 1913 hemicellulose, and lignin are the main components of biomass,
by Bergius, but this process has gained interest in recent years due each component shares different transformation mechanism dur-
to its efficiency and convenience (Liu and Balasubramanian, 2014; ing pyrolysis process and biochar formation (Bridgwater et al.,
Reza et al., 2014). In HTC, biomass is thermo-chemically con- 1999). Detailed study showed that hemicellulose decomposes at
verted into biochar or hydro-char in the presence of water and low low-temperature range (200e260
C) following to break down of
amount of oxygen, high pressure (14e22 MPa) and temperature cellulose (240e350
C), and degradation of lignin usually take place
(120e300
C) for 1 h to several hours (Meyer et al., 2011). The solid at elevated temperature range (280e500
C) because of more
end-product of HTC has chemical properties same like biochar and complex structure (Shen et al., 2011; Babu, 2008). Fig. 3 describes
coal. A small amount of liquid (bio-oil mixed with water) and CO2 themo-chemical conversion mechanism of cellulose, hemicellu-
gas is also produced during this carbonization process (Axel and lose, and lignin with their end-products.
Felix, 2010; Kim et al., 2016). Different researchers reported that The unique structure and surface properties of biochar make it
biomass having a high amount of lignin, cellulose, hemicellulose, an excellent adsorbent for acid gases. Moreover, biochar is low cost
and waste containing high moisture contents such as sewage material, having high surface area, hydrophobic nature, and easy
sludge and cow manure can be used for the production of carbon regeneration. This makes the biochar an attractive material for re-
nano-materials using HTC technique (Liu et al., 2010). Char pro- searchers to control the emission of different gaseous pollutants in
duced by this process contains high carbon contents, numerous environment. It has been found that adsorption of pollutants on
oxygen-containing surface functionalities, dissolved minerals and biochar surface is mainly through physisorption (physically) pro-
porous structure just like char produced by pyrolysis (Chen et al., cess as it contains micro and macro pores which acts storage place
2017; Kang et al., 2012; Roland et al., 2014). HTC uses low energy for gas molecules (Mohd et al., 2013). Bae and Lee produced
due to mild operational conditions for controllable conversion of modified biochar through hydrothermal carbonization from the
watery wastes into useful products that can be used in various lignocellulosic waste of palm fruit to examine its adsorption ca-
applications such as, sequestration of CO2, water purification and pacity of CO2 at different temperatures. Initial analysis suggested
energy source (Cao et al., 2011; Elaigwu et al., 2014). that adsorption of CO2 on biochar surface was due to high surface
Pyrolysis is relatively old method for the production of biochar area, micropores and variety of functional groups (Bae and Lee,
as compared to above-discussed methods (Liu et al., 2015). It is an 2005). Similarly, biochar made of cotton stalk has also shown CO2
efficient, environmentally safe and low-cost method to get energy sequestration properties. Results of adsorption kinetics illustrated
from biomass in the form of biochar, bio-oil, and gas. In the process that adsorption of CO2 at low temperature (20
C) is due to the
of pyrolysis, biomass is thermally degraded to its constituents at a presence of micropores on biochar while, at high temperature
temperature of 200e1200
C in limited or no air/oxygen (Neves (120
C) adsorption is attributed to chemisorption due to the
et al., 2011). As a result of pyrolysis, released volatile compounds presence of N functionalities on biochar surface (Xiong et al., 2013).
from biomass condensate into bio-oil, while the remaining solid CO2 capture performance of some biomass-derived biochars under
material is converted to a more stable compound (biochar) (Laird different conditions are shown in Table 1.
et al., 2009; Lehmann et al., 2006). Pyrolysis of biomass is catego- From previous studies it is clear that for CO2 adsorption porous
rized into slow, fast and flash pyrolysis, depending on experimental structure of biochar is much important as adsorption mainly occur
conditions such as retention time, rate of heating and final tem- due to pores of accurate size (0.5e0.8 nm) present on biochar
perature. During slow pyrolysis, biomass is pyrolyzed at tempera- surface. However, if the diameter of pores increases, surface
ture ranging from 200 to 500
C for few minutes to hours with very complexation capacity of biochar reduces considerably. Moreover,
slow heating rate (1e10
C min1). The yield of biochar produced in the presence of natural functional sites or biochar basic surface also
slow pyrolysis process is higher as compared to other products plays a key role in adsorption process.
(bio-oil and synthesis gas) (Bamdad et al., 2018; Brownsort and
Masek, 2009; Tripathi et al., 2016). In fast pyrolysis, feedstock is 5.1.2. Physicochemical activation of carbons and their capture
pyrolyzed at a fast rate (10e200
C min1) for short time (1e10 s) at performance
temperature ranging from 800 to 1250
C which produces charred Carbonaceous materials having large number of micro and
material, bio-oil and some quantity of gas. The yield of biochar in macro pores are considered useful for CO2 adsorption (Patel et al.,
fast pyrolysis is less than other pyrolysis products (bio-oil and gas). 2012). The feedstock used for the synthesis of carbon-based
This type of pyrolysis usually adopted to produce high quantity of porous materials can be natural or synthetic polymers. These ma-
bio-oil as in this process yield of bio-oil is 60e75% (Laird et al., terials may or may not possess porous structure, high specific
2009; Suttibak et al., 2012). Flash pyrolysis is the advanced or surface area, and uniformity in structure, which are basic require-
modified form of fast pyrolysis. In flash pyrolysis heating of biomass rka and Jaroniec,
ment for a good adsorbent (Alabadi et al., 2015; Go
is done at high temperature (1000
C) for short time (few seconds) 2011; Wang et al., 2012). Activated porous carbons or activated
(Yu et al., 2007). Fast heating with short retention time results high carbons (ACs) is a class of carbonaceous materials that have been
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 9

Fig. 3. Thermo-chemical conversion of (a) cellulose, (b)hemicellulose and (c) lignin. Reprinted with permission from (Liu et al., 2015).

Table 1
Biochar performance as adsorbent for CO2.

Adsorbent Activation/Modification/ Working conditions Surface area (m2/ Adsorption capacity (mmol/ Ref.
Technique g) g)
Temperature Pressure
(
C) (bar)

SD 850 Thermal treatment 30 - 182.04 1.0795 Madzaki et al. (2016)

NSD 850 Monoethanolamine (MEA) 30 - 3.17 1.0182 Madzaki et al. (2016)
Perilla Thermal treatment 0 1 473.4 2.312 Sethupathi et al.
(2017)
Korean oak Thermal treatment 0 1 270.8 0.597 Sethupathi et al.
(2017)
SS-biochar Thermal treatment 25 - 10.12 0.413 Xu et al. (2016)
PM-biochar Thermal treatment 25 - 31.57 0.534 Xu et al. (2016)
WS-biochar Thermal treatment 25 - 20.20 0.781 Xu et al. (2016)
U-char 800 Thermal treatment 20 224 2.2595 Zhang et al. (2014b)
MP-200A Microwave pyrolysis 20 1 122 1.8182 Huang et al. (2015)
Eucalyptus wood H3PO4 þ Ammonia 30 1 - 3.22 Heidari et al. (2014)
Palm kernel char (PKC) Thermal treatment 30 4 24.50 5.58 Nasri et al. (2014)
Palm activated carbon CO2 30 4 167.08 7.32 Nasri et al. (2014)
(PAC)

used extensively for adsorption of CO2 from point sources at materials such as coal (Karacan et al., 2007). For the large scale
adequate temperature and pressure due to their tunable properties production of inexpensive ACs, use of agricultural waste biomass is
(Boyjoo et al., 2017). Use of ACs as adsorbent at large scale was first highly desirable as it is a renewable and cheap resource
started in gas masks during Second World War (Harry and Reinoso, (Kwiatkowski et al., 2017; Kwiatkowski and Broniek, 2012). The
2006). Since that time, the AC is being used in a large number of composition of feedstock plays a crucial role on physiochemical
fields such as wastewater treatment, gas purification, energy stor- properties of the produced ACs. Thus the selection of an appro-
age and as heterogeneous catalyst. Activated carbons can be pre- priate feedstock material prior to activated carbon production is
pared using waste biomass materials including agricultural, very important (Rashidi and Yusup, 2016). In addition, biomass
livestock, house waste, and also from synthetically produced containing heteroatoms such as O, S, P, and N tends to produce
organic polymers (Creamer and Gao, 2016; Herawan et al., 2013; hydrophilic activated carbons of basic nature with improved cata-
Machnikowski et al., 2012). lytic reactivity, resulting better adsorption of CO2 (Boyjoo et al.,
Moreover, ACs can also be prepared from naturally charcoal 2017; Harry and Reinoso, 2006). According to previous studies,
10 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

biomass-derived including corncob, lignin, chitosan, fungi, starch, the operation and installation cost and make the process more
and gelatin possess high specific surface area and better gas economical to produce activated carbons with well-defined porous
adsorption capacity (Alabadi et al., 2015). structure and enhanced surface area (Yaumi et al., 2017). Ello and
The adsorption capacity of ACs for CO2 is equivalent to other coworkers produced AC using coconut shell in the presence of CO2
porous materials like zeolites that are used for capturing CO2 as an activation agent via single stage activation process at a tem-
(Zhang et al., 2010). Suitable physiochemical properties like pore perature of 800
C. It was determined that use of CO2 as oxidant
volume, shape, surface functional groups and specific surface area increased the surface area up to 1327 m2 g1 and CO2 adsorption
of adsorbent can be controlled through the type of feedstock, capacity to 5.6 mmol/g at 0
C. Moreover, porosity and surface area
activating chemical, ratio of precursor and the activating chemical of ACs was increased considerably with prolong activation time
and reaction conditions (Alabadi et al., 2015; Nunell et al., 2012). In (Ello et al., 2013). Similarly, microporous ACs were developed by
addition, functional groups present on material's surface can also Gonzalez and coworkers, from waste olive stone along with almond
be controlled using different activation conditions (Lee and Park, shells as feedstocks and used CO2 as an activator in single step
2015). Two types of activation have been used by researchers i.e. activation process. The produced material showed the highest
physical activation and chemical activation (Rashidi and Yusup, adsorption performance at 0
C with CO2 adsorption capacity of
2016). 4.8 mmol/g (Gonz alez et al., 2013).
Balsamo with his colleagues developed activated carbon from
5.1.2.1. Physical activation. Production of ACs by means of physical blend of furfural with coal tar pitch in equal proportion and acti-
activation is usually a two-step procedure. In first step, the biomass vated through steam. In the synthesized material, suitable porous
or precursor is converted into pyrogenic carbon via heat treatment structure was developed for the adsorption of gaseous pollutants.
under controlled condition (Song et al., 2013). Then in second step, Moreover, the material showed basic nature, suitable for the
the pyrogenic carbon is physically activated at elevated tempera- capturing of acidic gases such as CO2 (Balsamo et al., 2013). Plaza
ture in the presence of oxidants like CO2, water vapor, O2, and other et al. produced ACs through one-step activation process from
gases (Arami-Niya et al., 2010; Aghdas Heidari et al., 2014a). During almond shell and olive stone at different temperatures with varied
initial step of physical activation, conversion of biomass into py- concentration of oxygen as an oxidant or activating agent. Fig. 5
rogenic carbon is performed at low temperature usually below shows CO2 adsorption isotherms of almond and olive stone bio-
800
C in the presence of inert gas to remove impurities and other char at different temperatures. At lower temperature use of oxygen
volatile. While the second step which is activation of produced as an oxidant creates inexpensive AC with narrow micropores
carbon, usually carried out at high-temperature range from 800 to (Plaza et al., 2014).
1000
C in the presence of oxidizing agents (steam, O2, and CO2)
(Budinova et al., 2006; Song et al., 2013).
5.1.2.2. Chemical activation. For the synthesis of chemically ACs,
In steam activation, lower size of activation molecules results
the precursors in raw form are first mixed with activating or
fast diffusion through porous network and conversion of micro-
dehydrating agent and then the mixture is subjected to activation
pores to mesopores and macropores (Alabadi et al., 2015; Rashidi
and carbonization process at the same time (Rashidi and Yusup,
and Yusup, 2016). Activation of carbonaceous materials with CO2
2016). Chemical activation can be performed via two methods,
is gaining attention because of its ability to produce ultra-
wet impregnation and solid-solid mixing (Yaumi et al., 2017). In wet
micropores suitable for adsorption of CO2. CO2 can be applied in
impregnation method, the raw biomass or feedstock is first mixed
both single step or two step activation techniques (Gonza lez et al.,
with the activator in appropriate ratio to prepare slurry. Then
2009; Yaumi et al., 2017).. SEM images of CO2 ACs can be seen in
prepared slurry is carbonized or activated under inert conditions to
Fig. 4. It is proved from recent findings that narrow micropores
get chemically activated carbon (Agrafioti et al., 2013). However, in
having a diameter of 0.55 nm offer sufficient space for the mole-
solid-solid mixing method, both raw precursor and activator are
cules of CO2 to adjust themselves in these pores (Wei et al., 2012). In
mixed in solid state. Then mixture is converted into activated car-
addition, activation with CO2 was found to be cheap and simple
bon with heat treatment process during which both processes
because the flow of CO2 can be controlled easily without the use of a
(carbonization and activation) take place simultaneously (Al Bahri
pump, as it is required in steam activation process (Katesa et al.,
et al., 2012). Acidic, alkaline and salt medium activation agents
2013). Whereas, use of CO2 also act as a purging gas which facili-
are mostly used for the activation of carbon materials. From pre-
tates the removal of water vapors and volatile substances, facili-
vious studies it is clear that zinc chloride (ZnCl2), potassium hy-
tating the conditions for pore formation (Yaumi et al., 2017).
droxide (KOH), nitric acid (HNO3) phosphoric acid (H3PO4),
Physical activation of biomass via single step can also be ach-
hydrogen peroxide (H2O2) and sodium hydroxide (NaOH) are most
ieved without separate carbonization of the precursor. This reduces
commonly usually activation agents (Singh et al., 2017a; Uçar et al.,

Fig. 4. SEM images of (a) CO2 activated dialdehyde cellulose (DAC-AC-CO2), (b) CO2
activated chitosan cross-linked cellulose (CLC-AC-CO2). reprinted with permission Fig. 5. CO2 adsorption on physically activated (a) almond shell (A-3-650-83), (b) olive
from (Xu et al., 2018). stone (O-3-650-110). reprinted with permission from (Plaza et al., 2014).
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 11

2009; Veksha et al., 2014). through mild dehydration of carbonaceous material. Whereas
In chemical activation, use of activating agent developed the stronger dehydration of carbonaceous materials occurs and porous
porous structure of end-product by preventing the production of structure with higher number of mesopores developed when high
undesired by-products such as tar and other volatile compounds amount of ZnCl2 is used (Aysu and Küçük, 2015). Synthesis of
(Sevilla and Fuertes, 2011). Pore size, specific surface area, textural chemically activated carbons using ZnCl2 as an activating agent is a
properties, and carbon yield of the activated material is dependent two-step process. In first step, feedstock is mixed or impregnated in
on the maxing ratio of feedstock/activating agent, carbonization ZnCl2 solution and then the impregnated precursor is carbonized
temperature, heating rate and activation time. ACs produced by and activated in the next step. Thus, activation with ZnCl2 is a time-
chemical activation have a very ultra-high specific surface area and consuming process. However, use of ZnCl2 for activation produces
can be more than 3000 m2 g1 (Deng et al., 2014; Haoran et al., activated carbons having high specific area. Carbon nanosheets
2012). Usually in chemical activation, the activation temperature prepared from coconut and activated with ZnCl2 attained a surface
is ranged between 400 and 800
C, with short retention or acti- area of 1847 m2g-1 upon carbonization at 900
C. This increase in
vating time making it economical technique. Moreover, the end surface area is attributed to complete conversion of feedstock into
product activated carbons also has high carbon contents (Mohamed activated carbon (Singh et al., 2017b; Sun et al., 2013).
et al., 2010). However; unlike physical activation, chemically acti- Recently many studies have shown the use of KOH for ACs
vated carbon materials need to be washed for the complete removal synthesize having enhanced gas adsorption capacity due to porous
of impurities and chemical residues from carbon structure (Lozano- structure development with high number of micropores (Deng
Castello et al., 2007; Rashidi and Yusup, 2016). As carbon dioxide is et al., 2014). Sivadas with his group produced nitrogen enriched
an acidic gas, activated carbons having basic surface functional carbons from the mixture of sucrose and urea, later activated with
groups should be used for its adsorption. By incorporating basic KOH results the formation of micropores structure. The surface area
functionalities on the surface of ACs, contact between activated was 2366 m2g-1 with adsorption capacity of 7.0 mmol/g at 0
C and
carbon and carbon dioxide can be enhanced through hydrogen 1 atm. Results suggest that the amount of KOH and urea used to
bonding, covalent bonding and dipole-dipole interactions (Creamer synthesize ACs determine the surface area, porosity and nitrogen
and Gao, 2016; G. et al., 2009). It has been found that treating contents in the end product (Sivadas et al., 2016). Biomass activa-
carbons at high temperature with nitrogenous compounds tends to tion with KOH during fast pyrolysis not only produce porous
produce basic activated carbons rich in nitrogenous functional structure but also enhances the number of nitrogen functionalities
groups. By treating activated carbons at a temperature between of ACs (Shahkarami et al., 2015). It was observed that activated
800 and 1000
C removed the oxygen containing acidic functional carbons produced by KOH activation along with nitrogen source
groups (Shafeeyan et al., 2010). Isosteric heat of activated carbons show high adsorption of CO2 even if adsorption temperature is
can provide information about the mechanism of CO2 adsorption increased as shown in Fig. 7. Deng et al. used pine nut-shell to
that may be physisorption and chemisorption. Fig. 6 shows the prepare ACs for the adsorption of CO2 with different Carbon/KOH
adsorption heat of activated carbons produced from different ratios at different activation temperature and pressure. Results
biomass sources and activated using KOH. Low isosteric heat shows showed that porosity of ACs was directly influenced by the ratio of
physical adsorption of CO2 on activated carbon surface due to the C/KOH as well as activation temperature. The highest CO2 adsorp-
presence of weak bonding (Zhou et al., 2018). tion recorded at 1 bar was 7.7 mmol/g and 5.0 mmol/g at 273 k and
Studies have shown that use of zinc chloride (ZnCl2) as an 298 k, respectively (Deng et al., 2014). The Adsorption capacity of
activator produces porous structure activated carbons with both ACs are tabulated in Table 2.
micro and mesopores. Moreover, the use of zinc chloride also re- Singh et al. used Arundo donax as a carbon source and solid KOH
duces the formation of tar during the carbonization process and as an activating agent to produce chemically active carbons via one-
overall helps in reducing pyrolysis temperature (Shang et al., 2015). pot process at 600
C. They examined that structure and specific
Mixing ratio of zinc chloride with the feedstock material also in- surface area of ACs influenced through changing the amount of
fluences the porous structure of end product. For example, when activating agent and precursor. The highest surface area (1122 m2g-
1
ZnCl2 is used in low amount more micropores are developed ) and micropore volume (0.50 cm3g-1) were developed by acti-
vated carbons having 2 wt ratio of KOH/Arundo donax. The syn-
thesized material has also showed high CO2 adsorption ability at
273 k and 1 bar i.e. 6.3 mmol/g. However, when the pressure was
increased to 30 bar the capacity of CO2 capture was enhanced to
15.4 mmol/g (Singh et al., 2017a). Despite good activation proper-
ties, use of KOH also have some limitations. As KOH is a strong
dehydrating agent, it causes corrosion of the instruments. The
corrosivity increases when activation temperature is increased,
making it unfavorable for large scale production and industrial
application (Wang et al., 2018).
In addition, KOH activated carbons when washed, release
harmful residues into the environment causes serious environ-
mental pollution. To overcome these issues, researchers begin to
use chemical activators which have environment-friendly and less
corrosive properties (Gurten et al., 2012). Recently, Yue et al. used
K2CO3 as an activating agent for the synthesis of coconut shell
derived ACs along with urea as a nitrogen source. Results showed
better CO2 adsorption capacity of the synthesized carbon materials.
Maximum CO2 uptake recorded at 1 bar and temperature 25
C was
3.17 mmol/g and at 0
C was 5.12 mmol/g. Nitrogenous functional
Fig. 6. Heat of CO2 adsorption of different activated carbons. reprinted with permis- groups and micropores with narrow structure played a key role in
sion from (Zhou et al., 2018). CO2 adsorption on ACs surface. Meanwhile, the synthesized
12 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

Fig. 7. Adsorption of CO2 on activated carbons at different temperatures. reprinted with permission from (Changming Zhang et al., 2016b).

Table 2
CO2 capture by activated carbon sorbents.

Adsorbent Activation/Modification/Technique Working conditions Surface area Adsorption capacity Ref.

(m2/g) (mmol/g)
Temperature (
C) Pressure (bar)

uGil-900 Pre-heat treatment þ KOH activation 25 54 4200 35 Jalilov et al. (2017)

IT-AC50 Ice templating þ KOH activation 25 10 1049 16.12 Roberts et al. (2017)
MAC-E-7 KOH activation 0 1 1647 6.0 Hao et al. (2017)
AMB3-500 ZnCl2 activation 0 30 3298 30.2 Singh et al. (2017b)
AC-DEA Diethanolamine impregnation þ KOH activation 50 1 82.10 5.63 Gholidoust et al. (2017)
AC-NH-800 H3PO4 activation þ NH3 modification 30 1 2079 3.22 Heidari et al. (2014)
CMC-3 Hydrothermal treatment þ KOH activation 25 1 1405 5.22 Boyjoo et al. (2017)
KLB2 KOH activation 0 1 1122 6.3 Singh et al. (2017a)
KLB2 KOH activation 0 30 1122 15.4 Singh et al. (2017a)
NAC-1.5-600 KOH activation 2 1 1317 5.39 Sethia and Sayari (2015)
LSC-450-2 NaNH2 0 1 2053 5.62 Rao et al. (2018)
LSC-500-1 NaNH2 25 1 1113 3.88 Rao et al. (2018)
NGC-650-4 K2CO3 activation 25 1 1824 3.92 Yue et al. (2018)
NGC-650-4 K2CO3 activation 0 1 1824 6.23 Yue et al. (2018)
NHC-650-1 H2O2 pretreatment þ ammoxidation þ KOH activation 25 1 1593 4.47 Guo et al. (2016)
NHC-700-1 H2O2 pretreatment þ ammoxidation þ KOH activation 0 1 2234 6.79 Guo et al. (2016)

material possess good CO2/N2 selectivity, with fast adsorption ki- environmental applications (Li and Zeng, 2017). Carbon nano-
netics and stable reusability properties (Yue et al., 2018b). materials included carbon nanotube, carbon nanofilms, and gra-
Heidari et al. synthesized ACs using eucalyptus wood biomass phene. Carbon based materials can be produced in bulk amount
and H3PO4 as an activating agent in the presence of ammonia so- through different processes such as self-assembly, polymerization,
lution at different temperatures (400 and 800
C). Adsorption of sol-gel method and heat treatment (Creamer and Gao, 2016; Goel
CO2 was observed through volumetric method at a temperature et al., 2015; Perreault et al., 2015).
ranged 288 k e 348 k and variable pressure (0e16 bar). CO2 Since the innovation of graphene in 2004 by Geim and Novo-
adsorption capacity of ammonia modified and K2CO3 AC at 1 bar selov, it has become one of the most studied nanomaterial among
and 303 k temperature was 3.22 mmol/g higher than original car- carbon-based nanomaterials. It has been widely used in different
bon material. It was found that textural properties of activated scientific and engineering fields because of its two-dimensional,
material were enhanced with the use of ammonia and K2CO3. hexagonal packed lattice structure similar like honeycomb with
Physisorption was the principal mechanism of CO2 adsorption on single carbon layer that gives it exceptional physical, chemical,
activated carbon surface (Ava Heidari et al., 2014b). Briefly, electrical, thermal and mechanical properties (Li and Zeng, 2017;
adsorption capacity of ACs materials depends on their precursor, Low et al., 2015; Nova 
cek et al., 2017). Fabrication of graphene
activating agents and experimental conditions used during their has been done via different methods such as electrochemical
production process. Thus, before the preparation and application of exfoliation of graphite, mechanical cleavage, chemical vapor
ACs for the CO2 adsorption these things should be kept in mind. deposition and through chemical exfoliation of graphene oxide
(Toh et al., 2014). In graphene, each single carbon atom is sp2-hy-
bridized and makes a single layer sheet, which is exposed to sur-
5.1.3. Graphene-based adsorbents, their production and CO2 rounding environment from both sides. These properties give
capture performance graphene a very high specific surface area with a value of 2630
Nanomaterials have been used in numerous fields such as, gas m2g1 (Peigney et al., 2001). Hexagonal lattice of sp2 hybridized pure
sensing, pollution sensing, energy production/storage, water carbon atom bonded with covalent bond along with graphene ox-
treatment and purification. All this is because of their distinctive ide and reduced graphene oxide can be seen in Fig. 8. It was found
structural properties and unique nanoscale dimensions which are that the structure of graphite is naturally held by graphene, that
less than 10 nm (Lu et al., 2014; Qu et al., 2013). Carbon-based acts as a main component of graphite structure due to the presence
nanomaterials are hierarchical porous materials containing both of attractive forces between graphene sheets with an interlayer
micropores and macropores with large surface area. These can be space of 3.34 Å (Perreault et al., 2015). Graphene-based materials
further modified to enhance their performance for effective
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 13

Fig. 8. Surface structure of (a) graphene, (b) graphene oxide and (c) reduced graphene oxide (Suvarnaphaet and Pechprasarn, 2017).

such as graphene oxide and reduced graphene oxide have shown graphite, its particle size, method of oxidation and oxidation pro-
excellent structural properties that are suitable for capturing, sep- cess time (Acik et al., 2011). Functionalization of graphene oxide has
aration and storage of gases (Pachfule et al., 2016; Russo et al., gained attention in order to get excellent separation and storage of
2013). These materials show superb thermal conductivity with a CO2 from other gases present in atmosphere and different in-
value up to 5000 W m1 K1 and mechanical strength of about dustries (Bhanja et al., 2016). In order to get selective and high
1 TPa (Young's modulus) (Chowdhury and Balasubramanian, adsorption capacity of CO2 on graphene-based adsorbents, inser-
2016a). tion of heteroatoms such as N, B, S and Al in material's structure is
Graphene based nanomaterials have been found efficient for fast required. Addition of heteroatoms on graphene structure changes
and high adsorption of CO2 from flue gas due to their highly porous its inert sp2 hybridized state into the active state as a result inter-
and layered structure which eventually gives them high specific action between CO2 and graphene surface take place during
surface area (Jiang and Fan, 2014). In addition, these materials have adsorption process (Li et al., 2017). Meanwhile, it also altered gra-
high mechanical strength and remain stable after multiple expo- phene electrical properties making graphene-based materials
sures even to humid and hot experimental conditions (Chowdhury favorable for application in multiple fields. Methods and types of
and Balasubramanian, 2016b; Yan et al., 2015). Graphene oxide and chemicals used for functionalization mainly depend on the purpose
reduced graphene oxide are chemically modified forms of graphene of material application (Arthi G and BD, 2015).
nanomaterial (Bhanja et al., 2016; Chen et al., 2016; Liu et al., 2017). Li group studied the adsorption mechanism of CO2 on nitrogen
Graphene oxide, an important graphene congener can be produced and sulfur-doped graphene-based materials using ab initio ther-
from graphite powder without much efforts, having nanoporous modynamics and density functional theories. They evaluated that
sheet-like structure and contains a large number of carboxyl, hy- graphene structure was defected with N, S doping created a change
droxyl, carbonyl and epoxy surface functional groups (Bhanja et al., in graphene's conjugated p bond which enhanced the adsorption
2016; Pandi and Viswanathan, 2016; Shen et al., 2015). Since the capacity of CO2 under mild environment. It was found that charge
invention of graphene oxide by Brodie first time in 1859, Stau- delivery channels were produced due to NeS covalence, creating
denmaier, Hummers, and Hofeman later modified the original more surface available electrons for CO2 molecule (Li et al., 2017).
method for the enhanced synthesis of GO with 0.625 nm interlayer Nitrogen and boron co-doped three-dimensional graphene aerogel
spacing and also 6-fold stacking symmetry (Acik et al., 2011; Xin material BN-GAs was prepared by Liu et al. through solvothermal
et al., 2015a). Modified Hummers' method is the mostly used method for the adsorption of CO2 and oil. Smooth surface
method for the synthesis of graphene oxide. In this method, strong morphology of unmodified (GA) and rough, porous morphology of
oxidizing compounds (sulfuric acid and potassium permanganate) modified graphene aerogel (BN-GA) can be seen in Fig. 9 (a, b, c and
are used for complete oxidation of graphite (Esmaeili and Entezari, d), respectively. Fig. 9 (e, f) shows CO2 adsorption isotherm of GA
2014). and BN-GAs at 0
C and 25
C, respectively, in which highest value
Chemical reactivity of graphene oxide is high as compared to of CO2 was adsorbed by BN-GA1-1 (Liu et al., 2017). Bhanja et al.
original graphene because of the presence of more oxygen- prepared graphene oxide functionalized with imine group to
containing reactive functional groups on its surface. This makes evaluate its CO2 adsorption capacity. Modified hummers method
graphene oxide a good material for further chemical modification was used for the synthesis of graphene oxide which further
(Nasrollahzadeh et al., 2016). Nova cek and Co. tuned graphene modified with 3-aminopropyltriethoxysilane and 2,6-diformyl-4-
oxide through multiple oxidations for the adsorption of CO2 and methylphenol. Results showed that prepared material adsorbed
potentially toxic elements (PTEs). Different oxidation methods i.e 2.10 mmol/g and 8.10 mmol/g CO2 at 298 and 273 K temperature,
Hummers, Staudenmaier, and Hofmann methods were used to respectively, and pressure up to 3 bar (Bhanja et al., 2016).
compare their oxidation efficiency. Results showed that oxygen- Chowdhury & Balasubramanian developed holey graphene
containing functional groups especially carboxylic group were framework (HGF) using graphene oxide and HNO3 through wet
greatly enhanced by reoxidation during the second and third chemical method. The prepared material consisted of a 3D porous
oxidation step. Moreover, results also showed a 15 wt% increase in structure with tunable pore arrangement and changeable pore
carboxylic groups on graphene oxide surface reoxidized by Hum- density properties. It was reported that prepared HGF exhibited
mers' method as compared to the other two methods (Nova cek enhanced porous structure. Moreover, HGF hydrophobic nature
et al., 2017). Presence of functional groups on the surface of gra- making it a good candidate for adsorption of CO2 released during
phene oxide usually depends on oxidizing agents, nature of combustion process (Chowdhury and Balasubramanian, 2016c).
14 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409

Figure 9. (aeb) SEM images of GA, (ced) SEM images of BN-GA2-1, (eef) CO2 adsorption of GA and BN-GAs at 0
C and 25
C respectively. reprinted with permission from (Liu et al.,
2017).

CO2 capturing capacities of graphene oxide and graphene oxide aerogel was alo noted after cyclic adsorption and desorption
composites along their working conditions are mentioned in (Alhwaige et al., 2013).
Table 3. Alhwaige et al. conducted research on CO2 adsorption Xin et al. developed a combined membrane made of graphene
through a hybrid aerogel sorbent prepared from chitosan and oxide functionalized with amino acid and sulfonated polymer
graphene oxide using freeze-dryer. From the experiment, it was matrix to test selective adsorption of CO2 from the mixture of gases.
observed that after increasing the amount of GO in composite The experiment revealed that the presence of graphene oxide
material its specific surface area was enhanced to 415 m2g-1 from nanosheet increased CO2 diffusivity. Furthermore, amino acid
153 m2g-1. Maximum adsorption of CO2 (4.15 mol kg1) was noticed functionalization improved reactivity and solubility selectivity.
when 20 wt% GO was used. Furthermore, good stability of hybrid Highest selectivity was observed in membrane GO-DA-Cys which

Table 3
Graphene based materials as adsorbents for CO2.

Adsorbent Activation/Modification/Technique Working conditions Surface area Adsorption capacity Ref.

(m2/g) (mmol/g)
Temperature (
C) Pressure (bar)

HU-GO-3x Multiple oxidation 30 9 - 3.54 Nova

cek et al. (2017)
GPN-800 Thermal activation 0 1 484 2.98 (Chowdhury and Balasubramanian, 2016a)
BN-GA1-1 Nitrogen þ boron co-doping 25 1 169.9 2.6 Liu et al. (2017)
EFBG-1000 Thermal activation 25 1 355.40 2.43 Parshetti et al. (2014)
IFGO - 0 2 190 8.10 Bhanja et al. (2016)
IFGO - 25 2 190 2.14 Bhanja et al. (2016)
CS-GO-20% CS aerogel modification 25 - 412 4.15 Alhwaige et al. (2013)
RGO650/ZIF-8 - 30 35 720 17 Kim et al. (2016)
a-GDC-2 Controlled KOH activation 25 20 3240 21.1 Ganesan and Shaijumon (2016)
NG7 N functionalized 25 1 979.6 2.7 Christian Kemp et al. (2013)
NG7 N functionalized 0 1 979.6 5.8 Christian Kemp et al. (2013)
a-NDC-6 N-doping 25 1 - 4.3 Chandra et al. (2012)
 R. Ahmed et al. / Journal of Cleaner Production 242 (2020) 118409 15

was modified with 8% of dopamine and cysteine as compared to the of carbonaceous adsorbents, there are still some challenges for
original membrane (Xin et al., 2015b). Similarly, Y. Cao and Co. commercial scale application of carbonaceous adsorbents. These
fabricated a composite of zirconium metal-organic framework challenges included fast kinetics, stability to other components of
(UiO-66) and graphene oxide to compare its CO2 adsorption ca- flue gas (NOx and SOx) for long time period, low regeneration en-
pacity with original UiO-66. Both materials were analyzed by ergy with high reusability and production from inexpensive sour-
different characterization techniques and multiple adsorptions and ces. In order to obtain optimum results from CCS technology, it is
desorption cycles. The adsorption capacity of graphene oxide crucial to understand the physical and chemical changes occurred
composite was determined from pore volume and surface area during adsorption of CO2 on material surface. In-addition to
results obtained after BET analysis. Findings revealed that com- capturing of CO2 from industries and point sources, Direct Air
posite material adsorbed more CO2 (3.37 mmol1) than UiO-66 and Capture (DAC) technique should also be considered with hybrid
some other zeolites and activated carbons (Cao et al., 2015). materials having the capability of capturing CO2 through low con-
Chowdhury and coworkers fabricated a nanocomposite of titanium centration medium to help in reducing global warming. For sus-
dioxide with graphene oxide using different mass ratios and tainable environment, such CCSU technologies should be
determined its selective CO2 capturing capacity. Adsorption results developed and used that have the capability of reusing industrial
suggested that prepared TiO2/GO nanocomposite showed a high emissions. Incentives should be provided to industries using carbon
CO2 selective adsorption over N2 even at low temperature. This capture, storage and utilization (CCSU) technology for decreasing
high adsorption may be due to interactive effect of TiO2 nano- CO2 and converting it into renewable energy/fuel source such as
particles and graphene oxide sheets with enhanced composite ethanol, bio-fuel. Moreover, use of biofuel and other renewable
porosity making it a favorable material for adsorption of CO2 from energy resources as an alternative of fossil fuel can help to meet the
power plants exhaust (Chowdhury et al., 2015). ever-increasing energy demand without negative impact on
environment.
6. Conclusions and future recommendations
Acknowledgment:
Excessive emission of CO2 from anthropogenic sources has
caused a rise in global temperature and created an imbalance in The authors acknowledge the support from the National Natural
earth's atmosphere. This alarming situation has attracted scientist Science Foundation of China (NO. 41173032) and Key Program for
to develop technologies for the sequestration or removal of CO2 Science and Technology Development of Anhui Province (No.
from the atmosphere. In order to sequester or capture the excessive 1804b06020358). We acknowledge editors and reviewers for pol-
amount of greenhouse gases especially CO2, various technologies ishing the language of the paper and for in-depth discussion.
have been developed in CCS technique including pre-combustion,
oxy-fuel combustion, and post-combustion along with different References
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