The Scientific World Journal

Volume 2014 (2014), Article ID 828131, 34 pages

http://dx.doi.org/10.1155/2014/828131

Review Article

Carbon Dioxide Separation from Flue Gases: A Technological Review Emphasizing Reduction in Greenhouse Gas Emissions

Mohammad Songolzadeh,¹ Mansooreh Soleimani,¹ Maryam Takht Ravanchi,² and Reza Songolzadeh³

¹Department of Chemical Engineering, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran

²Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company, P.O. Box 1435884711, Tehran, Iran

³Department of Petroleum Engineering, Petroleum University of Technology, P.O. Box 6198144471, Ahwaz, Iran

Received 17 August 2013; Accepted 31 October 2013; Published 17 February 2014

Academic Editors: D.-W. Han and V. A. Rogov

Copyright © 2014 Mohammad Songolzadeh et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Increasing concentrations of greenhouse gases (GHGs) such as CO₂ in the atmosphere is a global warming. Human activities are a major cause of increased CO₂ concentration in atmosphere, as in recent decade, two-third of greenhouse effect was caused by human activities. Carbon capture and storage (CCS) is a major strategy that can be used to reduce GHGs emission. There are three methods for CCS: pre-combustion capture, oxy-fuel process, and post-combustion capture. Among them, post-combustion capture is the most important one because it offers flexibility and it can be easily added to the operational units. Various technologies are used for CO₂ capture, some of them include: absorption, adsorption, cryogenic distillation, and membrane separation. In this paper, various technologies for post-combustion are compared and the best condition for using each technology is identified.

1. Introduction

There are ten primary GHGs including water vapor (H₂O), carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) that are naturally occurring. Perfluorocarbons (CF₄, C₂F₆), hydrofluorocarbons (CHF₃, CF₃CH₂F, and CH₃CHF₂), and sulfur hexafluoride (SF₆), are only present in the atmosphere due to industrial processes. Water vapor is the most important, abundant and dominant greenhouse gas, and CO₂ is the second-most important one (Table 1). Concentration of water vapor depends on temperature and other meteorological conditions, and not directly upon human activities. So it was not indicated in Table 1 [1–3].

Table 1: The main greenhouse gases and their concentration [2, 3].

Compound
Preindustrial concentration (ppmv)
Concentration in 2011 (ppmv)
Atmospheric lifetime (years)
Main human activity source
GWP**

Carbon dioxide (CO₂)
280
388.5
~100
Fossil fuels, cement production, land use
1

Methane (CH₄)
0.715
1.87/1.748
12
Fossil fuels, rice paddies, waste dumps, livestock
25

Nitrous oxide (N₂O)
0.27
0.323
114
Fertilizers, combustion industrial processes
298

CFC-12 (CCL₂F₂)
0
0.000533
100
Liquid coolants, foams
10,900

CF-113 (CCl₂CClF₂)
0
0.00000075
85
n.a.
6,130

HFC 23 (CHF₃)
0
0.000018
270
Electronics, refrigerants
11,700

HCFC-22 (CCl₂F₂)
0
0.000218
12
Refrigerants
1,810

HFC 134 (CF₃CH₂F)
0
0.000035
14
Refrigerants
1,300

HCFC-141b (CH₃CCl₂F)
0
0.00000022
9.3
n.a.
725

HCFC-142b (CH₃CClF₂)
0
0.00000020
17.9
n.a.
2,310

HFC 152 (CH₃CHF₂)
0
0.0000039
1.4
Industrial processes
140

Perfluoromethane (CF₄)
0.00004
0.00008*
50,000
Aluminum production
6,500

Perfluoroethane (C₂F₆)
0
0.000003*
10,000
Aluminum production
9,200

Sulfur hexafluoride (SF₆)
0
0.00000712*
3,200
Dielectric fluid
22,800

 *Concentration in 2011.

**Global warming potentials (GWPs) measure the relative effectiveness of GHGs in trapping the Earth’s heat.

CO₂ is the primary anthropogenic greenhouse gas, accounting for 77% of the human contribution to the greenhouse effect in recent decade (26 to 30 percent of all CO₂ emissions). Main anthropogenic emissions of CO₂ come from the combustion of fossil fuels. CO₂ concentration in flue gases depends on the fuel such as coal (12–15 mol-% CO₂) and natural gas (3-4 mol-% CO₂). In petroleum and other industrial plants, CO₂ concentration in exhaust stream depends on the process such as oil refining (8-9 mol% CO₂) and production of cement (14–33 mol-% CO₂) and iron and steel (20–44 mol-%). From 2004 to 2011, global CO₂ emissions from energy uses were increased 26% (Figure 1) [4–10]. Figure 2 indicates that power plant (55% of global CO₂ emissions), transportation (23%), and industry (19%) have highest share in the CO₂ emission in USA. Cement and petrochemical plants are two major industries for CO₂ emission, such that cement industry contributes about 5% to global anthropogenic CO₂ emissions. Also, petrochemical industries are a large share of CO₂ emission; for example, only in Iran, petrochemical industries emission was about 15 Mton CO₂/year [11–16].

Figure 1: Global CO₂ emissions from fossil fuel combustion and cement production [23].

Figure 2: U.S. GHG Emissions Allocated to Economic Sectors [2].

The Kyoto Protocol is the first international agreement on emissions of GHGs. In this protocol, industrialized countries agreed to stabilize or reduce the GHGs emissions in the commitment period 2008–2012 by 5.2% on average (compared to their 1990 emissions level). Overall, the result of global CO₂ emissions (Figure 1) shows the failure of Kyoto protocol; therefore, in 2011 Durban COP meeting, this protocol was extended until 2017. Several countries with high GHGs emission like China, India, Brazil, and even Iran have added to this Protocol. Intergovernmental Panel on Climate Change (IPCC) predicted the atmosphere may contain up to 570 ppmv CO₂ by the year 2100, causing a rise of mean global temperature and sea level around 1.9°C and 38 m, respectively [15, 17–20]. Given that the earth’s average temperature continues to rise, Intergovernmental Panel on Climate Change (IPCC) stated, global GHG emissions must be reduced by 50 to 80 percent by 2050 to avoid dramatic consequences of global warming [21–23].

Carbon capture and storage (CCS) is the most indicated technology to decrease CO₂ emission from fossil fuels sources to atmosphere. Also, CO₂ separated from flue gases can be used in enhanced oil recovery (EOR) operations where CO₂ is injected into oil reservoirs to increase mobility of oil and reservoir recovery [24, 25]. Pure CO₂ has many applications in food/beverage and different chemical industries such as urea and fertilizer production, foam blowing, carbonation of beverages and dry ice production, or even in the supercritical state as supercritical solvent [26–28].

From this definition, CCS consists of three basic stages: (a) separation of CO₂, (b) transportation, and (c) storage. Operating costs of these stages have been estimated in 2008:

(i)CO₂ separation from exhausting gases: 24 to 52 /ton-CO₂,(ii)transportation to storage location: 1 to 6 /ton-CO₂ per 100 km,(iii)storage: −28 to 42 /ton-CO₂.

Therefore, CO₂ separation is a major stage in CCS. The CCS total costs can vary from −3 to 106 /ton-CO₂ (negative values are expected for the injection of CO₂ in EOR). There are three major approaches for CCS: pre-combustion capture, oxy-fuel process, and post-combustion capture (Figure 3) [25, 30, 31].

Figure 3: Three basic approaches of CO₂ capture [29].

Pre-combustion capture involves reaction of a fuel with oxygen or air and in some cases steam to produce a gas mainly composed of carbon monoxide and hydrogen, which is known as synthesis gas (syngas) or fuel gas. The produced carbon monoxide is reacted with steam in a catalytic reactor, called shift converter, to give CO₂ and more hydrogen. CO₂ is then separated, usually by cryogenic distillation or chemical absorption process, resulting in a hydrogen-rich fuel that can be used in many applications, such as furnaces, gas turbines, engines and fuel cells [32, 33].

A main advantage of post-combustion is the higher CO₂ concentration and pressure achieved in the output stream. The main disadvantage of pre-combustion capture is system needs long-term development in a number of enabling technical areas to achieve targeted efficiency towards a hydrogen economy. This disadvantage has limited application of this approach and increased investments costs of pre-combustion capture [34, 35].

In oxy-fuel combustion, nearly pure oxygen is used for combustion instead of ambient air, and this results in a flue gas that is mainly CO₂ and H₂O, which are separated by condensing water. Three major advantages of this method are high CO₂ concentration in output stream (above 80% v/v), high flame temperature, and easy separation of exhaust gases. The major disadvantages of oxy-fuel combustion are high capital cost and large electric power requirement to separate oxygen from air [36–38].

The principle of post-combustion capture is CO₂ separation from flue gas after combustion. Generally, the CO₂ in flue gas is diluted (8–15% CO₂) with inert gases such as nitrogen, argon, and water in addition to oxygen. Flue gases are normally at atmospheric pressure and high temperatures (between 320 K and 400 K) [39–41]. Post-combustion capture does not require expensive technologies such as syngas separation, hydrogen turbine, fuel cell. Post-combustion capture is the most important to prevent CO₂ emissions, because it offers flexibility and does not need to change combustion cycle. If the capture plant shuts down, the power plant can still operate [42, 43]. Major disadvantage of this method is unfavorable condition of flue gases.

Because of the importance in selecting suitable process for CO₂ separation, in this research various technologies for this purpose have been focused.

2. CO₂ Separation Technologies

Based on economical and environmental considerations, it is necessary to apply efficient and suitable technology for CO₂ separation with low operating cost and energy consumption. Up to now, there are several gas separation technologies being investigated for post-combustion capture, namely, (a) absorption, (b) adsorption, (c) cryogenic distillation, and (d) membrane separation (Figure 4) [39, 44]. Although various new methods were suggested for CO₂ separation, Granite and Brien [45] reviewed some of the most novel methods for carbon dioxide separation from flue and fuel gas streams, such as use of electrochemical pumps and chemical looping for CO₂ separation.

Figure 4: Different technologies for CO₂ separation [29].

2.1. Absorption

Absorption stripping is an important technology for CO₂ capture from fuel gas; in this technology desired component in mixed gases are dissolved in a solvent (bulk phase) [46]. The general scheme of this process is depicted in Figure 5.

Figure 5: Schematic diagram of CO₂ absorption pilot plant.

The flue gas (containing CO₂) is cooled (between 318 and 323 K), and fed to the absorption column (scrubber) where the solvent absorbs CO₂. The CO₂-rich solution is fed into a heater to increase the temperature of solution, then to a stripper column to release the CO₂. The released CO₂ is compressed, and the regenerated absorbent solution is cooled and recycled to the absorber column [47, 48].

Energy required for post-combustion CO₂ capture is an important issue. Thus, recent studies suggest that reduction of the cost of this capture could be achieved by finding suitable solvents that could process larger amounts of CO₂ for a given mass and require less energy for stripping stage [49, 50].

2.1.1. Solvents

In absorption process, flue gas is contacted with a liquid “absorbent” (or “solvent”), and CO₂ is absorbed by this solvent [21]. However, the absorbent should have a suitable capacity for CO₂ absorption, high kinetic rate for CO₂ absorption, negligible vapor pressure, and high chemical and thermal stability and should be harmless for labor persons [51–53].

The solvents used for CO₂ absorption can be divided into two categories: physical and chemical solvents. Physical solvent processes use organic solvents to physically absorb acid gas components rather than reacting chemically, but chemical absorption depends on acid-base neutralization reactions using alkaline solvents [54, 55]. In the recent years, many studies have compared the performance of different solvents as listed in Table 2.

Table 2: Various solvents suggested for CO₂ separation.

Group of solvents
Advantage
Disadvantage
Application
Reference

Physical

Dimethyl ether of polyethylene glycol (Selexol)
(i) Require low energy for regeneration (less than 20% of the value for chemical absorbent)

(ii) Low vapor pressure, low toxicity, and less corrosive solvent
(i) Dependent on temperature and pressure; therefore they are not suitable for post-combustion process

(ii) Low capacity for CO₂ absorption
Natural gas sweetening
[29, 39, 57, 62, 63]

Glycol
Capturing CO₂ and H₂S at higher concentration

Glycol carbonate
Separating CO₂ from other gases

Methanol (Rectisol)
CO₂ removal from various streams

Fluorinated solvent
(i) CO₂ removal from various streams

(ii) Separating CO₂ from other gases

Chemical

Alkanolamines: monoethanolamine (MEA), diethanolamine (DEA), and methyl diethanolamine (MDEA)
(i) React rapidly

(ii) High selectively (between acid and other gases)

(iii) Reversible absorption process

(iv) Inexpensive solvent
(i) Low CO₂ loading capacity

(ii) Solvent degradation in existence of SO₂ and O₂ in flue gas (concentrations must be less than 10 ppm and 1 ppm)

(iii) High equipment corrosion rate

(iv) High energy consumption
Important for removing acidic components from gas streams
[58, 60, 61, 64–66]

Amino acid and aqueous amino acid salt
(i) The possibility of adding a salt functional group.

(ii) The nonvolatility of solvents

(iii) Having high surface tension

(iv) Having better resistance to degradation than other chemical solvents

(v) Better performance than MEA of the same concentration for CO₂ absorption
Decreased performance in the presence of oxygen
Suggested for CO₂ separation from flue gases
[65, 67–69]

Ammonia
(i) No degradation in the presence of SO₂ and O₂ in the flue gases

(ii) No corrosion effect

(iii) Require low energy to regeneration (1/3 that required with MEA)

(iv) Low costs with aqueous ammonia, respectively, 15% and 20% less than with MEA
(i) Reversible at lower temperatures (not suitable for post-combustion)

(ii) Production of solid products and their operating problems

(iii) Explosion of dry CO₂-NH₃ reaction in the high concentration of CO₂ in the flue gas (explosive limit for NH₃ gas is 15–28%)
Suggested for CO₂ separation from flue gases
[39, 70]

Ionic liquid (IL)
(i) Very low vapor pressure

(ii) Good thermal stability

(iii) High polarity

(iv) Nontoxicity
Increased viscosity with CO₂ absorption
Suggested for CO₂ separation from flue gases
[71–74]

Aqueous piperazine (PZ)
(i) Fast absorption kinetics (CO₂ absorption rate with aqueous PZ is more than double that of MEA)

(ii) Low degradation rates for CO₂ separation

(iii) Negligible thermal degradation in concentrated PZ solutions

(iv) Favorable equilibrium characteristics

(v) Very low heat of absorption (10–15 kCal/mol CO₂), 80–90% energy required for aqueous amine system
Lower oxidative degradation of concentrated PZ (i.e., 4 times slower than MEA in the presence of the combination of Fe²⁺/Cr³⁺/Ni²⁺ and Fe²⁺/V⁵⁺)
(i) Effective for treating syngas at high temperatures

(ii) Application of additional amine promoters for natural gas treating and CO₂ separation from flue gases
[29, 66, 75, 76]

(1) Alkanolamines. Between various solvent groups, alkanolamines group is the most important and more used for CO₂ separation. A major problem in the usage of amines for CO₂ absorption is equipment corrosion, so Albritton et al. [56] examined corrosion rate of various amine solvents and suggested corrosion rate could reduce in the following order: monoethanolamine (MEA) > 2-amino-2-methyl-1-propanol (AMP) > diethanolamine (DEA) > methyl diethanolamine (MDEA).

On the other way, MEA can react more quickly with CO₂ than MDEA, but MDEA has higher CO₂ absorption capacity and requires lower energy to regenerate CO₂ [39, 57, 58]. Thus, it can be concluded that MEA is one of the best amine solvents for CO₂ separation. Idem et al. [59] reported substantial reduction in energy requirements and modest reduction in circulation rates for amine blends relative to the corresponding single amine system of similar total amine concentration. Wang et al. [57] found that when MEA and MDEA are mixed at the appropriate ratio, the energy consumption for CO₂ regeneration is reduced significantly. Dave et al. [28] compared the performance of several amine solvents and ammonia solutions at various concentrations. They showed that 30 wt% AMP based process has the lowest overall energy requirement among the solvents considered in their study (30% MEA, 30% MDEA, 2.5% NH₃, and 5% NH₃) [28, 60].

Knudsen et al. [61] studies showed that it is possible to run the post-combustion capture plant continuously while achieving roughly 90% CO₂ separation levels and CASTOR-2 (blended amine solvents), operated in pilot scale with lower steam requirement and liquid-to-gas ratio (L/G) than the conventional MEA solvent.

Besides alkanolamines, carbonate-bicarbonate buffers and hindered amines are used in the bulk removal of CO₂ owing to the low steam requirement for its regeneration. Mitsubishi Heavy Industries and Kansai Electric have employed other patented chemical solvents—strictly hindered amines called KS-1, KS-2, or KS-3. The regeneration heat of KS solvents is said to be ~3 GJ/t CO₂, that is, 20% lower than that of MEA with ~3.7 GJ/t CO₂ [60, 64, 77]. Generally, the overall cost of amine absorption/stripping technology for CO₂ capture process is 52–77 US$/ton CO₂ [71].

(2) Amino Acid. Amino acids have the same functional groups as alkanolamines and can be expected to behave similarly towards CO₂ but do not deteriorate in the presence of oxygen. Based on the results of tests, the aqueous potassium salts (composed of sarcosine and proline) are considered to be the most promising solvents. The most common amino acids used in the gas treating solvents are glycine, alanine, dimethyl glycine, diethyl glycine, and a number of sterically hindered amino acids [65, 67, 68].

Results of many research groups showed that these solvents are suitable for application in membrane gas absorption units, because these solvents have better performance and degradation resistance than other chemical solvents [78]. Amino acid salts formed by neutralization of amino acids with an organic base such as amine showed better CO₂ absorption potential than amino acid salts from neutralization of amino acid salts from an inorganic base such as potassium hydroxide [79, 80]. Aronu et al. [69] studied the performance of amino acids neutralized with 3-(methylamino)propylamine (MAPA), glycine, β-alanine, and sarcosine. Their results indicated that sarcosine neutralized with MAPA has the best CO₂ absorption performance. Its performance is also enhanced by promoting with excess MAPA [69].

(3) Ammonia. Since ammonia is a toxic gas, prevention of ammonia “slip” to the atmosphere is a necessity. Despite this disadvantage, chilled ammonia process (CAP) was used for CO₂ separation (Figure 6). In the CAP, CO₂ is absorbed in an ammoniated solution at a lower absorption temperature (275–283 K) that reduced ammonia emissions from the CAP absorber. Ammonium carbonate solution resulted in approximately 38% carbon regeneration compared to MEA solution [70, 81, 82].

Figure 6: Schematic layout of CO₂ separation block based on the chilled ammonia process [92].

(4) Aqueous Piperazine (PZ). Piperazine (PZ) is as an additive used for amine systems to improve kinetics of CO₂ absorption, such as MDEA/PZ or MEA/PZ blends. Because PZ solubility in water is low, concentration of PZ is between 0.5 and 2.5 M. As indicated in Table 2, increasing the concentration of PZ in solution allows for increased solvent capacity and faster kinetic. The presence of potassium in solution increases the concentration of / in solution; therefore, solution has buffering property. These competing effects yield a maximum fraction of reactive species at potassium to piperazine ratio of 2 : 1 [75, 83, 84].

2.2. Adsorption

Adsorption operation can reduce energy and cost of the capture or separation of CO₂ in post-combustion capture. To achieve this goal, it is necessary to find adsorbents with suitable properties. In general, CO₂ adsorbent must have high selectivity and adsorption capacity and adequate adsorption/desorption kinetics, remain stable after several adsorption/desorption cycles, and possess good thermal and mechanical stability [51, 85–88]. The adsorbents used for CO₂ separation placed into two main categories: physical and chemical adsorbents.

2.2.1. Chemical Adsorption

Chemisorption is a subclass of adsorption, driven by a chemical reaction occurring at the exposed surface. Adsorption capacities of different chemical adsorbents are summarized in Table 3.

Table 3: Adsorption capacity of chemical adsorbents for post-combustion CO₂.

Sorbent
Operating temperature (K)
Operating pressure (kPa)
CO₂ capture capacity (mol CO₂/kg sorbent)
Regeneration cycles,
CO₂ capture capacity remained after cycles (%)
Reference

Mesoporous (MgO)
298
101
1.8
3
100
[93]

CaO nanopods
873
101
17.5
50
61.1
[94]

CaO derived from nanosized CaCO₃
923
101
16.7
100
22.2
[93]

CaO-MgAl₂O₄ (spinel nanoparticles)
923
101
9.1
65
84.6
[93]

Nano CaO/Al₂O₃
923
101
6.0
15
61.7
[93]

Lithium silicate nanoparticles
883
101
5.77
n.a.
n.a.
[93]

Nanocrystalline Li₂ZrO₃ particles
843
101
6.1
8
100
[93]

CaO/Al₂O₃
923
101
6.02
n.a.
n.a.
[93]

Lithium silicate
993
n.a.
8.18
n.a.
n.a.
[17]

Lithium zirconate
673
100
5.0
n.a.
n.a.
[93]

Lithium orthosilicate
873
100
6.13
n.a.
n.a.
[93]

Calcium oxide
873
100
17.3
n.a.
n.a.
[93]

Magnesium hydroxide
473
1034
3.0
n.a.
n.a.
[93]

Mesoporous magnesium oxide
373
100
2.27
n.a.
n.a.
[93]

Lithium Silicate nano particles
873
101
5
n.a.
n.a.
[95]

HTI-HNa
573
134
1.109
50
93.3
[93]

A wide range of metals have been studied including [89]

(i)metal oxides: CaO, MgO,(ii)metal salts from alkali metal compounds: lithium silicate, lithium zirconate to alkaline earth metal compounds (i.e., magnesium oxide and calcium oxide),(iii)hydrotalcites and double salts.

In general, one mole of metal compound can react with one mole of CO₂ with a reversible reaction. The process consists of a series of cycles where metal oxides (such as CaO) at 923 K are transformed into metal carbonates form (such as CaCO₃) at 1123 K in a carbonation reactor to regenerate the sorbent and produce a concentrated stream of CO₂ suitable for storage [90, 91].

Considerable attention was paid to calcium oxide (CaO) as it has a high CO₂ adsorption capacity and high raw material availability (e.g., limestone) at a low cost. Lithium salts was recorded a good performance in CO₂ adsorption, but it gained less focus due to its high production cost. Although double salts can be easily regenerated due to low energy requirement, their stability has not been investigated [93, 96].

The reaction of CO₂ adsorption with Li₂ZrO₃ is reversible in the temperature range of 723–863 K. The capacity of lithium silicate (8.2 moL CO₂/kg sorbent at 993 K) is larger than that of lithium zirconate (4.85 moL/kg sorbent) [17].

Hydrotalcite (HT) contains layered structure with positively charged cations balanced by negatively charged anions [97, 98]. Adsorption and final capacity of different adsorption/desorption cycles are listed in Table 3.

One way for improving CO₂ adsorption efficiency is application of nanomaterials. Different nano-materials can be used for CO₂ separation (Table 3). However, nanomaterials always have high production cost with complicated synthesis process such as carbon nanotubes and graphite nanoplatelets [99, 100].

The main disadvantage of chemical adsorbents is difficult regeneration process, and application of these adsorbents needs more studies for finding new adsorbents [88, 95].

2.2.2. Physical Adsorption

Physisorption, also called physical adsorption, is a process in which the electronic structure of the atom or molecule is barely perturbed upon adsorption. If the CO₂ adsorption capacity of solid adsorbents reaches 3 mmoL/g, the required energy for adsorption will be less than 30–50% energy for absorption with optimum aqueous MEA [101]. The major physical adsorbents suggested for CO₂ adsorption include activated carbons and inorganic porous materials such as zeolites [102, 103]. The adsorption capacities of various physical adsorbents are summarized in Table 4.

Table 4: Adsorption capacity of physical adsorbents for post-combustion CO₂.

Sorbent
Operating temperature (K)
Operating pressure (kPa)
CO₂ capture capacity (mol CO₂/kg sorbent)
Regeneration cycles,
CO₂ capture capacity remained after cycles (%)
Reference

Activated carbon
303
110
1.58
n.a.
n.a.
[93]

AC (4% KOH)
303
30
0.55
n.a.
n.a.
[93]

AC (EDA + EtOH)
303
30
0.53
n.a.
n.a.
[93]

AC (4% KOH + EDA + EtOH)
303
30
0.64
n.a.
n.a.
[45, 70, 79]

NiO-ACs
298
101
2.227
n.a.
n.a.
[104]

13X
393
15.198
0.7
n.a.
n.a.
[105]

5A
393
15.198
0.38
n.a.
n.a.
[105, 106]

4A
393
15.198
0.5
n.a.
n.a.
[105]

WEG-592
393
15.198
0.6
n.a.
n.a.
[105]

APG-II
393
15.198
0.38
n.a.
n.a.
[105]

Na-Y
273
10.132
4.9
n.a.
n.a.
[105]

Na-X
373
101.32
1.24
2
n.a.
[105]

NaKA
373
101.32
3.88
—
n.a.
[105]

NaX-h
323
101.32
2.52
2
n.a.
[105]

NaX-h
373
101.32
1.37
2
n.a.
[105]

Na-X-c
323
101.32
2.14
2
n.a.
[105]

Na-X-c
373
101.32
1.41
2
n.a.
[105]

Cs-X-h
323
101.32
2.42
2
n.a.
[105]

Cs-X-h
373
101.32
1.48
2
n.a.
[105]

Cs-X-c
323
101.32
1.76
2
n.a.
[105]

Cs-X-c
373
101.32
1.15
n.a.
n.a.
[105]

MCM-41
298
100
0.62
n.a.
n.a.
[93]

MCM-41 (DEA)
348
100
1.26
n.a.
n.a.
[93]

MCM-41 (50% PEI)
348
100
2.52
n.a.
n.a.
[93]

Activated carbon
303
30
0.35
n.a.
n.a.
[93]

MCM-41 (50% PEI) “molecular basket”
348
100
2.95
n.a.
n.a.
[93]

PE-MCM-41
298
100
0.50
n.a.
n.a.
[93]

PE-MCM-41 (TRI)
298
100
2.85
n.a.
n.a.
[93]

PE-MCM-41 (DEA)
348
100
2.36
n.a.
n.a.
[93]

MCM-48
298
100
0.033
n.a.
n.a.
[93]

MCM-48 (APTS)
298
100
0.639
n.a.
n.a.
[93]

MCM-41
298
100
0.62
n.a.
n.a.
[93]

Molecular basket’

MCM-41 (50% PEI)
348
100
2.5
8
96.0
[93]

PE-MCM-41 (TRI)
298
100
1.8
10
94.4
[93]

PE-MCM-41 (DEA)
298
100
2.9
7
96.6
[93]

MWNT
303
101
1.7
20
n.a.
[4, 93]

Unmodified [(Cu₃(btc)₂]*
298
1818
6.7
n.a.
n.a.
[101]

CNT@ (Cu₃(btc)₂)
298
1818
13.52
n.a.
n.a.
[101]

MIL-101**
298
1010
0.84
n.a.
n.a.
[101]

MWCNT@MIL-101
298
1010
1.35
n.a.
n.a.
[101]

MOF-2
298
4545
3.20
n.a.
n.a.
[107]

MOF-177
298
4545
33.5
n.a.
n.a.
[107]

Zr-MOFs
273
988
8.1
n.a.
n.a.
[107]

Ca-Al LDH with
406
1
3.55
n.a.
n.a.
[108]

Pd-GNP nanocomposite
298
1111
5.1
n.a.
n.a.
[109]

f-GNP
298
1111
4.3
n.a.
n.a.
[109]

Pd-GNP nanocomposite
298
1111
4.5
n.a.
n.a.
[109]

f-GNP
298
1111
3.8
n.a.
n.a.
[109]

Pd-GNP nanocomposite
298
1111
4.1
n.a.
n.a.
[109]

f-GNP
298
1111
3.3
n.a.
n.a.
[109]

Ceria-based oxides doped with 5% gallium (III)
298
101
0.282
n.a.
n.a.
[110]

Amine modified layered double hydroxides (LDHs)
298–353
101
0.74–1.75
n.a.
n.a.
[108]

 *Cu₃(btc)₂; btc: 1,3,5-benzene-tricarboxylate.

**MIL-101 or Cr₃(F,OH)(H₂O)₂O[(O₂C)C₆H₄(CO₂)]₃· H₂O () is one of the metal organic frameworks with Lewis acid sites that can be activated by removal of guest water molecules.

Coal is one of the adsorbents being suggested for CO₂ separation. The total amount of CO₂ that can be adsorbed in coal depends on its porosity, ash, and affinity for this molecule [111, 112]. Sakurovs et al. [113] showed that the ratio of maximum sorption capacity between CO₂ and methane decreases with increasing carbon content. The average CO₂/CH₄ sorption ratio is higher for moisture-equilibrated coal and decreases with increasing coal rank (1.4 for high rank coals to 2.2 for low rank coals) [114–116].

Activated carbon (AC) has a number of attractive characteristics, such as its high adsorption capacity, high hydrophobicity, low cost, and low energy requirement for regeneration [117–119]. Activated carbons are inexpensive, insensitive to moisture, and easy for regeneration. These adsorbents have well developed micro- and mesopore structures that are suitable for high CO₂ adsorption capacity at ambient pressure [120–122].

However, activated carbon CO₂/N₂ selectivities (ca. 10) are relatively low; zeolitic materials offer CO₂/N₂ selectivities 5–10 times greater than those of carbonaceous materials. The adsorption capacity and selectivity of zeolites are largely affected by their size, porous diameter, charge density, and chemical composition of cations in their porous structures. The average value of heat adsorption on zeolites (36 kJ/moL) is larger than for activated carbon (30 kJ/moL), confirming the mentioned affirmation. Moreover, activated carbon can be regenerated easily and completely. Also its capacity did not decay after 10 consecutive processes cycles [122–124].

Due to the increase in cost of raw materials, growing research interest has been focused on producing AC from agricultural wastes. Some of the agricultural wastes include the shells and stones of fruits, wastes resulting from the production of cereals, bagasse, and coir pith [100]. Rosas et al. [125] prepared hemp-derived AC monolith by phosphoric acid activation. The activated carbons from hemp stem are microporous materials and therefore suitable ones for hydrogen storage and CO₂ capture [126].

Siriwardane et al. [127] studied CO₂ adsorption on the molecular sieve 13X, 4A and activated carbon. The molecular sieve 13X showed better CO₂ separation than molecular sieve 4A. At lower pressures (<50 psi), activated carbon had a lower CO₂ separation than the molecular sieves, but adsorption was higher for activated carbon than molecular sieves at higher pressures [127, 128].

Liu et al. [129] indicated that zeolite 5A has higher volumetric capacities and less severe heat effect of the zeolite 13X. Chabazite zeolites were prepared and exchanged with alkali cations: Li, Na, K and alkaline-earth cations: Mg, Ca, Ba. Zhang et al. [130] studied the potential of these zeolites for CO₂ separation from flue gas by vacuum swing adsorption. It was found that NaCHA and CaCHA hold comparative advantages for high temperature CO₂ separation whilst NaX showed superior performance at relatively low temperatures [130]. In physical adsorption, the size and volume of the pores are important. Micropores are defined as pores, 2 nm in size, mesopores between 2 and 50 nm, and macropores, 50 nm in size. The micropores make better selective adsorption of CO₂ over CH₄ [131, 132].

Carbon nanotubes (CNTs) are the most famous among nano-hollow structured materials and their dimension ranges from 1 to 10 nm in diameter and from 200 to 500 nm in length [133]. Cinke et al. [134] indicated that purified single-walled carbon nanotubes (SWNTs) adsorbed CO₂ better than unpurified SWNT. In addition, multiwalled carbon nanotubes (MWNTs) showed stability for 20 cycles of adsorption and regeneration [135].

More recently, nanosystems researchers have synthesized and screened a large number of zeolitic-type materials known as zeolitic imidazolate frameworks (ZIFs). CO₂ capacities of the ZIFs are high, and selectivity against CO and N₂ is good [136, 137]. The results of researchers (Burchell and Judkins [138], Dave et al. [28], and Yong et al. [139]) indicated that the CO₂ adsorption efficiency of the honeycomb monolith is twice than activated carbon and 1.5 times greater than ZIF material [29]. Results of Kimber et al. [140] showed that CO₂ selectivity of honeycomb monolithic composite decreased with increasing in burn-off.

Graphite nanoplatelets (GNP) were prepared by acid intercalation followed by thermal exfoliation of natural graphite. Functionalized graphite nanoplatelets (f-GNP) were prepared by further treatment of GNP in acidic medium. Palladium (Pd) nanoparticles were decorated over f-GNP surface by chemical method [109, 141, 142]. Adsorption capacity of this adsorbent is presented in Table 4.

The presence of several impurity gases (//H₂O) greatly complicates the CO₂ separation processes. Therefore, conventional adsorption-based CO₂ separation processes rely on using a pretreatment stage to remove water, , and , which adds considerably to the overall cost. Also this prelayer can be used before the amine absorption column [143, 144]. Deng et al. [145] showed that the adsorption capacities follows the order SO₂ > CO₂ > NO > N₂ on both zeolites (5A and 13X). Comparing two different adsorbents, the better separation efficiency can be achieved by 5A zeolite [145].

Zhang et al. [130] focused on the effect of water vapour on the pressure/vacuum swing adsorption process. The selected adsorbents in this study were CDX (an alumina/zeolite blend), alumina, and 13X zeolite as these adsorbents are either the prelayer for water adsorption or the main CO₂ adsorption layer in the packed bed [130].

Metal-organic framework (MOF) materials are crystalline with two- or three-dimensional porous structures that can be synthesised with many of the functional capabilities of zeolites. Several MOFs have been proposed as adsorbents for CO₂ separation processes, and among these Cu-BTC [polymeric copper (II) benzene-1,3,5-tricarboxylate] has proved to be dedicated with CO₂ adsorption performances that are higher than those of typical adsorbents such as 13X zeolite [105, 107, 146, 147].

The MCM-41 material is one of the mesoporous products which was prepared by the hydrothermal method from mobil composition of matter (MCM) powders. Lu et al. [148] showed that mesoporous silica spherical particles (MSPs) can be synthesized using low-cost Na₂SiO₃ thus they can be cost-effective adsorbents for CO₂ separation from flue gas [149, 150].

Layered double hydroxides (LDHs) have general formula with typically in the range between 0.10 and 0.33. These materials can be readily and inexpensively synthesized with the desired characteristics for a particular application such as CO₂ adsorption [108, 151].

2.2.3. Adsorbent Modification

The role of CO₂ as a weak Lewis acid is well established. Because of the nature of CO₂, the surface of the physical adsorbents can be modified by adding basic groups, such as amine groups and metal oxides to improve CO₂ adsorption capacity or selectivity [152–154]. Three different methods for the production of these adsorbents were investigated: activation with CO₂, heat treatment with ammonia gas (amination and ammoxidation), and heat treatment with polyethylenimine (PEI). However, it has been suggested that amine modification can produce better and cheaper CO₂ adsorbents [24, 104, 155, 156].

Xu et al. [157, 158] designed selective “molecular basket” by grafting polyethylenimine (PEI) uniformly on MCM-41. CO₂ adsorption capacity of the adsorbent was 24 times higher than MCM-41 and 2 times higher than PEI [93]. The addition of ammonium hydroxide resulted in the Zr-MOF with a slight lower adsorption of CO₂ and CH₄; however, the selectivity of CO₂/CH₄ is significantly enhanced [159, 160]. Results of Abid et al. [107] showed that the selectivity of CO₂/CH₄ on Zr-MOF is between 2.2 and 3.8, while for Zr-MOF-NH₄ selectivity is between 2.6 and 4.3.

A nitrogen-rich carbon with a hierarchical micro-mesopore structure exhibited a high CO₂ adsorption capacity (141 mg/g at 298 K, 1 atm), excellent separation efficiency (CO₂/N₂ selectivity is ca. 32), and excellent stability [161]. Plaza et al. [162] results showed that CO₂ adsorption capacity of the DETA-impregnated alumina (≥2.3 mmoL/g) exhibited is the highest.

Amine modified layered double hydroxides (LDHs) have been prepared by several different methods. Park et al. [163] used dodecyl sulfate (DS) intercalated LDH as precursor and added (3-aminopropyl) triethoxysilane (APTS) together with N-cetyl-N,N,N-trimethylammonium bromide (CTAB) [164]. The highest adsorption capacity of amine modified LDHs for CO₂ was achieved at 1.75 mmoL/g by MgAl N3 at 353 K and 1 bar. According to data in Table 4, this adsorbent has high CO₂ capacity at high temperature; therefore, this adsorbent is suitable for post-combustion CO₂ capture [108].

Wang et al. [114] reported that porous carbons with well-developed pore structures were directly prepared from a weak acid cation exchange resin (CER) by the carbonization of a mixture with Mg acetate in different ratios [108]. The main parameters of this adsorbent (such as CO₂ capacity) are indicated in Table 4.

Shafeeyan et al. [165] prepared different adsorbents based on the central composite design (CCD) with three independent variables (i.e., amination temperature, amination time, and the use of preheat treated (HTA) or preoxidized (OXA) sorbent as the starting material). They demonstrated that the optimum condition for obtaining an efficient CO₂ adsorbent is using a preoxidized sorbent and amination at 698 K for 2.1 h [165].

Table 4 compares CO₂ adsorption capacities and stability of different absorbents, which were studied for post-combustion CO₂ capture.

2.2.4. Different Cycles for CO₂ Adsorption

Five different regeneration strategies were demonstrated in a single-bed CO₂ adsorption unit: pressure swing adsorption (PSA), temperature swing adsorption (TSA), vacuum swing adsorption (VSA), electric swing adsorption (ESA), and a combination of vacuum and temperature swing adsorption (VTSA). The difference between these technologies is based on the strategy for regeneration of adsorbent after the adsorption step (Figure 7). In PSA applications, the pressure of the bed is reduced. VSA is preferred to the special PSA application where the desorption pressure is below atmospheric, whereas in TSA, the temperature is raised while pressure is maintained approximately constant, and in ESA the solid is heated by the Joule effect [166–169].

(a)

(b)

(c)

(d)

Figure 7: Schematic diagrams of various adsorption cycles, (a) TSA, (b) PSA, (c) VSA, and (d) ESA; thin lines indicated operation streams in regenerated step.

For the single-bed cycle configurations, the productivity and CO₂ recovery followed the sequence:

The performances of PSA, TSA, VSA, VTSA, and ESA processes for CO₂ separation are reported in Table 5. Since application of adsorption process for CO₂ capture in industrial scale is very important, in recent years some researches have been focused on this area; for example, Lucas et al. [170] studied the scale-up CO₂ adsorption with activated carbon.

Table 5: Comparison between several adsorption cycles for CO2 separation process [166].

Process
CO₂ feed molar fraction

(%) (other gases present)
CO₂ purity (%)
CO₂ recovery (%)

PSA
13 (O₂)
99.5
69

TSA
10
95
81

TSA
17
n.a.
40

ESA
10
23.33
92.57

VSA
15
90
90

VSA
17
n.a.
87

3-bed VSA
12
90–95
60–70

PSA/VSA
20
58–63
70–75

PSA/VSA
15 (H₂O)
59
87

VPSA
17
99.5–99.8
34–69

VPSA
16 (O₂)
99
53–70

PTSA
10
99
90

2-bed-2-step PSA
n.a.
18
90

VTSA
17
n.a.
97

2.3. Cryogenic Distillation

Cryogenic method utilized low temperatures for condensation, separation, and purification of CO₂ from flue gases (freezing point of pure CO₂ is 195.5 K at atmospheric pressure). Therefore, under the cryogenic separation process, the components can be separated by a series of compression, cooling, and expansion steps. It enables direct production of liquid CO₂ that can be stored or sequestered at high pressure via liquid pumping [171–173].

The advantages of this technology can be summarized as follows [6, 8, 174].

(1)Liquid CO₂ is directly produced, thus making it relatively easy to store or send for enhanced oil recovery.(2)This technology is relatively straightforward, involving no solvents or other components.(3)The cryogenic separation can be easy scaled-up to industrial-scale utilization.

The major disadvantages of this process are the large amount of energy required to provide the refrigeration and the CO₂ solidification under a low temperature, which causes several operational problems [176–178]. Therefore, more studies are required for reducing the cost of cryogenic separation.

Clodic et al. [179] indicated that the energy requirement for cryogenic process was in the range of 541–1119 kJ/kg CO₂. Zanganeh et al. [6] have constructed a pilot-scale CO₂ capture and compression unit (CO₂ CCU) that can separate CO₂ as liquid phase from the flue gas of oxy-fuel combustion. Their results showed that cryogenic is the most cost effective when the feed gas is available at high pressure. Therefore, cryogenic is not suitable for post-combustion and it is well effective for separation stream with high CO₂ concentration such as oxy-fuel combustion. Amann et al. [180] reported that conversion of O₂/CO₂ cycle was more efficient than amine scrubbing but more difficult to implement because of the specific gas turbine.

Xu et al. [175] studied a novel CO₂ cryogenic liquefaction and separation system (Figure 8). In this system, two-stage compression, two-stage refrigeration, two-stage separation, and sufficient recovery of cryogenic energy were adopted. The energy consumption for CO₂ recovery is only 0.395 MJ/kg CO₂. Furthermore, this CO₂ cryogenic separation system is more suitable for gas mixtures with high initial pressure and high CO₂ concentration [175].

Figure 8: Novel CO₂ cryogenic liquefaction and separation system [175].

Song et al. [181] developed a novel cryogenic CO₂ capture system based on Stirling coolers (SC). The operation of Stirling cooler contains four processes: isothermal expansion, refrigeration under a constant volume, isothermal compression, and heating under a constant volume condition. This novel cryogenic system can condense and separate H₂O and CO₂ from flue gas. Their results showed that under the optimal temperature and flow rate, CO₂ recovery of the cryogenic process can reach 96% with 1.5 MJ/kg CO₂ energy consumption.

Tuinier et al. [182] exploited a novel cryogenic CO₂ capture process using dynamically operated packed beds (Figure 9). By the developed process, above 99% of CO₂ could be recovered from a flue gas containing 10 vol.% CO₂ and 1 vol.% H₂O with 1.8 MJ/kg CO₂ energy consumption [181].

(a)

(b)

(c)

Figure 9: Schematic axial temperature and corresponding mass deposition profiles for the cryogenic; (a) capture, (b) recovery, and (c) cooling cycles [182].

Chiesa et al. [183] proposed an advanced cycle that a molten carbonate fuel cell (MCFC) was used to separate the CO₂ from the gas turbine exhaust of a natural gas fired combined cycle power plant. In this cycle, gas turbine flue gases actually are used as cathode feeding for MCFC. While CO₂ is moved from the cathode to anode side, concentrate CO₂ in the anode exhaust. Then the CO₂ is concentrated on the anode side of MCFC allowing to easily treat this spent fuel stream in a cryogenic process to split combustible species (routed back to gas turbine combustor) from the CO₂ addressed to storage (Figure 10) [183].

Figure 10: Plant layout showing the integration of the MCFC in a combined cycle, with cryogenic CO₂ separation after oxygen combustion of the cell an anode exhaust [183].

2.4. Membrane Separation

The membrane separation method is a continuous, steady-state, clean and simple process, and ideal as an energy-saving method for CO₂ recovery. Gas separation using membranes is a pressure-driven process. Due to the low pressure of flue gases, driving force is too low for membrane processes in post-combustion (low pressure and low CO₂ concentration). Membrane processes offer increased separation performances when CO₂ concentration in the feed mixture increases [184–186].

Membrane separation processes have several advantages over other CO₂ separation technologies. The required process equipment is very simple, compact, relatively easy to operate and control, clear process and easy to scale up [187, 188].

The energy required for the recovery of CO₂ by membrane processes depends on the target purity, flue gas composition, and membrane selectivity for CO₂. Howevre membrane processes require too much energy for post-combustion CO₂ capture; therefore, low partial pressure of CO₂ in the flue gas is a possible disadvantage for the application of membranes. Another disadvantage of membrane process is that the membrane selectivity for the separation of CO₂ from and is very low. Membrane process is not useful for high flow rate applications [189–191].

Therefore, the useful membrane for post-combustion CO₂ capture should have some specification such as [192, 193]

(i)high CO₂ permeability,(ii)high selectivity for CO₂ separatation from flue gases,(iii)high thermal and chemical stability,(iv)resistant to plasticisation,(v)resistant to aging,(vi)cost effective,(vii)low production cost for different membrane modules.

Many efforts have been made to find new material with suitable properties (Table 6).

Table 6: Carbon dioxide and nitrogen gas permeability data for different membranes.

Name
Feed pressure (atm)
Temperature (K)
(CO₂) (barrer)
(N₂) (barrer)
α (CO₂/N₂)
Reference

Ion-exchanged zeolites membrane

Y (FAU) with α-A1₂O₃ support
n.a.
308
n.a.
n.a.
139
[197]

ZSM-5 (MFI) with α-A1₂O3 support
n.a.
n.a
n.a.
n.a.
3
[197]

ZSM-5/polymeric silica
n.a.
373
1140
n.a.

[198]

Stainless steel support infiltrated with a eutectic molten carbonate mixture (Li/Na/K)
n.a.
923
7780
n.a.
16
[199]

Y-type
n.a.
303–403
35900–89800
n.a.
5
[200]

NaY
n.a.
313
359000
n.a.
5
[200]

Li(20%)Y
n.a.
308
210000
n.a.
3
[200]

K(30%)Y
n.a.
308
269000
n.a.
9
[200]

K(62%)Y
n.a.
313
150000
n.a.
6
[200]

Rb(38%)Y
n.a.
313
150000
n.a.
3
[200]

Cs(32%)Y
n.a.
313
59900
n.a.
2
[200]

20% K₂CO₃, 80% Li₂CO₃
n.a.
798
2990
n.a.
4
[199]

MCM-48
n.a.
n.a.
10200
n.a.
0.8
[189]

PEI-modified MCM-48
n.a.
363
14100
n.a.
80
[201]

Chitosan
1.75
295
100
n.a.
100
[192]

Swollen chitosan
1.5
383
482
n.a.
250
[192]

Arginine salt-chitosan
1.5
383
1500
n.a.
852
[194]

Polyacetylene

Polytrimethyl-prop-1-ynyl-silane
n.a.
298
19000
1800
10.6
[193]

Poly-3,3-dimethyl-but-1-yne
n.a.
298
560
43
13.0
[193]

Poly-1-(dimethyl-trimethylsilanylmethyl-silanyl)-propyne
n.a.
298
310
21
14.8
[193]

Poly-1-[dimethyl-(2-trimethylsilanyl-ethyl)-silanyl]-propyne
n.a.
298
150
14
10.7
[193]

Polytrimethyl-(2-prop-1-ynyl-phenyl)-silane
n.a.
298
290
24
12.1
[193]

Poly-1-prop-1-ynyl-2-trifluoromethyl-benzene
n.a.
298
130
7.3
17.8
[193]

Poly-dec-2-yne
n.a.
298
130
14
9.3
[193]

Poly-1-chloro-dec-1-yne
n.a.
298
170
16
10.6
[193]

Poly-1-chloro-oct-1-yne
n.a.
298
130
11
11.8
[193]

Poly-1-chloro-hex-1-yne
n.a.
298
180
10
18
[193]

Polyhexyl-dimethyl-prop-1-ynyl-silane
n.a.
298
71
4.3
16.5
[193]

Polytrimethyl-(1-pentyl-prop-2-ynyl)-silane
n.a.
298
120
8.7
13.8
[193]

Polyhexyl-dimethyl-(1-propyl-prop-2-ynyl)-silane
n.a.
298
70
6.3
11.1
[193]

Polyprop-1-ynyl-benzene
n.a.
298
25
2.2
11.4
[193]

Polybut-1-ynyl-benzene
n.a.
298
40
4.5
8.9
[193]

Polyoct-1-ynyl-benzene
n.a.
298
48
5.5
8.7
[193]

Polychloroethynyl-benzene
n.a.
298
23
1.0
23.0
[193]

Poly-1-ethynyl-2-methyl-benzene
n.a.
298
15
3.0
5.0
[193]

Polydimethyl-phenyl-(1-propyl-prop-2-ynyl)-silane
n.a.
298
54
2.5
21.6
[193]

Polyarylene ether

6FPT-6FBPA
1.0
308
25.29
2.18
11.6
[193]

6FPT-BPA 1.0 35
1.0
308
18.53
1.37
13.5
[193]

6FPPy-6FBPA
1.0
308
29.46
2.39
12.32
[193]

6FPPy-BPA
1.0
308
21.44
1.70
12.6
[193]

Fixed site carrier membrane (FSCM)

Polarix
2.0
303
10⁷
n.a.
50
[202]

PAAM-PVA/PS
10
298
2.4 × 10⁵
n.a.
80
[203]

PVAm/PVA blend
1.45
298
2.12 × 10⁶
n.a.
145
[204]

PEI/PVA
n.a.
298
10⁴
n.a.
230
[184]

PDMA/PS
2
296
3 × 10⁵
n.a.
53
[143]

Polyamine

PA12
10
308
120
n.a.
51
[152]

PA6
10
308
66
n.a.
56
[152]

Polyethyleneimine/polyvinyl butyral
0.132
318
380
n.a.
32
[193]

Poly[(2-N,N-dimethyl) aminoethyl methacrylate]
0.237
298
370
n.a.
111
[193]

Poly(vinylbenzyltrimethyl ammonium fluoride)
0.224
296
113
n.a.
983
[193]

Polyethyleneimine/poly(vinyl alcohol)
0.355
298
650
n.a.
235
[193]

PEI/PDMS/PEBA1657/PDMS
5
298
1.57 × 10⁶
n.a.
64
[205]

Polyarylate

BPA/IA
10
308
5.4
0.24
22.5
[193]

BPA/tBIA
10
308
24.2
1.20
20.2
[193]

HFBPA/IA
10
308
19.1
1.11
17.2
[193]

HFBPA/tBIA
10
308
56.9
3.88
14.7
[193]

PhTh/IA
10
308
6.74
0.28
24.1
[193]

PhTh/tBIA
10
308
23.8
1.09
21.8
[193]

FBP/IA
10
308
12.4
0.57
12.4
[193]

FBP/tBIA
10
308
36.8
1.93
19.1
[193]

TBBPA/IA
10
308
4.93
0.18
27.4
[193]

TBBPA/tBIA
10
308
21.5
0.90
23.9
[193]

TBHFBPA/IA
10
308
25.6
1.07
23.9
[193]

TBHFBPA/tBIA
10
308
85.1
4.47
19.0
[193]

TBPhTh/IA
10
308
8.34
0.29
28.8
[193]

TBPhTh/tBIA
10
308
30.6
1.28
23.9
[193]

TBFBP/IA
10
308
20.4
0.70
29.1
[193]

TBFBP/tBIA
10
308
69.5
2.94
23.6
[193]

DMBPA/IA
10
308
1.24
0.063
19.7
[193]

DMBPA/Tbia
10
308
8.0
0.39
20.5
[193]

TMBPA/IA
10
308
12.0
0.58
20.7
[193]

TMBPA/tBIA
10
308
44.6
2.52
17.7
[193]

DiisoBPA/IA
10
308
5.16
0.27
19.1
[193]

DiisoBPA/tBIA
10
308
16.1
1.08
14.9
[193]

DBDMBPA/IA
10
308
5.45
0.22
24.8
[193]

PhAnth/IA
10
308
9.0
0.36
25
[193]

PhAnth/tBIA
10
308
25.9
1.35
19.2
[193]

FBP/IA
10
308
12.4
0.57
21.8
[193]

FBP/tBIA
10
308
36.8
1.93
19.1
[193]

Polycarbonates

PC
1–10
308
6.0–6.8
0.289–0.32
21
[193]

TMPC
1–10
308
17.58–18.6
1.0
18.6
[193]

TCPC
1
308
6.66
0.36
18.5
[193]

TBPC
1
308
4.23
0.182
23.2
[193]

HFPC
10
308
24
1.6
15.0
[193]

TMHFPC
10
308
111
7.4
15.0
[193]

NBPC
10
308
9.1
0.47
19.4
[193]

PCZ
10
308
2.2
0.105
21.0
[193]

PC-AP
2
308
9.48
0.361
26.3
[193]

FBPC
2
308
15.1
0.592
25.5
[193]

Polyethylene oxide

PEO
7.8
298
8.1
0.07
140
[193]

PEO
4.4–14.6
308–318
13–52
0.24–1
55
[193]

PEO-PBT
n.a.
308
120
2
60
[193]

EO/EM/AGE (80/20/2)
n.a.
308
773
16.8
46
[193]

EO/EM/AGE (77/23/2.3)
n.a.
308
680
15.5
44
[193]

EO/EM/AGE (96/4/2.5)
n.a.
308
580
12.1
48
[193]

Polyimides

Amine modified polyimide
0.368
308
186
n.a.
38
[193]

PMDA-BAPHF
6.8
308
11.8
0.66
17.8
[193]

PMDA-3BAPHF
6.8
308
6.12
0.29
21.1
[193]

PMDA-4,4′-ODA
6.8–10
308
1.14–2.7
0.049–0.1
23.3
[193]

PMDA-3,3′-ODA
6.8–10
308
0.50–3.55
0.018–0.145
24.5–27.8
[193]

PMDA-MDA
10
308
4.03
0.20
20.2
[193]

PMDA-IPDA
10
308
29.7
1.50
19.8
[193]

PMDA-BAPHF
10
308
17.6
0.943
18.7
[193]

PMDA-BATPHF
10
308
24.6
1.50
16.4
[193]

BPDA-BAHF
1–10
298–308
23–27.7
0.6–1.39
19.9–37.7
[193]

BPDA-mTrMPD
10
308
137
8.42
16.3
[193]

BTDA-4,4-ODA
10
308
0.625
0.0236
26.5
[193]

BTDA-BAPHF
10
308
4.37
0.195
22.4
[193]

BTDA-BAHF
10
308
10.1
0.45
22.4
[193]

BTDA-mTrMPD
10
308
30.9
1.55
19.9
[193]

BTDA-BAFL
1
298
15
0.39
38.5
[193]

PI
10
308
2.00
0.063
31.7
[193]

oMeCat-durene
1
303
27
0.83
33
[193]

mMeCat-durene
1
303
20
0.59
34
[193]

DMeCat-durene
1
303
63
2.05
31
[193]

mtBuCat-durene
1
303
71
2.55
28
[193]

oMeptBuCat-durene
1
303
67
2.5
27
[193]

TMeCat-durene
1
303
200
8.1
25
[193]

mMetCat-MDA
1
303
22
0.65
34
[193]

mtBuCat-MDA
1
303
63
2.2
29
[193]

TMeCat-MDA
1
303
110
3.8
30
[193]

TMeCat-TMB
1
303
39
1.2
33
[193]

DBuCat-TMB
1
303
95
4.9
19
[193]

mtBuCat-DMOB
1
303
6.7
0.21
32
[193]

TMeCat-6FiPDA
1
303
54
1.9
28
[193]

6F
3
n.a.
114
5.8
19.6
[193]

TMMPD
3
n.a.
600
35.1
17.1
[193]

IMDDM
3
n.a.
196
10.8
18.1
[193]

ODA
3
n.a.
25
0.97
25.8
[193]

Matrimid 5218
10
308
6.5
0.25
25.6
[193]

6FDA-based polyimides

6FDA-pPDA
10
308
15.3
0.80
19.12
[193]

6FDA-pDiMPDA
10
303
42.7
2.67
16.0
[193]

6FDA-durene
10
308
440
35.60
12.4
[193]

6FDA-durene
10
303
456
35.50
12.85
[193]

6FDA-mPDA
6.8–10
308
8.23–9.20
0.36–0.447
20.6–22.7
[193]

6FDA-mMPDA
6.8–10
303
40.1–42.5
2.12–2.24
17.9–20.1
[193]

6FDA-mTrMPDA
10
308
431
31.6
13.6
[193]

6FDA-DATr
6.8
303
28.63
1.31
21.9
[193]

6FDA-DBTF
6.8
308
21.64
1.17
18.5
[193]

6FDA-PHDoeP
6.8
303
8.59
4.50
1.91
[193]

6FDA-PEPE
6.8
308
6.88
0.255
27.0
[193]

6FDA-PBEPE
6.8
303
2.50
0.099
25.3
[193]

6FDA-PMeaP
6.8
308
2.41
0.086
28.0
[193]

6FDA-3,4′ODA
10
303
6.11
0.259
23.6
[193]

6FDA-APAP
10
308
10.7
0.473
22.6
[193]

6FDA-pp′ODA
10
303
16.7
0.733
22.8
[193]

6FDA-BAPHF
10
308
19.1
0.981
19.5
[193]

6FDA-BATPHF
10
303
22.8
1.30
17.5
[193]

6FDA-BAHF
10
308
51.2
3.11
16.5
[193]

6FDA-1,5-NDA
10
308
23
1.1
21
[193]

6FDA-durene 24 h amidation
10
n.a.
11.6
1.33
8.75
[193]

6FDA-durene/mPDA (50/50)
10
n.a.
84.6
5.18
16.4
[193]

6FDA-durene/mPDA (50/50) 4 h amidation
10
n.a.
54.9
3.38
16.2
[193]

6FDA-durene/mPDA (50/50) 6 h amidation
10
n.a.
49.1
3.27
15.0
[193]

6FDA-durene/mPDA (50/50) 12 h amidation
10
n.a.
46.0
2.94
15.6
[193]

6FDA-durene/mPDA (50/50) 24 h amidation
10
n.a.
36.0
2.06
17.5
[193]

6FDA-durene/mPDA (50/50) 48 h amidation
10
n.a.
24.5
1.38
17.8
[193]

6FDA-FDA/HFBAPP (1/1)
1.1 kg/cm²
303
465.0
19.9
23.4
[193]

6FDA-ODA
10
308
23
0.83
27.7
[193]

6FDA-4,4-ODA
6.8
303
22.0
0.94
23.4
[193]

6FDA-MDA
10
308
19
0.81
23.5
[193]

6FDA-4BDAF
6.8
303
19
0.98
19.4
[193]

6FDA-3,3′-ODA
6.8
308
2.1
0.10
21
[193]

6FDA-3BDAF
6.8
303
6.3
0.24
26.3
[193]

6FDA-IPDA
10
308–328
24.3–27.4
0.87–1.39
19.7–27.9
[193]

6FDA-DAF
10
308–328
19.5–21.3
0.81–1.15
18.5–24.1
[193]

PI-1
1
303
32
1.4
22.9
[193]

PI-3
1
303
360
16.5
21.8
[193]

PI-4
1
303
62
2.4
25.8
[193]

PI-5
1
303
190
7.3
26.0
[193]

6FDA-BAFL
1
298
98
3.3
29.7
[193]

Poly(phenylene oxide)

PPO (hollow fiber)
4
308
10⁶

21
[205]

PPS
1.5
308
1.60
0.046
34.8
[193]

PDMPO
1.5
308
65.5
3.5
18.7
[193]

PDPPO
1.5
308
39.9
1.5
26.6
[193]

PDMPO
6.891
295
90.0
3.7
24.3
[193]

PDMPO (20.0% brominated)
6.891
295
93.6
3.8
24.6
[193]

PDMPO (37.4% brominated)
6.891
295
97.1
3.7
26.2
[193]

PDMPO (60.0% brominated)
6.891
295
159.9
8.0
20.0
[193]

Polypyrrole

6FDA-TAB
10
308
54.0
2.6
20.8
[193]

6FDA-TADPO
10
308
27.6
1.2
23.0
[193]

BBL
10
308
0.12
0.003
46.3
[193]

Polysulfones

PSF
10
308
5.6
0.25
22.4
[193]

TMPSF
10
308
21
1.06
19.8
[193]

HFPSF
10
308
12
0.67
17.9
[193]

TMHFPSF
10
308
72
4.0
18
[193]

PSF-F
10
308
4.5
0.20
22.5
[193]

PSF-O
10
308
4.3
0.20
21.5
[193]

PSF-P
10
308
6.8
0.32
21.3
[193]

TMPSF-F
10
308
5.5
0.61
9.0
[193]

TMPSF-P
10
308
13.2
0.57
23.2
[193]

BIPSF
10
308
5.6
0.24
23.3
[193]

TMBIPSF
10
308
31.8
1.21
26.3
[193]

1,5-NPSF
10
308
1.6
0.057
28.1
[193]

2,6-NPSF
10
308
1.5
0.051
29.4
[193]

2,7-NPSF
10
308
1.8
0.074
24.3
[193]

DMPSF
10
308
2.1
0.091
23.1
[193]

HMBIPSF
10
308
25.5
1.2
23.3
[193]

DMPSF-Z
10
308
1.4
0.057
24.6
[193]

PSF-AP
2
308
8.12
0.278
29.2
[193]

FBPSF
2
308
13.8
0.484
28.5
[193]

PSF-M
1
308
2.8
0.11
25.5
[193]

TMPSF-M
10
308
7.0
0.28
25.0
[193]

PSF-BPFL
1
308
10
0.25
40
[193]

3,4′-PSF
1
308
1.5
0.066
22.7
[193]

1,3-ADM PSF
35
308
7.2
0.33
21.8
[193]

2,2-ADM PSF
35
308
9.5
0.46
20.6
[193]

PSF (6% Br, 92% C≡CSiMe₃)
1
308
36.5
2.1
17.4
[193]

PSF (3% Br, 47% C≡CSiMe₃)
1
308
18.5
1.24
14.9
[193]

PSF (21% Br, 77% C≡CSiMe₃)
1
308
28.2
1.7
16.6
[193]

PSF (5% Br, 45% C≡CSiMe₃)
1
308
16.4
0.9
18.2
[193]

PSF
1
308
5.6
0.25
22.4
[193]

PSF-s-HBTMS
1
308
21
0.96
22.2
[193]

PSF-o-HBTMS
1
308
70
3.29
21.3
[193]

PSF-CH2-TMS
1
308
18
0.95
18.9
[193]

EM3
1
308
29
1.3
22
[193]

EM2
1
308
6.2
0.24
26
[193]

EM1
1
308
4.8
0.16
30
[193]

SM3 (degree of substitution = 2.0)
1
308
18
0.77
23
[193]

SM3 (degree of substitution = 1.0)
1
308
10
0.38
26
[193]

SM1
1
308
5.1
0.17
30
[193]

PPSF
1
308
3.2
0.10
32
[193]

RM3
1
308
27
1.9
14
[193]

RM2
1
308
6.7
0.60
11
[193]

RM1
1
308
6.9
0.61
11
[193]

HFPSF
1
308
12.0
0.67
17.9
[193]

HFPSF-o-HBTMS
1
308
105
5.63
18.6
[193]

HFPSF-s-TMS
1
308
41
2.0
20
[193]

HFPSF-o-TMS
1
308
84
4.7
18
[193]

HFPSF-TMS
1
308
110
6.3
18
[193]

TM6FPSF
1
308
72
4.0
18
[193]

TM6FPSF-s-TMS
1
308
96
5.2
19
[193]

TMPSF-TMS
1
308
32
1.51
21.3
[193]

TMPSF-s-TMS
1
308
66.3
3.07
21.6
[193]

TMPSF-HBTMS
1
308
72
3.36
21.4
[193]

Other membranes

HQDPA-PDA
7
303
0.598
0.016
37.4
[193]

HQDPA-PDA
7
373
1.70
0.111
15.3
[193]

HQDPA-DBA
7
303
0.683
0.015
45.5
[193]

HQDPA-DBA
7
373
2.10
0.125
16.8
[193]

HQDPA-MDBA
7
303
1.18
0.034
34.7
[193]

HQDPA-MDBA
7
373
2.37
0.160
14.8
[193]

HQDPA-EDBA
7
303
2.26
0.077
29.4
[193]

HQDPA-EDBA
7
373
4.18
0.292
14.3
[193]

12H
5
308
4.6
0.21
21.9
[193]

6H6F
5
308
8.6
0.44
19.5
[193]

6F6H
5
308
8.9
0.42
21.2
[193]

12F
5
308
12.9
0.76
17.0
[193]

PBK
10
308
3.3
0.13
25.4
[193]

PBK-S
10
308
3.27
0.11
29.7
[193]

PBSF
10
308
10.8
0.47
23.0
[193]

PES/PI
4
308
1.15 × 10⁵
n.a.
30
[193]

PPES
n.a.
273
0.92
0.027
34
[193]

PPESK
n.a.
273
0.75
0.042
18
[193]

20 percent DEA immobilized in 25.4 μm microporous polypropylene supports
0.16–1.67
298
974–4825
n.a.
56–276
[200]

Copolymers and polymer blend

PEBA 2533 (hollow fiber)
6.8
273
260
n.a.
32
[206]

PEBA/PSF composite
3.4
273
6.1 × 10⁵
n.a.
30
[206]

COPNA
n.a.
373
2990
n.a.
14
[200]

Pebax
n.a.
303
73
n.a.
15.6
[207]

Pebax/PEG10
n.a.
303
75
n.a.
15.8
[207]

Pebax/PEG20
n.a.
303
80
n.a.
15.9
[207]

Pebax/PEG30
n.a.
303
105
n.a.
15.1
[207]

Pebax/PEG40
n.a.
303
132
n.a.
15.1
[207]

Pebax/PEG50
n.a.
303
151
n.a.
15.5
[207]

Pebax/PEG-DME10
n.a.
303
123
n.a.
44
[208]

Pebax/PEG-DME20
n.a.
303
206
n.a.
45
[208]

Pebax/PEG-DME30
n.a.
303
300
n.a.
46
[208]

Pebax/PEG-DME40
n.a.
303
440
n.a.
42
[208]

Pebax/PEG-DME50
n.a.
303
606
n.a.
43
[208]

6FDA-TAB
10
308
54.0
2.8
19.3
[193]

6FDA/PMDA-TAB (50 : 50)
10
308
15.8
0.70
22.6
[193]

6FDA/PMDA-TAB (25 : 75)
10
308
3.13
0.098
31.9
[193]

6FDA/PMDA-TAB (10/90)
10
308
1.11
0.036
30.8
[193]

6FDA-TAB/DAM (75/25)
3
308
73.7
3.1
23.8
[193]

6FDA-TAB/DAM (50/50)
3
308
155
6.6
23.5
[193]

6FDA-DAM
3
308
370
29.5
12.5
[193]

6FDA/TMPDA
n.a.
308
400
23.5
17.02
[193]

6FDA/PMDA (1 : 6)-TMMDA (CH₂Cl₂ cast)
10
308
187
11.7
16.0
[193]

6FDA/PMDA (1 : 6)-TMMDA (NMP cast)
10
308
144
8.76
16.4
[193]

6FDA/PMDA (1 : 6)-TMMDA (DMF cast)
10
308
88.6
5.16
17.2
[193]

MDI-BPA/PEG (75)
2
308
31
0.70
44
[193]

MDI-BPA/PEG (80)
2
308
48
1.0
47
[193]

MDI-BPA/PEG (85)
2
308
59
1.20
49
[193]

L/TDI (20)-BPA/PEG (90)
2
308
47
0.92
51
[193]

L/TDI (40)-BPA/PEG (85)
2
308
35
0.72
48
[193]

IPA-ODA/PEO3 (80)
2
308
58
1.1
53
[193]

BPDA-pp′ODA
n.a.
303
18000
n.a.
31
[155]

BPDA-ODA/DAT (oxidized)
n.a.
308
599
n.a.
40
[155]

BPDA-ODA/DABA/PEO1 (75)
2
308
2.7
0.048
56
[193]

BPDA-mDDS/PEO1 (80)
2
308
3.8
0.066
58
[193]

BPDA-ODA/DABA/PEO2 (70)
2
308
14
0.25
57
[193]

BPDA-ODA/DABA/PEO2 (80)
2
308
36
0.64
56
[193]

BPDA-ODA/PEO3 (75)
2
308
75
1.4
52
[193]

BPDA-mDDS/PEO3 (75)
2
308
72
1.4
53
[193]

BPDA-mPD/PEO4 (80)
2
308
81
1.5
54
[193]

BPDA-ODA/PEO4 (80)
2
308
117
2.3
51
[193]

PMDA-ODA/DABA/PEO1 (80)
2
308
14
0.27
52
[193]

PMDA-ODA/PEO2 (75)
2
308
40
0.74
54
[193]

PMDA-mPD/PEO3 (80)
2
308
99
2.0
50
[193]

PMDA-APPS/PEO3 (80)
2
308
159
3.1
51
[193]

PMDA-APPS/PEO4 (70)
2
308
136
2.6
53
[193]

PMDA-mPD/PEO4 (80)
2
308
151
2.9
52
[193]

PMDA-ODA/PEO4 (80)
2
308
167
3.2
52
[152]

PMDA-pDDS/PEO4 (80)
2
308
238
4.9
49
[152]

PMDA/BTDA-BAFL (50 : 50)
1
298
43
1.3
33
[193]

PMDA/BTDA–BAFL (90 : 10)
1
298
130
3.8
34
[193]

BPDA-BAFL/HMDA (50 : 50)
1
298
0.54
0.014
39
[193]

PPES
n.a.
298
0.92
0.027
34
[193]

PPES/PPEK (3 : 1)
n.a.
298
2.94
0.074
40
[193]

PPES/PPEK (1 : 1)
n.a.
298
4.12
0.089
46
[193]

PPES/PPEK (1 : 3)
n.a.
298
2.06
0.026
39
[193]

PPES/PPEK (1 : 4)
n.a.
298
1.77
0.052
34
[193]

PPEK 18
n.a.
298
0.75
0.042
18
[193]

HQDPA-DPA/MDPA
7
303
0.957
0.023
41.2
[193]

HQDPA-DPA/MDPA
7
373
2.34
0.147
15.9
[193]

HQDPA-DPA/EDPA
7
303
1.334
0.036
37.6
[193]

HQDPA-DPA/EDPA
7
373
3.25
0.207
15.7
[193]

PI
10
308
2.00
0.063
31.7
[193]

PI/10PS
10
308
2.33
0.085
27.4
[193]

PI/15PS
10
308
2.32
0.09
25.8
[193]

PI/20PS
10
308
2.90
0.91
3.19
[193]

PI/25PS
10
308
4.29
0.91
4.71
[193]

PI/10PSVP
10
308
3.58
0.13
28.4
[193]

PI/15PSVP
10
308
3.71
0.14
26.5
[193]

PI/20PSVP
10
308
5.65
0.15
38.4
[193]

PI/25PSVP
10
308
6.55
1.55
4.31
[193]

NTDA-BDSA (30)/CARDO/ODA
3
303
70
1.7
41
[193]

NTDA-BDSA (30)/CARDO]
3
303
164
4.5
36
[193]

NTDA-BDSA (30)/BAPHF
3
303
23
0.64
36
[193]

NTDA-BDSA (30)/ODA
3
303
5.2
0.1
52
[193]

6FDA-FDA/HFBAPP (1/1)
1.1 kg/cm²
303
465
19.9
23.4
[193]

6FDA-durene/pPDA (80/20)
10
308
230
16.88
13.62
[193]

6FDA-durene/pPDA (50/50)
10
308
126
7.74
16.28
[193]

6FDA-durene/pPDA (20/80)
10
308
59.26
2.81
21.09
[193]

6FDA-durene/3,3′-DDS (75/25)
10
308
84.7
5.91
14.3
[193]

6FDA-durene/3,3′-DDS (50/50)
10
308
19.8
1.09
18.2
[193]

6FDA-durene/3,3′-DDS (25/75)
10
308
5.12
0.26
19.7
[193]

6FDA-3,3′-DDS
10
308
1.84
0.08
22.7
[193]

6FDA-6FpDA-DABA-12.5
4
308
34.0
2.01
16.9
[193]

6FDA-6FpDA–DABA-12.5 annealed
4
308
70.8
4.50
15.7
[193]

6FDA-6FpDA-DABA-12.5 (22.5% TMOS)
4
308
30.9
1.70
18.2
[193]

6FDA-6FpDA-DABA-12.5 (22.5% TMOS) annealed
4
308
47.6
3.16
15.1
[193]

6FDA-6FpDA-DABA-12.5 (15.0% MTMOS)
4
308
44.0
2.53
17.4
[193]

6FDA-6FpDA-DABA-12.5 (15.0% MTMOS) annealed
4
308
110
7.07
15.6
[193]

6FDA-6FpDA-DABA-12.5 (15.0% PTMOS) 4 35
4
308
32.3
1.80
17.9
[193]

6FDA-6FpDA-DABA-12.5 (15.0% PTMOS) annealed
4
308
91.8
5.59
16.4
[193]

6FDA-6FpDA-DABA-12.5 (22.5% PTMOS)
4
308
30.7
1.88
16.3
[193]

6FDA-6FpDA-DABA-12.5 (22.5% PTMOS) annealed
4
308
90.9
5.87
15.5
[193]

6FDA-6FpDA-DABA-25
4
308
20.3
1.20
16.9
[193]

6FDA-6FpDA-DABA-25 annealed
4
308
77.3
4.85
15.9
[193]

6FDA-6FpDA-DABA-25 (22.5% TMOS)
4
308
15.7
1.06
14.8
[193]

6FDA-6FpDA-DABA-25 (22.5% TMOS) annealed
4
308
79.8
4.87
16.4
[193]

6FDA-6FpDA-DABA-25 (15.0% MTMOS)
4
308
16.6
1.07
15.5
[193]

6FDA-6FpDA-DABA-25 (15.0% MTMOS) annealed
4
308
81.1
5.07
16.0
[193]

6FDA–6FpDA-DABA-25 (22.5% MTMOS)
4
308
16.6
1.07
15.5
[193]

6FDA-6FpDA-DABA-25 (22.5% MTMOS) annealed
4
308
60.1
3.837
15.7
[193]

6FDA-6FpDA-DABA-25 (15.0% PTMOS)
4
308
18.4
0.94
19.6
[193]

6FDA-6FpDA-DABA-25 (15.0% PTMOS) annealed
4
308
104
6.25
16.6
[193]

6FDA-6FpDA-DABA-25 (22.5% PTMOS)
4
308
19.1
0.98
19.5
[193]

6FDA-6FpDA-DABA-25 (22.5% PTMOS) annealed
4
308
104
6.25
16.6
[193]

Poly(5 : 5 BPA/BN)
5
308
5.71
0.19
30.1
[193]

Poly(7 : 3 BPA/BN)
5
308
4.62
0.16
28.9
[193]

Cross-linking polymers

Poly(ethylene oxide-co-epichlorohydrin) (1 : 1) 1.1%
300
298
15.0
2.3
6.52
[193]

Poly(ethylene oxide-co-epichlorohydrin) (1 : 1) 2%
300
298
14.9
1.0
14.9
[193]

Poly(ethylene oxide-co-epichlorohydrin) (1 : 1) 5%
300
298
16.1
0.5
32.2
[193]

DM14/MM9 (100/0)
0.967
298
45
0.66
68
[193]

DM14/MM9 (100/0)
0.967
323
107
2.8
38
[193]

DM14/MM9 (90/10)
0.967
298
62
0.90
69
[193]

DM14/MM9 (90/10)
0.967
323
133
3.4
39
[193]

DM14/MM9 (70/30)
0.967
298
96
1.5
66
[193]

DM14/MM9 (70/30)
0.967
323
195
5.4
36
[193]

DM14/MM9 (50/50)
0.967
298
144
2.25
64
[193]

DM14/MM9 (50/50)
0.967
323
260
7.2
36
[193]

DM14/MM9 (30/70)
0.967
298
210
3.3
63
[193]

DM14/MM9 (30/70)
0.967
323
350
10.6
33
[193]

DB30/MM9 (100/0)
0.967
298
93
1.5
63
[193]

DB30/MM9 (100/0)
0.967
323
200
5.7
35
[193]

DB30/MM9 (90/10)
0.967
298
105
1.6
64
[193]

DB30/MM9 (90/10)
0.967
323
210
5.8
36
[193]

DB30/MM9 (70/30)
0.967
298
141
2.1
67
[193]

DB30/MM9 (70/30)
0.967
323
270
7.7
35
[193]

DB30/MM9 (50/50)
0.967
298
179
2.9
62
[193]

DB30/MM9 (50/50)
0.967
323
330
9.7
34
[193]

DB30/MM9 (30/70)
0.967
298
250
4.2
60
[193]

DB30/MM9 (30/70)
0.967
323
410
12.4
33
[193]

DM9/MM9 (90/10)
0.967
298
18.3
0.3
68
[193]

DM9/MM9 (90/10)
0.967
323
51
1.3
38
[193]

DM23/MM9 (90/10)
0.967
298
145
2.2
66
[193]

DM23/MM9 (90/10)
0.967
323
290
7.6
38
[193]

DB10/MM9 (90/10)
0.967
298
6.7
0.11
61
[193]

DB10/MM9 (90/10)
0.967
323
27
0.79
34
[193]

DB69/MM9 (90/10) (cooling)
0.967
298
240
4.3
56
[193]

DB69/MM9 (90/10) (cooling)
0.967
323
510
14.2
36
[193]

DB69/MM9 (90/10) (heating)
0.967
298
98
1.6
62
[193]

DB69/MM9 (90/10) (heating)
0.967
323
400
11.4
35
[193]

DM14/MM23 (30/70) (cooling)
0.967
298
240
3.9
62
[193]

DM14/MM23 (30/70) (cooling)
0.967
323
420
12
35
[193]

DM14/MM23 (30/70) (heating)
0.967
298
250
4.0
62
[193]

Matrimid 5218
10
308
6.5
0.25
25.6
[193]

Matrimid 5218, 1-day cross-linking
10
308
7.4
0.29
25.6
[193]

Matrimid 5218, 3-day cross-linking
10
308
6.0
0.24
25.2
[193]

Matrimid 5218, 7-day cross-linking
10
308
5.1
0.21
24.6
[193]

Matrimid 5218, 14-day cross-linking
10
308
4.7
0.19
24.1
[193]

Matrimid 5218, 21-day cross-linking
10
308
3.4
0.15
22.2
[193]

Matrimid 5218, 32-day cross-linking
10
308
1.9
0.13
15.0
[193]

6FDA-durene, 5 min cross-linked
10
308
136
11.1
12.3
[193]

6FDA-durene, 10 min cross-linked
10
308
91.8
6.53
14.1
[193]

6FDA-durene, 15 min cross-linked
10
308
70.0
6.05
11.6
[193]

6FDA-durene, 30 min cross-linked
10
308
30.3
2.87
10.6
[193]

6FDA-durene, 60 min cross-linked
10
308
2.14
0.40
5.35
[193]

 *Permeability.

Various groups of materials have been already proposed and experimentally investigated for post-combustion CO₂ capture with membrane process. By modifying membrane their properties can be improved. For example, when amine functional groups are randomly dispersed in the silica matrix, this membrane can separate CO₂ with high selectivity. On the other hand, membrane structure can be modified by adding arginine salts [194–196].

2.4.1. Inorganic Membranes

Based on structure, inorganic membranes can be classified into two categories: porous and dense. In porous inorganic membranes, a porous thin top layer is supported on a porous metal or ceramic support. Zeolite, silicon carbide, carbon, glass, zirconia, titania, and alumina membranes are mainly used as porous inorganic membranes supported on different substrates, such as -alumina, -alumina, zirconia, zeolite, or porous stainless steel [17, 199, 209, 210].

Zeolite membrane is the most important group of inorganic membranes. Zeolite membranes are considered more expensive than polymeric membranes, and therefore their unique properties of size selectivity and thermal and chemical stability should be exploited for successful application [211–213].

The dense inorganic membranes (nonporous material) consist of a thin layer of metal, such as palladium and its alloys (metallic membrane), or solid electrolytes, such as zirconia. Another form of inorganic membrane is the liquid-immobilized membrane, where the pores of a membrane are completely filled with a liquid, which is permselective for certain compounds. Recently, attempts have been made to develop dense molten carbonate selective membranes for CO₂ separation at high temperatures (>723 K). The inorganic membranes have high thermal stability for CO₂ separation, but their selectivity and permeability are very low [200, 214, 215].

2.4.2. Polymeric Membranes

In polymeric membranes, the selective layer is generally a nonporous film that transports gases across by the solution-diffusion mechanism. Polyacetylenes, polyaniline, polyarylene ethers, polyarylates, polycarbonates, polyetherimides, polyethylene oxide, polyimides, polyphenylene oxides, polypyrroles, polysulfones, and amino groups such as polyethyleneimine blends, polymethacrylates are examples of polymeric membranes used for CO₂ separation [17, 216–218].

Selective polymeric membranes can be divided into two basic categories: glassy and rubbery. Almost glassy polymeric membranes are more suitable than rubbery polymeric membranes for CO₂ separation because of their high gas selectivity and good mechanical properties. On the other hand, rubbery membranes are flexible and soft and they have a high permeability but a low selectivity, whereas glassy polymers exhibit a low permeability but a high selectivity [206, 219–221].

Several advantages of polymeric membranes are (i) low cost of production; (ii) high performance separation; (iii) ease of synthesis; and (iv) mechanical stability. Although the polymeric membranes have high selectivity and permeability for CO₂ separation, but their thermal stability is very low, and these membrane may be plasticized with influence of CO₂ in membrane. Therefore, application of these membranes for post-combustion capture is limited, and flue gas must first be cooled down to 313–333 K for membrane process [184, 222, 223].

Ren et al. [205] prepared polymeric membranes with block copolymers; the balance of the hard and soft blocks can provide a good CO₂ separation performance without loss of its permeability.

Improved polymeric membrane materials with superior separation performance can be obtained by synthesizing new polymers or modification or blending existing commercial polymers with organic or inorganic compounds [208, 224].

Due to high operating cost of membrane processes, it is necessary to perform more researches and studies about preparation of suitable membranes.

2.4.3. Mixed Matrix Membranes

Zeolites, carbon molecular sieves (CMS), and many polymeric materials offer attractive transport properties for CO₂ separation. By mixing membrane material, excellent membrane with high performance for CO₂ separation (selectivities of CO₂/) can be prepared [200]. A group of scientists proposed the use of membrane based on polymer/immobilized liquid system especially polymerized ionic liquid membrane (PILM) or gelled ionic liquid membrane. ILMs consisting of aqueous solutions of 20% DEA immobilized in 25.4 μm microporous polypropylene supports have low permeability and suitable selectivity (974 barrer, 276, resp.) in 2 atm at 298 K [225–228].

2.4.4. Hollow Fiber Membrane

Most industrially important membranes for gas separations are hollow fiber ones. Asymmetric hollow fiber membranes (such as polyvinylidene difluoride (PVDF)) with inner skinless structures are favourable for CO₂ separation and absorption in gas-liquid membrane by low mass-transfer resistance and high permeability. In addition, this process can achieve significantly high adsorption efficiencies due to the much larger surface area for gas-liquid interface than conventional gas absorption processes [206, 229–232].

According to data in Table 6, inorganic membranes have high permeability (about 150000 barrer) and low selectivity (about 15). Of course, some of inorganic membranes such as Y (FAU) with -A1₂O₃ support and chitosan group are highly selective for CO₂/N₂ separation (selectivity () ≈ 100–800). Among polymeric membranes, polyamines have high permeability and selectivity (10⁶ (barrer) and 980, resp.), and the second FSCM membranes have high permeability and fine selectivity (10⁵ (barrer), 230, resp.). Other polymeric membrane groups are not selective for CO₂/N₂ separation, and maximum selectivity of these membranes is about 30.

2.5. Novel CO₂ Capture Technologies

These methods include electrochemical pumps and chemical looping approaches to CO₂ separation. The molten carbonate and aqueous alkaline fuel cells have been studied for use in separating CO₂ from both air and flue gases. Electrochemical pumps discussed include carbonate and proton conductors. Molten carbonate is nearly 100% selective for CO₂ separation, but major disadvantage in the application of molten carbonate electrochemical cells for CO₂ separation is that this process is not repeatedly. Other disadvantages of these technologies are: corrosion, difficult operating condition ( K), and sensitivity to the presence of   [45, 233].

In chemical looping combustion, the oxygen for combustion of the fuel is provided by a regenerable metal oxide catalyst. The chemical looping scheme can be presented in the general form [45]:

Nickel oxide is one main candidate for the chemical looping combustion of methane, as low as 673 K, because it is extensive and effective for the chemical looping combustion [45].

2.6. Discussion

Various technologies such as absorption, adsorption, cryogenic distillation, and membrane have been suggested for CO₂ separation from flue gases (Table 7). In this paper, various technologies for different feed conditions were investigated. Absorption is an important technology for CO₂ separation. Although physical solvents required low energy for regeneration, they have low absorption capacity and selectivity for CO₂ separation. Selexol is the best physical solvent and suitable for sweetening natural gas. However, physical absorption is not economical for flue gas streams with CO₂ concentration lower than 15 vol% (95 US$/ton CO₂ [234]).

Table 7: Comparison between various technologies used for CO₂ capture.

Technology
Advantages
Disadvantages
Scale

Absorption
(i) React rapidly

(ii) High absorption capacities

(iii) Very flexible
(i) Equipment corrosion

(ii) High energy required for regenerating solvent
Industrial

Adsorption
(i) Low energy consumption and cost of CO₂ capture

(ii) Suitable for separating CO₂ from dilute stream
Low adsorption capacities (in flue gases conditions)
Pilot

Cryogenic distillation
(i) Liquid CO₂ production

(ii) Not requiring solvents or other components

(iii) Easy scaled-up to industrial-scale application
Require large amount of energy
Pilot

Membrane separation
(i) Clean and simple process

(ii) Continuous, steady-state technology
Require high energy for post-combustion CO₂ capture
Experimental

Chemical solvents are classified in main groups such as alkanolamines, ammonia, aqueous piperazine (PZ), and amino acids. Chemical absorbents such as monoethanolamine (MEA) have high absorption capacities and are very flexible for CO₂ separation; therefore, these solvents are usually preferred to physical solvents. Chemical absorption with alkanolamines is the only technology that is used in an industrial scale for post-combustion capture. Amines react rapidly, selectively, and reversibly with CO₂ and are relatively nonvolatile and inexpensive solvents. In this process, the corrosion is the main problem; therefore, in recent studies, new amines and various mixtures of them were proposed and compared with previous ones to find suitable solvents. Suitable solvents for CO₂ separation must have high CO₂ absorption capacity, less corrosion, less viscosity and less regeneration energy. These studies showed that CASTOR 1 and 2, which are blended amine solvents (MEA/MDEA), are the best chemical adsorbents so far proposed for post-combustion CO₂ capture. Experimental results indicated that amine amino acid salts (AAAS) have better performance than MEA of the same concentration for CO₂ absorption, but do not deteriorate in the presence of oxygen. However, absorption has several disadvantages such as it requires high energy to regenerate solvents (3.0 GJ/ton CO₂ for absorption with 40%wt MEA in 210 kPa [235]), therefore need more efforts in the future to reduce energy consumption in post-combustion CO₂ capture with chemical absorption.

Adsorption is the one effective technology that can reduce energy and cost of the capture or separation of CO₂ in post-combustion capture. Adsorption is suitable for separating CO₂ from dilute and low flow rate stream, but flue gases conditions are the main problem against industrialization adsorption process. The CaO-MgAl₂O₄ and nano CaO/Al₂O₃ are the best chemical adsorbents. Although, the chemical adsorbents have high capacity and selectivity, but their regeneration is difficult. Physical adsorption is the most suitable for CO₂ capture at high pressures and low temperatures. At higher pressure (above 4 bar) activated carbons are more efficient than zeolites. The energy and cost of adsorption for activated carbons are nearly half of that of zeolites. On the other hand, zeolites (particularly 13X and 5A) have high selectivity for CO₂ separation. Generally, zeolite 5A may have better adsorption efficiency at co-adsorption of SO₂, NO and CO₂ than zeolite 13X.

In order to achieve more selective CO₂ separation from flue gases, the modified adsorbent surface was considered. New adsorbents such as honeyncomb monolith, MOFs, CHAs (NaCHA and CaCHA), PMO (MCM and SBA) and MSPs (Na₂SiO₄) are suitable adsorbents for selective CO₂ separation but they require more researches and studies. However, the development of suitable adsorbents with high CO₂ adsorption capacity, which can be replaced absorption with chemical adsorbent, is still demanded.

Cryogenic distillation separation can be used for CO₂ separation but its major disadvantage is the large amount of energy required to provide the refrigeration. Many new processes have been proposed for using cryogenic, but generally this technology is not suitable for post-combustion capture and is appropriate for oxy-fuel combustion method and CO₂ separation from exhaust of cement industry (stream with high CO₂ concentration).

The membrane separation method is a continuous, steady-state, clean and simple process for CO₂ recovery. Since the pressure drop is driving force for membrane process, the flue gas stream must compress. Since compressing flue gas is very difficult and expensive, membrane separation is suitable for high pressure stream with high concentration (>10 vol%). Inorganic membrane have high thermal and chemical stability but their selectivity is lower than polymeric membranes. Although Y (FAU) with -Al₂O₃ support and arginine salt chitosan are the best inorganic membrane, zeolite mambranes are suitable ones for CO₂ separation. Polymeric membranes are very selective for CO₂ separation but they have low thermal stability. Therefore, polymeric membranes are suitable for application in pre-combustion processes. Glassy polymeric membranes have higher selectivity, while the rubbery polymeric membranes have higher thermal stability. Perfect membrane with high performance for CO₂ separation (selectivities of CO₂/) can be prepared by mixing various membranes.

Because of operating problems and high cost of compressing, membrane separation is not suitable for post-combustion capture, but membrane technology is suitable for producing oxygen-enriched streams from air, in oxy-fuel combustion systems.

Electrochemical pumps and chemical looping are two new technologies suggested for CO₂ capture. Now these technologies are not effective in comparison with other technologies. Therefore, application of electrochemical pumps and chemical looping in CCS needs more research.

3. Conclusion

Because of economical and environmental incentives, researchers have mainly focused on CO₂ separation from different process streams, especially from the flue gases. In recent years, post-combustion capture has been the topic of many researches, because it is more flexible and can be easily added to the fossil fuel power plants.

Based on above findings, it can be concluded that flue gases properties (mainly concentration of CO₂, temperature and pressure) are the most effective factors for selection of suitable process for CO₂ separation.

Since flue gases have high temperature (about 373 K), low pressure, and low CO₂ concentration (1 atm and 10–15% moL), bulk absorption and adsorption processes may be the best suitable process for CO₂ separation from these streams. Due to simplicity of absorption process, this process has been applied in industrial plants, although many researches have been focused on preparation of adsorbents with high selectivity and capacity, in recent years. For industrial application, more studies about adsorbents are necessary. Cryogenic distillation and membrane processes are efficient for gas streams with high CO₂ concentration. Therefore, these process are economically efficient for pre-combustion capture. In recent years, different studies have been performed to optimize cryogenic cycles and preparation of suitable membrane for CO₂ separation from post-combustion flue gases.

By the result of this study, future research direction on the scale-up and industrialization of adsorption (with modified adsorbent), and membrane process for CO₂ separation is suggested. Therefore more studies must be focused on modeling and simulation of these processes (membrane and adsorption), although research for finding new adsorbent, suitable mambrane (with mixed or modified present membrane) and blending amine solvents can reduce CCS cost.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

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