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Recent Trends in the Development of Adsorption Technologies for Carbon Dioxide

Capture: A Brief Literature and Patent Reviews (2014-2018)

Farihahusnah Hussin, Mohamed Kheireddine Aroua

PII: S0959-6526(19)34577-9
DOI: https://doi.org/10.1016/j.jclepro.2019.119707
Reference: JCLP 119707

To appear in: Journal of Cleaner Production

Received Date: 03 August 2019

Accepted Date: 12 December 2019

Please cite this article as: Farihahusnah Hussin, Mohamed Kheireddine Aroua, Recent Trends in
the Development of Adsorption Technologies for Carbon Dioxide Capture: A Brief Literature and
Patent Reviews (2014-2018), Journal of Cleaner Production (2019), https://doi.org/10.1016/j.jclepro.
2019.119707

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© 2019 Published by Elsevier.

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Recent Trends in the Development of Adsorption Technologies for Carbon

Dioxide Capture: A Brief Literature and Patent Reviews (2014-2018)

Farihahusnah Hussin [1]*, Mohamed Kheireddine Aroua [1, 2]

[1] Research Centre for Carbon Dioxide Capture and Utilisation (CCDCU), School of Science

and Technology, Sunway University, No. 5 Jalan Universiti, Bandar Sunway, 47500, Petaling

Jaya, Selangor, Malaysia

[2] Department of Engineering, Lancaster University, Lancaster, LA1 4YW, UK

*Corresponding author email: [email protected]

Abstract

According to a recent report published by the United Nations in 2018, the increase in

global temperature is possible to hit the 1.5°C mark (the limit at which the detrimental impacts

of climate change will be the most significant) between the year 2032 and 2050 due to the

cumulative CO2 emissions within the atmosphere. Therefore, it is crucial to tackle global

warming because of its serious repercussions such as extreme changes in global weather, which

can significantly impact human health and ecosystem. Global warming is caused by the

emissions of greenhouse gases; therefore, many countries have established laws and policies

to lessen the emissions of greenhouse gases. This study highlights the recently published

articles and patents on CO2 capture technologies through adsorption process from the year 2014

to 2018. Various types of adsorbent that can be potentially used to capture CO2 are discussed.

The published patents were obtained from the Derwent World Patents Index and it was found

that over 500 patents have been published on the diverse categories of adsorbents which can

be used to capture CO2. The top five countries in the world with patents for CO2 capture

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technology via adsorption are China, United States, World Intellectual Property Organisation,

Japan and Korea. This study not only provides a summary of the recent innovations in this area,

but also shows relevant information and technologies, which will benefit a wide range of

readers including academics, researchers and industry professionals. In addition, it also

highlights the patents with current innovation technology, application of CO2 adsorption

process in a real scale, patent applications filed in the past years in this field and knowledge

gained from these patents which can be a guideline to develop various novel types of adsorbent

and invent advanced technology in future.

Keywords: Carbon dioxide capture; Post-combustion; Adsorption; Adsorbents; Patents

1. Introduction

1.1 Status of global CO2 emissions

The increase of greenhouse gases (GHG) emissions into the atmosphere leads to global

warming, which is now one of the main environmental concerns (Kaithwas et al. 2012). Global

warming is also referred to as climate change because it leads to changes in precipitation

patterns and other environmental changes (Brennan and Grandison, 2012). Global warming

leads to coastal erosion, increases the growing season in some regions, increase in temperatures

(and consequently melting of glaciers and ice sheets, and the rise of sea levels), extreme

changes in global weather and climate patterns (e.g., floods, droughts, typhoons, and cyclones)

as well as ozone depletion (Murty, 1998; Raveendranathan, 2018). Some of these changes are

already occurring in most countries. Based on statistical data published by the World Health

Organisation (WHO), it is predicted that around 250,000 additional deaths per year will occur

from 2030 to 2050 because of climate-related malnutrition, malaria, diarrhoea, and extreme

heat exposure (WHO, 2018).

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The steady increase in atmospheric GHG concentration is the biggest critical factor

leading to global warming. Since the dawn of industrialisation, the significant release of CO2

emission into the atmosphere by anthropogenic activities has been a major contributor to the

greenhouse effect and is now a major environmental problem that needs to be addressed in the

world today. However, other gases such as methane (CH4), nitrous oxide (N2O), ozone-

depleting substances (ODSs) including fluorinated gases are also contributing to climate

change (Checa-Garcia et al. 2016; Montzka et al. 2011). In addition, 33,444 million tonnes of

CO₂ emissions were released worldwide in 2017, as reported by The British Petroleum

Company (BP) statistical review on world energy (BP, 2018). Based on the International

Energy Agency (IEA) report, global carbon releases due to energy consumption hit a new

record in 2017 (with an increase of 1.4%) after a relatively stagnant three years growth

(OECD/IEA, 2017). The amount of CO2 concentration in the atmosphere has remained in the

range of 172 to 300 parts per million (ppm), whereby the value has been lowered over the past

few years and never higher than 300 ppm. However, in December 2018, the atmospheric CO2

concentration reached up to 409.50 ppm (NOAA-ESRL, 2018). The safety limit is estimated

to be 350 ppm for an atmospheric carbon dioxide. The concentration of carbon dioxide has

been increasing gradually, higher than 350 ppm since the beginning of 1988 (Keeling curve,

2015). Human activities, including burning fossil fuels for power generation and transportation,

as well as deforestation for agriculture purposes are the critical factors that lead to significant

CO2 emissions (Reddy, 2014).

As a potential technology to mitigate CO2 emissions, carbon capture and storage (CCS)

is gaining considerable attention from scientists and researchers (Hester and Harrison, 2010).

CCS is conceptually a simple approach where it involves capturing, transporting, and storing

CO2. However, much effort is needed to study, develop, and implement this technology in

industrial settings to cut the operating cost and energy penalty of this technology (Bains et al.,

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2017; CCS, 2017). Various CCS techniques have been developed such as post-combustion,

pre-combustion capture, oxyfuel, and chemical looping processes (Xu and Hedin, 2014). Post-

combustion separation processes include absorption, adsorption, membrane, cryogenic, and

micro algal bio-fixation (Olajire, 2018a, 2018b). Among various types of post-combustion

separation methods, the adsorption process is preferable due to its low-energy requirement, low

cost of adsorbent material, cost-effective process technology and high CO2 adsorption capacity

(Olajire, 2018a, 2018b; Ben-Mansour et al., 2016). These advantages have driven further in-

depth research regarding the use of adsorption process technology in capturing CO2.

Patent filings are typically used to protect new inventions or innovative products which

have high technological and economic values. Patent is a connection between successful

innovative activities and advancement in research, development and commercialisation (pilot

scale/industrial scale application). Companies, universities and research institutes usually file

patents to protect their intellectual assets which have high technological and economic values.

Patents provide a detailed and complete view regarding the context of current technology as

well as the condition of the art and development possibilities for researchers and industrial

player by providing policymakers and analysts with a rich source of data to determine the

efficacy of technology and/or innovation (Shubbak et al., 2019). However, less data regarding

the advanced technology, product innovation and the use of inventions in a real scale can be

found. In regard to this matter, the innovation study enables new markets to be perceived

according to the adoption and dissemination of novel inventions; thus portraying as the most

favourable field for economic investments. (Amato and Beolchini, 2018). At present, there is

a lack of review on recently published patents on CO2 capture technology, primarily focusing

on adsorption method. Quintella et al. (2011) presented a summary of patent applications on

CO2 capture technologies, with an emphasis on absorption, adsorption, membrane, cryogenic,

enzymatic, and hybrid technologies. Li et al. (2013) also presented the current status of patents

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related to CO2 capture with an emphasis on solvent, sorbent, and membranes. Recently, Luis

Míguez et al. (2018) reported a review of patents on CO2 capture technologies (absorption and

adsorption processes), including information on assigned nationality, country, company and

their patents.

So far, there is no report on patent innovations with an emphasis on the adsorption

process technology for CO2 capture. Therefore, the current study aims to fill this gap between

integrating the scientific literature with a deep study of the available patents and to collect

information from lab scale technology with a current technology from patent on large

scale/industrial scale. It is vital to produce novel, highly effective adsorbent material to attain

techno-economic systems for adsorption technology. Despite having efforts and promising

outcomes in a lab-scale, a huge gap is still emerged between the industry and laboratory. In

addition, this is a major research gap in this important and emerging technology for CO2

capture. This review directly addresses the CO2 capture technology needed to support the

United Nations (UN) Sustainable Development Goal under climate action (SDG 13) and SDG

12 (sustainable consumption and production/waste management) (SDGs, 2019). This review

also seeks to provide knowledge and patent analysis of adsorption technology with emphasis

on new researcher that involves in this field. This review is therefore written to summarise the

recently published patents for various adsorbents used in 2014 and 2018 for CO2 capture. This

review also reports new insights based on recently published articles regarding innovative

adsorption-based technology for commercialisation. The published patents are downloaded

from an international patent database from the Derwent World Patents Index. This paper is

organised as follows: Section 1 presents a summary of the recent status of global CO2

emissions, including history, recent CO2 capture technologies issues and techno-economic

impact. Section 2 describes the methodology used to search patent literature. Section 3

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discusses the recently published patents and articles for different types of adsorbents. Lastly,

Section 4 presents the directions for future work on CO2 adsorption.

1.2 History and latest issues on reducing CO2 emissions

At the 1988 World Conference on the Changing Atmosphere in Toronto, international

efforts to combat climate change began in the 1980s. This conference was the first international

conference focused on policy development and climate change solutions (Cohen and Waddell,

2009; Quintella et al. 2011). Next, The United Nations Framework Convention on Climate

Change (UNFCCC) organised the Rio Earth Summit (IUC, 2000; Morna and Glenwright,

2018). The Kyoto Protocol (KP) was then set up at the third meeting of the Conference of the

Parties (COP) on 11 December 1997. KP’s main objective was to decrease the overall of GHG

emissions level by at least 5% from 1990 to 2012 (Oberthür and Ott, 1999). Subsequently, in

2015, the Paris Agreement was an agreement on the threat of climate change, where a new

benchmark was established to keep the average temperature increase strictly lower than 2°C

and to maintain the global temperature rise to below 1.5°C (Figure 1). Under the Convention,

all countries are committed to reduce CO2 emissions and are willing to set targets to support

CO2 emissions (UNFCCC, 2018).

Figure 1 Key objective of the Paris Agreement (adapted from The Intergovernmental Panel
on Climate Change (IPCC) (IPCC, 2013; Meinshausen, 2015)).

The Paris Agreement was held on 12 December 2015 in conjunction with the 21st

Conference of the Parties (COP 21) in Paris and it was the first convention to combat climate

change by 2020. The agreement to combat climate change was signed by around 195

representative countries under the UNFCCC. Following the 2015 COP 21, the United Nations

asked the Intergovernmental Panel on Climate Change (IPCC) to provide a comprehensive

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report by 2018 analysing the effect of global warming when the global temperature rise exceeds

1.5oC above the agreed pre-industrial level of global temperature rise and global greenhouse

gas emission pathways (UN, 2018). At the IPCC’s 43rd session in April 2016, the IPCC official

agreed and approved the preparation of a sixth assessment report (AR6), consisting of three

working contributions under the Paris Agreement (IPCC, 2018a). Many developing countries

also support reducing GHG emissions to help ensure that global temperature is below 1.5°C

above pre-industrial levels. Recently, in Incheon, South Korea, on Monday 8th October 2018 -

The UN Intergovernmental Panel on Climate Change (IPCC) issued a warning to keep the

global temperature rise to a maximum of 1.5 degrees Celsius. Furthermore, by 2030 carbon

pollution would have to be reduced by 45% and reach "net zero" after 2050. This means that

by removing CO2 from the air, any remaining emissions should be balanced (IPCC, 2018b).

The Paris Agreement in 2015 and the POST-2020 framework, together with all

developed and developing countries in the world, were announced to address environmental

issues, particularly global warming caused by rising levels of GHG emissions. Members of the

UNFCC (around 195 countries) have submitted their “intended nationally determined

contributions” reports (INDCs) to establish the CO2 emissions targets and they are strongly

committed to reducing GHG emissions by 2030 (OECD, 2015). For instance, the European

Union (EU) set a CO2 emissions reduction target of 40% by 2030, the United States set national

CO2 emission reduction target of 26–28% by 2025. China has set a carbon emissions reduction

target (CERT) of 60–65% by 2030 whereas South Korea has set a national CO2 emissions

reduction target of 37% by 2030. Japan has set a national CERT of 26% by 2030 while

Malaysia has set to reduce GHG emissions at the national level by 45% by 2030 (INDC, 2018).

Other countries that are not listed in this review have also submitted their INDC reports to the

UNFCCC. Based on the INDC reports, monitoring and reducing GHG emissions (particularly

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CO2) are crucial in the future development of the world economy and society (Gu and Wang,

2018).

1.3 Carbon capture and storage (CCS)

As previously stated, CCS is a vital technology for managing GHG emissions and

fighting global warming. Figure 2 shows the CO2 capture and storage frameworks. Figure 3

shows the process flow of three types of CO2 capture technologies.

Figure 2 Summary of CO2 capture and storage. (Reproduced from Lee and Park, 2015,
Copyright 2005, with permission from Elsevier)

Figure 3 Flowchart with three types of CO2 capture technologies. (Reproduced from Gibbins
and Chalmers, 2008, Copyright 2008, with permission from Elsevier)

According to a report published by the IEA, CCS is able to reduce CO2 emissions by

19% by 2050. The exclusion of CCS technology will result in an increase of 70% for CO2

mitigation technologies in order to fight climate change (IEA, 2010). According to The Global

Carbon Capture and Storage Institute, 37 large-scale CCS projects have been installed globally,

where 17 projects are currently on-going, 4 projects are under construction, 11 projects are in

the early phase of development, and 5 CCS projects are currently under advanced development,

as shown in Table 1. CCS technologies have been used in a wide range of industries and the

first CCS project (natural gas processing facilities) has been in operation since 1972 in the Val

Verde area of Texas (CCS, 2017).

Table 1 Global CCS projects. (Adapted from the Global Carbon Capture and Storage
Institute project database (CCS, 2017)).

Numerous international and intergovernmental agencies, including the Global Carbon

Capture and Storage Institute, IEA, IPCC, and U.S. Energy Information Administration (EIA),

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described CCS technology’s vital role and recommended its use for sustainable development.

However, there are two factors which needed to be considered before these technologies are

used on a large scale. First, low-cost facilities are required for advanced CCS technology and

second, regulatory and policy framework needs to be set in place in order to provide financial

stability, which will instil confidence in investors to undertake CCS projects (Durmaz, 2018;

Leung et al. 2014). Many studies have been published over the past few decades concerning

innovative technologies on the large scale application for CO2 capture and storage. Table 2

describes summary of the published articles on CCS technologies in many industrial

applications such as power plant generation (Mansouri Majoumerd and Assadi, 2014; Dieter

et al., 2014; Vega et al. 2014; Stanger et al., 2015; Molina and Bouallou, 2015; Roussanaly et

al., 2016; Sandhu et al. 2016; Hu and Zhai, 2017; Petrescu et al., 2017; Shijian et al., 2018;

Gładysz et al., 2018; Giuliano et al., 2018 ), biogas plant (García-Gutiérrez et al., 2016; He et

al., 2017; Shen et al., 2018; Cau et al., 2018; He et al., 2018; Santori et al., 2018; Cloete et al.,

2018), natural gas processing (Cormos, 2015), hydrogen production, cement plant (Bjerge and

Brevik, 2014; Zhou et al. 2016; Roussanaly et al., 2017; Nwaoha et al., 2018; Dubois and

Thomas, 2018), steel industry (Oda and Akimoto, 2017; Chung et al. 2018), oil refining, and

pulp and paper industry (Garðarsdóttir et al. 2018). It can be seen from Table 2 that most of the

studies to date are focused on the application of CCS technologies for power plant generation.

Table 2 Summary of the literature on the application of CCS technologies in various

industrial applications.

1.4 Post-combustion CO2 capture

Post-combustion CO2 capture is the simplest technology that can be used to capture

existing emission sources among the currently available CCS technologies. Several

technologies that are applied in post-combustion CO2 capture are summed up in Table 3. This

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table describes the advantages and challenges of effective separation approaches to lessen the

emissions of CO2. Figure 4 shows the classification of different approaches to CO2 capture

post-combustion.

Table 3 Highlights the advantages and challenges of the most promising separation methods
to reduce CO2 emissions

Figure 4 Various approaches to CO2 capture technologies (Ben-Mansour et al. 2016; Lee and
Park, 2015; Yu et al. 2012).

The chemical absorption using amine-based solvent is regarded as the first CO2 capture

technology that is applied in industrial scale in post-combustion technology for CO2 capture,

where the first commercial large scale (Sleipner gas field project) was installed and started in

1996 in Norway due to high carbon tax (Raza et al., 2018). The application of amine-based

solvent for CO2 capture has drawn a large amount of interest, thus leading to a substantial

improvement in CO2 post-combustion technology. It is currently the most promising approach

and become a benchmark for CO2 capture technology. Besides that, it is most probably to

appear as the first CO2 capture technology which will be installed globally on a large

scale/industrial scale (Bui et al., 2014). Schematic process of the conventional chemical

absorption process is demonstrated in Figure 5.

Figure 5 Schematic process of the conventional chemical absorption process. (Reproduced

from Wang et al., 2011, Copyright 2011, with permission from Elsevier)

A flue gas is contacted counter-currently with amine solvents in an absorber column,

which works typically at a temperature between 40 °C and 60 °C and at 1.0 atmosphere

pressure. The CO2 rich with aqueous amine solution leaves the bottom part of the absorber

column and is directed via a counter-current heat exchanger. Before being directed to the

stripper column, it is pre-heated using the lean amine solution. In the stripper, heat is supplied

by the steam from the reboiler, where temperature usually set between100°C and 120°C and

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pressure (slightly higher than atmosphere pressure). In this stripper system, the CO2 is released

from the amine solution. Before undergoing the process of transportation and sequestration,

the gas exiting the stripper is first dehydrated and compressed. The cross-heat exchanger is use

to passed back the hot lean amine solvent to the system. It is then transferred back to the

absorber to remove unwanted/additional CO2 with a slip stream being transferred to a reclaimer

to clear solvent impurities (Wang et al., 2015).

Monoethanolamine (MEA) is the most frequently used solvent in chemical absorption

approach for remove CO2. It is well known that MEA has exceptional reactivity and high

absorption capacity, which comes with a low-cost solvent and high absorption rate (Bui et al.,

2014). Some research groups attempt to find out the capability of new solvents and advanced

process technology in order to attain better overall properties for the purpose of capturing CO2.

For example, Nwaoha et al., 2016 conducted an investigation in a lab-scale using tri-solvent

blends which comprise 2-amino-2-methyl-1-propanol (AMP), piperazine (PZ) and MEA for

CO2 capture. The findings revealed that tri-solvent blends are indeed feasible to capture CO2

using chemical absorption process. This mixture is likely to be useful when it is used in

separating CO2 from high pressure systems. These capabilities will increase the

CO2 absorption–desorption performance of the mixture solutions. Ferrara et al., 2017

developed an exergy-based study with the use of CO2 chemical absorption. A

complete flowsheet model is designed for the chemical absorption of a MEA-solvent by

ASPEN PlusTM in a coal-fired power plant. They observed that the

highest irreversibility occurs to the CO2 chemical capture with 77% of total losses and about

9% of total losses in the CO2 pipeline compressor. With an upgrading in the design and

modelling of the system of the plant, it decreases the unit cost of carbon capture from 35.0

US$/tonCO2 to 31.8 US$/tonCO2, respectively. Dinca et al., 2018 investigated the biomass

gasification system with the combination cycle of CO2 capture technology with MEA as the

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solvent in power plant application. The results revealed that the combined cycle system of the

CO2 capture causes the decrease in overall efficiency from 50.9% to 45.8%, decrease in energy

penalty, low energy requirement and increase in levelised cost of energy (LCOE) value from

37% to 41% in the integration process of capturing CO2. However, the drawbacks of chemical

absorption comprise, high equipment corrosion rate, amine degradation, high energy

consumption (during regeneration) and low CO2 loading capacity (Fauth et al. 2005; Resnik et

al. 2004; Yeh et al. 2005). Therefore, amine solvents used for CO2 chemical absorption should

have the following conditions to produce excellent performance: 1) fast reaction rate of

CO2 absorption/desorption, 2) large capacity of CO2, 3) low degradation and 4) low energy

consumption (Bui et al., 2014).

Membrane process includes the application of polymer/ceramic membranes to separate

CO2 from the plant/system. Membrane technology can be used to capture CO2 due to its high

driving force, high selectivity, simple installation, low capital cost and energy consumption

despite having low partial pressure of CO2 (Ben-Mansour et al., 2016). The membrane CO2

separation is presently a well-known technology. Nevertheless, the compromise between

selectivity and permeability hinders the use of membrane technology on a large-scale basis.

The main drawback of membrane-based systems is the need for high-cost modules, which is

not appropriate in dealing the emission of large volume of gases. In addition, the relatively low

CO2 concentration and pressure weaken the driving force for membranes to function effectively

during the post-combustion CO2 capture (Kenarsari et al., 2013). Figure 6 shows a schematics

of membrane carbon capture process.

Figure 6 Schematic of CO2 membrane process. (Reproduced from Khalilpour et al., 2015,
Copyright 2015, with permission from Elsevier)

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Cryogenic CO2 separation is applied commercially for high concentration and high

pressure gases. Due to high capital cost of cryogenic separation system, this approach is

economically practicable only when the CO2 percentage in the stream is high (Kenarsari et al.,

2013). Due to its high energy consumption, cryogenics is also not an attractive approach (Favre,

2011; Oh, 2010; Olajire, 2010). Schematics of cryogenic carbon capture process is illustrated

in Figure 7.

Figure 7 Schematic of cryogenic carbon capture process. (Reproduced from Knapik et al.,
2018, Copyright 2018, with permission from Elsevier)

Generally, adsorption is referred to the process in which atoms, ions or molecules that

are present from a substance (gas, liquid or dissolved solid), concentrated spontaneously on a

solid surface of the adsorbent. The film created by the adhered ions, atoms or molecules on the

surface of materials to which they are attached is known as adsorbate, whereas the material that

they are attached on is known as the adsorbent. Adsorption is not the same as absorption as the

adsorption happens on the surface, whereas absorption includes the whole material or liquid

volume. Desorption is the reverse process of adsorption. This can occur because of physical

forces or by chemical bonds. Usually it is reversible (the reverse process is called desorption);

then it is responsible not only for a subtraction of substances but also for release. Adsorption

may occur physically since it will entail weak van der Waals forces (physi-sorption). It may

happen chemically as well, which will entail covalent bonding (chemi-sorption) because of

electrostatic attraction (Verhaverbeke, 2007; Artioli, 2008; Flores, 2014; Ben-Mansour et al.,

2016). Different materials portray dissimilar chemisorption mechanisms in adsorption process.

For instance, in the context of metal-organic frameworks, the chemical interaction or reaction

mechanism happens via uncoordinated metal sites as well as functional groups which exist on

the surface of MOFs; whereas in the context of biomass materials, the chemisorption process

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occurs via functional groups which are naturally formed or introduced by chemical

modification (Bui et al., 2018). Adsorption via porous materials is deemed to be an interesting

and alternative material in capturing CO2 from flue gases as low energy consumption is needed

to regenerate the adsorbent. Capturing CO2 with physical sorbents materials such as

carbonaceous materials and zeolites will use less energy (during regeneration) than chemical

sorbents.

However, some well-known materials such as activated carbon have a weakness, which

is poor selectivity of CO2/N2 (Ben-Mansour et al., 2016). Recently, there are several

technological successes that are reported in the study of adsorption carbon capture processes.

As mentioned previously, adsorption may be an alternative process to capture CO2 because of

its low-cost raw materials, fast kinetics, low heat capacity, high CO2 selectivity and high CO2

adsorption capacity (Choi et al., 2009; Sayari et al., 2011). There are various kinds of

adsorption technologies such as pressure-swing adsorption (PSA), temperature-swing

adsorption (TSA), electric-swing adsorption (ESA) vacuum swing adsorption (VSA) and

combination of pressure/vacuum- swing adsorption (PVSA) (Mukherjee et al., 2019). The PSA

is a process that separates gases based on the pressure which carried out at high pressure. TSA

is one of the methods for adsorption and desorption processes under certain temperature

conditions, which can be utilised in many applications. Usually PSA and TSA processes are

combined in the large scale application. Other adsorption process system such as

pressure/vacuum swing adsorption (PVSA) are also being studied regularly due to their low

energy requirements and simplicity. For example, Grande et al., (2017) discussed on the

performance of metal-organic framework using Pressure Swing Adsorption Unit (PSA) for

capture of CO2. They used simulation and mathematical modelling for design. Zhao et al.,

(2017) developed pressure-vacuum swing adsorption (PVSA) unit with a single-stage 4-step

process using zeolite13X as adsorbent. Zhao et al., (2018) designed solar-assisted pressure

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temperature swing adsorption (SOL-PTSA) to study different type of adsorbent materials and

the energy consumption of SOL-PTSA system. They reported that the important parameters to

be evaluated is the effect of adsorbent materials on the energy-efficiency of SOL-PTSA,

CO2 capacity and recycle time (Figure 8).

Figure 8 Schematic of solar-assisted pressure temperature swing adsorption (SOL-PTSA).

(Reproduced from Zhao et al., 2018, Copyright 2018, with permission from Elsevier)

Luberti et al., (2017) designed a novel Rapid Vacuum Pressure Swing Adsorption

(RVPSA) for removal of CO2 in the biogas plant. They produced excellent results with

CO2 recovery of 90.9%, CO2 purity of 95.0%, bed productivity of 21.2 molCO2/kg/h and power

consumption of 822.9 kJ/kgCO2. The productivity of the RVPSA unit was 20-30 times higher

than those of the conventional CO2 capture Vacuum Pressure Swing Adsorption (VPSA)

processes. Lillia et al., (2018) used activated carbon and zeolite 13X as adsorbent for hybrid

process termed Temperature Electric Swing Adsorption (T/ESA) in the power plant. However,

they reported that the energy penalty of the T/ESA is significant due to electric consumptions

required for the heating and fast cooling of the adsorbent. He et al., (2017) developed a design

for temperature swing adsorption (TSA) using zeolite 13X as adsorbents and this system shows

a great potential on energy-saving because combined with solar integration system. In

conclusion, all the technologies focus on the separation process.

Figure 9 Schematic of hybrid process Temperature Electric Swing Adsorption (T/ESA).

(Reproduced from Lillia et al., 2018, Copyright 2018, with permission from Elsevier)

Different kinds of adsorbents are proposed with different structures, compositions,

adsorption mechanisms and regeneration. Recent studies on the adsorption process for CO2

capture have shown that much efforts have been made to develop new materials in order to

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enhance the adsorption capacity at a low cost. Numerous studies have been published on the

progress of carbon capture via adsorption process (Table 4).

Table 4 Recent research on the adsorbent modification for CO2 capture

Many studies have been published on the progress of carbon capture by adsorption

using different type of solid adsorbents such as biomass-based activated carbon produced from

pine sawdust, nitrogen enriched carbon adsorbents, silica gel, zeolites prepared using silica

extracted from rice hull ash as a raw material, honeycomb carbon monolith, nanozeolite,

nanoporous carbon, magnesium oxide-based adsorbents, amine-based silica sorbents,

commercial zeolite 13X, titania nanotubes (TNTs), yellow mombin fruit stones (fruit juice),

commercially available palm shell activated carbon, layered double hydroxide (LDH)

and graphene oxide (GO) nanosheets, adsorbents based on calcium oxide (CaO) lithium

orthosilicate (Li4SiO4), zirconium metal–organic framework (UiO-66) and graphene oxide

(GO), eucalyptus wood based activated carbons, pine nutshell, rapeseed oil cake/walnut shell

and biochar (Table 4). For example, Jing et al. (2014) developed a novel adsorbent and

modified by functionalizing mesoporous silica (SBA-15) with melamine-based and acrylate-

based amine dendrimers to enhance the CO2 adsorption performance. In another study,

Vilarrasa-García et al., (2014) performed a study mesoporous silica functionalised with 3-

aminopropyltriethoxysilane (APTES) to obtain high CO2 adsorption capacity up 2.4 mmol/g.

Deng et al., (2014) prepared adsorbent from pine nut shell-derived activated carbon modified

with chemical activation and produced high CO2 adsorption capacity up to 7.7 mmol/g at

273 K and 5.0 mmol/g at 298 K, the highest capacities at ambient pressure among all the

biomass-derived carbons and show a promising application in CO2 capture. New composites

material of zirconium metal–organic framework (UiO-66) were developed as CO2 adsorbents

by Cao et al., (2015). The results showed that the new composite adsorbent exhibited the

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maximum CO2 uptake of 3.37 mmol/g at 298 K and 1 bar. Kim, et al., (2015) conducted a

study using macroporous Li4SiO4 and synthesized this material by a simple solid-state

conversion technique using LiOH and fumed silica as a precursor for Li and SiO2. The results

showed that this adsorbent enhanced CO2 adsorption performance and the adsorption–

desorption cycles could be recycled/reused 10 times without a significant reduce in the

adsorption capacity. Wang et al., (2015) demonstarted for the first time a new method for the

preparation layered double hydroxides (LDHs) as adsorbent for CO2 capture. The results

showed good CO2 adsorption/desorption performance with could be recycled more than 22

cycles. Salehi et al. (2018) suggested a strategic approach to improve the surface propertise of

zeolites by combined this material with the multi-wall carbon nanotubes (MWCNTs). The

authors also developed a noveladsorbents modified with cation-exchanged nanozeolite (Nano-

Z/Cd) composite and polyethylenimine functionalized multiwalled carbon nanotubes/Cd-

nanozeolite composites (PEI/CNT@Nano-Z/Cd) to enhance the adsorption capacity. The

combination of Nano-Z/Cd with PEI/CNT could produce high CO2 adsorption performance

compared to the performance of Nano-Z/Cd when used individually. Wang et al., (2018)

synthesized NaA zeolite (cubic crystal with a 3-D 8-membered ring vertical channel), NaX

zeolite (cubic crystal with a 3-D 12-membered ring channel) system and NaZSM-5 zeolite (10-

membered ring channel with a 2-D orthogonal system) using silica extracted from rice hull in

the hydrothermal method. The results showed that the highest adsorption capacity of NaA, NaX

and NaZSM-5 were 1.46, 3.12 and 2.20 mmol/g, respectively.

1.5 Techno-economic impacts

Capture of CO2 is currently a technologically feasible and small-scale industrial

practice worldwide. But there was still uncertainty as to how easily for its industrial application

the CO2 capture unit designed in a laboratory scale could be scaled up (Bonijoly et al. 2009).

The challenge for large-scale CO2 capture applications is due to lack of incentives and potential

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sources, high costs for large-scale applications and advanced CO2 recovery technologies

(Bonijoly et al. 2009; Lackner et al. 2012). Many researchers have demonstrated the process

of adsorption as a promising process of CO2 capture that requires more cost-effective operation

than conventional amine-based absorption processes. To date, both experimentally and

numerically it has been recognised and confirmed that an adsorption process could capture CO2

with low energy consumption compared to the conventional amine-based absorption process

(Zhang et al. 2008; Wang et al. 2013). Additional research on economic impacts should

accompany advances in technology, including energy consumption and carbon capture cost

estimation results. Research and development efforts are needed for the various possible

adsorbent materials and advanced technology with minimal energy costs (power consumption)

with excellent productivity would be essential to be immediately scaled up for industrial CO2

capture application.

In this section, we present a summary of the recent techno-economic literature on

carbon capture to provide a broad picture of CO2 capture in industrial use. Researchers have

carried out extensive experimental and research efforts to capture and separate CO2 based on

pressure, temperature and vacuum swing adsorption. For example, a four-step cycle (shortcut

model) was developed by Joss et al. (2015) using temperature swing adsorption (TSA) process

with 13 X zeolite as adsorbent. They reported that the shortcut model predicted low specific

energy consumption with a value of 3.2–4.2 MJ / kg CO2 and above 30 percent CO2 recovery.

In addition, Mendes et al. (2017) used a binderless 5A zeolite as an adsorbent to capture CO2

using pressure and temperature swing adsorption (PTSA) process. The PTSA experiment

showed good performance with 95.2 percent high CO2 purity, with 94.8 percent CO2 recovery

and 3.8 MJ/kg CO2 energy consumption. Hybrid Temperature Electric Swing Adsorption

(T/ESA) performance was investigated by Lillia et al. (2018) using activated carbon and zeolite

13X as an adsorbent for CO2 capture. The results showed that when the performance of two

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T/ESA with and without the exhaust gas recycle (EGR) was compared, the T/ESA without the

EGR had a low energy consumption of 9.64 MJLHV/kg CO2 compared to T/ESA with an EGR

of 13.05 MJLHV/kg CO2. Ben-Mansour and Qasem (2018) presented a detailed study on

modelling for CO2 capture using temperature swing adsorption (TSA). The performance of the

TSA showed high purity of CO2 (96.22 percent) and recovery (86.5 percent) with low power

consumption of 663.8 kWh per ton of CO2 captured. The performance of commercial zeolite

APGIII (new generation molecular sieve) and granular activated carbon studied as adsorbents

for CO2 capture by 2-stage vacuum swing adsorption (VSA) technology was investigated in

the works of Ling et al. (2016). The outcomes show that CO2 purity and power consumption

was approximately 95.3 percent with 0.55 MJ/kg CO2 specific power consumption.

Furthermore, Luberti et al. (2017) designed a novel rapid vacuum pressure swing adsorption

(RVPSA) using zeolite 13X pellets for CO2 capture. The results showed good 90.9% CO2

recovery performance, 95.0% CO2 purity and 822.9 kJ/kg CO2 low power consumption. Zhao

et al. (2017) compared the results of different adsorption processes by using zeolite 5A based

on minimum separation work and second-law efficiency. They reported that the second-law

efficiency maximum values for VPSA and PTSA were 24.30 percent and 19.09 percent

respectively. Qasem and Ben-Mansour (2018) developed a model for CO2 separation using a

system with a five-step adsorption process. Results exhibited that the optimal CO2 purity was

95.3 percent with power consumption of 68.71 kWh tonne/CO2. Bahamon et al. (2018) studied

the behaviour of various processes. Results reveal that adsorbents using metal organic

frameworks (MOFs) offer higher working capacity than 13X zeolite. TSA obtained the

minimum energy requirement using Mg-MOF-74 with 0.55 GJ/t CO2 values. In addition,

hybrid VTSA processes with Mg-MOF-74 achieve low energy performance of 0.36 GJ/t CO2.

2. Methodology for adsorption process patent search

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In order to prepare this review, more than 2,500 international patents were accessed to

obtain a more detailed overview of recently published patents. There were only 500 patents

related to CO2 adsorption from the 2,500 patents published in the Derwent World Patents Index

database. The literature search was conducted from May to November 2018. The patent

database was accessed for this work and only published patents pertaining to CO2 adsorption

were included and evaluated. The international patent databases accessed in this work was the

Derwent World Patents Index created by Thomson Reuters, whereby archives of more than

500 patents were considered for further evaluation. Figure 10 shows the distribution of the

patent search versus published articles on CO2 adsorption. Only 500 patents documents were

published between 2014 to 2018. In contrast, there were 1,000 scientific articles published on

CO2 capture by adsorption. From Figure 10, it is evident that the number of patents is increasing

significantly from 2014 until 2017. However, in 2018 the number of patents decreases

significantly because of patent search was conducted until December 2018 and data does not

include all potential patents in 2018. The information about 2018 patents does not disclosed

yet in the Derwent World Patents Index database. Similarly, there is a slight decrease in the

number of published scientific papers in journals and conferences in the year 2018.

The strategy used for the literature search involves using keywords and their variants,

combined with adsorbent classification codes. Specific keyword search terms were used to

search for published patents related to adsorption methods for CCS applications, as shown in

Table 5. Microsoft Office Excel 2016 software program (Microsoft Corporation, USA)

extracted and analysed the information and statistics. In the Microsoft Excel spreadsheet, the

information was organised in tabular form under the headings: (1) patent title, (2) applicant(s),

(3) inventor(s), (4) patent priority date, and abstract. All the patent details recorded were then

thoroughly reviewed and collected into the matching group. An advanced keyword search for

patent titles and abstracts was performed when the database and information was retrieved. The

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following keywords (CO2 adsorbent and carbon dioxide adsorbent) as well as keywords

combinations (search as title, abstract and vice versa) have been used to search published

patents related to CO2 capture technologies.

Table 5 Search strategy used for the patent literature search.

Figure 10 Number of patents (Based on sources from Derwent World Patents Index created
by Thomson Reuters) vs scientific articles (Based on sources from science direct/Web of
Science)

2.1 Limitations

Patents that were not related to the CO2 adsorption process were excluded from the

Derwent World Patents Index database. Potential CO2 capture technology patents not

mentioned in the title of the patent and abstract were not included. Because of database

limitations, it was not possible to explore for complete details of all patents. The literature

search was conducted between 2014 and 2018 for patents published. It is noteworthy that

because of the limitations of the record, a few published patents in languages other than English

were not accessible and therefore the analysis was based on the abstract and claims in English.

3. Patents on adsorbents

A total of 500 patents have been filtered and shortlisted on various adsorbents including

carbon-based adsorbents, zeolite, metal-organic frameworks, metal-organic polymers, alkali

metal carbonate, amine-based adsorbents, double-layered hydroxides, and calcium-based

adsorbents. As shown in Table 5, the total number of patents searched was evaluated based on

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the categories of patent database. Figure 11 shows the number of CO2 adsorption patents

published annually. The number of patent filings has increased since 2016, but without

consistency.

Figure 11 Number of patent filings per year.

Based on the country or organisation where the patent application was assigned or

granted, China (CN), United States (US), World Intellectual Property Organization (WO),

Japan (JP) and South of Korea (KR) are the top five countries or organisation having the highest

number of patents related to various types of adsorbents. CN alone has more than 300 patents.

JP, US, KR, and WO each has more than 60 patents related to CO2 adsorption in the Derwent

World Patents Index database, as shown in Figure 12. Interestingly, CN has a significant

number of patented technologies such as carbon-based adsorbents (>20 patents), alkali metals

(>20 patents), amine-based adsorbents (>10 patents), microporous organic polymers (>30

patents), metal-organic frameworks (>100 patents), zeolite (>90 patents), layered double

hydroxides (20 patents), and calcium-based adsorbents (>10 patents).

Figure 12 Number of patent filings by country of origin.

3.1 Types of CO2 adsorbents by the adsorption temperature

The CO2 adsorbents can be categorised into three types depending on the adsorption

process reaction temperature, such as low-temperature adsorbents (below 200ºC),

intermediate-temperature adsorbents (200 ~ 400ºC) and high-temperature adsorbents (above

400 ºC) (Wang et al. 2011).

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3.1.1 Low-temperature adsorbents (<200°C)

For carbon-based adsorbents such as carbon-based adsorbent, zeolite, alkali metals,

amine-based adsorbents, microporous organic polymers, and metal-organic frameworks

various materials have been studied. Method that used to capture CO2 in industrial production

was low-temperature adsorbents. This section reviews a summary of some of the recently

patented low-temperature adsorbents published between 2014 and 2018 (Table 6-10) (Index,

2018).

There are several patents developed using various type of adsorbents for CO2 capture.

Among them, in 2018, numerous patents were reported and released on the metal-organic

frameworks (MOF) as outstanding adsorbent for CO2 capture. For example, Sinopec Corp

(SNPC-C) and Sinopec Fushun Res Petroleum & Petrochem (SNPC-C) disclosed a patent

CN107774234-A to develop new MOF material useful for gas adsorption preferably in carbon

dioxide and separation of methane from methane/carbon dioxide mixture (Fang et al. 2018).

CN108452771-A reported on the MOF-derived carbon-based photonic crystal, tetra(p-

aminophenyl)porphyrin and terephthalaldehyde for CO2 removal. They proved that this

adsorbent has high adsorption capacity for carbon dioxide (Yu et al., 2018). Other patents such

as CN108384020-A reported on the new metal-organic framework compound for carbon

dioxide capture. KR1707821-B1/WO2017026619-A1 prepared new magnesium metal-organic

framework used as adsorbent. Advantages of this technology is that the magnesium metal-

organic framework has a high surface area and high crystallinity as well as produces excellent

carbon dioxide adsorption performance (Hong et al. 2017). KR1894780-B1 described on MOF

combined with nanosheet, and co-hybridisation nanocomposite containing layered double

oxide. A recent patent (patent no. WO2018152438-A1) was also published on metal-organic

framework in 2018, which involves the application of adsorption material (MOF) in biogas

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plant (Long et al. 2018). CN106693896-A from the company Cas Dalian Chem & Physical

Inst(CACP-C) demonstrated that heterogeneous composite structure from metal organic

framework(s) and silica-alumina molecular sieve or activated carbon material have excellent

adsorption separation characteristics. CN106732390-A (modified zeolitic imidazolate

frameworks material for carbon dioxide adsorption. CN106732407-A (developed a new MOF

synthesized from benzene triacrylic acid-indium complex. KR1707821-B1/WO2017026619-

A1 described on new MOF material for removing carbon dioxide in power plant.

JP2017088542-A claimed that new MOF material has excellent performance and offers

adsorbing material with high water-vapor adsorption amount in low pressure side.

CN105664893-A/CN105664893-B reported that new three-dimensional indium metal-organic

framework material has large specific surface area and pore size. CN20161120603 described

on novel adsorbent from zirconium-based metal organic framework for reducing CO2.

CN104826610-A Prepared polyethyleneimine-impregnated UiO-66 MOF material used for

carbon dioxide capture and provides high adsorption capacity and good hydrothermal stability.

JP2015074604-A reported on the X-ray diffraction measurement for MOF material.

Cambridge Enterprise Ltd (UYCA-C) and Cambridge Enterprise Say (UYCA-C) in 2015

disclosed a patent WO2015189599-A1, AU2015273283-A1, KR2017015495-A, CA2951200-

A1, EP3154948-A1, CN106573225-A, US2017113205-A1, JP2017519752-W and

US9884309-B2 on the use of metal-organic framework particles e.g. metal-organic framework

monolith includes ZIF-4, ZIF-8, ZIF-90, ZIF-zni, UIO-66, UIO-67, UIO-68, HKUST-1, MIL-

47 and MIL-53 for carbon capture (Garcia et al. 2015). US2014212944-A1 claimed that new

metal organic framework-based hierarchical porous material used have several advantages

such as economical, has high thermal stability and favorable reproducibility.

Many patents also were developed on the modification of amine as an adsorbent for

CO2 capture. In this regard, patent KR2018067172-A described a method to modify amine

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using wet impregnation method with a mixture of amine compound and metal salt additive

(Sung et al. 2018). This method produces excellent impregnation rate and high carbon dioxide

adsorption performance. Another patent (patent no. US2018008958-A1; KR2018006147-A;

US10010861-B2) which was published in 2018 disclosed a method of modification of

polymeric amine as adsorbent for carbon capture. The advantages of this modified adsorbent

are that it is superior in high-temperature stability, has high adsorption capacity, selectivity,

long-term stability, is environment-friendly and economically efficient (Choi et al. 2018).

CN106517186-A reported on the amine functionalised activated carbon as an adsorbent used

for carbon dioxide treatment, which was published in 2017 (Wei et al. 2017). The method

produces high performance and high carbon dioxide adsorption performance. In addition, there

are several patents published on the chemical modification of amines as adsorbent such as

CN107899545-A (spherical core-shell nano composite-amine nano-structured),

CN108067180-A (magnesium-calcium-based adsorbent), PL417365-A1 (spherical

carbonaceous materials modified with ethylenediamine), CN107321317-A (solid amine

prepared by supporting tetraethylenepentamine, US2016175808-A1; KR2016074844-A

(amino acid-based amine), US2016199810-A1; WO2016114991-A1; AU2016207044-A1

(solid sorbent modified by polyamine), CN105061757-A (new keto-enamine-bond-containing

conjugated microporous polymer), CN104056599-A; CN104056599-B (graphite based-metal-

organic framework with organic amine), CN103657610-A; CN103657610-B (porous

polymeric adsorbent using primary amine as monomer).

Several patent documents were published regarding the use of zeolites, which is also

called as molecular sieves adsorbent, for carbon capture. For example, in 2018, CN107746064-

A reported a method for preparing calcium-doped MCM-48 molecular sieve. The inventor

developed a simple technology which produces large specific surface area, has an excellent

carbon dioxide adsorption performance and energy efficient treatment (Ji et al. 2018).

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CN106669613-A published an impregnation method to produce amino-functionalized

adsorbent material obtained from the synthesis of zeolite socony mobil-5 (ZSM-5) zeolite with

tetraethylenepentamine (Du et al. 2017). MX2015008315-A1 discussed an impregnation

method using copper nitrate trihydrate and synthesis with zeolite for adsorbing carbon dioxide

(Salmones Blasquez et al. 2017). BR102014009903-A2 described the use of zeolites using the

ashes of sugar cane bagasse, for carbon dioxide adsorption (Radovanovic et al. 2016). In 2015,

WO2015191962-A1 and US2017173555-A1 disclosed a method for carbon capture using

zeolite as adsorbent that contains micropores, mesopores, and macropores structures (Akhtar

and Seo, 2015). KR2015116334-A and KR1595741-B1 reported an invention for amine-

modified zeolite socony mobil-5 for carbon capture (Kim et al. 2015). KR2018051455-A

reported on the carbon dioxide adsorbent involving merlinoite zeolite with high purity,

environmentally friendly material and economical. WO2018110559-A1; AU2017329099-A1;

CN108495813-A described on the GIS-type zeolite (silica-alumina) as adsorbent with

excellent selectivity of carbon dioxide and methane. CN106925235-A prepared 13X zeolite

molecular sieve by mixing with cetyltrimethylammonium bromide, water and adding ferric

chloride solution for CO2 adsorption. JP2017170380-A from the company Panasonic IP

Management Co Ltd (Matu-C) reported on type A zeolite for CO2 capture. KR1696395-B1;

WO2017090825-A1 prepared adsorbent from diamine-zeolite complex for removal of CO2.

WO2017142056-A1 described on the zeolite crystal structure used for separating CO2 which

contains fluoride-free. KR2015116334-A; KR1595741-B1 modified amine-modified zeolite

socony mobil-5 used for carbon dioxide adsorption. CN103691399-A; CN103691399-B

reported on the carbon molecular sieve used for separating carbon dioxide and methane.

KR20140085472 described on the separation method using ZSM-25 zeolites as adsorbents

A recent patent developed by Cas Dalian Chem & Physical Inst (CACP-C) (patent no.

CN108117513-A) reported a new adamantyl-containing bipyridine compound as three-

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dimensional organic porous material can be used for carbon capture. This adsorbent has a high

specific surface area, a high capacity for gas adsorption and an excellent micro/mesoporous

property (Gao et al. 2018). The use of mesoporous carbon nitride material used to capture or

activated carbon dioxide was reported by WO2018037320-A1 (Vinu et al. 2018). Another

patent (patent no. CN107488261-A) described a method for the adsorption and separation of

carbon dioxide using new carboxyl-rich microporous organic polymer (Yu et al. 2018).

Another patent US2017354949-A1; KR2017140556-A was also published on the use of

magnesium oxide/titanium dioxide composite with a mesoporous structure capable of

producing high surface area, large pore volume, and good thermal stability (Hiremath et al.

2017).

Because of their comparatively high adsorption capacity, low cost, and wide availability

alkali-metal-based oxides are also promising adsorbents for CO2 capture (Wang et al. 2011).

EP3375517-A1 reported on the alkali metal as an excellent adsorbent for removing carbon

dioxide (Lau et al. 2018). CN107321296-A described the removal of CO2 using composite

magnesium oxide-based which comprises four alkali metal salts and magnesium oxide/calcium

oxide composite with multi-layered flower structure (Zhou et al. 2017). CN107115845-A

discussed carbon dioxide adsorbent using aluminum oxide, silicon oxide, analcime, calcium

analcime, carbon nano tube, carbon molecular sieve and alkali metal compound (Zhang et al.

2017). KR2017037520-A developed a new alkali metal nitrate co-precipitated hydrotalcite

useful for adsorbing carbon dioxide (Lee and Kim, 2017). FR3024378-A1; WO2016015923-

A1; CN106573224-A described on the adsorbent from the alkali metal element (sodium) for

removing of CO2. CN104958996-A; CN104958996-B reported on the azole-based alkali metal

salt formed from synthesis of imidazole, pyrazole, triazole and tetrazole and mixed with

hydrazine hydrate then produce material with good stability, large adsorption capacity and

good absorbing efficiency. US2014305302-A1; KR2014123849-A; US9205404-B2 from the

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company Samsung Electronics Co Ltd documented a patent on high surface area of mesoporous

inorganic oxide formed from crystalline halide of alkali metal or alkaline earth metal.

Activated carbon is commonly known as promising adsorbent for carbon capture.

Numerous patents were published on the potential of activated carbon modification to enhance

adsorption capacity performance. For example, Shaanxi Shengmai Petroleum Co. Ltd. patented

a method (patent no.: CN107876009-A) to synthesise a zeolite-activated carbon composite

adsorbent, which was published in 2018. It was claimed that the zeolite-activated carbon

composite adsorbent synthesised by this method has a large specific surface area and

micropore, resulting in a large adsorption performance (Wang, 2018). CN108310900-A

described a method using nano-molecular carbon useful for adsorbing carbon dioxide (Wang,

2018). PL418158-A1 discussed a method using the addition of carboxymethyl starch-based

film to potassium hydroxide to form activated carbon (Michalkiewicz et al. 2018). EP3338875-

A1 from the company Solvay Sa(Solv-C) explained a thermal swing adsorption process for

removing carbon dioxide which this method allows reducing time (during

desorption/regeneration) and improving efficiency of the process. CN108126660-A described

on solid adsorbent-based impregnated activated carbon used for adsorption of carbon dioxide.

A similar study was published by CN108126659-A and JP2014083488-A; JP6089579-B2 on

activated carbon material used as adsorbent for CO2 capture. CN108067208-A described a

method of regenerating organic gas adsorption saturated activated carbon. CN106517181-A

described on the biomass-based activated carbon useful for high-efficient adsorption of carbon

dioxide. KR2017013440-A; KR1824771-B1 used pressure swing adsorption for separating

carbon dioxide from gas mixture using modified activated carbon. WO2017048742-A1;

US2018036671-A1; IN201717042843-A; EP3349878-A1 reported on the multilayer adsorbent

bed for purifying feed stream. CN105950241-A used pressure swing adsorption in the biogas

plant using activated carbon as adsorbent. CN104907045-A; CN104907045-B compared the

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performance of various types of adsorbent such as granular, columnar, spherical or honeycomb

activated carbon, alkali/alkaline earth metal salt of active silica-alumina gel, and nitrogen-

containing organic compound for CO2 separation. CN104445188-A; CN104445188-B was

published and explained a method to produce rice husk-based activated carbon as adsorbent

material.

Table 6 Patents dealing with metal organic framework material (MOF) as adsorbent for CO2
capture

Table 7 Patents dealing with amines as adsorbent for CO2 capture

Table 8 Patents dealing with zeolite, molecular sieve and silica as adsorbent for CO2 capture

Table 9 Patents dealing with alkali metal as adsorbent for CO2 capture

Table 10 Patents dealing with activated carbon as adsorbent for CO2 capture

3.1.2 Intermediate temperature adsorbent (200–400°C)

Layered double hydroxides (LDHs) are layered basic solids, also known as hydrotalcite

or anionic clays. LDHs have been widely used for various catalytic applications as adsorbents,

ion exchangers, base catalysts, and precursors of well-mixed oxides. LDHs consists of

positively charged brucite-like layers within the interlayer space with charge compensating

anions and water molecules. However, the relatively low capacity for CO2 adsorption is

typically a problem with adsorbents based on LDH. There has been considerable effort to

improve the capacity for CO2 adsorption, particularly on Mg-Al-CO3 LDH and its derivatives

(Wang et al. 2011). In recent years, LDHs are the most promising candidates for the above

applications, due to the characteristics of eco-friendly, cheap, easy to regenerate, wide range

of process technology that the LDH possesses (Ramírez-Moreno et al. 2014)

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This section is focused on a review of the patented intermediate-temperature adsorbents

from 2016 to 2018 because there are no patents published in the year 2014-2015. A summary

of some of the recently patented adsorbents published for LDHs are depicted in Table 11.

For instance, a patented preparation method was published in 2018 (patent no.:

RO132424-A2), which involves the use of cobalt oxide nanoparticles assembled with layered

double hydroxides, with applications in carbon dioxide capture. It is reported that this invention

results in an excellent adsorption performance (Carja et al. 2018). A patent (patent no.:

KR1894780-B1) which involves a process to capture CO2 using graphene oxide nanosheet and

layered metal oxide nanosheet, and co-hybridization nanocomposite comprising layered double

oxide (Hwang et al. 2018). Another patent KR2017042520-A; KR1808554-B1 described a

method to prepare carbon dioxide adsorbent containing mesoporous layered nano-hybrid

comprises layered double hydroxide nano-sheet and metal nanocluster (Chang et al. 2017).

KR2016111703-A developed a technology to produce nano-hybrid mesoporous layer which is

formed by the recombination reaction of metal nanocluster and peeled metal layered double

hydroxides nanosheet with opposite charge surface (Hwang et al. 2016).

Table 11 Patents dealing with layered double hydroxide (LDH) as adsorbent for CO2 capture

3.1.3 High temperature adsorbent (>400°C)

It is well-accepted that calcium-based materials are good adsorbent candidates to

capture CO2 because of their high reactivity with CO2, high capacity, and cost-effective

material. The reversible reaction between calcium oxide (CaO) sorbents and CO2 offers great

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potential to reduce CO2 released from various CO2 capture processes (Ezechi et al. 2014). The

temperature of carbonation (highly exothermic reaction) for calcium oxide-based adsorbents is

within a range of 600–700°C and the temperature of regeneration typically exceeds 950°C

(Wang et al. 2011). The energy discharged during CO2 capture can be recovered proficiently.

This method is cost-effective due to limestone (CaCO3) is widely available and relatively low-

cost, making it feasible for industrial scale of carbon capture. The key drawback with calcium-

based adsorbents, despite its simple chemistry, is the loss of reversibility during the carbonation

reaction. The loss of reversibility is because of the following reasons: (1) exothermic reaction

of carbonation process, (2) the capacity rises significantly from CaO to CaCO3, and (3) CaCO3

temperature is significantly lower than typical carbonation temperatures (Lee and Park, 2015).

Table 12 shows a summary of some of the recently patented calcium-based adsorbents.

In 2018, CN108067180-A reported a method with high adsorption efficacy and good

adsorbent circulation stability using magnesium-based calcium generated in chemical chain

reforming enhanced hydrogen production process, including calcium oxide, yttrium oxide and

magnesium oxide (Qin et al. 2018). CN107029660-A described a method using modified

calcium-based adsorbent by high temperature carbon-dioxide using oil sands pyrolysis residue

as calcium source and adding kaolinite complex (Miao et al. 2017). The method produces a

product with high adsorption capacity, which is good for removing carbon-dioxide in the high

temperature flue gas of thermal power plant, has a simple technique, convenient operation and

low cost, and is environmental-friendly. US2017014799-A1 and US9649619-B2 have

developed a method for removing CO2 using the composition of calcium-sodium-silicon oxide-

aluminum oxide/sodium-calcium-aluminosilicate containing gehlenite in a fixed bed column

to improve adsorption performance (Shawabkeh et al. 2017). Based on the findings of this

review, it can be concluded that only a few recent patents on calcium-based adsorbents have

been published. CN108187628-A discussed a method for preparing adsorption material using

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microwave pyrolysis and reported that this process is simple and economical with produce has

high adsorption capacity. Another interesting patent was published and reported by

CN107746064-A using calcium-doped MCM-48 molecular sieve as adsorbent for carbon

dioxide adsorption and stated that this material has high surface area, excellent adsorption

performance and environmentally-friendly adsorbent.

CN106861601-A discussed on Ytterbium-doped adsorbent contains ytterbium oxide

and calcium oxide for CO2 capture and the results showed that this adsorbent has high

temperature adsorption performance, high cycle (regeneration) performance and high

adsorption capacity. CN106582491-A prepared high-temperature carbon dioxide calcium-

based adsorbent doped with silicon nitride and the advantages of this material are easily

available, simple process and good adsorption capacity. JP2016193957-A was published and

described by Tosoh Corp(Toyj-C) developed adsorbent from porous coordination polymer for

carbon dioxide adsorption which contains calcium outside the skeleton. CN105498710-A

reported on the new adsorbent based on calcium composite produced from fishbone and

produced excellent performance, fast adsorption and this material can be reused and recycled.

CN103657582-A disclosed a method on the modified calcium oxide-based CO2 adsorbent

which can enhanced adsorption and desorption performance, high adsorption capacity, good

cycle stability, economical and high efficiency.

Table 12 Patents dealing with calcium based as adsorbent for CO2 capture

4. Conclusion and future outlook

This review is written to summarise the recently published patents for various adsorbents in

2014 and 2018 for CO2 capture. This review also reports new insights based on recently

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published articles regarding the innovative adsorption-based technology for

commercialisation. The following conclusion and suggestions are made:

1. The main challenge faced in developing adsorption technology successfully is the

development of adsorbents with high adsorption capacity, low-cost materials, easy

regeneration and low production cost. Therefore, exploring and developing a cost-effective

CO2 capture technology is essential. Various factors need to be taken into account when a novel

adsorbent is synthesis in order to create a sustainable CO2 removal system. Sustainability of

the adsorbent material will be the prior factor to be looked into. While encompassing a high

capacity of CO2 capture, the adsorbent material has to be sustainable through multiple sorption

or desorption cycles, low production cost, widely available raw material and a simple synthesis

process. Furthermore, more focus ought to be placed on the possible impact on environmentally

friendly solvents, non-toxic solvent or green solvent for adsorbent modification of CO2 capture

processes. Other technical factors such as the effect of mass transfer, fast kinetics (both

adsorption and desorption) of CO2 transport in adsorbents and bed type should be taken into

account in the future standards in order to find the most appropriate adsorbents in capturing

CO2. The selection of adsorbent, parameters, synthesis methods and adsorption performance

will be more precise and focused. Hence, an improvement towards all the stated criteria can

lead to a substantial cost in capturing CO2.

2. The use of mathematical modelling, simulation and optimisation of CO2 adsorption process

with pilot plants is an additional research area which requires to be considered and taken into

account. However, it is essential to upgrade the innovative lab-based technologies to suit the

industrial usage.

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3. Furthermore, it is important to include techno-economic analysis and estimations in the

adsorption process, especially in developing the large-scale process. Techno-economic studies

can help to predict unsuccessful investments and can be used to estimate operation and

maintenance costs. The development of new highly efficient adsorbents for CO2 capture is

essential to acquire techno-economic systems. It is vital to attain information regarding

selecting adsorption reactors, regeneration process and overall cost of the process especially

on the large scale application. Therefore, it is necessary to carry out techno-economic studies

on CO2 adsorption technologies in order to guarantee their practicality and viability in industry

and market place.

4. This study presented a review of recently published patents for various types of CCS

adsorbents such as carbon-based adsorbents, alkali metals, amine-based adsorbents,

microporous organic polymers, metal-organic frameworks, zeolite, layered double hydroxides

and calcium-based adsorbents. In general, most recently published patents are related to

adsorbents of low-temperature such as metal-organic frameworks and carbon-based adsorbents

which are followed by zeolite. Only a few patents on calcium-based and layered double

hydroxide (LDH) adsorbents have been published recently and this indicates that there is room

for further development in this area. CaO-based adsorbents have the capability to be applied in

capturing CO2 at high temperature. The application of a low-cost material as a support for CaO

reveals an alternative approach that is economically feasible with the performance of the

adsorbent being enhanced. Meanwhile, layered double hydroxides (LDHs) are favourable

materials due to its versatile properties and the large number of composition available for fine-

tuning. LDHs demonstrate good capability for the adsorption of CO2 and they can be applied

in a variety of potential applications because of their low cost, thermal stability, facile synthesis

and chemical versatility. More comprehensive studies on the development of LDHs should be

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carried out in future. This is because this material is not fully developed at a commercial level

and thus more research is required to be done in this area.

5. More comprehensive research on development of novel multi-cycle CO2 adsorption via

hybrid or combined processes should be studied with combined process of vacuum and

temperature swing adsorption (VTSA) or vacuum and pressure swing adsorption (VPSA) that

makes use of a sustainable process.

Acknowledgments

The authors wish to acknowledge Sunway University, for funding this work through

the internal grant of Research Centre for Carbon Dioxide Capture and Utilisation.

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Figure captions

Figure 1 Key objective of the Paris Agreement (adapted from The Intergovernmental Panel on
Climate Change (IPCC) (IPCC, 2013; Meinshausen, 2015)).

Figure 2 Summary of CO2 capture and storage. (Reproduced from Lee and Park, 2015,
Copyright 2015, with permission from Elsevier)

Figure 3 Flowchart with three types of CO2 capture technologies. (Reproduced from Gibbins and
Chalmers, 2008, Copyright 2008, with permission from Elsevier)

Figure 4 Various approaches to CO2 capture technologies (Ben-Mansour et al. 2016; Lee and
Park, 2015; Yu et al. 2012).

Figure 5 Schematic process of the conventional chemical absorption process. (Reproduced from
Wang et al., 2011, Copyright 2011, with permission from Elsevier)

Figure 6 Schematic of membrane-based CO2 separation process from flue gas streams.
(Reproduced from Khalilpour et al., 2015, Copyright 2015, with permission from Elsevier)

Figure 7 CO2 cryogenic liquefaction and separation system. (Reproduced from Knapik et al.,
2018, Copyright 2018, with permission from Elsevier)

Figure 8 Schematic of solar-assisted pressure temperature swing adsorption (SOL-PTSA).

(Reproduced from Zhao et al., 2018, Copyright 2018, with permission from Elsevier)

Figure 9 Schematic of hybrid process Temperature Electric Swing Adsorption (T/ESA).

(Reproduced from Lillia et al., 2018, Copyright 2018, with permission from Elsevier)

Figure 10 Number of patents (Based on sources from Derwent World Patents Index created by
Thomson Reuters) vs scientific articles (Based on sources from science direct/Web of Science)

Figure 11 Number of Patent Filings in year

Figure 12 Number of patent filings by country of origin

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Fig. 1.
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Fig. 2.
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Fig. 3.
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Fig. 5
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Fig. 6
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Fig. 7.
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Fig. 8.
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Fig. 9.
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Patents vs Scientific Articles (distribution time)

2018

2017

2016 Published patents

Published articles

2015

2014

0 200 400 600 800 1000 1200 1400

Fig. 10.
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12%
21% 2018
15% 2017
2016
2015
20% 32% 2014

Fig. 11.
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Fig. 12.
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Research highlights

 This review reports new insights based on recently published articles regarding

innovative adsorption-based technology for commercialisation

 A patent review on CO2 capture technology by adsorption process

 Compilations of patents on various adsorbents including carbon-based adsorbent, zeolite,

metal-organic frameworks, alkali metal, amine-based, layered double hydroxides and

calcium based.
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List of Tables

Table 1 Global CCS projects. (Adapted from the Global Carbon Capture and Storage Institute
project database (CCS, 2017)).

Table 2 Summary of the literature on the application of CCS technologies in various industrial
applications.

Table 3 Summary of different post-combustion CO2 capture technologies.

Table 4 Recent research on the adsorbent modification for CO2 capture

Table 5 Search strategy used for the patent literature search.

Table 6 Patents dealing with metal organic framework material (MOF) as adsorbent for CO2
capture

Table 7 Patents dealing with amines as adsorbent for CO2 capture

Table 8 Patents dealing with zeolite, molecular sieve and silica as adsorbent for CO2 capture

Table 9 Patents dealing with alkali metal as adsorbent for CO2 capture

Table 10 Patents dealing with activated carbon as adsorbent for CO2 capture

Table 11 Patents dealing with layered double hydroxide (LDH) as adsorbent for CO2 capture

Table 12 Patents dealing with calcium based as adsorbent for CO2 capture
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Table 1 Global CCS projects. (Adapted from the Global Carbon Capture and Storage Institute
project database (CCS, 2017)).

Operation Lifecycle stage Industry Country CO2

date capture
capacity
(Mtpa)
1972 In operation Natural gas processing United States 0.4–0.5

1982 In operation Fertiliser production United States 0.7

1986 In operation Natural gas processing United States 7.0

1996 In operation Natural gas processing Norway 1
2000 In operation Synthetic natural gas Canada 3.0
2008 In operation Natural gas processing Norway 0.7
2010 In operation Natural gas processing United States 8.4
2013 In operation Hydrogen production United States 1.0
2013 In operation Fertiliser production United States 1.0
2013 In operation Natural gas processing United States 0.9
2013 In operation Natural gas processing Brazil ≤1.0
2014 In operation Power generation Canada 1.0
2015 In operation Hydrogen production Canada ≤1.0
2015 In operation Natural gas processing Saudi Arabia 0.8
2016 In operation Iron and steel United Arab 0.8
production Emirates
2017 In operation Ethanol production United States 1.0
2017 In operation Power generation United States 1.4
2018 In operation Natural gas processing China 0.6
2018 In construction Natural gas processing Australia 3.4–4.0
2019 In construction Fertiliser production Canada 0.3–0.6
2019 In construction Oil refining Canada 1.2–1.4
2019 In construction Chemical production China 0.4
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Table 1 Continued (Adapted from the Global Carbon Capture and Storage Institute project
database, (CCS, 2017))

Operation Lifecycle stage Industry Country CO2

date capture
capacity
(Mtpa)
2020 In construction Chemical production China 0.41
2024 Early development Power generation United 3
Kingdom
2025 Early development Fertiliser production and Australia 2.5
power generation
2020–2021 Early development Fertiliser production China 0.5
2020s Early development Power generation China 1.0
2020s Early development Power generation China 2.0
2020s Early development Power generation South Korea 1.0
2020s Early development Power generation South Korea 1.0
2020s Early development Power generation China 2.0
2020s Early development Coal-to-liquids (CTL) China 2.0
2020s Early development Power generation China 1.0
2020s Early development Various industries United 0.8
Kingdom
2023-2024 Advanced Various industries Norway 1.2
development
2020s Advanced Under evaluation Australia 1.0–5.0
development
2022 Advanced Chemical production United States 4.2
(Institute development
estimate)
2022 Advanced Chemical production United States 1.5–2.0
(Institute development
estimate)
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Table 2 Summary of the literature on the application of CCS technologies in various industrial
applications.

Year Methods Application/Industry References

2014 Amine-based chemical absorption Fossil fuel power (Mansouri

plants generation Majoumerd and
Assadi, 2014)
2014 Four carbon capture technologies Cement plant (Bjerge and
(Amine-based chemical absorption, Brevik, 2014)
temperature swing adsorption,
membrane and regenerative calcium
cycle)
2014 Calcium looping Fossil-fuels power (Dieter et al.
plants generation 2014)
2014 Partial oxy combustion Fossil-fuels power (Vega et al. 2014)
plants generation
2015 Oxyfuel combustion Power plant generation (Stanger et al.
2015)
2015 Amine-based chemical absorption Natural gas processing (Cormos, 2015)
and calcium looping
2015 Temperature swing adsorption Coal-fired power plants (Swernath et al.
2015)
2015 Membrane contactor Coal-fired power plant (Molina and
Bouallou, 2015)
2016 Ionic liquids physical absorption Biogas plant (García-Gutiérrez
et al. 2016)
2016 Polyethylenimine (PEI)-impregnated Power plant generation (Sandhu et al.
commercial grade silica in a packed 2016)
bed reactor
2016 Membrane-based processes Coal power plant (Roussanaly et al.
2016)
2016 Post-combustion and Oxy-fuel Cement plant (Zhou et al. 2016)
combustion
2017 Post-combustion and Oxy-fuel Cement plant (Roussanaly et al.
combustion 2017)
2017 Amine-based post-combustion Coal-fired power plants (Hu and Zhai,
2017)
2017 Post-combustion CO2 capture using Coal-fired power plants (Petrescu et al.
amine, aqueous ammonia and 2017)
calcium looping
2017 CO2 absorption Biogas/Fertiliser (He et al. 2017)
production
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Table 2 Continued., Summary of the literature on the application of CCS technologies in various
industrial applications.

Year Methods Application/Industry References

2017 Amine-based post-combustion Steel industry (Oda and Akimoto,

2017)
2017 Hollow fiber membrane-based Cements plants (Hägg et al. 2017)
processes
2018 Adsorption processes by vacuum Biogas (Shen et al. 2018)
pressure swing
2018 MEA-based CO2 absorption process Various industries (pulp (Garðarsdóttir et al.
and paper, oil and gas, 2018)
etc.)
2018 Amine scrubbing, membrane and Steel plant (Chung et al. 2018)
hybrid separation processes
2018 Amine absorption processes Cement plant (Nwaoha et al. 2018)
2018 Amine absorption processes coal-fired plant (Shijian et al. 2018)
2018 Oxy-fuel combustion Power plant (Gładysz et al. 2018)
2018 Oxy-fuel and chemical absorption Coal-fired power plant (Cau et al. 2018)
2018 Chemical absorption Cement plant (Dubois and
Thomas, 2018)
2018 Chemical absorption and membrane Biogas (He et al. 2018)
contactor
2018 Membrane process IGCC power plant (Giuliano et al.
2018)
2018 Adsorption Solar thermal energy (Santori et al. 2018)
industry
2018 Swing adsorption reactor cluster Power plant (Cloete et al. 2018)
 Table 3 Summary of different post-combustion CO2 capture technologies.

CO2 capture Description/ characteristics Existing challenges Future References

technologies recommendations
Absorption Chemical absorption using amine-  High equipment corrosion Future improvement in (Zhao et al.
based solvent (Monoethanolamine rate chemical absorption 2014; Bishnoi
(MEA)) is the first post-  High energy consumption. approach are: (a) and Rochelle,
combustion technology that be  Large energy penalty for developing new 2002;
applied worldwide on a large scale regeneration solvents with better Aaron and
in several industrial processes.  Large absorber volume performance, including Tsouris, 2005;
MEA has excellent reactivity  Solvent degradation due to high CO2 absorption Wang et al.
(faster reaction rate), low cost SO2 and O2 in flue gas capacity, lower 2011; Sreedhar
solvents and high absorption  Environmental impacts regeneration and non- et al. 2017;
capacity. due to solvent emissions toxic solvent, (b) Song et al.
 Additional compression developing advance 2018.
work requirement for the technologies which
captured CO2 able to reduce energy
transportation and storage consumption.
Adsorption The adsorption process is suitable  Challenges in selecting To achieve high (Samanta et al.
to be used for CO2 capture because adsorbent materials capture performance 2012; Ben-
it is reversible, high adsorption  Low CO2 selectivity and high selectivity, Mansour et al.
capacity, less energy extensive and  Intermittent operation and the modification on 2016; Li et al.
low cost of adsorbent material. it needs periodic structure/surface of the 2013; Kenarsari
There are different types of regeneration of the adsorbent materials are et al. 2013; Gao
adsorption technologies such as: (i) adsorbents needed. Adsorbent et al. 2017;
pressure-swing adsorption (PSA),  Pressure drop can be large material should be Song et al.
(ii) temperature-swing adsorption in flue gas applications economical, high CO2 2018).
(TSA), (iii) electric-swing capacity,
adsorption (ESA), (iv) vacuum environmental friendly
swing adsorption (VSA) and (v) and simple operation.
combination of pressure/vacuum-
swing adsorption (PVSA) or etc.,
 Table 3 Continued.,

CO2 capture Description/ characteristics Existing challenges Future References

technologies recommendations
Membrane Membrane technology can be used  Requirement of compression Developing new (Luis et al.
to capture CO2 due to its offer a very work for driving force membrane 2012;
high selectivity, high driving force,  High membrane manufacturing materials and Kenarsari
simple of installation, low capital cost fabricate highly et al. 2013;
cost and energy consumption in  Requirement of high selectivity effective Song et al.
spite of the low partial pressure of (due to CO2 concentration and membranes for the 2018; Xu
CO2. The membrane gas separation low pressure ratio) CO2 capture. et al.
is currently an established  Fouling effect In addition, need 2018).
technology, but the compromise  High membrane surface area is more research on
between permeability and required to accommodate the high transform
selectivity hinders the application of flow rate of industrial flue gas experimental data
membrane technology on a large-  Moisture adversely affected the from lab-scale to
scale. In addition, due to relatively permeability of polymeric the real application
low CO2 concentration and pressure, membrane in the
the driving force for membranes to  Performance is affected by industry.
perform properly is weak in post- operating condition (i.e.
combustion CO2 capture. temperature and pressure)
 Not proven industrially
Cryogenic Cryogenic separation is used  High energy requirement to More efficient (Hart et al.
commercially for high concentration provide sufficient refrigeration cryogenic 2009;
and high pressure gases. Because of  More suitable for high CO2 processes need to Kenarsari
the high capital expenditure of concentration (> 50%) be designed and et al. 2013;
cryogenic separation, this method is  Moisture must be removed from optimized in the Song et al.
economically feasible only if the the gas mixture before cooling to future 2018).
percentage of CO2 is high in the prevent blockage
stream.  Continuous build-up of solidified
CO2 on heat-exchanger surfaces
adversely affect heat transfer and
reduces the process efficiency
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Table 4 Recent research on the adsorbent modification for CO2 capture

Year Adsorbent Methods Operating Reference
parameters
2014 Mesoporous SBA- Mesoporous SBA-15 Maximum CO2 (Jing et al.
15 adsorbents functionalised adsorption 2014)
with melamine-based and capacities (20.4,
acrylate-based amine 23.6, 16.6 and
dendrimers 19.7 mg/g)
2014 Porous precipitated Silica precursor Highest CO2 (Quang et
silica (PPS) impregnated with various adsorption al. 2014)
amines such as 2- capacity up to
aminomethylpropanol, 233 mg/g
monoethanolamine,
diethanolamine and
polyethyleneimine
2014 Mesoporous silica Functionalisation with 3- CO2 adsorption (Vilarrasa-
aminopropyltriethoxysilane capacity up 2.4 García et
(APTES) mmol/g al. 2014)
2014 Rapeseed oil Impregnation with an CO2 adsorption (David and
cake/walnut shell aqueous monoethanolamine capacity was Kopac,
solution 34.72 ml/g. 2014)
2014 Pine nutshell Impregnated by KOH CO2 adsorption (Deng et al.
solution capacity up to 2014)
7.7 mmol/g at
273 K and 5.0
mmol/g at 298 K
at 1 bar
2014 Eucalyptus Eucalyptus wood based CO2 adsorption (Heidari et
camaldulensis wood activated carbons was capacity up to al. 2014)
residue functionalised with 3.22 mmol/g at 1
ammonia bar and 303 K
2015 Biochar Biochar was impregnated CO2 adsorption (Shahkara
with KOH capacity up to mi et al.
1.8 mol/kg 2015)
2015 Microporous carbon Enhance microporosity in CO2 adsorption (Ludwinow
spheres the carbon spheres prepared of 6.6 mmol/g at icz and
by Stöber method, which 0°C and 1 atm. Jaroniec,
involves the addition of 2015)
potassium oxalate to the
ethanol–water–ammonia
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Table 4 Recent research on the adsorbent modification for CO2 capture

Year Adsorbent Methods Operating Reference

parameters
2015 Zirconium metal– The synthesis of UiO- Maximum CO2 (Cao et al.
organic framework 66/GO composites with uptake of 3.37 2015)
(UiO-66) and terephthalic acid (H2BDC) mmol/g at 298 K
graphene oxide and dissolved in N,N- and 1 bar
(GO) dimethylformamide
(DMF)
2015 Honeycomb Aminopropyltriethoxysila CO2 uptakes (2.3 (Vilarrasa-
arrangement ne (APTES) grafting and mmol CO2/g or 4.6 Garcia et
mesoporous silica polyethyleneimine mmol/g PEI at 25 al. 2015)
SBA-15 ethylenediamine (PEI) °C and 1 bar)
impregnation on pure
siliceous hydrothermal
SBA-15
2015 Adsorbents based Macroporous Li4SiO4 was CO2 adsorption (Kim, H. et
on calcium oxide synthesized by a simple capacity al. 2015)
(CaO) lithium solid-state transformation (29.8 wt%) and
orthosilicate method using LiOH and rate
(Li4SiO4) fumed silica as a (56.1 mg/g/min)
precursor for Li and SiO2
2015 Mg-Al layered Synthesis of Mg-AL-NO3- The highest CO2 (Wang et
double hydroxide NS and graphene oxide capture capacity of al. 2015)
(LDH) nanocomposite (Mg-Al- ca. 0.6 mmol/g
and graphene NO3 LDH-NS/GO) and was obtained with
oxide (GO) nanoshe doping with 15 wt% 15 wt% K2CO3
ets K2CO3
2016 Commercially MEA- and DEA- A maximum CO2 (Kongnoo
available palm shell impregnated AC adsorption et al. 2016)
activated carbon capacity of 5.3
(AC) mol/kg was
obtained for the
AC-DEA at 400
kPa and 70°C
2016 Yellow mombin Preparation of the KOH- CO2 adsorption (Fiuza-Jr et
fruit stones (Fruit activated carbon capacity up to al. 2016)
juice) (10.5, 7.3 and 4.9
mmol CO2/g) at (0
°C, 25 °C and 75
°C)
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Table 4 Recent research on the adsorbent modification for CO2 capture

Year Adsorbent Methods Operating Reference

parameters
2016 Nano zeolite (NZ) Modified with CO2 adsorption (Pham et al.
ethylenediamine (EDA) capacity of 7.48 2016)
mmol/g at 70 °C.
The CO2
adsorption–
desorption of NZ
and NZ-EDA
remained above
80% after 15
cycles
2016 Nanoporous Ammonia-treated porous CO2 adsorption (Ma et al.
carbons carbon derived from capacity up to 59.1 2016)
zeolitic imidazolate mg/g
framework-8 (ZIF-8)
2016 Zeolite (ZSM-5) Synthesis of ZSM-5 ZSM-5 CO2 (Frantz et
zeolites with high-sodium adsorption al. 2016)
content at three Si/Al capacity increased
ratios
2017 Titania nanotubes Synthesized using TiCl4 Adsorption (Bhatta et
(TNTs) by acid-hydrolysis method capacity (0.35 al. 2017)
mmol/g) compared
with nano TiO2
(0.17 mmol/g) at
30°C, 1 bar.
2017 Commercial zeolite Vacuum swing adsorption At 5 kPa (Webley et
13X desorption al. 2017)
produced >75%
recovery with a
purity of > 95%
CO2.
2017 Amine-based silica PEI-impregnated sorbents Adsorption (Jung et al.
sorbents capacity up to 2.6 2017)
mmol/g
2017 Silica (Si-MCM-41) Polyethylenimine- CO2 adsorption (Ahmed et
functionalised capacity up to al. 2017)
mesoporous Si-MCM-41 99.44 mg/g at 100
°C for 50 wt%
PEI-Si-MCM-41
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Table 4 Recent research on the adsorbent modification for CO2 capture

Year Adsorbent Methods Operating Reference

parameters
2017 MgO-based MgO-based adsorbents CO2 adsorption (Elvira et
adsorbents were synthesised via capacity of 1.47 al. 2017)
solution–combustion mmol/g at five
method and treated by cycle
ball-milling process.
2018 Nanozeolite (Nano- The novel zeolitic Adsorption (Salehi et
Z) nanocomposites were capacity of Nano- al. 2018)
prepared by Z/Cd in 25 °C and
functionalisation 100 °C are
MWCNT by PEI and 3.7 mmol/g and
adding to the Cd- 2.46 mmol/g
exchanged Nano-Z.
2018 Honeycomb carbon Temperature swing Optimum (Querejeta
monolith adsorption condition at 47 °C et al. 2017)
and at a pressure
of 105 kPa
2018 NaA, NaX and The hydrothermal method The maximum (Wang et
NaZSM-5 zeolites with seed technique was equilibrium al. 2018)
were prepared by used to increase adsorption
using silica crystallinity and to capacity of NaA-
extracted from rice facilitate the production of RS, NaX-RS and
hull ash as a raw smaller sized NaZSM-5-RS was
material nanoparticles. 1.46, 3.12 and
2.20 mmol/g at
0 °C and 101.3 kPa
2018 Silica gel Vacuum pressure swing 96.74% CO2 purity (Shen et al.
adsorption (VPSA) and 97.58% CO2 2018)
recovery.
2018 Nitrogen enriched Nitrogen enriched carbon Maximum CO2 (Tiwari et
carbon adsorbents adsorbents were uptake of al. 2018)
successfully prepared by 2.43 mmol/g.
carbonising the low-cost
urea formaldehyde resin,
followed by KOH
activation.
2018 Biomass-based Pressure swing adsorption Pine sawdust (Durán et
activated carbon carbon best al. 2018)
produced from pine performs in the
sawdust lower pressure
range to separate
CO2/CH4.
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Table 5 Search strategy used for the patent literature search.

Category Keyword terms

Adsorption Adsorption CO2, Adsorption carbon dioxide

Low-temperature adsorbents Carbon-based adsorbent, zeolite, metal
organic framework, alkali metal carbonate,
microporous organic polymer, amine-based
adsorbent
Intermediate-temperature adsorbents Layered double hydroxides
High-temperature adsorbents Calcium-based adsorbent
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Table 6 Patents dealing with metal organic framework material (MOF) as adsorbent for CO2
capture

Patent title Patent number Year

New metal organic framework material useful for gas CN107774234-A 2018
adsorption, gas adsorption storage, gas adsorption separation,
and selective adsorption and separation of methane from
methane/carbon dioxide mixture.
Metal-organic frameworks-derived carbon-based photonic CN108452771-A 2018
crystal-porphyrin-containing covalent organic frameworks
composite material useful for adsorbing carbon dioxide,
comprises e.g. tetra(p-aminophenyl) porphyrin and
terephthalaldehyde.
New metal-organic framework compound for carbon dioxide CN108384020-A 2018
capture in flue gas of thermal power plant and purification of
natural gas.
New magnesium metal-organic framework used as adsorbent KR1707821-B1 2018
for adsorbing and collecting carbon dioxide gas in exhaust WO2017026619-A1
gas discharged from thermoelectric power plant.
Carbon dioxide adsorbent comprises hybrid matrix formed KR1894780-B1 2018
by hybridising reduced graphene oxide nanosheet and
layered metal oxide nanosheet, and co-hybridisation
nanocomposite comprising layered double oxide.
Adsorption material for removing carbon dioxide from e.g. WO2018152438-A1 2018
flue gas and biogas, comprises metal-organic framework,
and several ligands, has preset carbon dioxide adsorption
capacity, and is configured to regenerate at preset
temperature.
Heterogeneous composite structure adsorbing material for CN106693896-A 2017
purifying composition containing nitrogen, carbon
dioxide and methane, has metal organic framework(s) and
silica-alumina molecular sieve or activated carbon material.
Modified zeolitic imidazolate frameworks material useful in CN106732390-A 2017
carbon dioxide adsorption on flue gas capture, prepared by
e.g. reacting imidazole with 1,6-dibromohexane, 1,8-
dibromoctane and 1,10-dibromo-decane in dimethyl
sulfoxide.
New (2E,2'E,2"E)-3,3',3"-(2,4,6-trimethyl) benzene triacrylic CN106732407-A 2017
acid-indium complex used as metal-organic framework
material in selective adsorption and separation of
acetylene/carbon dioxide, and acetylene/methane.
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Table 6 Continued., Patents dealing with metal organic framework material (MOF) as adsorbent
for CO2 capture

Patent title Patent number Year

New magnesium metal-organic framework used as KR1707821-B1 2017
adsorbent for adsorbing and collecting carbon dioxide WO2017026619-A1
gas in exhaust gas discharged from thermoelectric
power plant.
New metal-organic framework used for manufacturing JP2017088542-A 2017
absorbing material used in adsorption-type heat pump
for removing carbon dioxide gas and hydrocarbon gas.
New three-dimensional indium metal-organic CN105664893-A; 2016
framework material i.e. (2E,2'E,2''E)-3,3',3''-(2,4,6- CN105664893-B
trimethylbenzene-1,3,5-triyl) triacrylic acid
tetrabenzoate useful in selective adsorption of carbon-
dioxide.
Carbon dioxide adsorption catalyst for use in CN105149002-A; 2016
cycloaddition reaction of epoxy compound i.e. CN105149002-B
epichlorohydrin, comprises metal organic framework
ZIF-8 as carrier and 1-(3-aminopropyl)-3-
methylimidazolium chloride as active ingredient.
Zirconium-based metal organic framework for CN105713030 (A) 2016
catalyzing and reducing CO2 under visible light and
preparation method of zirconium-based metal organic
framework.
Preparing polyethyleneimine-impregnated UiO-66 CN104826610-A 2015
metal organic framework material used in adsorptive
separation of carbon dioxide comprises e.g. adding
ethanol in polyethyleneimine, mixing, obtaining pasty
mixture, and drying.
Selective carbon dioxide adsorptive separation metal- CN104258814-A; 2015
organic framework material for selective carbon CN104258814-B
dioxide adsorptive separation comprises cobalt salt
complexed with 4,4'-terephthalate and 3,3',5,5'-
tetramethyl-1,1'-diamino-4,4'-bipyrazol.
Metal complex used in adsorbent for e.g. carbon JP2015074604-A 2015
dioxide, comprises preset ratio of terephthalic acid
compound and monocarboxylic acid compound, and
has diffraction peaks within preset range measured by
X-ray diffraction measurement.
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Table 6 Continued., Patents dealing with metal organic framework material (MOF) as adsorbent
for CO2 capture

Patent title Patent number Year

Metal-organic framework particles e.g. metal-organic WO2015189599- 2015
framework monolith used for A1;
gas adsorption/separation applications AU2015273283-A1;
e.g. carbon capture, comprise crystallites adhered to KR2017015495-A;
each other through metal-organic framework binder. CA2951200-A1;
EP3154948-A1;
CN106573225-A;
US2017113205-A1;
JP2017519752-W;
US9884309-B2
Metal-organic framework used in gas separation WO2015142954- 2015
device/gas storage device e.g. fuel storage tank in A1;
vehicles, comprises specific linked secondary building IN201617025042-A;
units optionally comprising pendant linker(s) and/or US2017081345-A1
modulator(s).
Metal complex used for e.g. adsorbent and occlusion WO2014007179- 2014
material for adsorbing and occluding e.g. carbon A1; CN104411673-
dioxide, and hydrogen, comprises polyhydric A; EP2868649-A1;
carboxylic acid compound, metal ion, organic ligand US2015144085-A1;
and monocarboxylic acid compound. JP2014523719-X;
US9586170-B2;
EP2868649-A4;
JP6270720-B2
Metal organic framework-based hierarchical porous US2014212944-A1; 2014
material used in e.g. adsorption and storage of gas, has EP2878366-A1;
structure of MIL-100, MIL-53 and MIL-101NDC, and JP2015105275-A;
comprise nanoparticles capable of generating desired
interparticle mesopores.
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Table 7 Patents dealing with amines as adsorbent for CO2 capture

Patent title Patent number Year

Carbon dioxide adsorbent comprises polymeric amine US2018008958-A1; 2018
consisting of polymer skeleton containing nitrogen KR2018006147-A;
atoms and branched chains bonded to nitrogen atoms US10010861-B2
of the polymer skeleton, and porous support on which
polymeric amine is supported.
Carbon dioxide adsorbent comprises a porous support, KR2018067172-A 2018
and an amine adsorbent formed inside the pores of the
porous support
Carbon dioxide adsorbent comprises polymeric amine US2018008958-A1; 2018
consisting of polymer skeleton containing nitrogen KR2018006147-A;
atoms and branched chains bonded to nitrogen atoms US10010861-B2
of the polymer skeleton, and porous support on which
polymeric amine is supported.
Spherical core-shell nano composite-amine nano- CN107899545-A 2018
structured carbon dioxide adsorbent.
Magnesium-calcium-based carbon dioxide adsorbent CN108067180-A 2018
useful for adsorption and separation of carbon dioxide
generated in chemical chain reforming enhanced
hydrogen production process, comprises calcium
oxide, yttrium oxide and magnesium oxide.
Making spherical carbonaceous materials modified PL417365-A1 2018
with ethylenediamine for carbon dioxide adsorption
involves e.g. making solution of water, ethanol,
ammonia water, ethylenediamine resorcinol,
potassium oxalate and formalin and pressurizing.
Carbon dioxide adsorbent comprises a porous support KR2017119829-A 2017
and an amine adsorbent comprising core layer formed
along the pore inner wall surface and a shell layer
formed on the core layer, formed inside the pores of
the porous support.
Solid amine carbon dioxide adsorbent used in carbon CN107321317-A 2017
dioxide adsorption process, is prepared by supporting
tetraethylenepentamine on ion exchange resin by
coordination method.
Carbon dioxide adsorbent comprises porous support, WO2017183745-A1 2017
and amine adsorbent comprising core layer composed
of amine compound and shell layer formed on core
layer composed of amine compound crosslinked with
crosslinking agent.
Carbon dioxide adsorbent is activated carbon whose CN106378095-A 2017
surface is treated with alcohol amine compound
having predetermined quality based on total weight of
adsorbent.
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Table 7 Continued., Patents dealing with amines as adsorbent for CO2 capture

Patent title Patent number Year

SAPO-34 Molecular sieve used for preparing CN105366687-A; 2016
methane/carbon dioxide adsorption and separation CN105366687-B
material and catalyst, comprises n-butylamine-silicon-
based anhydrous zeolite.
Carbon dioxide adsorption agent used in carbon JP6055134-B1; 2016
dioxide separation collecting system, is formed by JP2017164656-A;
supporting amine compound to silica gel having WO2017159663-A1
specified value of particle diameter, mean pore
diameter and pore volume.
Carbon dioxide adsorbent used for prevention of US2016175808-A1; 2016
environmental pollution produced by carbon dioxide KR2016074844-A
release, comprises ionic liquid-loaded porous support
with amino acid-based amine functional group grafted
on support.
Solid sorbent used for absorbing carbon dioxide from US2016199810-A1; 2016
gas mixture, comprises modified polyamine, which is WO2016114991-
reaction product of amine and epoxide and supported A1;
upon and within or bound to solid support. AU2016207044-A1;
Preparation of super-molecular composite for CN104437383-A; 2015
adsorbing carbon dioxide, involves reacting organic CN104437383-B
amine and macrocyclic compound with solvent,
precipitating and filtering insoluble, washing and
drying obtained solid.
New keto-enamine-bond-containing conjugated CN105061757-A 2015
microporous polymer useful for adsorption-separation
of carbon dioxide.
Composite material used for adsorbing carbon dioxide CN104056599-A; 2014
in flue gas, is synthesized by reacting graphite based- CN104056599-B
metal-organic framework with organic amine in
certain molar ratio.
Adsorbent, useful for adsorbing carbon dioxide in flue CN104056598-A 2014
gas, comprises metal organic framework and organic
amine supported on metal organic framework.
Porous polymeric adsorbent used for separating and CN103657610-A; 2014
purifying carbon dioxide from gas mixture by CN103657610-B
selective adsorption comprises benzyl halide monomer
and primary amine monomer.
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Table 8 Patents dealing with zeolite, molecular sieve and silica as adsorbent for CO2 capture

Patent title Patent number Year

Selectively adsorbing and separating carbon dioxide KR2018051455-A 2018
from gas containing carbon dioxide by contacting with
merlinoite zeolite.
Preparing calcium-doped MCM-48 molecular sieve CN107746064-A 2018
used for carbon dioxide adsorption, by dissolving
templating agents in water, adding alkali source,
silicon source and calcium source, carrying out
hydrothermal crystallization and calcining.
GIS-type zeolite e.g. silica-alumina used in e.g. WO2018110559- 2018
adsorption agent, comprises aluminum atom and A1;
phosphorus atom, and has preset carbon dioxide AU2017329099-A1;
saturated adsorption amount measured when zeolite CN108495813-A
and carbon dioxide are placed in system.
Adsorbent useful in separating carbon dioxide from CN106925235-A 2017
moisture, prepared by e.g. mixing 13X zeolite
molecular sieve, cetyltrimethylammonium bromide
and water, adding ferric chloride solution in
suspension, aging suspension and post-processing.
Amino porous carbon dioxide adsorbent comprises CN106669613-A 2017
amino-functionalized adsorbent material obtained
from impregnation and synthesis of zeolite socony
mobil-5 type zeolite with tetraethylenepentamine.
Preparing copper impregnated zeolite for adsorbing MX2015008315-A1 2017
carbon dioxide, involves dissolving copper nitrate
trihydrate in deionized water, soaking zeolite in
obtained solution, heating soaked zeolite and calcining
at high temperature.
Carbon dioxide adsorbing material useful in gas JP2017170380-A 2017
adsorption material for e.g. performing separation and
recovery of carbon dioxide from mixed gas and
maintenance of freshness of food, comprises calcium
ion-containing type A zeolite.
Producing diamine-zeolite complex used as carbon KR1696395-B1; 2017
dioxide adsorbent, comprises replacing zeolite cations WO2017090825-A1
with ammonium ions, heating to remove ammonia,
adding diamine, reacting, and heating to remove
unreacted diamine
Zeolite separation membrane used for separating WO2017142056-A1 2017
carbon dioxide from natural gas e.g. methane in oil
field, comprises framework of zeolite crystal structure,
which is all silica, formed on porous support which is
fluoride-free.
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Table 8 Continued., Patents dealing with zeolite, molecular sieve and silica as adsorbent for CO2
capture

Patent title Patent number Year

Preparing molecular sieve adsorption profiles CN105363411-A; 2016
comprises e.g. preparing material by method a1 CN105363411-B
comprising e.g. titanium dioxide powder and/or
method a2 comprising mixture of fiber, extruding,
adhering, stacking, oxidizing and drying.
Use of zeolites synthesized by using the ashes of sugar BR102014009903- 2016
cane bagasse, for carbon dioxide adsorption by A2
performing zeolite vacuum activation and adsorption
of carbon dioxide by gravimetric method.
Carbon dioxide adsorbent for carbon dioxide gas WO2015191962- 2015
separation comprises hierarchical zeolite defining A1; US2017173555-
micropores, mesopores, and macropores. A1
Manufacturing amine-modified zeolite socony mobil- KR2015116334-A; 2015
5, useful for carbon dioxide adsorption, comprises KR1595741-B1
adding alumina solution after adding triethylamine
and tripropylamine compound in silica solution.
Preparing carbon molecular sieve used for separating CN103691399-A; 2014
carbon dioxide and methane, involves crushing raw CN103691399-B
materials, mixing and extruding agricultural waste and
adhesive, and then mixing crushed material, phenolic
resin and obtained mixture
A selective carbon dioxide separation method using KR20140085472 2014
ZSM-25 zeolites as adsorbents 20140708
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Table 9 Patents dealing with alkali metal as adsorbent for CO2 capture

Patent title Patent number Year

Adsorbent for adsorption unit for use in removing EP3375517-A1 2018
carbon dioxide from gas mixture containing carbon
dioxide comprises alumina, carbonate compound, and
alkali metals in which adsorbent has predetermined
carbonate to alumina intensity ratio.
Composite magnesium oxide-based carbon dioxide CN107321296-A 2017
medium temperature adsorbent comprises four alkali
metal salts and magnesium oxide/calcium oxide
composite with multi-layered flower structure.
Carbon dioxide adsorbent comprises aluminum oxide, CN107115845-A 2017
silicon oxide, analcime, calcium analcime, carbon
nano tube, carbon molecular sieve and alkali metal
compound.
New alkali metal nitrate co-precipitated hydrotalcite KR2017037520-A 2017
useful in adsorbent for trapping and adsorbing carbon
dioxide.
Adsorbent useful for removing an acid molecule that FR3024378-A1; 2016
is carbonyl sulfide and/or carbon dioxide, from a WO2016015923-
hydrocarbon stream, comprises an aluminum support, A1; CN106573224-
and at least one alkali metal element e.g. sodium. A;
Mixed solution for capturing carbon dioxide, is CN104958996-A; 2015
obtained by mixing hydrazine hydrate and azole-based CN104958996-B
alkali metal salt, where azole-based alkali metal salt is
formed by utilizing imidazole, pyrazole, triazole and
tetrazole.
Adsorbent for separating carbon dioxide from gas US2014305302-A1; 2014
mixture comprises mesoporous inorganic oxide having KR2014123849-A;
crystalline halide of alkali metal or alkaline earth US9205404-B2
metal and chemical species having phosphorus, sulfur
or boron supported on the oxide.
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Table 10 Patents dealing with activated carbon as adsorbent for CO2 capture

Patent title Patent number Yea

r
Method for performing thermal swing adsorption for removing EP3338875-A1 2018
component i.e. carbon dioxide, from flue gas, involves passing
gas mixture in contact with adsorbent material to adsorb
component from gas mixture on adsorbent material.
Carbon dioxide solid adsorbent-based impregnated activated CN108126660-A 2018
carbon c used for adsorption of carbon dioxide, contains
activated carbon carrier, carbonate or hydroxide-containing
Group (IA) element or Group (IIA) element and promoter.
Activated carbon composite material used as adsorbent for CN108126659-A 2018
adsorbing e.g. volatile organic compounds from flue gas,
comprises integrally formed activated carbon and inorganic heat-
conducting particles including silicon carbide particles.
Regenerating organic gas adsorption saturated activated carbon CN108067208-A 2018
involves initially calcining organic gas adsorption saturated
activated carbon to obtain calcined material, and then finally
calcining under carbon dioxide atmosphere.
Nano-molecular carbon useful as toxic gas purification material, CN108310900-A 2018
comprises activated carbon powder, silicate, effervescent tablet
and titanium dioxide.
Adsorbing carbon dioxide using activated carbon, comprises PL418158-A1 2018
adding carboxymethyl starch-based film to potassium hydroxide
to form activated carbon, leaving mixture to impregnate, and
drying obtained mixture by carbonizing, washing and drying.
Preparation of biomass-based activated carbon useful for high- CN106517181-A 2017
efficient adsorption of carbon dioxide, involves washing
biomass shell and crushing into powder, adding activating agent
and distilled water, carbonizing mixture, and drying.
Adsorbing and separating carbon dioxide from gas mixture by a KR2017013440- 2017
pressure-cyclic adsorption method using surface modified A; KR1824771-
activated carbon as adsorbent. B1
Multilayer adsorbent bed for purifying feed stream comprises WO2017048742 2017
adsorbent section which contains activated carbon layer, and -A1;
adsorbent sections which contain layer of molecular sieve of US2018036671-
faujasite structure type. A1;
IN20171704284
3-A;
EP3349878-A1
Pressure swing adsorption biogas purification membrane and CN105950241-A 2016
mixing system includes filtration system for filtering solid
particles in raw biogas material, desulfurization system, heat
exchanger, and protecting bed of activated carbon.
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Table 10 Continued., Patents dealing with activated carbon as adsorbent for CO2 capture

Patent title Patent number Year

Preparing activated carbon with high adsorption of PL410488-A1 2016
carbon dioxide involves mixing active carbon with
solution mixture of modifiers for 1-6 hours, where
modifiers are potassium hydroxide, sodium hydroxide,
zinc chloride and sodium carbonate.
High-efficient carbon dioxide trapping material CN104907045-A; 2015
comprises granular, columnar, spherical or CN104907045-B
honeycomb activated carbon, alkali/alkaline earth
metal salt of active silica-alumina gel, and nitrogen-
containing organic compound.
Producing rice husk-based activated carbon useful as CN104445188-A; 2014
e.g. adsorbent material, involves crushing rice husk CN104445188-B
containing carbon to obtain powder containing carbon
particles, activating using carbon dioxide, and adding
alkaline solution.
Carbon dioxide adsorption agent for carbon dioxide JP2014083488-A; 2014
separation collection comprises oxide particles which JP6089579-B2
contains copper oxide, zinc oxide, and/or manganese
oxide as activated carbon carrier.
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Table 11 Patents dealing with layered double hydroxide (LDH) as adsorbent for CO2 capture

Patent title Patent number Year

Cobalt oxide nanoparticles assembled with layered RO132424-A2 2018
double hydroxides, with applications in carbon
dioxide capture from wet gases and photocatalytic
reduction thereof.
Carbon dioxide adsorbent comprises hybrid matrix KR1894780-B1 2018
formed by hybridizing reduced graphene oxide
nanosheet and layered metal oxide nanosheet, and co-
hybridization nanocomposite comprising layered
double oxide.
Carbon dioxide adsorbent containing mesoporous KR2017042520-A; 2017
layered nano-hybrid comprises layered double KR1808554-B1
hydroxide nano-sheet and metal nano cluster having
opposite surface charge and mesopore formed by
inserting metal nano clusters.
Carbon dioxide adsorbent useful as environmental KR2016111703-A 2016
catalyst, comprises nano-hybrid mesoporous layer is
formed by recombination reaction of metal
nanocluster and peeled metal layered double
hydroxides nanosheet with opposite charge surface.
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Table 12 Patents dealing with calcium based as adsorbent for CO2 capture

Patent title Patent number Year

Preparation of carbon dioxide adsorption material, involves CN108187628-A 2018
mixing gangue, calcium carbonate and zinc chloride, carrying
out microwave pyrolysis, adding alkali solution, heating and
reacting with calcium nitrate aqueous solution.
Magnesium-calcium-based carbon dioxide adsorbent useful for CN108067180-A 2018
adsorption and separation of carbon dioxide generated in
chemical chain reforming enhanced hydrogen production
process, comprises calcium oxide, yttrium oxide and
magnesium oxide.
Preparing calcium-doped MCM-48 molecular sieve used for CN107746064-A 2018
carbon dioxide adsorption, by dissolving templating agents in
water, adding alkali source, silicon source and calcium source,
carrying out hydrothermal crystallization and calcining.
Preparing calcium-based adsorbent modified by high CN107029660-A 2017
temperature carbon-dioxide, comprises calcium-based
adsorbent preparation carried out using oil sands pyrolysis
residue as calcium source, and adding kaolinite complex.
Ytterbium-doped carbon dioxide adsorbent comprises CN106861601-A 2017
ytterbium oxide and calcium oxide, where ytterbium oxide is
uniformly distributed in the calcium oxide.
Preparing high-temperature carbon dioxide calcium-based CN106582491-A 2017
adsorbent doped with silicon nitride involves carbonizing
wood powder in inert gas atmosphere, mixing carbon powder
and ethyl orthosilicate, and adding liquor ammonia.
Adsorption column used for adsorbing carbon dioxide, has US2017014799- 2017
carbon dioxide gas inlet, gas outlet and fixed bed column A1; US9649619-
comprising calcium-sodium-silicon oxide-aluminum B2
oxide/sodium-calcium-aluminosilicate composition containing
gehlenite.
Porous coordination polymer for carbon dioxide adsorption JP2016193957-A 2016
agent comprises magnesium ion and 2,5-dihydroxy
terephthalic acid, in which porous coordination polymer
contains calcium outside the skeleton.
Preparing calcium composite carbon dioxide adsorbent CN105498710-A 2016
comprises taking fishbone, crushing, placing powder into a
container, aging, adding methyl acrylate to obtain composite
calcium base carbon dioxide initial adsorbent, drying and
crushing.
Calcium oxide-based carbon dioxide adsorbent used in high- CN103657582-A 2014
temperature gas separation, comprises doped chemical additive
present in calcium carbonate ore powder by high temperature
calcination.