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Lignocellulose-based adsorbents: A spotlight review of the effective parameters on carbon dioxide capture process
Journal Pre-proof Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process
Zahra Rouzitalab, Davood Mohammady Maklavany, Shahryar Jafarinejad, Alimorad Rashidi PII:
S0045-6535(19)32997-2
DOI:
https://doi.org/10.1016/j.chemosphere.2019.125756
Reference:
CHEM 125756
To appear in:
Chemosphere
Received Date:
27 September 2019
Accepted Date:
24 December 2019
Please cite this article as: Zahra Rouzitalab, Davood Mohammady Maklavany, Shahryar Jafarinejad, Alimorad Rashidi, Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process, Chemosphere (2019), https://doi.org/10. 1016/j.chemosphere.2019.125756
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Graphical Abstract
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Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process
Zahra Rouzitalaba, Davood Mohammady Maklavanyb, Shahryar Jafarinejadc, Alimorad Rashidib,*
a
Civil Engineering Division, College of Environment, Karaj, P.O. Box 31746-74761, Alborz,
Iran b
Carbon & Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI),
Tehran, P.O. Box 14857-33111, Tehran, Iran c
Department of Chemical Engineering, College of Engineering, Tuskegee University, Tuskegee,
P.O. Box 5899, Alabama 36088, USA
Declarations of interest: none
*
Corresponding author. Address: Carbon & Nanotechnology Research Center, Research Institute of Petroleum
Industry (RIPI), West Blvd. Azadi Sport Complex, P.O. Box 14857-33111, Tehran, Iran. E-mail: [email protected] (Alimorad Rashidi).
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Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process
Abstract The increasing demand for energy all around the world has led to a rise in greenhouse gases (GHGs), of which carbon dioxide (CO2) is the most important. CO2 is largely responsible for global warming and climate change. Processes such as carbon dioxide capture and storage (CCS), which have an effective role in climate mitigation, seem to be promising. In recent years, porous carbons, particularly activated carbons (ACs), have rapidly emerged as one of the most effective adsorbents of CO2. However, the implementation of pristine ACs in the real world is still hindered due to their physical and weak adsorption, which makes these adsorbents sensitive to temperature and relatively poor in selectivity. Hence, the surface modification of ACs is essential in order to improve their surface area, pore structure and alkalinity. Numerous studies have reported lignocellulose-based ACs as very promising adsorbents of CO2. In this review, the sources, health and environmental effects of CO2, and the abatement methods of GHGs are described. In addition, the capture and separation of CO2 from gas stream using various types of lignocellulose-based ACs are summarized. Furthermore, the key factors controlling the adsorption of CO2 by ACs (characteristics of adsorbents, preparation conditions, as well as adsorption conditions) are comprehensively and critically discussed. Finally, future research needs and prospective research challenges are summarized. Keywords:
Carbon dioxide capture and storage (CCS), CO2, Adsorption,
Lignocellulose-based material, Controlling factors
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Contents 1. Introduction................................................................................................................................................4 2. An Overview of CO2 and Reduction Technologies ...................................................................................5 2.1. Sources of CO2 Emission....................................................................................................................5 2.2. Health and Environmental Effects of CO2 ..........................................................................................7 2.3. An Overview of Advanced GHG Reduction Technologies..............................................................15 2.3.1. Carbon dioxide Capture Methods ..............................................................................................15 3. Lignocellulose-based Adsorbents for CO2 Capture .................................................................................23 4. Key Factors Controlling CO2 Adsorption onto Lignocellulose-based Adsorbents .................................35 4.1. Adsorbent Features ...........................................................................................................................35 4.1.1. Surface Area...............................................................................................................................35 4.1.2. Pore Structure.............................................................................................................................36 4.1.3. Surface Chemistry......................................................................................................................39 4.1.4. Other Factors..............................................................................................................................42 4.2. Preparation Conditions......................................................................................................................43 4.2.1. Carbonization Condition............................................................................................................43 4.2.1.1. Carbonization Type.............................................................................................................43 4.2.1.2. Carbonization Temperature ................................................................................................45 4.2.1.3. Carbonization Flow Rate ....................................................................................................45 4.2.2. Activation Condition..................................................................................................................46 4.2.2.1. Number of Activation Steps................................................................................................46 4.2.2.2. Activating Agent.................................................................................................................47 4.2.2.3. Activating Agent Dosage....................................................................................................49 4.2.2.4. Activation Temperature ......................................................................................................50 4.2.2.5. Activation Time ..................................................................................................................51 4.2.2.6. Activation Flow Rate ..........................................................................................................52 4.2.2.7. Activation Heating Rate......................................................................................................52 4.3. Adsorption Conditions ......................................................................................................................53 4.3.1. Temperature ...............................................................................................................................53 4.3.2. Humidity ....................................................................................................................................58 4.3.3. Multicomponent Adsorption......................................................................................................60 5. Conclusion and Future Research Needs ..................................................................................................61
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1. Introduction Triatomic Carbon dioxide (CO2) molecule is a gas under ambient conditions. It sublimates from solid state to gas at ‒78 °C under atmospheric pressure. A comparatively inert gas, carbon dioxide is neither explosive nor flammable, which does not support combustion process. Naturally occurring in the Earth’s atmosphere, carbon dioxide is crucial to the plants that photosynthesize carbon dioxide and water into sugars using solar energy. As shown in Fig. 1, the natural carbon cycle controls carbon dioxide level in the Earth’s atmosphere (North, 2015).
Fig. 1 Natural carbon cycle. Modified from reference (EarthHow, 2017).
Despite the 20-fold emission of CO2 by natural sources in comparison with the sources resulting from human activity, over times longer than a couple of years, natural sources are nearly balanced by natural sinks (Songolzadeh et al., 2012). Sources leading to anthropogenic CO2 emission are increasing more than ever with the growing population and the associated energy consumption, and subsequent emissions seem to be unavoidable. As a result of air 4
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pollution, which directly affects human well-being, there is growing concern about global environmental problems and sustainable development (Višković et al., 2014; Tehrani et al., 2019). Great biological and physiochemical endeavors have been made over recent years in order to develop highly efficient CO2 reduction methods, however, this review article focuses more on physiochemical methods, amongst which adsorption by porous carbon materials is recognized as one of the most economical and promising strategies owing to their highly firm and hydrophobic surface, adjustable textural properties, and high adsorption affinity towards CO2. A large number of studies have been conducted to survey the adsorption of CO2 on a wide range of carbonaceous resources comprising lignocellulose-based porous adsorbents due to the potential demand for huge amounts of low cost CO2 adsorbents and the importance of waste resources. The main objective of this review is to undertake a comprehensive review of peer-reviewed articles concerning the adsorption of CO2 only by lignocellulose-based porous adsorbents, and to identify the prospective research challenges. First, the main sources of CO2 emission and its impacts are discussed, and then the GHGs abatement methods and CO2 capture technologies are studied. Finally, the factors that control the adsorption of CO2 by lignocellulose-based porous adsorbents are thoroughly discussed.
2. An Overview of CO2 and Reduction Technologies 2.1. Sources of CO2 Emission CO2 comes from both anthropogenic and natural emissions. The proportion of anthropogenic source is increasing, and their impact is deteriorating since almost all human daily activities lead 5
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to the emission of CO2. According to Fig. 2 there are various sources of anthropogenic carbon dioxide, and amongst them the combustion of fossil fuels, industrial process emissions, waste treatment (IPCC, 2008b; Liu, 2016), land use change (IPCC, 2008b; Liu, 2016; Davis, 2017; Lal, 2019) and soil degradation processes (such as erosion, nutrient depletion, salinization, decline of soil structure)(Lal, 2019) are the most important. Based on the Environmental Protection Agency (EPA) report (2019), nearly 77% of CO2 emission is the result of fossil fuel use (EPA, 2019). The major fossil fuel users are transportation, utilities (power, gas, oil, etc.), and industrial production.
Fig. 2 Main sources of CO2 emission (EPA, 2019).
Capturing CO2 directly from large point sources like industries seems easier and more economical than from small point sources. The main concerns of industrial production are agriculture, mining, construction as well as manufacturing. Manufacturing is the largest one and can be subdivided into five principal categories, namely chemicals, petroleum refineries, metal/mineral products, paper, and food (Fig. 3). These categories constitute the majority of the 6
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energy consumption and CO2 emission by the sector (U.S. Department of Energy and Energy Information Administration, 2005; Davis and Diegel, 2007; Liu, 2016).
Fig. 3 Manufacturing CO2 emission segments.
Natural carbon cycle cannot balance the subsequent CO2 emission, so the CO2 level in the atmosphere gradually increases. The emitted CO2 from the burning of fossil fuel elevates the atmospheric CO2 level by 1 ppm by volume (North, 2015).
2.2. Health and Environmental Effects of CO2 Accommodating over half of the global population, cities are responsible for approximately 75% of global energy consumption as well as greenhouse gas (GHG) emissions (Gouldson et al., 2016; Wu et al., 2018a; Mi et al., 2019). It is well established that variations in GHG levels due to human activities are the main cause of global warming, through adsorbing and trapping the infrared radiation (IR) occurring over the last century (The Royal Society, 2010), which can sequentially lead to climate change (VijayaVenkataRaman et al., 2012; Karimi et al., 2018). The mean surface temperature would fall to about ‒21 °C without this greenhouse effect (Karl et al., 2009; Anderson et al., 2016). 7
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The impressions of greenhouse gases on Earth’s climate is contingent on the retention time of these gases in the atmosphere (Karl et al., 2009). It is largely believed that CO2 is the most potent greenhouse gas (after water vapor with human activities contribution by 0.18% (Babu, 2014)), contributing to global warming more than other GHGs (Xu, 2014; North, 2015), with increasingly devastating effects on the environment (Biasin, 2015). As shown in Fig. 4, in recent years the CO2 level of atmosphere has exponentially risen and the overall CO2 concentration in the atmosphere has increased from 317.10 ppm (in June 1958) to 410.79 ppm (in June 2018). Such a significant growth in CO2 level has also been the cause of major local weather changes and increases in the average surface temperature of the earth (Kumar and Kim, 2016).
Fig. 4 Atmospheric CO2 concentration from 1958 to 2018 (CO2.Earth, 2019).
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As indicated in the EPA report, greenhouse gas outflows can bring about an upward push in temperature by 1‒2 °C in the following century (Dassanayake et al., 2016). Such an increase can have serious consequences on water resources, agriculture, forestry, marine ecosystems, animals and human health, as shown in Table 1.
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Table 1. Health and environmental effects of CO2 Type
Advantages
Disadvantages
Water Resources
Rainfall pattern variations and a surge in the frequency and severity of extreme weather across different regions on account of climate change may lead to more hot days, heat waves, heavy precipitation events and fewer cold days (Lindner et al., 2010; Bender and Weigel, 2011; Wheeler and von Braun, 2013; Marengo et al., 2017; Karimi et al., 2018).
Drought risk has magnified the problem of high temperatures and an anticipated decrease in rainfall (Lindner et al., 2010).
Water resources are changing in terms of quantity and quality as a result of thermal expansion and melting of Arctic and Antarctic ice sheets. In addition, warming is causing the sea level and runoff waters to rise (Karl et al., 2009; Doney et al., 2012; Biasin, 2015; IPCC, 2015).
Agriculture
CO2 fertilization effect, i.e. the stimulation of photosynthesis
Increased heavy precipitation, growing season temperature, flooding
through elevated CO2 concentration, is conducive for both crop
and drought seriously affect crop yield (Karl et al., 2009; Wang et al.,
growth and crop productivity (DaMatta et al., 2010; Bender and
2017b).
Weigel, 2011; Erbs et al., 2015; Wang et al., 2017b; Karimi et al., 2018).
Climate change affects both crop biomass production and crop quality (Erbs et al., 2015).
10
Moreover, stomatal conductance reduction, as a consequence of
Decrease in the nitrogen concentration of vegetative plant parts as
CO2 fertilization effect, not only improves drought tolerance by
well as in seeds and grains, which exemplifies CO2 effect, leads to a
diminishing transpiration loss but also reduces O3 (and other
decrease in protein concentration. Variability of macro- and
gaseous pollutants) uptake (Bender and Weigel, 2011).
microelements composition (Ca, K, Mg, Fe, Zn), secondary compounds, vitamins, and sugars concentrations, as well as lipid composition of plants, are among other examples of CO2 enrichment (DaMatta et al., 2010; Bender and Weigel, 2011; Dietterich et al., 2015; Medek et al., 2017).
Forestry
Elevated CO2 offers various advantages to trees alike to
Limiting factors such as nutrient availability do not allow trees to
agriculture crops (Field et al., 1995; Picon-Cochard et al., 1996;
grow sufficiently as a result of the enhancement of photosynthesis rate
DeLucia et al., 1999; Wullschleger et al., 2002; Ainsworth and
(Hungate et al., 2003; Luo et al., 2004; Lindner et al., 2010).
Long, 2005; Vetter et al., 2005; Lettens et al., 2008; Saxe et al.,
2008; Lindner et al., 2010; FAO, 2012).
Enhancement of temperature may affect forest productivity as well as interaction and competition processes among tree species (Lasch et al., 2002; Ogaya et al., 2003; Lloret et al., 2004; Lindner et al., 2010).
Forest fire is likely to occur at prolonged drought situations, which would lead to build-up soil erosion owing to increased hydrophobicity and reduced plant regeneration (Certini, 2005; Delitti et al., 2005; Lindner et al., 2010; FAO, 2012; Manoj Kumar and Abhishek, 2014; Stephens et al., 2018).
11
Tree mortality occurs owing to trees’ inability to swiftly adapt to
environmental changes in terms of its life-span (Hänninen, 2006; Lindner et al., 2010; FAO, 2012; Biasin, 2015).
Alternations of disturbance regimes such as storms, insect herbivores and thermophilic pathogens are among the main effects of climate change on temperate forests (Thürig et al., 2005; Schütz et al., 2006; Eliasch, 2008; Lindner et al., 2010; FAO, 2012),
Marine Ecosystem
Species or populations may profit from environmental changes
Ocean acidification occurs as a consequence of elevated atmospheric
due to the availability of food or nutrients, reduction of the
CO2 and reduced subsurface oxygen concentration (due to warming
physiological cost of maintenance, as well as the emergence of
and altered ocean circulation) (E Keeling et al., 2010; Doney et al.,
novel ecosystems (Doney et al., 2012).
2012).
An increase in aqueous CO2, total inorganic carbon and also a decrease in pH, carbonate ion, and calcium carbonate saturation states are caused by ocean acidification (Doney et al., 2009; Doney et al., 2012; Mostofa et al., 2015; Mollica et al., 2018).
Coral skeletons and the accretion of reefs may be severely weakened by ocean acidification (Kleypas et al., 1999; Hughes et al., 2003; Foden and Stuart, 2009; Doney et al., 2012). Moreover, species replacement, bleaching, and cover reduction are among the other effects of warming on corals and their reefs (Hoegh-Guldberg et al., 2008; Hoegh-Guldberg et al., 2017).
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CO2 enhancement and climate change, as well as chemical effects may change population size, population growth rates and also cause seasonal variations in organisms (Doney et al., 2012; Mostofa et al., 2015; Matear and Lenton, 2018).
Animal
Higher temperatures, rainfall, and CO2 boost the productivity of
Birds migrate and arrive at their nesting grounds earlier. Also, they
pastures (Oyhantçabal et al., 2010).
lay eggs earlier in the year than usual (IPCC, 2008a; Biasin, 2015;
Lesser thermal regulation requirement and lower average winter
Taddeo, 2017). Moreover, mammals’ hibernation is shorter (Taddeo,
weight losses are possible consequences (Oyhantçabal et al.,
2017).
2010).
Enhancement of global temperatures affects the distribution of animals through shifting many species closer to the poles (Taddeo, 2017).
Impairment of animal body immune system due to the proliferation of disease producing microbes in favorable higher temperature and higher humidity and also ecological shifts of pests (insects and mites) (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Digestibility reduction of enhanced plant tissues lignificataion owing to high temperatures (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Reduction of pastoral farming, livestock productivity and fertility as a result of increased heat, disease, and weather extremes (Beitz, 1985;
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Karl et al., 2009; Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Significant losses of animals as a result of scarcity of fodder and water in recurrent droughts (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Human Health
Warming is likely to reduce the risk of death related to severe
cold weather (Karl et al., 2009).
Limited growth, tissue repair and turnover together with the impairment of muscle function and immune system, as well as wasting, stunting, intrauterine growth restriction, and low birth weight are the impacts of insufficient protein intake with plant-based diets (Castaneda et al., 1995; Black et al., 2008; Medek et al., 2017).
In general, protein deficiency coexists with energy and micro nutrient deficiencies, which resulting in disability-adjusted life years (DALYs) or death (Millward and Jackson, 2004; Black et al., 2008; Medek et al., 2017).
High staple food prices as a result of minimum maintenance requirements is likely to make it more challenging for families’ income to meet food security (Wheeler and von Braun, 2013).
Air quality standard is already being adversely affected by the rising temperature (Karl et al., 2009).
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2.3. An Overview of Advanced GHG Reduction Technologies
3
Greenhouse gas emissions from fossil fuel combustion can be decreased through (i) reducing
4
fossil fuel consumption by finding alternatives for fossil fuels and generating less electricity,
5
which is mightily challenging; (ii) improving the performance of coal-fired plants; (iii) carbon
6
capture and storage (CCS); and (iv) enhancing CO2 partial pressure in exhaust gas, which can
7
improve power efficiency in the previous step (Plaza et al., 2007; Ben-Mansour et al., 2016).
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CCS is the most widely applied technique for the capture of CO2 from gas stream, and as Herzog et al. (Herzog et al., 2009) have recommended, it can make continuous application of
10
fossil fuels and reduction of emissions related to fossil fuel combustion possible; besides, it
11
would provide enough time for finding a suitable source instead of fossil fuels.
12
Intergovernmental Panel on Climate Change (IPCC) has also suggested CCS as a promising
13
technology for controlling the development of the atmospheric CO2 concentration and it is
14
obvious that industries should be considered as a prime target (IPCC, 2005; Sanz-Pérez et al.,
15
2016). CCS is a riskless and effective climate mitigation tool, which has a special role in some
16
rising economies, essentially because developing countries are significant carbon dioxide
17
emitters controlling vast fossil fuel reserves; following such policies practically guarantees the
18
reduction of CO2 emission in the future and in spite of recent difficulties, critical advance has
19
been made over the previous decade (CCS, 2015).
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2.3.1. Carbon dioxide Capture Methods
21
CO2 capture, the most demanding step of the CCS process, makes up the majority of the total
22
costs, i.e. 70-80% (Benedetti et al., 2019). Thus, identifying a capture procedure suitable for this
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purpose with minimal energy penalty is a major issue. As indicated, carbon capture in fossil fuel
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combustion process can be classified as (i) pre-combustion capture, (ii) oxy-fuel combustion,
25
(iii) post-combustion capture (Brunetti et al., 2010), and (iv) capture from industrial process
26
streams (IPCC, 2005). The general scheme of the different CO2 capture routes is shown in Fig. 5.
27
CO2 capture from industrial streams could be performed using techniques prevalent in the
28
other three routes (IPCC, 2005). Excessive prices, limited technical knowledge about its proper
29
performance, lack of a single concise process for total operational efficiency and the absence of a
30
development plan for industrial applications are among the major challenges facing pre-
31
combustion capture. Large energy requirement for providing pure oxygen and the absence of a
32
complete preparation method for this technology without trying it on a commercial scale are the
33
drawbacks of oxy-fuel combustion capture. Further, the necessity of energy for the compaction
34
of captured carbon dioxide, the need to deal with high gas volumes owing to the fact that the
35
concentration of CO2 and its partial pressure in flue gas are low, as well as the huge energy
36
supplies required for sorbent regeneration are the major difficulties in post-combustion capture
37
methods (Figueroa et al., 2008; Mondal et al., 2012; Ben-Mansour et al., 2016; Mukherjee et al.,
38
2019).
39
Among these technologies, the post-combustion carbon capture is advantageous because:
40
(a) It is less difficult to combine into a present plant without radical changes in them.
41
(b) It is more appropriate for gas plants than the other methods;
42
(c) It is adaptable as its repair does not discontinue the power plant’s procedure and it can
43
be regulated or managed easily (Ben-Mansour et al., 2016; Mukherjee et al., 2019);
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(d) It needs shorter time for creation; and
45
(e) It produces high purity CO2 (>99 %) at high CO2 capture ratio (90%) (Najmi, 2015).
46
Fig. 5 General scheme of the different CO2 capture routes. Modified from reference (IPCC, 2005). 47 48
Absorption, membrane, cryogenic, micro-algal bio-fixation, and adsorption are common post-
49
combustion separation technologies proposed in Fig. 6 and compared in Table 2. Of the
50
aforementioned technologies, adsorption with low investment and operational cost, as well as its
51
simple application over a wide variety of operating temperatures and pressures may be
52
considered as practical solutions. Adsorption using selective sorbents can produce high purity
53
CO2 streams with minimal pressure drop compared to other technologies while using low energy
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without generating pollution or by-products. On the other hand, adsorption efficiency is
55
contingent on the development of easily regenerative adsorbent with high CO2 adsorption
56
capacity and selectivity (Upendar et al., 2014; Chaiw et al., 2016; Hong et al., 2016; Vilella et
57
al., 2017; Yang et al., 2017; Peredo-Mancilla et al., 2018; Yue et al., 2018; Han et al., 2019).
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Fig. 6 Classification of methods used to remove CO2 in post-combustion processes. Modified from reference (Ben-Mansour et al., 2016), with permission from Elsevier, license number: 4731710456675.
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Table 2. Advantages and disadvantages of CO2 reduction technologies in post-combustion process Technology
Advantages
Type Absorption
Disadvantages
High development in its process (Leung et al., 2014).
Environmental impacts due to solvent degradation (Mukherjee et al., 2019).
High absorption proficiency (Leung et al., 2014).
Solvents’ corrosiveness (chemical absorption) (Yoro and Sekoai, 2016).
High thermal energy requirement due to solvent regeneration (Yoro and Sekoai, 2016).
Micro-Algal
bio fixation
Applicability in various CO2 concentrations (Zhang,
High capital and operational costs (Kenarsari et al., 2013).
Micro-algal growth sensitivity to local climatic conditions and gas stream
2015).
Revenue generation by high value commercial
impurities (Klinthong et al., 2015; Seth and Wangikar, 2015).
products (Zhang, 2015; Ben-Mansour et al., 2016).
Membrane
High separation proficiency (Leung et al., 2014)
Environmentally friendly (Kenarsari et al., 2013)
Low capital and operational costs (Kenarsari et al.,
High energy requirement due to blending during growth period (Seth and Wangikar, 2015).
Low volumetric productivity (Seth and Wangikar, 2015).
Low rate of CO2 fixation (Ho et al., 2011)
Additional energy requirement for differential pressure across the membrane (Yoro and Sekoai, 2016).
Plug of membranes by gas stream impurities (Leung et al., 2014; Yoro and Sekoai, 2016).
2013)
Low thermal stability (Yoro and Sekoai, 2016).
Reduction in CO2 permeation at low concentrations (< 20%) (Mondal et al., 2012).
Cryogenic
limited economy of scale (Li et al., 2013)
Several steps requirement (Mondal et al., 2012; Li et al., 2013)
Applicability without chemical absorbent (Mondal et
Applicability in high CO2 concentration > 90% v/v (Leung et al., 2014).
al., 2012)
Limitation on the operating temperature (Leung et al., 2014; Yoro and Sekoai, 2016).
Atmospheric pressure operation (Mondal et al., 2012)
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Direct production of liquid CO2 (Mondal et al., 2012)
High energy requirement for the refrigeration (Mondal et al., 2012; Kenarsari et al., 2013)
Significant energy penalty (Leung et al., 2014; Yoro and Sekoai, 2016)
Process disruption due to gas stream impurities (Mondal et al., 2012; Kenarsari et al., 2013)
Adsorption
High capital cost (Kenarsari et al., 2013)
High adsorption proficiency (Kenarsari et al., 2013)
Low selectivity without surface modification (Kenarsari et al., 2013)
CO2 adsorption at low partial pressures (Li et al., 2013)
Loss of sorption capacity over multiple cycles (Kenarsari et al., 2013)
Cost-effectiveness (Yoro and Sekoai, 2016).
Minimum energy requirements for the regeneration (Yoro and Sekoai, 2016).
Reversibility of the process and recyclability of the adsorbent (Leung et al., 2014)
High efficiency in long-term use (Mukherjee et al., 2019).
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Tuning the sorbent structure is a feasible approach for the enhancement of CO2 adsorption
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capacity, which is amended by a complex and difficult step of sorbent selection (Lee and Park,
63
2015). The sorbent materials should meet vital requirements to be both economical and
64
operational in the process of capturing CO2. These criteria are as follows:
65
Regeneration facility of sorbent over many cycles;
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High CO2 adsorption capacity;
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Good selectivity toward CO2;
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Fast adsorption/desorption kinetics;
69
Mechanical strength of sorbent particles;
70
Chemical stability/tolerance against impurities and moisture; and
71
Cost/ease of adsorbent synthesis (Samanta et al., 2012; Sevilla et al., 2012; Sehaqui et al., 2015; Álvarez-Gutiérrez et al., 2017a; Chomiak et al., 2017).
72 73
Amongst diverse adsorbents, the outstanding characteristics of porous carbon materials,
74
including controllable textural properties (surface area and pore structure), superb chemical,
75
thermal and mechanical stability, hydrophobicity, comprehensive availability of resources,
76
excellent environmentally benignity, swift adsorption kinetic and favorable cooperativeness to
77
surface functionalization as well as heterogeneous doping, motivate researchers to closely
78
scrutinize CO2 capture applications (Bae and Su, 2013; Heo and Park, 2015; Chen et al., 2016;
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Liang et al., 2016; Tian et al., 2016; Peredo-Mancilla et al., 2018). Activated carbons (AC), a
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processed form of carbons, which is extremely porous, comprises reciprocally connected cavities
81
between graphitic-like layers, which culminate in a high internal surface area (Dobele et al.,
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2012). 21
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It is well known that chemical and physical activation processes can increase the specific
84
surface area substantially and introduce developed porous structures. In the chemical activation
85
process, first, the raw materials are impregnated by employing the dehydrating agent (i.e., KOH,
86
NaOH, K2CO3, C2K2O4, H3PO4, and ZnCl2), which affects the pyrolytic decomposition of the
87
starting materials. Second, the thermal treatment of impregnated materials and the resultant tars
88
indicated that the thermal treatment has a determining impact on carbonization process, which
89
enhances carbon yield and introduces porosity. After removing the applied chemicals by
90
washing, the formed porosity would be accessible. Producing wastewater and other negative
91
environmental impacts, complexity, and high cost are the specific disadvantages of chemical
92
activation. Carbon can also be physically activated through two steps: at first, the high
93
temperature pyrolysis (carbonization) of carbonaceous material occurs, in which inert
94
atmosphere is used for removing a great part of the hydrogen and oxygen content, then the
95
activation is performed at a high temperature in presence of oxidizing gases. Using steam, CO2
96
gas, water vapor or air, the carbon atoms would be extracted from the structure of the porous
97
carbon. However, physical activation is not so costly and is rather more ecofriendly than
98
chemical activation. Furthermore, an integration of these two activation processes is another
99
technique to prepare AC (Arami-Niya et al., 2010; Heo and Park, 2015; Yahya et al., 2015).
100
For the success of CO2 capture, how a proper biomass precursor is selected for the preparation
101
of carbons is of crucial importance. Actually, any carbonaceous material could be used as a
102
precursor for the production of activated carbon only if it has a high proportion of carbon in
103
addition to a low ash content, and is preferably available, cheap and renewable (Peredo-Mancilla
104
et al., 2018).
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3. Lignocellulose-based Adsorbents for CO2 Capture
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Lignocellulosic biomasses, the most abundant non-edible biomasses, such as wood and
108
agricultural/forestry wastes are based on cellulose, hemicellulose, lignin, and a minor amount of
109
extractives (Dotan, 2014; Wang et al., 2017c). Converting lignocellulosic biomass into
110
functional materials, like carbon based CO2 adsorbents, is one promising approach not only to
111
recover this biomass waste but also to cut down the growing amounts of waste being landfilled
112
and their consequent environmental pollution (water, soil, air) (Wang et al., 2014). The
113
production of AC from agricultural waste residuals has received growing attention, aimed at not
114
only supplying a possible remedy for reusing these materials but also decreasing the cost of
115
production of commercial ACs in comparison to traditional precursors such as coal. Waste
116
recycling and reuse are two energy-efficient processes that have become more prevalent because
117
of their environmentally benignity and cost-reduction advantages (Nasri et al., 2014; Erto et al.,
118
2016; Suhas et al., 2016). Fig. 7 shows different categories of used lignocellulosic materials as
119
the precursor of ACs for CO2 capture. In addition, a brief summary of the application of
120
lignocellulose-based adsorbents for the CO2 capture and separation from gas stream is shown in
121
Table 3 and discussed in the following section.
23
Journal Pre-proof
Fig. 7 A summary of the lignocellulose-based adsorbents for CO2 capture 122
24
Table 3. A detailed review of preparation conditions and characteristics of lignocellulose-based adsorbents for CO2 capture (year 2008-2020)
NO.
Precursor
1
Wood
2
Bamboo
3
Almond Shell
Activation/ Modification Process
H3PO4 Treatment + NH3 Treatment H3PO4 Treatment NH3 Activation CO2 Activation + PEIa Impregnation CO2 Activation ZnCl2 Activation + CO2 Activation ZnCl2 Activation
4
Olive Stone
5
Almond Shell
6
Soybean
7
Rice Husk
8
Sugarcane Bagasse
ZnCl2 Activation
9
Nano-fibrillated Cellulose
Freeze-drying + AEPDMSb Impregnation
10 11
Almond Shell Olive Stone
12
Wood
13
Sawdust
14
Palm Shell
15
Corncob
16
Corncob
17
Coconut Shell
18 19
Coconut Shell Sugarcane Bagasse
Carbonization Temp./Time (Heating ramp rate)
Activation Temp./Time (Heating ramp rate)
SBET
Smicro
D
Vmicro
Vnarrow
Vmeso
Vtot
Pressure
Temp.
CO2 Uptake
Qst
KH
Refs.
℃h
℃h
(℃ min)
(℃ min)
m2 g
m2 g
nm
cm3 g
cm3 g
cm3 g
cm3 g
bar
°C
mmol g
kJ mol
mmol g. bar
Commercial
800/2
1190
n/am
2.79
n/a
0.22
0.35
0.83
1
25
1.92
‒
‒
(Pevida et al., 2008)
1567
n/a
n/a
n/a
n/a
n/a
n/a
37
2
36.00
‒
‒
(Wang et al., 2008)
600/0.5 (15)
800/3 (15)
653× 10‒4
510
n/a
n/a
0.19
n/a
0.28
n/a
25
2.22
‒
‒
(Plaza et al., 2009b)
‒
900
1179
n/a
0.8
0.43
0.43
0.09
0.61
1
25
2.52
‒
‒
(Plaza et al., 2009a)
600
700
1090
n/a
1.2
0.42
0.12
n/a
0.50
1
25
2.68
‒
‒
(Plaza et al., 2010)
600/2 (1)
600/2.5 (1)
811
n/a
n/a
n/a
n/a
n/a
n/a
‒
120
0.52
‒
‒
(Thote et al., 2010)
500/1 (10)
927
n/a
0.80
n/a
n/a
n/a
0.56
n/a
30
1.30
‒
‒
(Boonpoke et al., 2011)
500/1 (10)
923
n/a
0.80
n/a
n/a
n/a
0.53
n/a
30
1.74
‒
‒
(Boonpoke et al., 2011)
500/4
(Gebald et al., 2011)
‒
‒
n/a
7.1
n/a
n/a
n/a
n/a
n/a
1
25
1.39
‒
‒
600 600
800 800
588 909
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
1 1
30 30
2.15 2.46
26.0 25.0
‒ ‒
(Plaza et al., 2011a) (Plaza et al., 2011a)
Commercial
800/2
1361
n/a
n/a
n/a
n/a
n/a
n/a
1
30
1.56
‒
‒
(Plaza et al., 2011b)
KOH Activation
250/2
600/1 (3)
1260
1360
0.8
0.61
0.52
n/a
0.62
1
25
4.8
20.0
9.02
(Sevilla and Fuertes, 2011)
NH3 Activation
‒
800/2.1 (10)
826
n/a
n/a
0.39
n/a
n/a
0.42
1
30
1.67
‒
‒
450/2
800/2
1425
1245
1.71
0.62
‒
‒
1.1
1
25
1.04
17.65
‒
1065
143
4.01
0.1
‒
‒
1.0
1
25
1.02
24.62
‒
600/2 (10)
n/a
1922
n/a
0.68
n/a
n/a
n/a
1
25
1.67
‒
3.06
(Yang et al., 2011)
600/3 (10) 800/2 (10) 500/1 (10j)
n/a 483
1575 n/a
n/a 2.18
0.53 0.25
n/a n/a
n/a n/a
n/a 0.28
1 1
25 75
1.14 0.2
‒ ‒
1.56 ‒
(Yang et al., 2011) (Boonpoke et al., 2012)
NH3 Activation CO2 Activation H3PO4 Treatment + NH3 Activation
K2CO3 Activation H3PO4 Activation H3PO4 Treatment KOH Activation ZnCl2 Activation
500/2 600/3 (10)
25
(Shafeeyan et al., 2011) (Sun and Webley, 2011) (Sun and Webley, 2011)
20
Kraft Cellulose
21
Kraft Cellulose
22
Birch Wood Chips
23
Palm Shell
24
Palm Shell
+ PEIa Impregnation NaOH Activation H3PO4 Treatment + NaOH Activation H3PO4 Treatment+ NaOH Activation MEAc Impregnation AMPd Impregnation
400/3
600/1.5
2032
1020
1.51
0.77
n/a
n/a
0.89
1
25
0.3
‒
‒
(Dobele et al., 2012)
400/3
600/1.5
1758
1096
1.35
0.74
n/a
n/a
0.84
1
25
3.22
‒
‒
(Dobele et al., 2012)
450/5
650/1.5
2119
1377
1.22
0.84
n/a
n/a
0.92
1
25
3.63
‒
‒
(Dobele et al., 2012)
Commercial
65
36
n/a
n/a
n/a
n/a
n/a
1
25
1.11
‒
‒
(Khalil et al., 2012)
Commercial
102
88
n/a
n/a
n/a
n/a
n/a
1
25
0.77
‒
‒
(Khalil et al., 2012)
840
n/a
1.0
0.34
0.36
n/a
0.37
1
25
3.0
‒
‒
(Plaza et al., 2012)
1940
n/a
0.92
n/a
0.47
n/a
0.82
1
25
4.5
25.0
8.26
(Sevilla et al., 2012)
1600
1551
0.84
0.66
n/a
n/a
0.72
1n
25
3.4
‒
‒
(Wang et al., 2012a)
3404
585
2.2
n/a
n/a
n/a
1.88
1
25
4.36
‒
6.64
2000
n/a
n/a
n/a
n/a
n/a
0.8
1
25
4.5
‒
9.24
(Wang et al., 2012b) (Wei et al., 2012)
1060
n/a
2.49
0.44
n/a
n/a
0.52
1
25
4.24
‒
‒
(Xing et al., 2012)
25
Coffee Waste
KOH Activation
400
600/1 (5j)
26
Algae + Glucose
KOH Activation
200/24
700
27
Fungi
KOH Activation
28
Celtuce leaves
KOH Activation
29
Bamboo
KOH Activation
30
Bean Dreg
KOH Activation
500/2 (2j) 600 500/1.5 (5j) 400/1
700/1 (3j) 800/1 600/1.5 (10j) 700/1 (5)
31
Enteromorpha Prolifera
KOH Activation
180/24
600/4 (2)
418
358
n/a
0.21
n/a
n/a
0.37
1
25
1.39
‒
‒
(Zhang et al., 2012)
32
Sewage Sludge
NaOH Activation
800 (10)
700/1 (5)
178
46
52
0.008
n/a
0.18
0.25
n/a
25
1.27
‒
‒
(de Andres et al., 2013)
33
Macadamia Nut Shell
CO2 Activation
600/1
900/0.5
512
n/a
n/a
n/a
n/a
n/a
0.17
1
25
3.37
‒
‒
(Bae and Su, 2013)
34
African Palm Shell
KOH Activation
600/1
850/1 (10)
1250
n/a
0.92
0.55
n/a
0.06
0.61
1
25
4.4
‒
11.05
(Ello et al., 2013b)
35
Coconut Shell
CO2 Activation
800/3.5
1327
n/a
0.83
0.55
n/a
0.10
0.65
1
25
3.9
‒
8.26
36
Olive Stone
CO2 Activation
800/6 (10)
1215
n/a
1.28
0.48
n/a
n/a
0.51
1
25
3.1
33.0
8.42
37
Almond Shell
CO2 Activation
750/4 (10)
38 39 40
Grass Cuttings Beer Waste Biosludge
41
Beer Waste
42
Palm Shell
CO2 Activation CO2 Activation CO2 Activation H3PO4 Activation Amination MgCl2 Impregnation CO2 Activation
43
Sawdust
44
Coconut Shell
862
n/a
0.75
0.33
n/a
n/a
0.36
1
25
2.7
33.0
12.07
Commercial Commercial Commercial
800/2 (10) 800/2 (10) 800/2 (10)
841 622 489
742 573 291
n/a n/a n/a
0.28 0.20 0.11
n/a n/a n/a
n/a n/a n/a
0.37 0.31 0.38
1 1 1
0 0 0
3.96 3.18 2.10
34.0 ‒ ‒
‒ ‒ ‒
(Ello et al., 2013a) (González et al., 2013) (González et al., 2013) (Hao et al., 2013) (Hao et al., 2013) (Hao et al., 2013)
Commercial
600/1 (10)
1073
238
n/a
0.10
n/a
n/a
0.97
0.1
0
0.80
‒
‒
(Hao et al., 2013)
30
n/a
n/a
n/a
n/a
n/a
0.03
1n
40-50
1.5
‒
‒
(Lee et al., 2013)
306
n/a
2.03
n/a
n/a
n/a
0.15
‒
80
5.45
‒
‒
(Liu et al., 2013)
370
295
1.63
0.11
n/a
n/a
0.15
1
25
1.79
‒
‒
(Rashidi et al., 2013; Rashidi et al.,
Commercial 600 900/0.75 (20)
‒
26
45 46 47 48
Coconut Fiber Rice Husk Palm Mesocarp Fibre Palm Kernel Shell
49
African Palm shell
50
African palm stone
51 52 53 54
Cotton Stalk Cotton Stalk Broom Corn Stalk Sugarcane Bagasse
CO2 Activation CO2 Activation
900/1 (10) 900/ 0.5 (5)
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
1 1
25 25
1.36 0.98
‒ ‒
‒ ‒
2014b) (Rashidi et al., 2013) (Rashidi et al., 2013)
CO2 Activation
800/1 (20)
n/a
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.17
‒
‒
(Rashidi et al., 2013)
CO2 Activation
800/1.5 (10)
n/a
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.28
‒
‒
(Rashidi et al., 2013)
450/2 (1j)
785
n/a
n/a
n/a
0.31
0.13
0.41
1
0
5.0
‒
‒
(Vargas et al., 2013)
500/2 (1j)
587
n/a
n/a
n/a
0.34
0.02
0.26
1
0
4.54
‒
‒
(Vargas et al., 2013) (Xiong et al., 2013) (Xiong et al., 2013) (Banisheykholeslami et al., 2015) (Creamer et al., 2014) (Creamer et al., 2014) (David and Kopac, 2014)
H3PO4 Activation + NH4OH Treatment ZnCl2 Activation + NH4OH Treatment CO2 Activation NH3 Activation ZnCl2 Activation
800 900
800 900
n/a n/a
610 434
n/a n/a
0.24 0.19
n/a n/a
n/a n/a
n/a n/a
1 1
20 20
2.30 1.81
‒ ‒
‒ ‒
300/0.33
800/1 (20)
1121
n/a
2.02
0.22
n/a
n/a
0.56
40
25
17.0
56.0
‒
Pyrolysis
600
‒
388
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.7
26.62
‒
55
Hickory Wood
Pyrolysis
600
‒
401
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.4
18.06
‒
56
Oil cake + Walnut
CO2 Activation
750/1 (5)
750/3
1080
n/a
1.90
n/a
n/a
n/a
0.46
1
25
34p
‒
‒
750/1 (5)
800/2
1207
n/a
1.90
n/a
n/a
n/a
0.53
1
25
30p
‒
‒
500/1.5
700/1.5
1486
n/a
n/a
n/a
n/a
n/a
0.64
1
25
5.0
53.4
23.72
(Deng et al., 2014)
‒
‒
n/a
7.5
n/a
n/a
n/a
n/a
n/a
4×10‒4
23
1.1
‒
‒
(Gebald et al., 2014)
450/1 (4)
900/1 (5)
2595
n/a
1.96
1.23
n/a
0.039
1.27
1
30
4.10
‒
‒
(Heidari et al., 2014b)
450/1 (4)
800/2 (10)
2079
n/a
1.21
1.16
n/a
0.127
1.29
1
30
3.22
16.7
‒
(Heidari et al., 2014a)
800 (10)
167
n/a
21.4
0.08
n/a
n/a
0.08
1
30
1.66
‒
‒
(Nasri et al., 2014)
n/a
557
n/a
n/a
0.21
n/a
n/a
1
25
2.11
32.2
22.45
(Plaza et al., 2014a)
n/a
697
n/a
n/a
0.27
n/a
n/a
1
25
2.02
31.5
10.67
57 58 59
Rapeseed Oil cake + Walnut Pine Nut Shell Nano-fibrillated Cellulose
60
Eucalyptus
61
Eucalyptus
62
Palm Kernel Shell
CO2 activation + NH3 treatment KOH Activation APDESe Impregnation H3PO4 Treatment + KOH Activation H3PO4 Treatment + NH3 Activation CO2 Activation
700/2 (10)
63
Almond Shell
O2 Activation
‒
64
Olive Stone
O2 Activation
‒
650/1.38 (15) 650/1.83 (15)
65
Coconut Shell
CO2 Activation
66 67
Poplar Anthers Sawdust
KOH Activation KOH Activation
500/1 250/2
68
Gelatin + Starch
KOH Activation
450 (10)
69
Cherry Stone
Steam Activation
70
Cherry Stone
CO2 Activation
Olive Stone
Water Vapor Activation
71
900/0.75 (20)
550 (5)
370
n/a
1.63
0.11
n/a
n/a
0.15
1
25
1.70
‒
9.84
3322 1643
n/a n/a
n/a n/a
0.89 0.62
n/a n/a
n/a n/a
2.31 0.85
1 1
25 25
2.04 4.72
‒ ‒
2.52 8.38
1636
n/a
1.94
n/a
n/a
n/a
0.51
1
25
3.84
62.9
8.02
850 (15)
998
847
0.89
0.38
0.33
n/a
0.53
1
25
2.41
‒
‒
885 (15)
1045
848
0.93
0.40
0.35
n/a
0.48
1
25
2.62
‒
‒
910
n/a
n/a
0.33
0.09
n/a
0.63
0.3
30
0.8
22.5
‒
800/2 700/1 (5) 700/0.17 (10)
800/1 (5)
27
(David and Kopac, 2014)
(Plaza et al., 2014a; Plaza et al., 2014b) (Rashidi et al., 2014a) (Song et al., 2014) (Zhu et al., 2014) (Alabadi et al., 2015) (Álvarez-Gutiérrez et al., 2015) (Álvarez-Gutiérrez et al., 2015) (Balsamo et al., 2015)
72
Apricot Stone
Water Vapor Activation
550 (5)
800/1 (5)
830
n/a
n/a
0.36
0.04
n/a
0.50
0.3
30
1.18
23.5
‒
(Balsamo et al., 2015)
73
Peach Stone
Water Vapor Activation
550 (5)
800/1 (5)
820
n/a
n/a
0.27
0.08
n/a
0.41
0.3
30
1.08
18.0
‒
(Balsamo et al., 2015)
74
Peanut Shell
KOH Activation
500 (1.5)
700/1.5 (5j)
956
n/a
n/a
n/a
n/a
n/a
0.43
1
25
4.02
60.0
15.44
(Deng et al., 2015)
1790
n/a
n/a
n/a
n/a
n/a
0.77
1
25
4.64
38.5
11.68
(Deng et al., 2015)
75
Sunflower Seed
KOH Activation
500 (1.5)
700/1.5 (5j)
76
Yellow Mombin Stone
HNO3 Activation
500/2 (10)
500/2 (10)
392
332
n/a
n/a
n/a
n/a
0.15
1
40
3.4q
1.28
‒
(Fiuza et al., 2015)
Yellow Mombin Stone Yellow Mombin Stone Yellow Mombin Stone
H3PO4 Activation
500/2 (10)
500/2 (10)
510
309
n/a
n/a
n/a
n/a
0.32
1
40
2.3q
0.55
‒
(Fiuza et al., 2015)
KOH Activation
500/2 (10)
500/2 (10)
246
274
n/a
n/a
n/a
n/a
0.12
1
40
6.3q
2.51
‒
(Fiuza et al., 2015)
1.58
‒
(Fiuza et al., 2015)
77 78 79
CO2 Activation
83 84
Mango Seed Shell Rice Husk Peanut Shell
Steam Activation Microwave Pyrolysis H3PO4 treatment KOH Activation KOH Activation
85
Molasses
80 81 82
86 87
Cellulose Fiber Rice Straw
Empty Fruit Bunch from Oil Palm Coffee Waste
88
Nano-fibrillated Cellulose
89
Waste Tobacco
90 91 92
By-product of Fast Pyrolysis of White Wood By-product of Fast Pyrolysis of White Wood By-product of Fast Pyrolysis of White Wood
500/2 (10)
500/2 (10)
278
235
n/a
n/a
n/a
n/a
0.17
1
40
4.5q
800/0.5
800/1
863
n/a
n/a
0.33
n/a
0.007
0.34
1
25
3.77
37.8
11.01
(Heo and Park, 2015)
200 W/ 0.33
‒
122
112
5.0
0.02
n/a
n/a
0.08
1
25
1.62
‒
‒
(Huang et al., 2015)
2503
n/a
n/a
0.06
n/a
n/a
2.35
1
25
1.24
‒
‒
400/2
(Munusamy et al., 2015) (Li et al., 2015b) (Li et al., 2015a) (Młodzik et al., 2015; J. Młodzik, 2016)
‒ ‒
710/1 (10) 780/1.5 (5)
1041 1871
n/a n/a
n/a n/a
0.42 0.80
0. 15 0.11
n/a 0.02
0.53 0.82
1 1
25 0
4.16 6.79
‒ ‒
‒ ‒
KOH Activation
‒
750/1 (10j)
1985
n/a
n/a
0.71
n/a
n/a
0.94
1
40
2.54
‒
‒
KOH Activation
250/0.33
800/0.5 (2)
2510
n/a
1.13
0.55
n/a
n/a
1.05
1
25
3.71
23.26
18.3
(Parshetti et al., 2015)
522
n/a
n/a
0.21
n/a
n/a
0.21
1
25
2.73
46.48
14.13
(Plaza et al., 2015)
CO2 Activation PEIa Impregnation + Freeze-drying Melamine Modification
‒ ‒
‒
8.3
n/a
n/a
n/a
n/a
n/a
n/a
n/a
25
2.22
‒
‒
(Sehaqui et al., 2015)
700/1 (1j)
‒
1104
826
n/a
n/a
n/a
n/a
0.37
1
25
2.72
28.6
17.23
(Sha et al., 2015)
Steam Activation
500/1k
700/1.4 (3)
840
n/a
n/a
n/a
0.2
0.19
0.55
‒
25
1.34
‒
‒
(Shahkarami et al., 2015a)
CO2 Activation
500/1k
890/1.6 (3)
820
n/a
n/a
n/a
0.17
0.13
0.45
‒
25
1.43
‒
‒
(Shahkarami et al., 2015a)
KOH Activation
500/1k
775/2 (3)
1400
n/a
n/a
n/a
0.40
0
0.62
‒
25
1.77
‒
‒
(Shahkarami et al., 2015a)
93
Sawdust
KOH Activation
500 (7)
775/2 (3)
1268
n/a
n/a
0.43
0.36
0
0.43
‒
25
1.77
‒
‒
94
Flax Straw
KOH Activation
500 (7)
775/2 (3)
1281
n/a
n/a
0.45
0.25
0
0.45
‒
25
1.64
‒
‒
95
Wheat Straw
KOH Activation
500 (7)
775/2 (3)
1212
n/a
n/a
0.40
0.24
0.04
0.44
‒
25
1.60
‒
‒
96
Willow Ring
KOH Activation
500 (7)
775/2 (3)
1563
n/a
n/a
0.57
0.31
0.03
0.62
‒
25
1.70
‒
‒
28
(Shahkarami et al., 2015b) (Shahkarami et al., 2015b) (Shahkarami et al., 2015b) (Shahkarami et al., 2015b)
97
Corn Stalk
CO2 Activation + HNO3 Treatment
98
Silk Fiber
KOH Activation
99
Coconut Shell
100
London Plane Leaves
101
Pili Nut Shell
102
Olive Stone
103
800/0.5
639
457
n/a
0.211
n/a
0.11
n/a
2n
25
1.68
‒
‒
(Song et al., 2015)
300/4 & 600/1
700/1
3000
n/a
n/a
n/a
n/a
n/a
1.38
1
25
4.8
‒
9.96
(Wang et al., 2015)
500/2 (5)
650/2 (5)
1483
n/a
n/a
0.66
0.61
n/a
0.66
1
25
4.26
42.5
10.22
(Yang et al., 2015)
600/1 (3)
700/1 (3)
1600
1550
n/a
0.54
n/a
n/a
0.65
1
25
4.43
28.5
12.34
(Zhu et al., 2015)
400/0.5
750/1
85
n/a
n/a
0.21
n/a
n/a
0.10
1
25
2.62
‒
12.60
(Yao et al., 2015)
CO2 Activation
800/2
800/7
1479
1667
n/a
0.59
0.34
0.08
0.73
1
25
3.05
‒
6.16
(Calvo-Muñoz et al., 2016)
Plywood
Water Vapor Activation + C4H6BaO4 Impregnation
800/2
800/2
708
805
n/a
0.28
0.72
0.16
0.45
1
25
1.98
‒
6.85
(Calvo-Muñoz et al., 2016)
104
Coffee Waste
K2CO3 Activation
800/1 (20)
700/1 (20)
189
n/a
n/a
0.07
n/a
0.02
0.09
2n
60
0.6
‒
‒
(Chaiw et al., 2016)
105
Coconut Shell
Urea Treatment + KOH Activation
500/2 (5)
650/1 (5)
1535
n/a
n/a
0.56
0.73
n/a
0.60
1
25
4.8
33.0
12.07
(Chen et al., 2016)
106
Jujun Grass
KOH Activation
250/2
700/1 (5)
3144
2753
n/a
1.23
n/a
n/a
1.56
1
25
4.1
‒
6.07
(Coromina et al., 2016)
107
Camellia Japonica
KOH Activation
250/2
700/1 (5)
1353
1283
n/a
0.56
n/a
n/a
0.67
1
25
5.0
‒
10.49
(Coromina et al., 2016)
108
Microcrystalline Cellulose
CO2 Activation
400/2 (1) & 800/3 (5)
850/4 (5)
753
n/a
0.9
0.27
n/a
n/a
0.43
1
25
3.34
‒
10.29
(Dassanayake et al., 2016)
109
Olive Stone
Water Vapor Activation
550 (5)
800/1 (5)
910
n/a
n/a
0.33
n/a
0.09
0.63
0.3
30
0.8
‒
‒
(Erto et al., 2016)
110
Apricot Stone
Water Vapor Activation
550 (5)
800/1 (5)
830
n/a
n/a
0.36
n/a
0.04
0.50
0.3
30
1.2
‒
‒
(Erto et al., 2016)
111
Peach Stone
Water Vapor Activation
550 (5)
800/1 (5)
820
n/a
n/a
0.27
n/a
0.08
0.41
0.3
30
1.1
‒
‒
(Erto et al., 2016)
112
Yellow Mombin Stone
KOH Activation
400/4 (3)
500 (3)
1384
1523
n/a
0.49
0.44
‒
0.62
1
25
7.3
27.5
12.38
(Fiuza-Jr et al., 2016)
113
Corncob particles
NH3 Activation
400 (5)
800/3 (5)
1154
n/a
n/a
n/a
n/a
n/a
0.57
1
25
2.81
55.1
20.76
(Geng et al., 2016)
Ammoxidation + KOH Activation KOH Activation NaOH Activation + HNO3 Modification
29
114
Wheat Flour
KOH Activation
900/2 (5)
Steam Activation + DEAf Impregnation Steam Activation + MEAc Impregnation
700/1 (5)
1438
n/a
n/a
0.58
0.38
n/a
0.65
1
25
3.48
28.1
7.54
(Hong et al., 2016)
Commercial
652
525
2.34
n/a
n/a
n/a
0.38
4
70
5.3
‒
‒
(Kongnoo et al., 2016)
Commercial
392
280
2.42
n/a
n/a
n/a
0.24
4
70
4.75
‒
‒
(Kongnoo et al., 2016)
115
Palm Shell
116
Palm Shell
117
Mesquite Biochar
KOH Activation
450/4
800/0.75 (25)
3167
n/a
n/a
n/a
n/a
n/a
1.65
30
25
26.0
21.0
‒
(Li et al., 2016c)
118
Pine Cone Shell
KOH Activation
500/2 (5)
650/1 (3)
3135
n/a
n/a
n/a
n/a
n/a
n/a
1
25
4.73
27.2
9.13
(Li et al., 2016b)
119
Popcorn
KOH Activation
400/1 (5)
800/1
867
794
n/a
0.37
n/a
n/a
0.40
1
25
4.60
24.3
16.40
(Liang et al., 2016)
‒
‒
n/a
n/a
n/a
n/a
n/a
n/a
n/a
2n
‒
5.01
‒
‒
(Luo et al., 2016)
850
‒
3.17
n/a
n/a
n/a
n/a
n/a
0.007
‒
30
1.01
‒
‒
‒
850
‒
182
n/a
n/a
n/a
n/a
n/a
0.003
‒
30
1.07
‒
‒
120
121 122
Sugarcane Bagasse Sawdust Biochar Sawdust Biochar
NaOH Treatment + Acrylamide Grafting + TETAg Impregnation MEAc Impregnation
(Madzaki et al., 2016) (Madzaki et al., 2016)
123
Walnut Shell
H3PO4 Treatment + KOH Activation
‒
700/1 (5)
2642
n/a
n/a
0.46
n/a
0.93
1.39
10
17
12.25
‒
‒
(Rashidi et al., 2016)
124
Chestnut Tannin
NH3 Activation
600/2 (5)
800/0.33 (20)
n/a
561
n/a
n/a
n/a
n/a
n/a
1
25
2.27
22.9
11.01
(Nelson et al., 2016)
125
Olive Stone
CO2 Activation
1248
1112
1.09
0.48
0.44
n/a
0.53
1
30
2.75
‒
‒
(Querejeta et al., 2016)
126
Potato Starch
KOH Activation
250/2
800/1 (3)
3000
n/a
n/a
1.09
n/a
0.32
1.41
1
25
2.8
‒
‒
(Sevilla et al., 2016)
127
Cellulose
KOH Activation
250/2
800/1 (3)
3100
n/a
n/a
1.05
n/a
0.41
1.46
1
25
2.8
21.0
‒
(Sevilla et al., 2016)
128
Eucalyptus Sawdust
Melamine + KOH Activation
250/2
800/1 (3)
3420
n/a
n/a
1.16
n/a
1.14
2.30
1
25
2.2
19.0
‒
(Sevilla et al., 2016)
129
White Wood
Steam Activation + MgO Impregnation
‒
700/1.4 (3)
615
n/a
n/a
0.14
0.12
0.33
0.49
0.24n
25
1.11
‒
‒
(Shahkarami et al., 2016)
130
Algae
Freeze-drying
‒
‒
416
117
n/a
n/a
n/a
n/a
0.38
1
25
2.03
‒
‒
(Tian et al., 2016)
131
Black Locust
KOH Activation
650/3 (2)
830/1.5 (3)
2511
2160
2.15
1.16
n/a
n/a
1.35
1
25
5.05
33.1
14.50
(Zhang et al., 2016)
132
Pinecone
KOH Activation
600/1 (3)
700/1 (3)
1680
1670
n/a
0.56
n/a
n/a
0.61
1
25
4.8
29.8
25.80
(Zhu et al., 2016)
800/6 (5)
30
847
n/a
n/a
n/a
0.28
n/a
n/a
1
25
2.75
25.72
9.73
(Álvarez-Gutiérrez et al., 2017b)
563
n/a
n/a
n/a
0.28
n/a
n/a
1
25
2.88
27.93
9.46
(Álvarez-Gutiérrez et al., 2017b)
1575
1535
ns/a
0.7
n/a
n/a
0.8
1
25
4.6
‒
8.67
(Balahmar et al., 2017)
1557
1294
n/a
0.53
n/a
n/a
0.75
1
25
4.6
‒
10.41
(Balahmar et al., 2017)
2349
1915
n/a
0.86
n/a
n/a
1.48
1
25
3.9
‒
6.85
(Balahmar et al., 2017)
600/1 (5)
1034
923
n/a
0.37
n/a
n/a
0.46
1
25
3.8
‒
‒
(Balahmar et al., 2017)
700/2 (0.5)
900/2 (5)
773
710
n/a
0.37
0.76
0.08
0.45
1
25
1.9
‒
‒
(Botomé et al., 2017)
CO2 Activation
700/2 (0.5)
900/4 (5)
949
856
n/a
0.44
0.20
0.13
0.58
1
25
1.7
‒
‒
(Botomé et al., 2017)
133
Almond Shell
CO2 Activation
134
Macadamia Nut Shell
CO2 Activation
135
Eucalyptus Sawdust
KOH Activation
136
Eucalyptus Sawdust
KOH Activation
137
Paeonia Lactiflora
KOH Activation
138
Sargassum fusiforme
KOH Activation
250/2
H3PO4 Treatment + CO2 Activation
139
140
Chromated Copper Arsenate-treated Wood Chromated Copper Arsenate-treated Wood
750/4 (10) 600/1
900/0.5 700/1 (5)
250/2
700/1 (5) 800/1 (5)
141
Walnut Shell
KOH Activation
520/2
800/1
2000
n/a
0.95
0.8
n/a
n/a
n/a
1
25
2.9
‒
‒
(Chomiak et al., 2017)
142
Camphor Leaves
KOH Activation
240/5 (5)
800/1 (3)
1633
1083
2.41
0.58
n/a
n/a
0.98
1
25
0.8
‒
‒
(Guangzhi et al., 2017)
143
Micro Algae
K2CO3 Activation
180/10
700/2 (5)
1396
1118
n/a
0.59
n/a
n/a
0.75
1
25
4.2
29.0
8.23
(Guo et al., 2017)
144
Micro Algae
K2CO3 Activation
180/10
800/4 (5)
1904
849
n/a
0.46
n/a
n/a
1.08
1
25
3.5
24.0
5.64
(Guo et al., 2017)
145
Chitosan Char
KOH Activation
550/0.5
600/1.5 (10)
728
n/a
n/a
0.31
0.12
n/a
0.33
1
25
4.17
39.0
27.79
(Li et al., 2017)
350/0.5
800/1 (10j)
1098
n/a
2.33
0.52
n/a
0.11
0.64
1
25
3.20
29.7
‒
(Mehrvarz et al., 2017)
350/0.5
800/1 (10j)
614
n/a
2.49
0.27
n/a
0.10
0.38
1
25
2.33
26.0
‒
(Mehrvarz et al., 2017)
KOH & H3PO4 Activation + TETAg Treatment KOH & H3PO4 Activation + Urea Treatment
146
Broom Sorghum Stalk
147
Broom Sorghum Stalk
148
Olive Stone
KOH Activation
300/1
850/3 (10)
n/a
1173
n/a
n/a
0.26
n/a
n/a
1
0
5.6
4.1
‒
149
Olive Stone
K2CO3 Activation
300/1
900/2 (5)
n/a
989
n/a
n/a
0.41
n/a
n/a
1
0
3.8
6.0
‒
150
Persian Ironwood
H3PO4 Treatment
‒
700
1904
n/a
n/a
0.81
n/a
0.77
1.58
1
30
5.05
18.0
‒
151
Persian Ironwood
KOH Activation
‒
800
1935
n/a
n/a
0.80
n/a
0.02
0.82
1
30
3.77
41.52
‒
152
Date Seed
CO2 Activation
800
900/1 (15)
723
678
n/a
0.26
n/a
n/a
n/a
n/a
20
3.2
‒
‒
31
(Moussa et al., 2017) (Moussa et al., 2017) (Nowrouzi et al., 2017) (Nowrouzi et al., 2017) (Ogungbenro et al., 2017)
153
Soya
NaOH Treatment
154
Palm Kernel Shell
CO2 Activation
155
Pomegranate Peels
156 157 158 159
1072
n/a
1.2
n/a
n/a
n/a
0.45
1
25
3.2
‒
‒
(Rana et al., 2017)
850/1 (5)
367
n/a
n/a
n/a
n/a
n/a
0.21
1
25
2.0
31.25
9.04
(Rashidi and Yusup, 2017)
KOH Activation
700/1
585
n/a
n/a
0.20
n/a
n/a
0.28
1
25
4.11
21.25
11.07
(Serafin et al., 2017)
Piptoporus Betulinus
KOH Activation
700/1
1267
n/a
n/a
0.40
n/a
n/a
0.45
1
25
3.5
‒
8.25
(Serafin et al., 2017)
Lioyd
KOH Activation
700/1
1346
n/a
n/a
0.46
n/a
n/a
0.57
1
25
3.25
‒
5.80
(Serafin et al., 2017)
KOH Activation
700/1
1699
n/a
n/a
0.48
n/a
n/a
0.80
1
25
2.0
‒
4.46
(Serafin et al., 2017)
KOH Activation
700/1
1111
n/a
n/a
0.33
n/a
n/a
0.55
1
25
2.5
‒
6.64
(Serafin et al., 2017)
Mistletoe Leaves Mistletoe Branches
300/3
1000/2 (5)
160
Kiwi Fruit Peel
KOH Activation
700/1
1381
n/a
n/a
0.49
n/a
n/a
0.62
1
25
2.75
‒
6.12
(Serafin et al., 2017)
161
Carrot Peel
KOH Activation
700/1
1379
n/a
n/a
0.51
n/a
n/a
0.58
1
25
4.18
‒
9.10
(Serafin et al., 2017)
162
Fern Leaves
KOH Activation
700/1
1593
n/a
n/a
0.54
n/a
n/a
0.74
1
25
4.12
‒
5.69
(Serafin et al., 2017)
163
Sugar Beet Pulp
KOH Activation
700/1
1263
n/a
n/a
0.41
n/a
n/a
0.62
1
25
2.80
‒
6.65
(Serafin et al., 2017)
164
Arundo Donax
KOH Activation
600/2
1122
n/a
0.56
0.5
n/a
n/a
0.59
1
25
3.6
31.0
‒
(Singh et al., 2017b)
165
Arundo Donax
500/2 (10)
1863
33
2.1
n/a
n/a
n/a
1.00
1
25
2.1
32.2
‒
(Singh et al., 2017a)
166
Arundo Donax
167
Coconut Shell
Chitosan + ZnCl2 Activation ZnCl2 Activation
500 (10)
3298
4
n/a
0
n/a
100
1.9
30
25
24.2
21.8
‒
(Singh et al., 2017c)
CO2 Activation
900/2.33 (10j)
1452
n/a
n/a
0.60
n/a
n/a
0.65
1
20
2.43
‒
‒
(Vilella et al., 2017)
168
Babassu Coconut
CO2 Activation
(10j)
809
n/a
n/a
0.32
n/a
n/a
0.39
1
20
2.20
‒
‒
(Vilella et al., 2017)
169
Pine Wood Pellet
CO2 Activation
561
n/a
n/a
0.22
0.31
n/a
0.1
10
30
4
28.4
‒
(Vivo-Vilches et al., 2017)
170
Stalks of Rice and Wheat Ash
TEPAh Impregnation
‒
‒
0.54
n/a
4.02
n/a
n/a
n/a
0.73×10‒3
138k
60
2.02
‒
‒
(Wang et al., 2017b)
171
Longan Shell
KOH Activation + Carbamide Modification
500/2 (5)
800/2 (5)
3260
2670
4.2
1.3×106
n/a
n/a
2.6×106
1
25
4.3
55.0
4.20
(Wei et al., 2017)
172
Coconut Shell
KOH Activation
500/2 (5)
600/1 (5)
1172
n/a
n/a
0.43
0.58
n/a
0.44
1
25
4.23
37.0
13.72
(Yang et al., 2017)
173
Rotten Strawberries
KOH Activation
180/12
650
1117
n/a
n/a
0.39
0.63
n/a
0.52
1
25
4.49
41.0
12.85
(Yue et al., 2017)
174
Argan Fruit Shell
KOH Activation
700/1 (10)
850/1 (5)
1889
1581
n/a
0.8
0.15
0.07
0.87
1
25
5.63
‒
11.75
(Boujibar et al., 2018)
175
Argan Fruit Shell
NaOH Activation
700/1 (10)
850/1 (5)
1826
1428
n/a
0.73
0.10
0.23
0.96
1
25
3.73
‒
6.71
(Boujibar et al., 2018)
900/2.33
900/5 (10)
32
Mg(NO3)2.6H2O Impregnation KOH Activation Ammoxidation + KOH Activation H3PO4 Activation + Cu(NO3)2:3H2O Impregnation H3PO4 Activation
176
Walnut Shell
177
Fir Bark
178
Coffee Grounds
179
Persian Ironwood
180
Olive Stone
181
Olive Stone
CO2 Activation
600/1 (5)
182
Olive Stone
H2O Activation
183
Vine Shoots
184
Vine Shoots
185
Walnut Shell
186
Walnut Shell
187
Arundo Donax
188
Arundo Donax
189
Water Chestnut
190
Lotus Stem
191
(Lahijani et al., 2018) (Luo et al., 2018)
900/1.5
500/0.25
292
n/a
n/a
0.11
n/a
n/a
0.15
1n
25
1.86
‒
‒
450/1 (5)
700/2 (3) 400/1 + 600/1
1377
n/a
n/a
0.51
0.07
0.12
0.74
1
25
5.2
22.47
30.15
990
n/a
n/a
0.45
n/a
n/a
0.55
-
35
2.67
49.9
‒
(Liu and Huang, 2018)
500
1954
n/a
n/a
1.60
n/a
0.02
1.63
1
30
6.78
‒
‒
(Nowrouzi et al., 2018)
170/0.5 (5j)
1178
n/a
n/a
0.45
n/a
0.04
0.49
32
30
10.87
‒
‒
(Peredo-Mancilla et al., 2018)
600/1 (5j)
757
n/a
n/a
0.3
n/a
0.02
0.32
32
30
5.87
‒
‒
(Peredo-Mancilla et al., 2018)
600/1 (5)
600/1 (5j)
754
n/a
n/a
0.28
n/a
0.3
0.58
32
30
7.96
8.5
‒
(Peredo-Mancilla et al., 2018)
CO2 Activation
600/1 (5)
800/3 (10)
767
526
n/a
0.24
0.10
0.04
0.37
1
25
3.00
27.5
13.63
(Manyà et al., 2018)
KOH Activation
600/1 (5)
700/1 (10)
1439
861
n/a
0.49
0.13
0.02
0.67
1
25
4.00
25.8
9.94
(Manyà et al., 2018)
600/1 (5)
600/2 (7.5)
1315
1121
1.99
0.48
n/a
n/a
0.65
1
25
7.42
7.0
‒
(Rouzitalab et al., 2018)
600/1 (5)
750/1.5 (7.5)
4230
611
2.30
0.24
n/a
n/a
2.43
10
25
14.03
4.0
‒
(Rouzitalab et al., 2018)
600 (3)
982
n/a
n/a
n/a
n/a
n/a
0.62
1
25
2.2
39.0
‒
(Singh et al., 2018b)
600/2
2232
n/a
n/a
n/a
n/a
n/a
1.01
1
25
3.2
15.4
‒
(Singh et al., 2018a)
Urea Treatment + KOH Activation Urea Treatment + KOH Activation Urea Treatment + KOH Activation H2SO4 Treatment + KOH Activation Melamine Treatment + KOH Activation
400/1
500/2 (5)
700/2 (5)
3401
3049
2.94
1.87
n/a
n/a
2.50
1
25
4.7
‒
20.54
(Wei et al., 2018)
KOH Activation
180/24
800/1 (2)
2091
n/a
1.67
0.65
n/a
n/a
0.87
1
25
3.85
36.0
6.68
(Wu et al., 2018b)
Camphor Leaves
KOH Activation
500/2
600/1 (5)
1146
n/a
n/a
0.47
0.27
n/a
0.54
1
25
3.74
24.0
8.87
(Xu et al., 2018)
192
Coconut Shell
K2CO3 Activation + Urea Modification
500/2 (5)
600/1 (5)
1082
n/a
n/a
n/a
0.49
n/a
0.39
1
25
3.71
29.0
9.72
(Yue et al., 2018)
193
Pine Wood
KOH Activation
906
n/a
n/a
n/a
n/a
n/a
n/a
1
15
3.86
39.7
‒
(Ahmed et al., 2019)
194
Pine Wood
ZnCl2 Activation
1122
n/a
n/a
n/a
n/a
n/a
1
15
3.20
29.6
‒
(Ahmed et al., 2019)
853/2 (10j)
633/1
853/2 (10j)
33
195
Sugarcane Bagasse
Urea Treatment + KOH Activation
600/0.5 (10)
600/1 (10)
1113
n/a
n/a
n/a
0.50
n/a
0.57
1
25
4.8
32.5
13.26
(Han et al., 2019)
196
Garlic Peel
KOH Activation
360/2 (4)
700/1 (2)
1248
919
2.19
0.52
n/a
n/a
0.68
1
25
4.1
17.0
7.85
(Huang et al., 2019b)
197
Garlic Peel
KOH Activation
200/24 + 400/2 (4)
600/1 (2)
947
928
n/a
0.50
n/a
n/a
0.51
1
25
4.22
40.0
10.92
(Huang et al., 2019a)
198
Date Sheet
KOH Activation
800/2 (10)
800/1 (10)
2367
2059
0.54
0.83
n/a
n/a
1.14
1
25
4.36
17.60
7.02
(Li et al., 2019)
199
Rice Husk
KOH Activation + PEIa Impregnation
200/6
700 /1 (5)
1190
n/a
n/a
0.42
0.17
n/a
0.77
1
25
4.48
36.0
24.18
(Liu et al., 2019b)
200
Lotus Leaf
NaNH2 Activation
500/1
550/1 (5)
1087
n/a
n/a
0.45
0.54
n/a
0.54
1
25
3.50
32.0
10.30
(Liu et al., 2019a)
201
Palm Kernel Shell
500/1 (10)
140 (0.16)
1700
1352
n/a
0.56
n/a
n/a
0.89
1
25
5.29
43.11
‒
(Ma et al., 2019)
202
Water Chestnut Shell
Urea Treatment + Steam Activation NaNH2 Activation
500/1 (5)
1416
n/a
n/a
0.53
0.62
n/a
0.58
1
25
4.50
37.0
10.12
(Rao et al., 2019)
203
Lumpy Bracket
KOH Activation
850/1
1968
n/a
n/a
0.55
0.40
n/a
1.14
1
25
4.62
26.5
16.73
(Serafin et al., 2019)
204 205 206 207 208
Walnut Shell Pineapple Waste Pineapple Waste Pineapple Waste Waste Tea
NaNH2 Activation K2C2O4 Activation Na2C2O4 Activation Li2C2O4 Activation KOH Activation + EDAi Treatment
500/1 (10)
450
1687
n/a
n/a
0.77
n/a
n/a
0.92
1
25
3.06
38.0
4.22
(Yang et al., 2019)
210/10
700/2 (5)
1076
n/a
n/a
n/a
0.92
n/a
0.08
1
25
4.25
‒
10.76
(Zhu et al., 2019)
210/10
700/2 (5)
397.3
n/a
n/a
n/a
0.09
n/a
0.26
1
25
1.59
22.0
6.01
(Zhu et al., 2019)
210/10
600/2 (5)
302.7
n/a
n/a
n/a
0.06
n/a
0.49
1
25
1.59
27.0
9.77
(Zhu et al., 2019)
11.80
n/a
n/a
n/a
n/a
n/a
n/a
‒
30
2.47
‒
‒
(Rattanaphan et al., 2020)
500/2
123 124
a
Polyethylenimine (PEI), b N-(2-aminoethyl)-3-aminopropylmethyldimethoxsilane (AEAPDMS), c Monoethanolamine (MEA), d 2-amino-2-methyl-1-propanol
125
(AMP), e 3-Aminopropylmethyldiethoxsilane (APDES), f Diethanolamine (DEA), g Triethylenetetramine (TETA), h Tetraethylenepentamine (TEPA), i
126
Ethylenediamine (EDA), j K/min, k s, m not analyzed (n/a), n h, p ml/g, q %CO2/g carbon.
34
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4. Key Factors Controlling CO2 Adsorption onto Lignocellulose-based Adsorbents
128
4.1. Adsorbent Features
129
It is generally believed that the performance of AC is closely associated with adsorbent porosity
130
and specific surface area (SSA); however, surface chemistry is another important factor
131
influencing CO2 adsorption capacity (Shafeeyan et al., 2010; Vargas et al., 2013; Tan et al.,
132
2017).
133
4.1.1. Surface Area
134
High surface area is an important driving force to have a larger uptake of CO2, as it provides
135
sites for the adsorption process (Yang et al., 2017; Wu et al., 2018b). Fig. 8 shows the CO2
136
adsorption capacity at 1 bar and 25 ℃ versus the specific surface area of the reported adsorbents
137
in Table 3. Boonpoke et al. reported that unmodified Bagasse-based activated carbon (BAC)
138
showed better CO2 adsorption than the amine-modified BAC due to its higher surface area
139
(Boonpoke et al., 2012). On the other hand, Li et al. observed the reverse influence of SSA on
140
the CO2 adsorption. A higher surface area of pine cone shell-derived ACs did not lead to higher
141
CO2 adsorption capacity. This was attributed to the unique pore size distribution (PSD) of the
142
adsorbent with unavailable regions for CO2 adsorption (Li et al., 2016b). Yang et al. summarized
143
the CO2 adsorption capacities of various carbonaceous materials in which coconut shells were
144
used as carbon precursors and CO2 adsorption was measured at 25°C and 0‒200 kPa. The results
145
showed that the micropore shape and size distribution affected the adsorption properties (Yang et
146
al., 2011). Similarly, Fiuza Jr. et al. prepared various ACs from the stones of yellow mombin
147
using KOH as activating agent. The prepared samples were tested as adsorbents in post-
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combustion capture conditions and observed that the activated sample at 700 ℃ had a lower CO2
149
uptake (8.6 mmol/g) compared to the samples with lower surface area, indicating a transference
150
of PSD to mesopore range (Fiuza-Jr et al., 2016). It can be noticed that there is an apparent
151
discrepancy with the physisorption concept, which denotes that the a higher surface area would
152
result in a higher CO2 adsorption (Yang et al., 2015).
153
Fig. 8 CO2 adsorption capacity (at 1 bar and 25 ℃) versus the surface area (data are from Table 3). 154
155
4.1.2. Pore Structure
156
As reported in the literature, materials with high surface area tend to possess large
157
micropores/small mesopores and exhibit high CO2 uptake at an elevated pressure (20 bar and
158
above) because in this case, the uptake mechanism is likely to occur by surface coverage 36
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159
(Coromina et al., 2016; Li et al., 2016b; Li et al., 2016c; Rashidi et al., 2016). While the
160
governing mechanism under low pressure adsorption (up to 1 bar) is pore filling (driven by the
161
gas molecules and pore walls interactions) in which the overlapping of the potential fields from
162
the neighboring walls would enhance CO2 adsorption, and therefore, small micropores become
163
more relevant (Banisheykholeslami et al., 2015; Coromina et al., 2016). Still, meso/macropores
164
facilitate the mass transport of CO2 within the skeleton of carbons (Sun and Webley, 2011; Bae
165
and Su, 2013).
166
Some earlier studies in the literature have suggested that pores smaller than five times of CO2
167
molecular size (pores lower than 1 nm) would provide the highest CO2 adsorption capacity at the
168
ambient atmospheric pressure (Maroto-Valer et al., 2005). A comparison of the porosity data and
169
CO2 uptake by Coromina et al. onto Jujun grass and Camellia japonica-derived ACs shows that
170
narrow micropores are the key determinant of CO2 uptake at pressures up to 1 bar (Coromina et
171
al., 2016). This observation was supported by earlier studies performed by Ello et al., who
172
produced ACs using African palm shells through carbonization and KOH activation and revealed
173
that ultramicropores ( ≤ 0.7 nm) intensified CO2 adsorption and the adsorbent interaction energy
174
in these narrow pores (Ello et al., 2013b). Similar observations have been reported for various
175
carbons (Deng et al., 2014; Deng et al., 2015; Li et al., 2015a; Coromina et al., 2016; Rashidi and
176
Yusup, 2017; Serafin et al., 2017). Fig. 9 shows the variation of the optimal micropore size with
177
CO2 adsorption at 0 and 25 °C under (a) sub-atmospheric (Deng et al., 2015; Li et al., 2015b;
178
Chomiak et al., 2017; Serafin et al., 2017) and (b) atmospheric pressures (Boonpoke et al., 2011;
179
Sevilla and Fuertes, 2011; Sevilla et al., 2012; Wei et al., 2012; Rashidi et al., 2013; David and
180
Kopac, 2014; Deng et al., 2014; Hong et al., 2016; Chomiak et al., 2017; Serafin et al., 2017;
181
Luo et al., 2018; Li et al., 2019). 37
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Fig. 9 The variation of the optimal micropore size with CO2 adsorption under (a) subatmospheric and (b) atmospheric pressures at 0 and 25 °C from different references. 183 184
Erto et al. carbonized a series of agricultural wastes (peach stones, olive stones, and apricot
185
stones) followed by water vapor activation to examine their CO2 adsorption capacity. Based on
186
the results, all the ACs exhibited pore sizes higher than CO2 molecule dimensions and the peach
187
stone-derived AC sample showed the highest CO2 adsorption capacity owing to its high
38
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188
micropore volume, mostly formed by ultramicropore, narrower PSD and its comparative higher
189
basic character of the surface (Erto et al., 2016). Besides, Yue et al. confirmed their results and
190
suggested that the highest CO2 adsorption for the AC derived from rotten strawberries, thanks to
191
high nitrogen content, narrow micropore volume and also adequate narrow micropore size (Yue
192
et al., 2017). Moreover, Heo and Park investigated the CO2 sorption capacities of steam-
193
activated cellulose fibers and proposed micropore volume fraction and ultramicropore size
194
distribution as two key factors in improving CO2 adsorption capacity under ambient conditions
195
(Heo and Park, 2015).
196
4.1.3. Surface Chemistry
197
In addition to the textural properties of ACs, numerous studies have been conducted to verify the
198
significance of surface chemistry in CO2 adsorption capacity (Shafeeyan et al., 2010; Fiuza-Jr et
199
al., 2016). As CO2 has an acidic character (Plaza et al., 2009b), surface modification of AC
200
through removing/neutralizing the acidic functionalities or replacing them with proper basic
201
groups is the common way to increase the adsorption capacity of AC toward CO2 (David and
202
Kopac, 2014).
203
Heteroatom (N, B, P, S, and O) doping plays an important role in CO2 adsorption as well (Luo
204
et al., 2018). The introduction of nitrogen-containing functional groups on the AC surface is the
205
most common type of functionalization due to the improvement of electrical conductivity
206
(Braghiroli et al., 2012; Sevilla et al., 2012), oxidation reduction (Xu et al., 2010) and surface
207
properties (surface polarity and base sites) (Sevilla et al., 2012; Creamer et al., 2014; Fiuza et al.,
208
2015; Han et al., 2019), as well as the electron-donor ability of the carbon matrix (Wang et al.,
209
2013; Sha et al., 2015). Moreover, Xing et al. have reported that the incorporation of N atoms 39
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210
into the carbon would facilitate the hydrogen bonding interactions of CO2 molecules with carbon
211
surface hydrogen atoms (from CH and NH), which is the reason for the superior CO2 adsorption
212
capacity (Xing et al., 2012; Song et al., 2014). Consequently, it remarkably provides a large
213
number of chemically active sites and boosts their potential applications (Rana et al., 2017; Wei
214
et al., 2018; Rattanaphan et al., 2020). Indeed, this increase depends on the precursor used and
215
the surface modification methodology (Plaza et al., 2009a; Sha et al., 2015; Xu et al., 2018).
216
There are mainly two methods for the synthesis of nitrogen-doped porous carbon materials,
217
namely: in-situ modification and post-modification. In-situ modification includes (i) the
218
carbonization of nitrogen-containing precursors such as agricultural residues or commercially
219
available monomers (Song et al., 2014; Sha et al., 2015; Zhu et al., 2015; Liang et al., 2016;
220
Yang et al., 2017; Xu et al., 2018), and (ii) the co-carbonization of nitrogen-containing and
221
nitrogen-free compounds (Chen et al., 2016; Rouzitalab et al., 2018; Han et al., 2019). Post-
222
modification comprises (i) thermal treatment of porous carbons with nitrogen-containing gases,
223
for instance, ammonia in the presence or absence of oxygen (Plaza et al., 2011a; Shafeeyan et al.,
224
2011; Heidari et al., 2014a; Geng et al., 2016; Nelson et al., 2016; Zhang et al., 2016) or
225
nitrogen-containing organic compounds, e.g. urea (Mehrvarz et al., 2017; Yue et al., 2018), and
226
(ii) impregnation with amine-functional groups (Plaza et al., 2009a; Boonpoke et al., 2012;
227
Calvo-Muñoz et al., 2016; Kongnoo et al., 2016; Luo et al., 2016; Wang et al., 2017a). The post-
228
modification technique demands high temperatures, and may cause the blockage of porous
229
structure, which consequently decreases the adsorption capacity; therefore, this method is not
230
preferred (Pevida et al., 2008; Mehrvarz et al., 2017; Rouzitalab et al., 2018).
231
In light of the above considerations, any lignocellulose-based activated carbon will exhibit
232
high CO2 adsorption performance as long as it has a high surface area, micropore volume, and 40
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233
basic surface functionalities simultaneously. Yang et al. demonstrated that the CO2 capture
234
capacity of carbonaceous adsorbents made by walnut shell and treated by NaNH2 can be
235
improved by doping a certain amount of nitrogen in conjunction with the adequate porous
236
texture. The best CO2 adsorption capacity of these one-step nitrogen-doped carbons, activated at
237
450 °C with a KOH to precursor ratio of 2.5:1, reached a high value of 3.06 mmol/g at 25 °C and
238
1 bar (Yang et al., 2019). This result is in good agreement with further studies reported by other
239
researchers (Heidari et al., 2014b; Yang et al., 2015; Chen et al., 2016; Rouzitalab et al., 2018).
240
Contrary to the previous reports in which CO2 adsorption under ambient conditions depends on
241
narrow micropores, Yue et al. demonstrated that nitrogen incorporation is indeed advantageous
242
for the enhancement of CO2 capture (Yue et al., 2018), which agrees with the results reported by
243
Xing et al. (Xing et al., 2012), Yao et al. (Yao et al., 2015), and Yang et al. (Yang et al., 2017).
244
Moreover, Li et al. suggested that the dominant parameter at very low pressure of CO2
245
adsorption is the nitrogen content, not the surface area or pore volume, which is in agreement
246
with Song et al.’s observation (Song et al., 2014; Li et al., 2015b). In addition, it was observed
247
that even if two samples have a comparable surface area or small micropore volume, the
248
nitrogen-enriched carbon would exhibit higher CO2 capture (Thote et al., 2010; Xu et al., 2018).
249
Furthermore, it was found that the CO2 adsorbent affinity is highly dependent on both a high
250
amount of nitrogen content and the type of N-functionalities introduced, allowing chemisorption
251
to operate predominantly, thus capturing more CO2 (Pevida et al., 2008; Sevilla et al., 2012;
252
Shafeeyan et al., 2012; Yao et al., 2015; Rashidi and Yusup, 2017), which is different from the
253
temperature of treatment (Shafeeyan et al., 2012).
254
Similarly, the presence of metal particles will affect the mechanism and effectiveness of CO2
255
adsorption (Hidayu and Muda, 2016; Shahkarami et al., 2016; Zhu et al., 2016; Botomé et al., 41
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256
2017). Hidayu and Muda studied the adsorption of several metal oxides (BaO, MgO, CuO, TiO2
257
and CeCO2) loading on the best physical and chemical AC from coconut and palm kernel shell.
258
The impregnation process can block access to fine microporosity through positioning metal
259
particles in the most internal part of the pores, thereby decreasing the adsorption. It was found
260
that irrespective of the adsorbent, the CO2 adsorption depends mainly on surface area, pore
261
volume and the reaction occurring between the CO2 and the loaded AC. Before any interaction
262
between CO2 and the surface of carbon occurs, the fixed impregnant provides active sites
263
through chemical bonds forming between metal oxides and carbon surface. Among the used
264
metal oxides, high basicity of BaO leads to strong reactivity, enabling it to transfer charge to the
265
adsorbed CO2 (Hidayu and Muda, 2016). Another study was conducted by Shahkarami et al. on
266
the MgO impregnated whitewood ACs made by different preparation techniques and MgO
267
contents as two governing factors. As observed by the authors, an increase in Mg content
268
enhances the CO2 adsorption, although the surface area becomes smaller (Shahkarami et al.,
269
2016). In this case, Lahijani et al. suggested that the contribution of chemisorption was more
270
than the share of physisorption (Lahijani et al., 2018), and even low metal contents are enough to
271
satisfy the improvement of CO2 adsorption capacity (Botomé et al., 2017).
272
4.1.4. Other Factors
273
The pyrolytic decomposition of the non-carbon elements, hydrogen, nitrogen, and oxygen,
274
namely volatile products, through carbonization process results in a solid residue rich in carbon
275
(Boujibar et al., 2018; Luo et al., 2018). As more volatile contents are removed, enhanced
276
reactivity of carbon would improve pore development on the carbonaceous material (Nasri et al.,
277
2014). The effect of carbon and ash contents of the rice husk-based AC and bagasse-based AC
278
was investigated by Boonpoke et al. The authors pointed out that with a comparable surface area 42
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279
and pore characteristics, bagasse-derived AC had a higher CO2 adsorption capacity in
280
comparison with rice husk-derived AC, owing to the low inorganic contents (Boonpoke et al.,
281
2012). Indeed, different laboratory studies indicated that the CO2 adsorption capacity is closely
282
related to low organic volatile content, high elementary carbon, and low ash of any carbonaceous
283
material (Bae and Su, 2013; Rashidi et al., 2013; David and Kopac, 2014).
284
4.2. Preparation Conditions
285
4.2.1. Carbonization Condition
286
A vital consideration in the evolution of primary pores within the carbon structure is
287
carbonization parameters, owing to the fact that volatile matters will be released from the matrix
288
of carbon during the carbonization process. As the textural properties of the produced carbon are
289
significantly affected by the pore development of the char, carbonization parameters need to be
290
brought up in calculations before the carbon production.
291
4.2.1.1. Carbonization Type
292
Lignocellulose-based materials convert to activatable carbonaceous matter through two main
293
processes, i.e. hydrothermal carbonization (HTC) and direct thermal pyrolysis. Hydrothermal
294
carbonization is a process of thermochemical decomposition of lignocellulose-based materials in
295
the presence of superheated water, which results in a so-called hydrochar, while direct pyrolysis
296
proceeds via a rise in the carbon content of lignocellulose-based materials precursors during
297
heating in the absence of oxygen (Coromina et al., 2016; Balahmar et al., 2017). Operating at a
298
relatively low temperature (typically up to 250 °C) and handling biomass without drying pre-
299
treatment are the advantages of HTC in comparison with the direct pyrolysis method (Coromina
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300
et al., 2016; Wu et al., 2018b). For example, Guangzhi et al. prepared N-doped camphor leaves-
301
derived porous biocarbons using HTC at different temperatures (180 to 270 °C) followed by
302
KOH activation at a constant condition (AHTCs). The AHTC-240 had the highest specific
303
surface area (up to 1633.71 m2/g) and microporosity ratio, both of which are adsorption-
304
enhancing factors (6.63 mmol/g at 25 °C under 4 bar) (Guangzhi et al., 2017).
305
It is noteworthy that there are two types of thermal direct pyrolysis process, namely fast and
306
slow. Comparative research was conducted by Shahkarami et al. to investigate the changes
307
occurring during fast and slow pyrolysis of forest and agriculture residue-based precursors
308
followed by chemical activation using KOH as a chemical agent. Apart from the precursor type,
309
the fast pyrolysis resulted in a higher surface area and total pore volume, smaller particle size
310
and ultra-pore volume, in addition to a large contribution of carboxylic and phenolic/ketone
311
groups. However, the slow pyrolysis process causes the formation of aromatic regions with
312
lower contribution of C=O on the surface. Furthermore, the maximum CO2 sorption (1.77
313
mmol/g in N2) was found to take place through the application of slow pyrolyzed sawdust based
314
AC with the highest ultramicropore volume (up to 0.36 cm3/g); however, the presence of oxygen
315
functional groups on its surface leads to a low selectivity (2.8) over O2. The obtained results
316
illustrate that the ultramicropores and surface chemistry of adsorbents play a crucial role in the
317
adsorption of CO2 rather than the internal surface area, total pore volume, and the particle size
318
(Shahkarami et al., 2015b).
319
Microwave-assisted pyrolysis (MWP) is a feasible alternative to conventional pyrolysis,
320
which supplies a temperature gradient from the center to the outer surface of lignocellulose-
321
based materials. Microwave heating (MWH) provides a non-contact, fast, volumetric, uniform
322
heating, resulting in a shorter processing time and better energy savings. It is a safe, 44
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323
environmentally friendly technique due to its low hazardous product formation and emission
324
pollutants. Moreover, the yield and quality of the products of microwave torrefaction are very
325
high (Huang et al., 2016; Li et al., 2016a; Ao et al., 2018). As an example, Huang et al.
326
investigated the effect of microwave pyrolysis of rice straw on CO2 adsorption capacity and
327
observed that the resultant biochar showed a 14-percent higher CO2 adsorption capacity
328
compared to the derived biochar from conventional pyrolysis (Huang et al., 2015).
329
4.2.1.2. Carbonization Temperature
330
It is generally agreed that defining optimal carbonization temperature is critical in controlling the
331
decomposition and release of volatile matters between 250 ℃ to 600 ℃, or their recombination
332
above 600 ℃, and consequently optimizing char yield (Collard and Blin, 2014; Boujibar et al.,
333
2018). Moreover, improving the graphitization degree of the carbon samples upon higher
334
carbonization temperature is confirmed by high resistance to the destruction of pores (Rashidi et
335
al., 2012; Song et al., 2014; Fiuza-Jr et al., 2016) and also higher surface area (Creamer et al.,
336
2014; Nelson et al., 2016; Li et al., 2019).
337
4.2.1.3. Carbonization Flow Rate
338
The inert gas flow rate during the carbonization process also affects the CO2 adsorption of the
339
adsorbents. The results reported by Chaiw et al. reveal that too high flow rate leads to incomplete
340
removal of volatile matter as a result of low surface temperature of the sample. Accordingly, the
341
pore structure development is probably limited owing to the high flow rate of gases. This
342
eventually results in the low surface area of the produced sample. Contrariwise, a low flow rate
343
of gases causes the released volatile matter not to be fully removed during the thermal reaction,
344
consequently resulting in the volatile matter’s re-deposition to the surface of the sample, which 45
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345
gives rise to pore blockage and impedes the forming of a more porous structure within the
346
sample. As a result, the optimization of the flow rate is a key factor in developing appropriate
347
carbonized lignocellulose-based material (Chaiw et al., 2016).
348
4.2.2. Activation Condition
349
Different activation methods and activation conditions lead to differences in both the physical
350
characteristics and the chemical properties of the resultant ACs (Sevilla and Fuertes, 2011;
351
Rashidi et al., 2012; Wei et al., 2012; González et al., 2013; Heidari et al., 2014a; Plaza et al.,
352
2014a; Álvarez-Gutiérrez et al., 2015; Li et al., 2016b; Madzaki et al., 2016; Nowrouzi et al.,
353
2017; Singh et al., 2017b; Peredo-Mancilla et al., 2018; Wu et al., 2018b).
354
4.2.2.1. Number of Activation Steps
355
In search of sustainable, cheaper ACs, simplifying the synthesis process and omitting the HTC or
356
direct carbonization step before activation are desirable; in other words, it is preferred to form
357
ACs with similar or improved yield and/or properties via direct activation process instead of the
358
conventional, longer, two-step routes (Balahmar et al., 2017).
359
Eucalyptus wood sawdust, seaweed (Sargassum Fusiforme), and the flowering plant Paeonia
360
Lactiflora-based ACs were produced by Balahmar et al. through a direct activation using KOH
361
as an activating agent, without any need for HTC or direct pyrolysis. Different characterization
362
techniques confirmed that the directly activated carbons offer a greener and easier route at a
363
lower cost and comparable to or higher features than those derived from conventional methods.
364
Furthermore, the degree of graphitic ordering and the textural properties of both directly and
365
conventionally generated ACs were found to be similar (Balahmar et al., 2017). Also, Singh et
46
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366
al. applied the resulting Arundo donax AC from a single step activation using KOH to remove
367
CO2 from gas stream. Compared with typical two-step carbonization and activation procedure,
368
the single step product (using similar temperature and activation conditions) has a higher surface
369
area and micropore volume and save energy better. Single step activated carbon with a KOH/C
370
ratio of 2:1 shows the highest CO2 adsorption capacity (up to 6.3 mmol/g at 1 bar and at 0 °C)
371
among the as-synthesized ACs (Singh et al., 2017b). Single step activation has been reported for
372
various precursors (Plaza et al., 2014a; Rashidi and Yusup, 2017; Vilella et al., 2017)
373
4.2.2.2. Activating Agent
374
The commonly used gases and chemicals for the activation of lignocellulose-based carbon
375
include CO2, steam, H3PO4, ZnCl2, K2CO3, and KOH among others (Shahkarami et al., 2015a;
376
Moussa et al., 2017; Manyà et al., 2018; Sevilla et al., 2018; Li et al., 2019).
377
It has been reported by Alvarez et al. that the CO2 activation of cherry-stone leads to
378
microporous ACs while steam activation results in newly developed pores and a larger
379
micropore widening (Álvarez-Gutiérrez et al., 2015; Heo and Park, 2015). Although physical
380
activation is less expensive and more eco-friendly, nowadays, the chemical activation process is
381
receiving more attention due to its superior ability to create highly developed porous structure
382
and increase the specific surface area at much lower temperatures and with a higher carbon yield
383
(Deng et al., 2015; Heo and Park, 2015).
384
Heidari et al. investigated the effect of two different activating chemicals (H3PO4 and ZnCl2)
385
on to the pore structure of activated carbon produced from eucalyptus camaldulensis wood and
386
observed a degree of macroporosity along with a high incidence of microporosity. Compared to
387
ZnCl2, H3PO4 provided larger mesopores and even macropores (Heidari et al., 2014a). Although 47
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388
H3PO4 is an acid, it supplies a high influential surface area in comparison with its negative effect
389
on the interactions between the basic surface groups and CO2 molecules (Peredo-Mancilla et al.,
390
2018). In another study, the effects of KOH and K2CO3 activation were compared on the olive
391
pomace-derived ACs by Moussa et al. Higher surface area and larger porosity as well as higher
392
CO2 adsorption capacity were obtained through KOH activation of the raw precursor (Moussa et
393
al., 2017).
394
Of the different activation approaches, activation by KOH is one of the most constraining
395
techniques for the development of highly microporous structure and functional groups on the
396
surface of carbons owing to the intercalation of potassium compounds between the carbon
397
lattices, integration of carbon oxidation and in-situ physical activation (with CO2) in high
398
temperature processes (Li et al., 2015b; Zhang et al., 2016; Singh et al., 2017b). It is worth
399
noting that ACs’ porosity is well-controlled by varying the activation conditions (Singh et al.,
400
2017b). In spite of the fact that KOH is a highly-effective activator that can create developed
401
porous structure advantageous for CO2 capture on different kinds of carbon precursor, its
402
corrosive effect and high temperature operation are two inherent disadvantages (Yue et al., 2018;
403
Rao et al., 2019). Rao et al. activated water chestnut shell via NaNH2 and demonstrated that
404
NaNH2 has great potential as an activating agent, since its corrosive effect is much less than that
405
of KOH, and thus simultaneous pore forming and nitrogen doping will reduce sample
406
preparation costs (Rao et al., 2019). Furthermore, Sevilla et al. suggested using potassium
407
oxalate (C2K2O4) as a versatile and less corrosive activating chemical agent rather than the
408
widely used KOH (Sevilla et al., 2018). Correspondingly, Zhu et al. synthesized a series of
409
pineapple-derived ACs using three different alkali metal oxalates (K2C2O4, LiC2O4, and NaC2O4)
410
and activation temperatures (500, 600, and 700 ℃). They found that the microporous structure of 48
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411
ACs activated by K2C2O4 led to remarkable CO2 adsorption performance in comparison with
412
non-porous and meso/macroporous carbons activated by LiC2O4 and NaC2O4 at a certain
413
temperature (Zhu et al., 2019). In addition, Yalcin and Sevinc found that besides the type of the
414
activating agent, its concentration influenced the textural parameters (Yalçın and Sevinç, 2000;
415
Mehrvarz et al., 2017).
416
4.2.2.3. Activating Agent Dosage
417
Luo et al. studied the effect of different KOH to carbon mass ratios of 0.5‒6 on heteroatom self-
418
doped activated carbons derived from fir bark. Although the higher weight ratio enhances the
419
surface area, micropore volume and micropore size distribution, excessive KOH treatment will
420
destroy pore walls or result in aggressive chemical reaction between KOH and the
421
lignocellulose-based adsorbent, thus promoting pore widening and reducing the surface area
422
(Wang et al., 2012a; Wei et al., 2012; Lee et al., 2014; Deng et al., 2015; Li et al., 2015a; Chaiw
423
et al., 2016; Luo et al., 2018; Wu et al., 2018b; Xu et al., 2018; Rao et al., 2019).
424
In another study, Rouzitalab et al. fabricated a series of highly nanoporous N-doped carbons
425
with walnut shell as the starting material through a combination of in-situ urea modification
426
coupled with KOH activation (mass ratios of 2-6), and pointed out that mild activation condition
427
(KOH/C mass ratio of 2) exhibited higher CO2 adsorption capacity (7.42 mmol/g under room
428
temperature) under atmospheric pressure than that prepared in severe condition (KOH/C mass
429
ratio of 6), which is favorable for CO2 adsorption under high pressures (14.03 mmol/g under 10
430
bar at room temperature) (Sevilla and Fuertes, 2011; Rouzitalab et al., 2018). As previously
431
reported, residual urea can react with KOH and promote its penetration into deep layers of the N-
432
doped samples to develop a highly porous structure (Chen et al., 2016; Rouzitalab et al., 2018). 49
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433
4.2.2.4. Activation Temperature
434
In 2015, Parshetti et al. examined a series of carbonaceous adsorbents, which were prepared
435
from empty palm fruit bunch by HTC coupled with KOH activation at two different temperatures
436
(600 °C and 800 °C) for CO2 capture. They concluded that regardless of the precursor, higher
437
activation temperature leads to a remarkable enhancement of the specific surface area, the total
438
pore volume and the micropore volume of the ACs. This development of adsorbents’ textural
439
properties can be ascribed to the removal of volatile matters and impurities in gaseous form
440
during thermal decomposition process (David and Kopac, 2014; Heo and Park, 2015; Parshetti et
441
al., 2015; Rashidi and Suzana, 2015; Geng et al., 2016). Moreover, Sun and Webley reported that
442
the pore widening begins to dominate at severe activation temperature and accordingly mesopore
443
surface area and mesopore volume increase (Sun and Webley, 2011; Plaza et al., 2012; Song et
444
al., 2014), which may cause structural collapse under over-intense activation conditions
445
(Rouzitalab et al., 2018).
446
It is mentioned in the literature that nitrogen groups incorporated into the carbon structure
447
have low thermal stability and tend to decrease by an increase in activation temperature (Xing et
448
al., 2012; Rashidi and Suzana, 2015; Yang et al., 2015; Xu et al., 2018; Han et al., 2019).
449
Nevertheless, Geng et al. utilized ammonia treatment as both the activating agent and nitrogen
450
source without preliminary oxidation to produce corncob-derived adsorbents and demonstrated
451
inconsistent results with literature. They observed that the increasing trend of N doping with
452
increasing temperature indicated a dynamic balance between N doping and removal during the
453
reactions and finally N doping extended beyond N removal (Geng et al., 2016). Furthermore,
454
Xing et al. proved that either low activation temperature or low KOH dosage will result in more
455
H atoms with more hydrogen bonding interactions between CO2 molecules and consequently 50
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456
higher CO2 uptakes than the carbons prepared at high temperature or high KOH dosage (Xing et
457
al., 2012).
458
4.2.2.5. Activation Time
459
David and Kopac used rapeseed oil cake and walnut shell as a precursor to prepare activated
460
carbon using CO2 as activating agent by similar pyrolysis and activation temperature and
461
variable activation time (0.5-3.5 h). With a short activation time, the applicable pores are not
462
developed due to an insufficient devolatilization reaction. Meanwhile, severe reactions between
463
CO2 and carbon surface will take place during prolonged activation time that causes
464
simultaneous pore opening and pore widening with a subsequent pore collapse and development
465
of mesopores or macropores, which are not suitable for CO2 adsorption under atmospheric
466
conditions. Further, more ash residues may form through intensified activation time and block
467
the existing pores with no more CO2 capture (Plaza et al., 2009b; Bhati et al., 2013; Ello et al.,
468
2013a; González et al., 2013; David and Kopac, 2014; Rashidi and Suzana, 2015; Ogungbenro et
469
al., 2017).
470
Li et al. also investigated the effect of activation time (1, 1.5 and 2 h) on the porosity
471
improvement of peanut shell-derived AC using KOH with an impregnation ratio of 2 at 780 °C.
472
They found that increasing activation time could not promote the elimination of char elements,
473
so ultramicropore volume hardly varied while ultramicropore fraction (V<0.7
474
decreased and then increased as prolonged activation time caused pore wall collapse and reduced
475
Vtot (Li et al., 2015a). According to both Ello et al. and David and Kopac, higher burn-off degree
476
through the activation time enhancement reduces the carbon yield (Ello et al., 2013a; David and
477
Kopac, 2014). 51
nm/Vtot)
first
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478
4.2.2.6. Activation Flow Rate
479
Rashidi et al. prepared a series of activated carbons simply by activating different agricultural
480
waste materials (palm shell, palm mesocarp fiber, coconut shell, coconut fiber, rice husk) in a
481
varied CO2 atmosphere flow rate. They observed that the variable CO2 flow rate did not present
482
any effective change in the porosity development and adsorption capacity of the adsorbents
483
(Rashidi and Suzana, 2015). On the contrary, Li et al. varied the protective-gas (N2) flow rate
484
(100, 450, 800 or 1040 mL/min) during the activation of chitosan derived ACs using KOH with
485
the impregnation ratio of 1:1. They demonstrated that the CO2 uptake as well as CO2/N2
486
selectivity of ACs could significantly increase owing to the significant effect of N/C ratio of
487
adsorbent surface, the flow rate on ultramicropore volume, and the nature of N-containing
488
species of the materials (Li et al., 2017).
489
4.2.2.7. Activation Heating Rate
490
Alvarez et al. studied the effect of heating rate on the CO2 adsorption capacity of cherry stone-
491
derived ACs prepared by physical activation (CO2/steam). They found that variable heating rate
492
(10.00 °C/min-1, 12.03 °C/min-1, 15.00 °C/min-1, 17.97 °C/min-1 and 20.00 °C/min-1) was
493
considerably ineffective in the CO2 capture capacity of any studied material, CO2 or steam
494
activated adsorbents (Álvarez-Gutiérrez et al., 2015). A similar finding was reported by Rashidi
495
and Suzana (Rashidi and Suzana, 2015).
52
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496
4.3. Adsorption Conditions
497
4.3.1. Temperature
498
According to the conclusions drawn by previous reports, as a typical process of physical
499
adsorption, during the enhancement of adsorption temperature the adsorption capacity reduces
500
through the desorption of the adsorbed gases on the AC surface. Nevertheless, lignocellulose-
501
based adsorbents have sufficient CO2 adsorption capacity under ambient condition (Maroto-
502
Valer et al., 2005; Huang et al., 2011; Shafeeyan et al., 2011; Boonpoke et al., 2012; David and
503
Kopac, 2014; Heidari et al., 2014b; Moussa et al., 2017; Rashidi and Yusup, 2017). Chemical
504
modification provides an effective approach to suppress this occurrence at high temperatures by
505
introducing base sites on the surface of lignocellulose-based adsorbents (Shafeeyan et al., 2011;
506
Xiong et al., 2013). Fig. 10 shows the essence of adsorption at low and high temperatures,
507
derived from the study by Xiong et al.
508
Fig. 10 The relationship between the CO2 adsorption capacity of the modified char and (a) the micropore volume, and (b) the nitrogen content. Reprinted from reference (Xiong et al., 2013), 53
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with permission from Springer Nature, license number: 4732400985852. 509 510
To explain this, fundamental thermodynamic concepts should be discussed. Quantification of
511
the isosteric heat of adsorption (Qst) is a pivotal factor for the design and development of CO2
512
adsorbents (Parshetti et al., 2015). For adsorption, Qst is negative since heat is released when the
513
molecules are adsorbed and as it is known, when the surface is energetically homogenous, no
514
interaction occurs between adsorbed molecules and Qst is independent of the surface coverage.
515
However, when the surface is heterogeneous, because of strong binding sites and the filling
516
ultramicropores, followed by the adsorption onto weak binding sites and the filling of larger
517
pores, Qst varies with the surface loading (Shafeeyan et al., 2015; Li et al., 2017). It decreases
518
gradually with increase in CO2 adsorption capacity, which is due to the disappearance of
519
favorable adsorption sites. However, the adsorbate/adsorbate interaction, which occurs mainly
520
after the complete surface coverage of porous sorbent, must not be ignored (Guan et al., 2018),
521
which may lead to the enhancement of Qst value along with increase in the CO2 adsorption
522
capacity owing to strong lateral interactions of CO2 molecules onto second and higher layers
523
(Rouzitalab et al., 2018).
524
It is a common hypothesis that the isosteric heat of adsorption is temperature-independent or
525
only slightly dependent on temperature; however, this hypothesis is not always confirmed.
526
Earlier studies focused their attention on the dispersion force, which is the interaction between
527
the solid and gas, and neglected the adsorbate-adsorbate interactions, or more precisely, the force
528
among the gas molecules, involving both the adsorbed phase and bulk phase (Guan et al., 2018).
529
In order to compare the effect of temperature on the CO2 adsorption of ZIF-8, in 2011, Grand
530
Canonical Monte Carlo (GCMC) simulations were conducted by Huang et al. They separated the 54
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531
overall isosteric heat of adsorption into the adsorbate-adsorbent (Qst-F-MOF) as well as the
532
adsorbate-adsorbate (Qst-F-F) isosteric heat of adsorption. The simulation outcomes prove that the
533
effect of temperature on Qst-F-MOF is not very large, while for Qst-F-F is much larger. Therefore,
534
high fluctuations of the interaction energy among adsorbate molecules caused by temperature
535
variations result in more significant temperature dependence (Huang et al., 2011). In other
536
words, at high temperatures, the molecules of gases have sufficient kinetic energy to overcome
537
the effects of intermolecular forces between adsorbate and adsorbent (Do, 1998). Recently, Guan
538
et al. defined a “critical temperature point” at which increasing adsorption temperature does not
539
change the adsorption capacity anymore and even makes similar isotherms above this point since
540
the kinetic energy of CO2 molecules cannot overcome the higher energy barriers that the
541
adsorbed molecules possess (Guan et al., 2018). As shown in Fig. 11, all the injection pressures
542
exhibit a linear decrease in CO2 capture up to 323.15 K coupled with an inclination of near zero
543
beyond that point.
544
Fig. 11 The relationship between the CO2 adsorption capacity and temperature with a critical
55
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temperature point of 323.15 K. Reprinted from reference (Guan et al., 2018), with permission from Elsevier, license number: 4731710708179. 545 546
The effect of basic surface functional groups on the Qst is another important factor that should
547
be discussed. Singh et al. prepared a series of nitrogen functionalized porous carbons from Giant
548
reed (Arundo donax) and the chitosan through single-step chemical activation. Their synthesized
549
samples, which consisted of lower nitrogen content (3.5 - 4.1 wt%) showed a low isosteric heat
550
of adsorption (26.5 kJ/mol and 24.6 kJ/mol); however, an increase in nitrogen content (5.41
551
wt%) resulted in a further enhancement of isosteric heat of adsorption (32.2 kJ/mol) (Singh et al.,
552
2017a). The higher isosteric heat of functionalized ACs is mainly due to strong electrostatic
553
interaction between polarizable CO2 and electronegative heteroatoms, hydrogen bonding and
554
acid-base interactions between acidic CO2 and nitrogen-containing basic functional groups rather
555
than relatively weak dispersion forces (Shafeeyan et al., 2015; Ashourirad et al., 2016).
556
Lim et al. investigated the impact of nitrogen-containing functional groups in carbon-based
557
adsorbents on CO2 adsorption as well as the surface interactions with CO2 using computational
558
calculation. The energy of adsorption (Eads), which is profoundly analogous to the isosteric heat,
559
was calculated for CO2 molecules in six different initial configurations (Inglezakis and Zorpas,
560
2012). Functionalization, irrespective of the type of nitrogen-containing functional group,
561
enhances binding energies with CO2 as follow: pyridone (21.58 kJ/mol) > pyridine (21.00
562
kJ/mol) > amine (14.16 kJ/mol) > quaternary nitrogen (12.04 kJ/mol) > pyridine nitrogen-oxide
563
(11.65 kJ/mol) > cyanide (10.79 kJ/mol) > pyrrole (10.60 kJ/mol). An adsorption process is
564
considered as physical, chemical or ion exchange regarding the adsorption energy when it is
565
respectively below 8 kJ/mol, over 16 kJ/mol and between 8-16 kJ/mol. For the pyridone group, 56
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566
the hydrogen bond between the negatively charged oxygen atom of CO2 and the positively
567
charged hydrogen of the hydroxyl group in pyridone group governs the CO2 adsorption behavior.
568
Regarding a pyridine-functionalized surface, adsorption energy, Eads, is approximately the same
569
as that of the pyridone-functionalized surface. Pyridinic-nitrogen is more appropriate for CO2
570
adsorption owing to its stronger electronegativity as compared to carbon atoms, even in the
571
absence of a hydroxyl group. Although the grafted amine group provides strong basicity, its
572
adsorption energy reduction, in comparison with pyridine group, is due to the basicity decrease
573
of the nitrogen atom in addition to steric hindrance by the hydrogen atom existing in amine
574
group. Moreover, quaternary nitrogen, pyridine nitrogen-oxide, pyrrole, and cyanide groups are
575
not effective enough in enhancing CO2 adsorption strength owing to the less discrepancy
576
between their Eads and pristine surface Eads (9.44 kJ/mol). The weak interaction in quaternary
577
nitrogen as well as cyanide groups can result from the lowest basicity of nitrogen atom.
578
Furthermore, the weaker bonding interactions of pyrrole group and pyridine nitrogen-oxide
579
group with CO2 molecule (‒NH⋯O and ‒NO⋯C, respectively) as compared to the hydrogen
580
bonding of pyridone group and the Lewis acid-base interaction of pyridine group result in lower
581
CO2 adsorption energy (Lim et al., 2016).
582
The Henry’s law constant (KH), which characterize adsorbent heterogeneity and adsorption
583
affinity toward CO2 molecule at low pressure (Henry’s law region) was calculated using Virial
584
model according to the equation that has been recorded elsewhere (Parshetti et al., 2015) in order
585
to have another quantitative estimate of CO2 adsorption. In this region, gas molecules can
586
separately explore the entire adsorbent surface, owing to the fact that adsorbate-adsorbate
587
molecule interactions are insignificant due to low densities (Schindler, 2008). The higher the
588
value of the constant was, the stronger affinity between adsorption pair would be. As shown in 57
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589
Table 3, heteroatom self-doped activated carbon from fir bark showed superior Henry constant
590
(30.15 mmol/g.bar) and consequently high CO2 adsorption capacity (5.2 mmol/g at 1 bar and
591
25℃) due to the strong dispersion forces between CO2 and fir bark-derived AC which arise from
592
suitable pore size and the presence of N- and O- containing groups on adsorbent surface (Luo et
593
al., 2018). Notwithstanding thermodynamics suggestion that Henry constant always exist, Do et
594
al. dismisses this issue with the fact that sometimes the linear portion of the isotherm will occur
595
at far too low pressure, and far too low in capacity owing to the few number of strong sites and
596
their considerable strength that makes KH unmeasurable (Do et al., 2008).
597
4.3.2. Humidity
598
Water vapor is one of flue gas components alongside CO2 and N2. The perpetual dipole moment
599
belonging to the molecules of water makes it adsorb a great deal of adsorbents (Plaza et al.,
600
2014b). Activated carbon hygroscopicity at low levels of relative humidity (RH) can come from
601
the affinity of hydrophilic surface oxygen functional groups to water and the linking of water
602
molecules to surface functional group and adsorbate water molecules via hydrogen bonds (Pego
603
et al., 2019), and at high RH capillary condensation begins to take place and adsorb significant
604
amounts of water (Plaza et al., 2016; You and Liu, 2019). The results can have a negative effect
605
on the CO2 adsorption capacity through partial closure of pore mouth and consequent reduction
606
of beneficial CO2 adsorption sites as well as enhancement of diffusion resistance of CO2
607
conveyance to the active sites of carbon (Cen et al., 2013). Thermal treatment under a flow of
608
hydrogen or inert gas, different types of coatings as well as different acid treatments are several
609
techniques to limit water vapor adsorption (Querejeta et al., 2016).
610
A restricted number of investigations have been carried out into the effect of wet flue gas on
611
the CO2 adsorption using activated carbons. Plaza et al. employed the single step activation 58
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612
method to produce an olive-derived microporous AC using rarefied air (3% O2, balance N2) at
613
650 °C. They suggested that overlapped CO2 breakthrough curves under dry and humid (RH =
614
65%) conditions reveal the fact that water vapor is not an impediment factor for CO2 adsorption
615
on a short time scale owing to the much slower adsorption kinetics of H2O (Plaza et al., 2014b).
616
Two years later they took a fresh look at adsorption behavior of ternary N2/CO2/H2O mixture
617
through wet flue gas on their previous adsorbent. Using the IAS theory, based on the Toth model
618
for CO2 and N2 adsorption and the extended Cooperative Multimolecular Sorption (CMMS)
619
model for H2O adsorption, they predicted a reduction in the CO2 adsorption capacity up to a
620
level of 64% for the inlet gas stream with RH value of 95% (Plaza et al., 2016). In another study
621
by Luo et al., the existence of water vapor promoted the CO2 chemisorption on the amine-
622
functionalized sugarcane bagasse (SB-AM-TETA) and resulted in a superior CO2 adsorption
623
amount (Luo et al., 2016). In a recent study, the CO2 adsorption and recovery from wet flue gas
624
were simulated on a fixed bed of AC by You and Liu. The Langmuir model and arc-tangent
625
expression were applied in order to justify the amount of water vapor adsorption instigated by
626
the presence of hydrophilic groups as well as the amount adsorbed due to capillary condensation,
627
respectively. Moreover, the multi-component Langmuir model was used with the assumption of
628
competitive adsorption equilibrium occurrence between H2O, CO2 and N2. They reported a large
629
prohibitive influence on the adsorption and recovery of CO2 with the enhancement of humidity
630
(50.00%-100.00%). Nevertheless, the competitive adsorption of H2O and CO2 is comparatively
631
minor, mainly because of the bed temperature variation produced by the heat of H2O
632
adsorption/desorption (You and Liu, 2019).
59
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633
4.3.3. Multicomponent Adsorption
634
It has been reported that the adsorption capacity of AC is contingent on the molecular size of
635
adsorbate, i.e. a decrease in the molecular size leads to an increase in the adsorbability (Zhang et
636
al., 2017). For instance, when N2 (molecular diameter of ~3.64 Å) interacts with the surface of
637
an adsorbent with a smaller pore size, the opportunity of its molecules to be ensnared in the
638
adsorbent pores is diminished, whereas for smaller molecules like CO2 (molecular diameter of
639
~3.30 Å) this chance is higher (Banisheykholeslami et al., 2015). Nonetheless, providing that the
640
microporosity in a sample is large enough to disregard shape selectivity impacts on the basis of
641
the kinetic diameter of gas molecules (molecular diameter of ~3.80 Å for CH4), the larger
642
quadrupolar moment of CO2 (CO2, 13.4 × 10‒40 C m2; N2, 4.7 × 10‒40 C m2; CH4, does not hold a
643
quadrupole moment) may be responsible for such a distinct adsorption capacity. The quadrupole
644
moment, yields a robust attraction to the surface of adsorbent, which results in an improved
645
uptake. The adsorption performance may also be affected by the polarizability (CO2, 29.1 × 10‒25
646
cm‒3; N2, 17.4 × 10‒25 cm‒3; CH4, 26 × 10‒25 cm‒3). As the polarizability as well as the
647
quadrupole moment of CO2 are superior to those of N2, a surpassing selectivity is expected
648
owing to a higher affinity of the pore surface for CO2 (Álvarez-Gutiérrez et al., 2015; Parshetti et
649
al., 2015). Although both CO2 and CH4 have high polarizability, the quadrupole moment is much
650
more powerful than this attraction force (Álvarez-Gutiérrez et al., 2015).
651
The flue gas produced from combustion of carbon-rich fuels also contains oxygen (O2), NOX
652
and SOX compounds as a result of reactions between oxygen and available nitrogen and sulfur,
653
as well as hydrogen sulfide (H2S) (Sass et al., 2005).
654
Notwithstanding the great potential of adsorbent materials in applications of CO2 capture, the
655
presence of SOX, NOx and H2S impurity gases and their negative impact on lifetime of the 60
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656
adsorbents remains a significant challenge. Prevalent CO2 capture processes, which are based on
657
adsorption, depend entirely on applying a pretreatment stage to eliminate the aforementioned
658
impurities, which noticeably increases the production cost, owing to their permanent adsorption
659
potential, falloff total available active sites and conveyance limitation through the porous
660
network. The higher acidity and permanent dipole moment of SO2 in conjunction with higher
661
polarity and adsorption strength of NO2 would not comply with the adsorption of CO2 (Rezaei et
662
al., 2015). Moreover, H2S parasitically affect CO2 adsorption with its chemisorption and the
663
consequent reduction of porous volume and surface area, which alter both physisorption and
664
chemisorption of CO2 (de Oliveira et al., 2019).
665
Furthermore, Boonpoke et al. (Boonpoke et al., 2012), Fiuza-Jr et al. (Fiuza-Jr et al., 2016),
666
and Erto et al. (Erto et al., 2016) investigated the CO2 sorption capacities of different biomass-
667
derived ACs as a function of influent CO2 concentration (balanced with N2). They concluded that
668
CO2 adsorption capacity is strongly enhanced through CO2 inlet concentration enhancement due
669
to an improvement in the partial pressure of CO2, faster mass transfer and also a more rapid solid
670
coverage and saturation occurrence.
671
672
5. Conclusion and Future Research Needs
673
Carbon dioxide is an inert gas that has no heating value of combustion. It is believed that CO2 is
674
the most potent GHG and contributes to global warming more than other GHGs. Thus, not only
675
is it an environmental concern but it is also crucial for developing a practicable implementation
676
strategy of GHG control, which can cover industrial facilities as well as power plants. For this
677
purpose, varied technologies have been developed for CO2 capture and storage. Despite the fact 61
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678
that every technology has its strengths and limitations, CCS from point source emissions has
679
appeared as one of the possible remedies for stabilizing the CO2 level in the environment. To
680
decrease CO2 capture and separation costs, as well as make CCS obtainable for concrete
681
application, gas-solid adsorption has been considered as a possible solution as it reveals several
682
advantages, such as cost/ease of adsorbent synthesis, enhancement of CO2 adsorption capacity,
683
regeneration facility, rapid reaction rated and the simplicity of practicability over a wide variety
684
of operating temperatures and pressures. If renewable resources are used as materials and the
685
costs of CO2 capture are reduced, lignocellulose-based nanomaterials can be a promising
686
precursor. A review of the lignocellulose-based adsorbents for CO2 capture was made, with a
687
focus on the key factors governing CO2 adsorption. Overall, the results showed that the
688
synergetic effect of the physical characteristics and surface chemistry of adsorbents determines
689
the CO2 adsorption capacity. In general, high specific surface area, ultramicropore volume and
690
alkalinity result in high CO2 adsorption capacity. Nevertheless, the aforementioned factors were
691
not the entire parameters determining adsorption capacities. Synthetic parameters such as
692
carbonization temperature, inert gases flow rate, activating agent type and dosage, activation
693
time and temperature can simply be changed to fulfill the requirements for CO2 adsorption at
694
various operating pressures. Moreover, incorporating nitrogen groups in the ACs structures is
695
one of the most feasible approaches for high temperature CO2 adsorption. Furthermore, almost
696
all ACs are hydrophobic and the presence of water not only does not reduce their adsorption but
697
also in some cases leads to higher adsorption.
698 699
Another important part of this review is the investigation into the health and environmental effects of CO2 and different techniques for its reduction.
62
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700
In summary, many practical solid sorbents are available for CO2 capture but future technology
701
should focus on promising solid sorbent candidates with high CO2 selectivity and adsorption
702
capacity, high cycle lifetime and multicycle durability, low price as well as environmental
703
friendliness to serve as a tool for CO2 adsorption in real scale application. This review
704
demonstrates that the use of lignocellulose-based materials can be a practical option for the
705
development of low-cost adsorbents and, as a result, it is suggested that more investigations
706
should be carried out on lignocellulose-based adsorbents for CO2 capture. While it can be the
707
first step for CO2 reduction, it may not be the comprehensive solution to climate change.
708 709
710
Compliance with Ethical Standards
711
Conflict of Interest: The authors declare that they have no conflict of interest.
712 713
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Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
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Lignocellulose is a feasible substitute for development of low-cost sorbents. Key factors controlling CO2 adsorption onto lignocellulose-based adsorbents are reviewed. Synthesis conditions change consequent adsorbent features. Prospective research challenges of lignocellulose-based adsorbents are summarized.
Zahra Rouzitalab, Davood Mohammady Maklavany, Shahryar Jafarinejad, Alimorad Rashidi PII:
S0045-6535(19)32997-2
DOI:
https://doi.org/10.1016/j.chemosphere.2019.125756
Reference:
CHEM 125756
To appear in:
Chemosphere
Received Date:
27 September 2019
Accepted Date:
24 December 2019
Please cite this article as: Zahra Rouzitalab, Davood Mohammady Maklavany, Shahryar Jafarinejad, Alimorad Rashidi, Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process, Chemosphere (2019), https://doi.org/10. 1016/j.chemosphere.2019.125756
This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier.
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Graphical Abstract
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Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process
Zahra Rouzitalaba, Davood Mohammady Maklavanyb, Shahryar Jafarinejadc, Alimorad Rashidib,*
a
Civil Engineering Division, College of Environment, Karaj, P.O. Box 31746-74761, Alborz,
Iran b
Carbon & Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI),
Tehran, P.O. Box 14857-33111, Tehran, Iran c
Department of Chemical Engineering, College of Engineering, Tuskegee University, Tuskegee,
P.O. Box 5899, Alabama 36088, USA
Declarations of interest: none
*
Corresponding author. Address: Carbon & Nanotechnology Research Center, Research Institute of Petroleum
Industry (RIPI), West Blvd. Azadi Sport Complex, P.O. Box 14857-33111, Tehran, Iran. E-mail: [email protected] (Alimorad Rashidi).
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Lignocellulose-based Adsorbents: A Spotlight Review of the Effective Parameters on Carbon Dioxide Capture Process
Abstract The increasing demand for energy all around the world has led to a rise in greenhouse gases (GHGs), of which carbon dioxide (CO2) is the most important. CO2 is largely responsible for global warming and climate change. Processes such as carbon dioxide capture and storage (CCS), which have an effective role in climate mitigation, seem to be promising. In recent years, porous carbons, particularly activated carbons (ACs), have rapidly emerged as one of the most effective adsorbents of CO2. However, the implementation of pristine ACs in the real world is still hindered due to their physical and weak adsorption, which makes these adsorbents sensitive to temperature and relatively poor in selectivity. Hence, the surface modification of ACs is essential in order to improve their surface area, pore structure and alkalinity. Numerous studies have reported lignocellulose-based ACs as very promising adsorbents of CO2. In this review, the sources, health and environmental effects of CO2, and the abatement methods of GHGs are described. In addition, the capture and separation of CO2 from gas stream using various types of lignocellulose-based ACs are summarized. Furthermore, the key factors controlling the adsorption of CO2 by ACs (characteristics of adsorbents, preparation conditions, as well as adsorption conditions) are comprehensively and critically discussed. Finally, future research needs and prospective research challenges are summarized. Keywords:
Carbon dioxide capture and storage (CCS), CO2, Adsorption,
Lignocellulose-based material, Controlling factors
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Contents 1. Introduction................................................................................................................................................4 2. An Overview of CO2 and Reduction Technologies ...................................................................................5 2.1. Sources of CO2 Emission....................................................................................................................5 2.2. Health and Environmental Effects of CO2 ..........................................................................................7 2.3. An Overview of Advanced GHG Reduction Technologies..............................................................15 2.3.1. Carbon dioxide Capture Methods ..............................................................................................15 3. Lignocellulose-based Adsorbents for CO2 Capture .................................................................................23 4. Key Factors Controlling CO2 Adsorption onto Lignocellulose-based Adsorbents .................................35 4.1. Adsorbent Features ...........................................................................................................................35 4.1.1. Surface Area...............................................................................................................................35 4.1.2. Pore Structure.............................................................................................................................36 4.1.3. Surface Chemistry......................................................................................................................39 4.1.4. Other Factors..............................................................................................................................42 4.2. Preparation Conditions......................................................................................................................43 4.2.1. Carbonization Condition............................................................................................................43 4.2.1.1. Carbonization Type.............................................................................................................43 4.2.1.2. Carbonization Temperature ................................................................................................45 4.2.1.3. Carbonization Flow Rate ....................................................................................................45 4.2.2. Activation Condition..................................................................................................................46 4.2.2.1. Number of Activation Steps................................................................................................46 4.2.2.2. Activating Agent.................................................................................................................47 4.2.2.3. Activating Agent Dosage....................................................................................................49 4.2.2.4. Activation Temperature ......................................................................................................50 4.2.2.5. Activation Time ..................................................................................................................51 4.2.2.6. Activation Flow Rate ..........................................................................................................52 4.2.2.7. Activation Heating Rate......................................................................................................52 4.3. Adsorption Conditions ......................................................................................................................53 4.3.1. Temperature ...............................................................................................................................53 4.3.2. Humidity ....................................................................................................................................58 4.3.3. Multicomponent Adsorption......................................................................................................60 5. Conclusion and Future Research Needs ..................................................................................................61
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1. Introduction Triatomic Carbon dioxide (CO2) molecule is a gas under ambient conditions. It sublimates from solid state to gas at ‒78 °C under atmospheric pressure. A comparatively inert gas, carbon dioxide is neither explosive nor flammable, which does not support combustion process. Naturally occurring in the Earth’s atmosphere, carbon dioxide is crucial to the plants that photosynthesize carbon dioxide and water into sugars using solar energy. As shown in Fig. 1, the natural carbon cycle controls carbon dioxide level in the Earth’s atmosphere (North, 2015).
Fig. 1 Natural carbon cycle. Modified from reference (EarthHow, 2017).
Despite the 20-fold emission of CO2 by natural sources in comparison with the sources resulting from human activity, over times longer than a couple of years, natural sources are nearly balanced by natural sinks (Songolzadeh et al., 2012). Sources leading to anthropogenic CO2 emission are increasing more than ever with the growing population and the associated energy consumption, and subsequent emissions seem to be unavoidable. As a result of air 4
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pollution, which directly affects human well-being, there is growing concern about global environmental problems and sustainable development (Višković et al., 2014; Tehrani et al., 2019). Great biological and physiochemical endeavors have been made over recent years in order to develop highly efficient CO2 reduction methods, however, this review article focuses more on physiochemical methods, amongst which adsorption by porous carbon materials is recognized as one of the most economical and promising strategies owing to their highly firm and hydrophobic surface, adjustable textural properties, and high adsorption affinity towards CO2. A large number of studies have been conducted to survey the adsorption of CO2 on a wide range of carbonaceous resources comprising lignocellulose-based porous adsorbents due to the potential demand for huge amounts of low cost CO2 adsorbents and the importance of waste resources. The main objective of this review is to undertake a comprehensive review of peer-reviewed articles concerning the adsorption of CO2 only by lignocellulose-based porous adsorbents, and to identify the prospective research challenges. First, the main sources of CO2 emission and its impacts are discussed, and then the GHGs abatement methods and CO2 capture technologies are studied. Finally, the factors that control the adsorption of CO2 by lignocellulose-based porous adsorbents are thoroughly discussed.
2. An Overview of CO2 and Reduction Technologies 2.1. Sources of CO2 Emission CO2 comes from both anthropogenic and natural emissions. The proportion of anthropogenic source is increasing, and their impact is deteriorating since almost all human daily activities lead 5
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to the emission of CO2. According to Fig. 2 there are various sources of anthropogenic carbon dioxide, and amongst them the combustion of fossil fuels, industrial process emissions, waste treatment (IPCC, 2008b; Liu, 2016), land use change (IPCC, 2008b; Liu, 2016; Davis, 2017; Lal, 2019) and soil degradation processes (such as erosion, nutrient depletion, salinization, decline of soil structure)(Lal, 2019) are the most important. Based on the Environmental Protection Agency (EPA) report (2019), nearly 77% of CO2 emission is the result of fossil fuel use (EPA, 2019). The major fossil fuel users are transportation, utilities (power, gas, oil, etc.), and industrial production.
Fig. 2 Main sources of CO2 emission (EPA, 2019).
Capturing CO2 directly from large point sources like industries seems easier and more economical than from small point sources. The main concerns of industrial production are agriculture, mining, construction as well as manufacturing. Manufacturing is the largest one and can be subdivided into five principal categories, namely chemicals, petroleum refineries, metal/mineral products, paper, and food (Fig. 3). These categories constitute the majority of the 6
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energy consumption and CO2 emission by the sector (U.S. Department of Energy and Energy Information Administration, 2005; Davis and Diegel, 2007; Liu, 2016).
Fig. 3 Manufacturing CO2 emission segments.
Natural carbon cycle cannot balance the subsequent CO2 emission, so the CO2 level in the atmosphere gradually increases. The emitted CO2 from the burning of fossil fuel elevates the atmospheric CO2 level by 1 ppm by volume (North, 2015).
2.2. Health and Environmental Effects of CO2 Accommodating over half of the global population, cities are responsible for approximately 75% of global energy consumption as well as greenhouse gas (GHG) emissions (Gouldson et al., 2016; Wu et al., 2018a; Mi et al., 2019). It is well established that variations in GHG levels due to human activities are the main cause of global warming, through adsorbing and trapping the infrared radiation (IR) occurring over the last century (The Royal Society, 2010), which can sequentially lead to climate change (VijayaVenkataRaman et al., 2012; Karimi et al., 2018). The mean surface temperature would fall to about ‒21 °C without this greenhouse effect (Karl et al., 2009; Anderson et al., 2016). 7
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The impressions of greenhouse gases on Earth’s climate is contingent on the retention time of these gases in the atmosphere (Karl et al., 2009). It is largely believed that CO2 is the most potent greenhouse gas (after water vapor with human activities contribution by 0.18% (Babu, 2014)), contributing to global warming more than other GHGs (Xu, 2014; North, 2015), with increasingly devastating effects on the environment (Biasin, 2015). As shown in Fig. 4, in recent years the CO2 level of atmosphere has exponentially risen and the overall CO2 concentration in the atmosphere has increased from 317.10 ppm (in June 1958) to 410.79 ppm (in June 2018). Such a significant growth in CO2 level has also been the cause of major local weather changes and increases in the average surface temperature of the earth (Kumar and Kim, 2016).
Fig. 4 Atmospheric CO2 concentration from 1958 to 2018 (CO2.Earth, 2019).
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As indicated in the EPA report, greenhouse gas outflows can bring about an upward push in temperature by 1‒2 °C in the following century (Dassanayake et al., 2016). Such an increase can have serious consequences on water resources, agriculture, forestry, marine ecosystems, animals and human health, as shown in Table 1.
9
Table 1. Health and environmental effects of CO2 Type
Advantages
Disadvantages
Water Resources
Rainfall pattern variations and a surge in the frequency and severity of extreme weather across different regions on account of climate change may lead to more hot days, heat waves, heavy precipitation events and fewer cold days (Lindner et al., 2010; Bender and Weigel, 2011; Wheeler and von Braun, 2013; Marengo et al., 2017; Karimi et al., 2018).
Drought risk has magnified the problem of high temperatures and an anticipated decrease in rainfall (Lindner et al., 2010).
Water resources are changing in terms of quantity and quality as a result of thermal expansion and melting of Arctic and Antarctic ice sheets. In addition, warming is causing the sea level and runoff waters to rise (Karl et al., 2009; Doney et al., 2012; Biasin, 2015; IPCC, 2015).
Agriculture
CO2 fertilization effect, i.e. the stimulation of photosynthesis
Increased heavy precipitation, growing season temperature, flooding
through elevated CO2 concentration, is conducive for both crop
and drought seriously affect crop yield (Karl et al., 2009; Wang et al.,
growth and crop productivity (DaMatta et al., 2010; Bender and
2017b).
Weigel, 2011; Erbs et al., 2015; Wang et al., 2017b; Karimi et al., 2018).
Climate change affects both crop biomass production and crop quality (Erbs et al., 2015).
10
Moreover, stomatal conductance reduction, as a consequence of
Decrease in the nitrogen concentration of vegetative plant parts as
CO2 fertilization effect, not only improves drought tolerance by
well as in seeds and grains, which exemplifies CO2 effect, leads to a
diminishing transpiration loss but also reduces O3 (and other
decrease in protein concentration. Variability of macro- and
gaseous pollutants) uptake (Bender and Weigel, 2011).
microelements composition (Ca, K, Mg, Fe, Zn), secondary compounds, vitamins, and sugars concentrations, as well as lipid composition of plants, are among other examples of CO2 enrichment (DaMatta et al., 2010; Bender and Weigel, 2011; Dietterich et al., 2015; Medek et al., 2017).
Forestry
Elevated CO2 offers various advantages to trees alike to
Limiting factors such as nutrient availability do not allow trees to
agriculture crops (Field et al., 1995; Picon-Cochard et al., 1996;
grow sufficiently as a result of the enhancement of photosynthesis rate
DeLucia et al., 1999; Wullschleger et al., 2002; Ainsworth and
(Hungate et al., 2003; Luo et al., 2004; Lindner et al., 2010).
Long, 2005; Vetter et al., 2005; Lettens et al., 2008; Saxe et al.,
2008; Lindner et al., 2010; FAO, 2012).
Enhancement of temperature may affect forest productivity as well as interaction and competition processes among tree species (Lasch et al., 2002; Ogaya et al., 2003; Lloret et al., 2004; Lindner et al., 2010).
Forest fire is likely to occur at prolonged drought situations, which would lead to build-up soil erosion owing to increased hydrophobicity and reduced plant regeneration (Certini, 2005; Delitti et al., 2005; Lindner et al., 2010; FAO, 2012; Manoj Kumar and Abhishek, 2014; Stephens et al., 2018).
11
Tree mortality occurs owing to trees’ inability to swiftly adapt to
environmental changes in terms of its life-span (Hänninen, 2006; Lindner et al., 2010; FAO, 2012; Biasin, 2015).
Alternations of disturbance regimes such as storms, insect herbivores and thermophilic pathogens are among the main effects of climate change on temperate forests (Thürig et al., 2005; Schütz et al., 2006; Eliasch, 2008; Lindner et al., 2010; FAO, 2012),
Marine Ecosystem
Species or populations may profit from environmental changes
Ocean acidification occurs as a consequence of elevated atmospheric
due to the availability of food or nutrients, reduction of the
CO2 and reduced subsurface oxygen concentration (due to warming
physiological cost of maintenance, as well as the emergence of
and altered ocean circulation) (E Keeling et al., 2010; Doney et al.,
novel ecosystems (Doney et al., 2012).
2012).
An increase in aqueous CO2, total inorganic carbon and also a decrease in pH, carbonate ion, and calcium carbonate saturation states are caused by ocean acidification (Doney et al., 2009; Doney et al., 2012; Mostofa et al., 2015; Mollica et al., 2018).
Coral skeletons and the accretion of reefs may be severely weakened by ocean acidification (Kleypas et al., 1999; Hughes et al., 2003; Foden and Stuart, 2009; Doney et al., 2012). Moreover, species replacement, bleaching, and cover reduction are among the other effects of warming on corals and their reefs (Hoegh-Guldberg et al., 2008; Hoegh-Guldberg et al., 2017).
12
CO2 enhancement and climate change, as well as chemical effects may change population size, population growth rates and also cause seasonal variations in organisms (Doney et al., 2012; Mostofa et al., 2015; Matear and Lenton, 2018).
Animal
Higher temperatures, rainfall, and CO2 boost the productivity of
Birds migrate and arrive at their nesting grounds earlier. Also, they
pastures (Oyhantçabal et al., 2010).
lay eggs earlier in the year than usual (IPCC, 2008a; Biasin, 2015;
Lesser thermal regulation requirement and lower average winter
Taddeo, 2017). Moreover, mammals’ hibernation is shorter (Taddeo,
weight losses are possible consequences (Oyhantçabal et al.,
2017).
2010).
Enhancement of global temperatures affects the distribution of animals through shifting many species closer to the poles (Taddeo, 2017).
Impairment of animal body immune system due to the proliferation of disease producing microbes in favorable higher temperature and higher humidity and also ecological shifts of pests (insects and mites) (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Digestibility reduction of enhanced plant tissues lignificataion owing to high temperatures (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Reduction of pastoral farming, livestock productivity and fertility as a result of increased heat, disease, and weather extremes (Beitz, 1985;
13
Karl et al., 2009; Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Significant losses of animals as a result of scarcity of fodder and water in recurrent droughts (Oyhantçabal et al., 2010; Padodara and Jacob, 2013).
Human Health
Warming is likely to reduce the risk of death related to severe
cold weather (Karl et al., 2009).
Limited growth, tissue repair and turnover together with the impairment of muscle function and immune system, as well as wasting, stunting, intrauterine growth restriction, and low birth weight are the impacts of insufficient protein intake with plant-based diets (Castaneda et al., 1995; Black et al., 2008; Medek et al., 2017).
In general, protein deficiency coexists with energy and micro nutrient deficiencies, which resulting in disability-adjusted life years (DALYs) or death (Millward and Jackson, 2004; Black et al., 2008; Medek et al., 2017).
High staple food prices as a result of minimum maintenance requirements is likely to make it more challenging for families’ income to meet food security (Wheeler and von Braun, 2013).
Air quality standard is already being adversely affected by the rising temperature (Karl et al., 2009).
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2
2.3. An Overview of Advanced GHG Reduction Technologies
3
Greenhouse gas emissions from fossil fuel combustion can be decreased through (i) reducing
4
fossil fuel consumption by finding alternatives for fossil fuels and generating less electricity,
5
which is mightily challenging; (ii) improving the performance of coal-fired plants; (iii) carbon
6
capture and storage (CCS); and (iv) enhancing CO2 partial pressure in exhaust gas, which can
7
improve power efficiency in the previous step (Plaza et al., 2007; Ben-Mansour et al., 2016).
8 9
CCS is the most widely applied technique for the capture of CO2 from gas stream, and as Herzog et al. (Herzog et al., 2009) have recommended, it can make continuous application of
10
fossil fuels and reduction of emissions related to fossil fuel combustion possible; besides, it
11
would provide enough time for finding a suitable source instead of fossil fuels.
12
Intergovernmental Panel on Climate Change (IPCC) has also suggested CCS as a promising
13
technology for controlling the development of the atmospheric CO2 concentration and it is
14
obvious that industries should be considered as a prime target (IPCC, 2005; Sanz-Pérez et al.,
15
2016). CCS is a riskless and effective climate mitigation tool, which has a special role in some
16
rising economies, essentially because developing countries are significant carbon dioxide
17
emitters controlling vast fossil fuel reserves; following such policies practically guarantees the
18
reduction of CO2 emission in the future and in spite of recent difficulties, critical advance has
19
been made over the previous decade (CCS, 2015).
20
2.3.1. Carbon dioxide Capture Methods
21
CO2 capture, the most demanding step of the CCS process, makes up the majority of the total
22
costs, i.e. 70-80% (Benedetti et al., 2019). Thus, identifying a capture procedure suitable for this
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purpose with minimal energy penalty is a major issue. As indicated, carbon capture in fossil fuel
24
combustion process can be classified as (i) pre-combustion capture, (ii) oxy-fuel combustion,
25
(iii) post-combustion capture (Brunetti et al., 2010), and (iv) capture from industrial process
26
streams (IPCC, 2005). The general scheme of the different CO2 capture routes is shown in Fig. 5.
27
CO2 capture from industrial streams could be performed using techniques prevalent in the
28
other three routes (IPCC, 2005). Excessive prices, limited technical knowledge about its proper
29
performance, lack of a single concise process for total operational efficiency and the absence of a
30
development plan for industrial applications are among the major challenges facing pre-
31
combustion capture. Large energy requirement for providing pure oxygen and the absence of a
32
complete preparation method for this technology without trying it on a commercial scale are the
33
drawbacks of oxy-fuel combustion capture. Further, the necessity of energy for the compaction
34
of captured carbon dioxide, the need to deal with high gas volumes owing to the fact that the
35
concentration of CO2 and its partial pressure in flue gas are low, as well as the huge energy
36
supplies required for sorbent regeneration are the major difficulties in post-combustion capture
37
methods (Figueroa et al., 2008; Mondal et al., 2012; Ben-Mansour et al., 2016; Mukherjee et al.,
38
2019).
39
Among these technologies, the post-combustion carbon capture is advantageous because:
40
(a) It is less difficult to combine into a present plant without radical changes in them.
41
(b) It is more appropriate for gas plants than the other methods;
42
(c) It is adaptable as its repair does not discontinue the power plant’s procedure and it can
43
be regulated or managed easily (Ben-Mansour et al., 2016; Mukherjee et al., 2019);
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(d) It needs shorter time for creation; and
45
(e) It produces high purity CO2 (>99 %) at high CO2 capture ratio (90%) (Najmi, 2015).
46
Fig. 5 General scheme of the different CO2 capture routes. Modified from reference (IPCC, 2005). 47 48
Absorption, membrane, cryogenic, micro-algal bio-fixation, and adsorption are common post-
49
combustion separation technologies proposed in Fig. 6 and compared in Table 2. Of the
50
aforementioned technologies, adsorption with low investment and operational cost, as well as its
51
simple application over a wide variety of operating temperatures and pressures may be
52
considered as practical solutions. Adsorption using selective sorbents can produce high purity
53
CO2 streams with minimal pressure drop compared to other technologies while using low energy
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without generating pollution or by-products. On the other hand, adsorption efficiency is
55
contingent on the development of easily regenerative adsorbent with high CO2 adsorption
56
capacity and selectivity (Upendar et al., 2014; Chaiw et al., 2016; Hong et al., 2016; Vilella et
57
al., 2017; Yang et al., 2017; Peredo-Mancilla et al., 2018; Yue et al., 2018; Han et al., 2019).
58
Fig. 6 Classification of methods used to remove CO2 in post-combustion processes. Modified from reference (Ben-Mansour et al., 2016), with permission from Elsevier, license number: 4731710456675.
18
Table 2. Advantages and disadvantages of CO2 reduction technologies in post-combustion process Technology
Advantages
Type Absorption
Disadvantages
High development in its process (Leung et al., 2014).
Environmental impacts due to solvent degradation (Mukherjee et al., 2019).
High absorption proficiency (Leung et al., 2014).
Solvents’ corrosiveness (chemical absorption) (Yoro and Sekoai, 2016).
High thermal energy requirement due to solvent regeneration (Yoro and Sekoai, 2016).
Micro-Algal
bio fixation
Applicability in various CO2 concentrations (Zhang,
High capital and operational costs (Kenarsari et al., 2013).
Micro-algal growth sensitivity to local climatic conditions and gas stream
2015).
Revenue generation by high value commercial
impurities (Klinthong et al., 2015; Seth and Wangikar, 2015).
products (Zhang, 2015; Ben-Mansour et al., 2016).
Membrane
High separation proficiency (Leung et al., 2014)
Environmentally friendly (Kenarsari et al., 2013)
Low capital and operational costs (Kenarsari et al.,
High energy requirement due to blending during growth period (Seth and Wangikar, 2015).
Low volumetric productivity (Seth and Wangikar, 2015).
Low rate of CO2 fixation (Ho et al., 2011)
Additional energy requirement for differential pressure across the membrane (Yoro and Sekoai, 2016).
Plug of membranes by gas stream impurities (Leung et al., 2014; Yoro and Sekoai, 2016).
2013)
Low thermal stability (Yoro and Sekoai, 2016).
Reduction in CO2 permeation at low concentrations (< 20%) (Mondal et al., 2012).
Cryogenic
limited economy of scale (Li et al., 2013)
Several steps requirement (Mondal et al., 2012; Li et al., 2013)
Applicability without chemical absorbent (Mondal et
Applicability in high CO2 concentration > 90% v/v (Leung et al., 2014).
al., 2012)
Limitation on the operating temperature (Leung et al., 2014; Yoro and Sekoai, 2016).
Atmospheric pressure operation (Mondal et al., 2012)
19
Direct production of liquid CO2 (Mondal et al., 2012)
High energy requirement for the refrigeration (Mondal et al., 2012; Kenarsari et al., 2013)
Significant energy penalty (Leung et al., 2014; Yoro and Sekoai, 2016)
Process disruption due to gas stream impurities (Mondal et al., 2012; Kenarsari et al., 2013)
Adsorption
High capital cost (Kenarsari et al., 2013)
High adsorption proficiency (Kenarsari et al., 2013)
Low selectivity without surface modification (Kenarsari et al., 2013)
CO2 adsorption at low partial pressures (Li et al., 2013)
Loss of sorption capacity over multiple cycles (Kenarsari et al., 2013)
Cost-effectiveness (Yoro and Sekoai, 2016).
Minimum energy requirements for the regeneration (Yoro and Sekoai, 2016).
Reversibility of the process and recyclability of the adsorbent (Leung et al., 2014)
High efficiency in long-term use (Mukherjee et al., 2019).
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Tuning the sorbent structure is a feasible approach for the enhancement of CO2 adsorption
62
capacity, which is amended by a complex and difficult step of sorbent selection (Lee and Park,
63
2015). The sorbent materials should meet vital requirements to be both economical and
64
operational in the process of capturing CO2. These criteria are as follows:
65
Regeneration facility of sorbent over many cycles;
66
High CO2 adsorption capacity;
67
Good selectivity toward CO2;
68
Fast adsorption/desorption kinetics;
69
Mechanical strength of sorbent particles;
70
Chemical stability/tolerance against impurities and moisture; and
71
Cost/ease of adsorbent synthesis (Samanta et al., 2012; Sevilla et al., 2012; Sehaqui et al., 2015; Álvarez-Gutiérrez et al., 2017a; Chomiak et al., 2017).
72 73
Amongst diverse adsorbents, the outstanding characteristics of porous carbon materials,
74
including controllable textural properties (surface area and pore structure), superb chemical,
75
thermal and mechanical stability, hydrophobicity, comprehensive availability of resources,
76
excellent environmentally benignity, swift adsorption kinetic and favorable cooperativeness to
77
surface functionalization as well as heterogeneous doping, motivate researchers to closely
78
scrutinize CO2 capture applications (Bae and Su, 2013; Heo and Park, 2015; Chen et al., 2016;
79
Liang et al., 2016; Tian et al., 2016; Peredo-Mancilla et al., 2018). Activated carbons (AC), a
80
processed form of carbons, which is extremely porous, comprises reciprocally connected cavities
81
between graphitic-like layers, which culminate in a high internal surface area (Dobele et al.,
82
2012). 21
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It is well known that chemical and physical activation processes can increase the specific
84
surface area substantially and introduce developed porous structures. In the chemical activation
85
process, first, the raw materials are impregnated by employing the dehydrating agent (i.e., KOH,
86
NaOH, K2CO3, C2K2O4, H3PO4, and ZnCl2), which affects the pyrolytic decomposition of the
87
starting materials. Second, the thermal treatment of impregnated materials and the resultant tars
88
indicated that the thermal treatment has a determining impact on carbonization process, which
89
enhances carbon yield and introduces porosity. After removing the applied chemicals by
90
washing, the formed porosity would be accessible. Producing wastewater and other negative
91
environmental impacts, complexity, and high cost are the specific disadvantages of chemical
92
activation. Carbon can also be physically activated through two steps: at first, the high
93
temperature pyrolysis (carbonization) of carbonaceous material occurs, in which inert
94
atmosphere is used for removing a great part of the hydrogen and oxygen content, then the
95
activation is performed at a high temperature in presence of oxidizing gases. Using steam, CO2
96
gas, water vapor or air, the carbon atoms would be extracted from the structure of the porous
97
carbon. However, physical activation is not so costly and is rather more ecofriendly than
98
chemical activation. Furthermore, an integration of these two activation processes is another
99
technique to prepare AC (Arami-Niya et al., 2010; Heo and Park, 2015; Yahya et al., 2015).
100
For the success of CO2 capture, how a proper biomass precursor is selected for the preparation
101
of carbons is of crucial importance. Actually, any carbonaceous material could be used as a
102
precursor for the production of activated carbon only if it has a high proportion of carbon in
103
addition to a low ash content, and is preferably available, cheap and renewable (Peredo-Mancilla
104
et al., 2018).
105 22
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106
3. Lignocellulose-based Adsorbents for CO2 Capture
107
Lignocellulosic biomasses, the most abundant non-edible biomasses, such as wood and
108
agricultural/forestry wastes are based on cellulose, hemicellulose, lignin, and a minor amount of
109
extractives (Dotan, 2014; Wang et al., 2017c). Converting lignocellulosic biomass into
110
functional materials, like carbon based CO2 adsorbents, is one promising approach not only to
111
recover this biomass waste but also to cut down the growing amounts of waste being landfilled
112
and their consequent environmental pollution (water, soil, air) (Wang et al., 2014). The
113
production of AC from agricultural waste residuals has received growing attention, aimed at not
114
only supplying a possible remedy for reusing these materials but also decreasing the cost of
115
production of commercial ACs in comparison to traditional precursors such as coal. Waste
116
recycling and reuse are two energy-efficient processes that have become more prevalent because
117
of their environmentally benignity and cost-reduction advantages (Nasri et al., 2014; Erto et al.,
118
2016; Suhas et al., 2016). Fig. 7 shows different categories of used lignocellulosic materials as
119
the precursor of ACs for CO2 capture. In addition, a brief summary of the application of
120
lignocellulose-based adsorbents for the CO2 capture and separation from gas stream is shown in
121
Table 3 and discussed in the following section.
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Fig. 7 A summary of the lignocellulose-based adsorbents for CO2 capture 122
24
Table 3. A detailed review of preparation conditions and characteristics of lignocellulose-based adsorbents for CO2 capture (year 2008-2020)
NO.
Precursor
1
Wood
2
Bamboo
3
Almond Shell
Activation/ Modification Process
H3PO4 Treatment + NH3 Treatment H3PO4 Treatment NH3 Activation CO2 Activation + PEIa Impregnation CO2 Activation ZnCl2 Activation + CO2 Activation ZnCl2 Activation
4
Olive Stone
5
Almond Shell
6
Soybean
7
Rice Husk
8
Sugarcane Bagasse
ZnCl2 Activation
9
Nano-fibrillated Cellulose
Freeze-drying + AEPDMSb Impregnation
10 11
Almond Shell Olive Stone
12
Wood
13
Sawdust
14
Palm Shell
15
Corncob
16
Corncob
17
Coconut Shell
18 19
Coconut Shell Sugarcane Bagasse
Carbonization Temp./Time (Heating ramp rate)
Activation Temp./Time (Heating ramp rate)
SBET
Smicro
D
Vmicro
Vnarrow
Vmeso
Vtot
Pressure
Temp.
CO2 Uptake
Qst
KH
Refs.
℃h
℃h
(℃ min)
(℃ min)
m2 g
m2 g
nm
cm3 g
cm3 g
cm3 g
cm3 g
bar
°C
mmol g
kJ mol
mmol g. bar
Commercial
800/2
1190
n/am
2.79
n/a
0.22
0.35
0.83
1
25
1.92
‒
‒
(Pevida et al., 2008)
1567
n/a
n/a
n/a
n/a
n/a
n/a
37
2
36.00
‒
‒
(Wang et al., 2008)
600/0.5 (15)
800/3 (15)
653× 10‒4
510
n/a
n/a
0.19
n/a
0.28
n/a
25
2.22
‒
‒
(Plaza et al., 2009b)
‒
900
1179
n/a
0.8
0.43
0.43
0.09
0.61
1
25
2.52
‒
‒
(Plaza et al., 2009a)
600
700
1090
n/a
1.2
0.42
0.12
n/a
0.50
1
25
2.68
‒
‒
(Plaza et al., 2010)
600/2 (1)
600/2.5 (1)
811
n/a
n/a
n/a
n/a
n/a
n/a
‒
120
0.52
‒
‒
(Thote et al., 2010)
500/1 (10)
927
n/a
0.80
n/a
n/a
n/a
0.56
n/a
30
1.30
‒
‒
(Boonpoke et al., 2011)
500/1 (10)
923
n/a
0.80
n/a
n/a
n/a
0.53
n/a
30
1.74
‒
‒
(Boonpoke et al., 2011)
500/4
(Gebald et al., 2011)
‒
‒
n/a
7.1
n/a
n/a
n/a
n/a
n/a
1
25
1.39
‒
‒
600 600
800 800
588 909
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
1 1
30 30
2.15 2.46
26.0 25.0
‒ ‒
(Plaza et al., 2011a) (Plaza et al., 2011a)
Commercial
800/2
1361
n/a
n/a
n/a
n/a
n/a
n/a
1
30
1.56
‒
‒
(Plaza et al., 2011b)
KOH Activation
250/2
600/1 (3)
1260
1360
0.8
0.61
0.52
n/a
0.62
1
25
4.8
20.0
9.02
(Sevilla and Fuertes, 2011)
NH3 Activation
‒
800/2.1 (10)
826
n/a
n/a
0.39
n/a
n/a
0.42
1
30
1.67
‒
‒
450/2
800/2
1425
1245
1.71
0.62
‒
‒
1.1
1
25
1.04
17.65
‒
1065
143
4.01
0.1
‒
‒
1.0
1
25
1.02
24.62
‒
600/2 (10)
n/a
1922
n/a
0.68
n/a
n/a
n/a
1
25
1.67
‒
3.06
(Yang et al., 2011)
600/3 (10) 800/2 (10) 500/1 (10j)
n/a 483
1575 n/a
n/a 2.18
0.53 0.25
n/a n/a
n/a n/a
n/a 0.28
1 1
25 75
1.14 0.2
‒ ‒
1.56 ‒
(Yang et al., 2011) (Boonpoke et al., 2012)
NH3 Activation CO2 Activation H3PO4 Treatment + NH3 Activation
K2CO3 Activation H3PO4 Activation H3PO4 Treatment KOH Activation ZnCl2 Activation
500/2 600/3 (10)
25
(Shafeeyan et al., 2011) (Sun and Webley, 2011) (Sun and Webley, 2011)
20
Kraft Cellulose
21
Kraft Cellulose
22
Birch Wood Chips
23
Palm Shell
24
Palm Shell
+ PEIa Impregnation NaOH Activation H3PO4 Treatment + NaOH Activation H3PO4 Treatment+ NaOH Activation MEAc Impregnation AMPd Impregnation
400/3
600/1.5
2032
1020
1.51
0.77
n/a
n/a
0.89
1
25
0.3
‒
‒
(Dobele et al., 2012)
400/3
600/1.5
1758
1096
1.35
0.74
n/a
n/a
0.84
1
25
3.22
‒
‒
(Dobele et al., 2012)
450/5
650/1.5
2119
1377
1.22
0.84
n/a
n/a
0.92
1
25
3.63
‒
‒
(Dobele et al., 2012)
Commercial
65
36
n/a
n/a
n/a
n/a
n/a
1
25
1.11
‒
‒
(Khalil et al., 2012)
Commercial
102
88
n/a
n/a
n/a
n/a
n/a
1
25
0.77
‒
‒
(Khalil et al., 2012)
840
n/a
1.0
0.34
0.36
n/a
0.37
1
25
3.0
‒
‒
(Plaza et al., 2012)
1940
n/a
0.92
n/a
0.47
n/a
0.82
1
25
4.5
25.0
8.26
(Sevilla et al., 2012)
1600
1551
0.84
0.66
n/a
n/a
0.72
1n
25
3.4
‒
‒
(Wang et al., 2012a)
3404
585
2.2
n/a
n/a
n/a
1.88
1
25
4.36
‒
6.64
2000
n/a
n/a
n/a
n/a
n/a
0.8
1
25
4.5
‒
9.24
(Wang et al., 2012b) (Wei et al., 2012)
1060
n/a
2.49
0.44
n/a
n/a
0.52
1
25
4.24
‒
‒
(Xing et al., 2012)
25
Coffee Waste
KOH Activation
400
600/1 (5j)
26
Algae + Glucose
KOH Activation
200/24
700
27
Fungi
KOH Activation
28
Celtuce leaves
KOH Activation
29
Bamboo
KOH Activation
30
Bean Dreg
KOH Activation
500/2 (2j) 600 500/1.5 (5j) 400/1
700/1 (3j) 800/1 600/1.5 (10j) 700/1 (5)
31
Enteromorpha Prolifera
KOH Activation
180/24
600/4 (2)
418
358
n/a
0.21
n/a
n/a
0.37
1
25
1.39
‒
‒
(Zhang et al., 2012)
32
Sewage Sludge
NaOH Activation
800 (10)
700/1 (5)
178
46
52
0.008
n/a
0.18
0.25
n/a
25
1.27
‒
‒
(de Andres et al., 2013)
33
Macadamia Nut Shell
CO2 Activation
600/1
900/0.5
512
n/a
n/a
n/a
n/a
n/a
0.17
1
25
3.37
‒
‒
(Bae and Su, 2013)
34
African Palm Shell
KOH Activation
600/1
850/1 (10)
1250
n/a
0.92
0.55
n/a
0.06
0.61
1
25
4.4
‒
11.05
(Ello et al., 2013b)
35
Coconut Shell
CO2 Activation
800/3.5
1327
n/a
0.83
0.55
n/a
0.10
0.65
1
25
3.9
‒
8.26
36
Olive Stone
CO2 Activation
800/6 (10)
1215
n/a
1.28
0.48
n/a
n/a
0.51
1
25
3.1
33.0
8.42
37
Almond Shell
CO2 Activation
750/4 (10)
38 39 40
Grass Cuttings Beer Waste Biosludge
41
Beer Waste
42
Palm Shell
CO2 Activation CO2 Activation CO2 Activation H3PO4 Activation Amination MgCl2 Impregnation CO2 Activation
43
Sawdust
44
Coconut Shell
862
n/a
0.75
0.33
n/a
n/a
0.36
1
25
2.7
33.0
12.07
Commercial Commercial Commercial
800/2 (10) 800/2 (10) 800/2 (10)
841 622 489
742 573 291
n/a n/a n/a
0.28 0.20 0.11
n/a n/a n/a
n/a n/a n/a
0.37 0.31 0.38
1 1 1
0 0 0
3.96 3.18 2.10
34.0 ‒ ‒
‒ ‒ ‒
(Ello et al., 2013a) (González et al., 2013) (González et al., 2013) (Hao et al., 2013) (Hao et al., 2013) (Hao et al., 2013)
Commercial
600/1 (10)
1073
238
n/a
0.10
n/a
n/a
0.97
0.1
0
0.80
‒
‒
(Hao et al., 2013)
30
n/a
n/a
n/a
n/a
n/a
0.03
1n
40-50
1.5
‒
‒
(Lee et al., 2013)
306
n/a
2.03
n/a
n/a
n/a
0.15
‒
80
5.45
‒
‒
(Liu et al., 2013)
370
295
1.63
0.11
n/a
n/a
0.15
1
25
1.79
‒
‒
(Rashidi et al., 2013; Rashidi et al.,
Commercial 600 900/0.75 (20)
‒
26
45 46 47 48
Coconut Fiber Rice Husk Palm Mesocarp Fibre Palm Kernel Shell
49
African Palm shell
50
African palm stone
51 52 53 54
Cotton Stalk Cotton Stalk Broom Corn Stalk Sugarcane Bagasse
CO2 Activation CO2 Activation
900/1 (10) 900/ 0.5 (5)
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
n/a n/a
1 1
25 25
1.36 0.98
‒ ‒
‒ ‒
2014b) (Rashidi et al., 2013) (Rashidi et al., 2013)
CO2 Activation
800/1 (20)
n/a
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.17
‒
‒
(Rashidi et al., 2013)
CO2 Activation
800/1.5 (10)
n/a
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.28
‒
‒
(Rashidi et al., 2013)
450/2 (1j)
785
n/a
n/a
n/a
0.31
0.13
0.41
1
0
5.0
‒
‒
(Vargas et al., 2013)
500/2 (1j)
587
n/a
n/a
n/a
0.34
0.02
0.26
1
0
4.54
‒
‒
(Vargas et al., 2013) (Xiong et al., 2013) (Xiong et al., 2013) (Banisheykholeslami et al., 2015) (Creamer et al., 2014) (Creamer et al., 2014) (David and Kopac, 2014)
H3PO4 Activation + NH4OH Treatment ZnCl2 Activation + NH4OH Treatment CO2 Activation NH3 Activation ZnCl2 Activation
800 900
800 900
n/a n/a
610 434
n/a n/a
0.24 0.19
n/a n/a
n/a n/a
n/a n/a
1 1
20 20
2.30 1.81
‒ ‒
‒ ‒
300/0.33
800/1 (20)
1121
n/a
2.02
0.22
n/a
n/a
0.56
40
25
17.0
56.0
‒
Pyrolysis
600
‒
388
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.7
26.62
‒
55
Hickory Wood
Pyrolysis
600
‒
401
n/a
n/a
n/a
n/a
n/a
n/a
1
25
1.4
18.06
‒
56
Oil cake + Walnut
CO2 Activation
750/1 (5)
750/3
1080
n/a
1.90
n/a
n/a
n/a
0.46
1
25
34p
‒
‒
750/1 (5)
800/2
1207
n/a
1.90
n/a
n/a
n/a
0.53
1
25
30p
‒
‒
500/1.5
700/1.5
1486
n/a
n/a
n/a
n/a
n/a
0.64
1
25
5.0
53.4
23.72
(Deng et al., 2014)
‒
‒
n/a
7.5
n/a
n/a
n/a
n/a
n/a
4×10‒4
23
1.1
‒
‒
(Gebald et al., 2014)
450/1 (4)
900/1 (5)
2595
n/a
1.96
1.23
n/a
0.039
1.27
1
30
4.10
‒
‒
(Heidari et al., 2014b)
450/1 (4)
800/2 (10)
2079
n/a
1.21
1.16
n/a
0.127
1.29
1
30
3.22
16.7
‒
(Heidari et al., 2014a)
800 (10)
167
n/a
21.4
0.08
n/a
n/a
0.08
1
30
1.66
‒
‒
(Nasri et al., 2014)
n/a
557
n/a
n/a
0.21
n/a
n/a
1
25
2.11
32.2
22.45
(Plaza et al., 2014a)
n/a
697
n/a
n/a
0.27
n/a
n/a
1
25
2.02
31.5
10.67
57 58 59
Rapeseed Oil cake + Walnut Pine Nut Shell Nano-fibrillated Cellulose
60
Eucalyptus
61
Eucalyptus
62
Palm Kernel Shell
CO2 activation + NH3 treatment KOH Activation APDESe Impregnation H3PO4 Treatment + KOH Activation H3PO4 Treatment + NH3 Activation CO2 Activation
700/2 (10)
63
Almond Shell
O2 Activation
‒
64
Olive Stone
O2 Activation
‒
650/1.38 (15) 650/1.83 (15)
65
Coconut Shell
CO2 Activation
66 67
Poplar Anthers Sawdust
KOH Activation KOH Activation
500/1 250/2
68
Gelatin + Starch
KOH Activation
450 (10)
69
Cherry Stone
Steam Activation
70
Cherry Stone
CO2 Activation
Olive Stone
Water Vapor Activation
71
900/0.75 (20)
550 (5)
370
n/a
1.63
0.11
n/a
n/a
0.15
1
25
1.70
‒
9.84
3322 1643
n/a n/a
n/a n/a
0.89 0.62
n/a n/a
n/a n/a
2.31 0.85
1 1
25 25
2.04 4.72
‒ ‒
2.52 8.38
1636
n/a
1.94
n/a
n/a
n/a
0.51
1
25
3.84
62.9
8.02
850 (15)
998
847
0.89
0.38
0.33
n/a
0.53
1
25
2.41
‒
‒
885 (15)
1045
848
0.93
0.40
0.35
n/a
0.48
1
25
2.62
‒
‒
910
n/a
n/a
0.33
0.09
n/a
0.63
0.3
30
0.8
22.5
‒
800/2 700/1 (5) 700/0.17 (10)
800/1 (5)
27
(David and Kopac, 2014)
(Plaza et al., 2014a; Plaza et al., 2014b) (Rashidi et al., 2014a) (Song et al., 2014) (Zhu et al., 2014) (Alabadi et al., 2015) (Álvarez-Gutiérrez et al., 2015) (Álvarez-Gutiérrez et al., 2015) (Balsamo et al., 2015)
72
Apricot Stone
Water Vapor Activation
550 (5)
800/1 (5)
830
n/a
n/a
0.36
0.04
n/a
0.50
0.3
30
1.18
23.5
‒
(Balsamo et al., 2015)
73
Peach Stone
Water Vapor Activation
550 (5)
800/1 (5)
820
n/a
n/a
0.27
0.08
n/a
0.41
0.3
30
1.08
18.0
‒
(Balsamo et al., 2015)
74
Peanut Shell
KOH Activation
500 (1.5)
700/1.5 (5j)
956
n/a
n/a
n/a
n/a
n/a
0.43
1
25
4.02
60.0
15.44
(Deng et al., 2015)
1790
n/a
n/a
n/a
n/a
n/a
0.77
1
25
4.64
38.5
11.68
(Deng et al., 2015)
75
Sunflower Seed
KOH Activation
500 (1.5)
700/1.5 (5j)
76
Yellow Mombin Stone
HNO3 Activation
500/2 (10)
500/2 (10)
392
332
n/a
n/a
n/a
n/a
0.15
1
40
3.4q
1.28
‒
(Fiuza et al., 2015)
Yellow Mombin Stone Yellow Mombin Stone Yellow Mombin Stone
H3PO4 Activation
500/2 (10)
500/2 (10)
510
309
n/a
n/a
n/a
n/a
0.32
1
40
2.3q
0.55
‒
(Fiuza et al., 2015)
KOH Activation
500/2 (10)
500/2 (10)
246
274
n/a
n/a
n/a
n/a
0.12
1
40
6.3q
2.51
‒
(Fiuza et al., 2015)
1.58
‒
(Fiuza et al., 2015)
77 78 79
CO2 Activation
83 84
Mango Seed Shell Rice Husk Peanut Shell
Steam Activation Microwave Pyrolysis H3PO4 treatment KOH Activation KOH Activation
85
Molasses
80 81 82
86 87
Cellulose Fiber Rice Straw
Empty Fruit Bunch from Oil Palm Coffee Waste
88
Nano-fibrillated Cellulose
89
Waste Tobacco
90 91 92
By-product of Fast Pyrolysis of White Wood By-product of Fast Pyrolysis of White Wood By-product of Fast Pyrolysis of White Wood
500/2 (10)
500/2 (10)
278
235
n/a
n/a
n/a
n/a
0.17
1
40
4.5q
800/0.5
800/1
863
n/a
n/a
0.33
n/a
0.007
0.34
1
25
3.77
37.8
11.01
(Heo and Park, 2015)
200 W/ 0.33
‒
122
112
5.0
0.02
n/a
n/a
0.08
1
25
1.62
‒
‒
(Huang et al., 2015)
2503
n/a
n/a
0.06
n/a
n/a
2.35
1
25
1.24
‒
‒
400/2
(Munusamy et al., 2015) (Li et al., 2015b) (Li et al., 2015a) (Młodzik et al., 2015; J. Młodzik, 2016)
‒ ‒
710/1 (10) 780/1.5 (5)
1041 1871
n/a n/a
n/a n/a
0.42 0.80
0. 15 0.11
n/a 0.02
0.53 0.82
1 1
25 0
4.16 6.79
‒ ‒
‒ ‒
KOH Activation
‒
750/1 (10j)
1985
n/a
n/a
0.71
n/a
n/a
0.94
1
40
2.54
‒
‒
KOH Activation
250/0.33
800/0.5 (2)
2510
n/a
1.13
0.55
n/a
n/a
1.05
1
25
3.71
23.26
18.3
(Parshetti et al., 2015)
522
n/a
n/a
0.21
n/a
n/a
0.21
1
25
2.73
46.48
14.13
(Plaza et al., 2015)
CO2 Activation PEIa Impregnation + Freeze-drying Melamine Modification
‒ ‒
‒
8.3
n/a
n/a
n/a
n/a
n/a
n/a
n/a
25
2.22
‒
‒
(Sehaqui et al., 2015)
700/1 (1j)
‒
1104
826
n/a
n/a
n/a
n/a
0.37
1
25
2.72
28.6
17.23
(Sha et al., 2015)
Steam Activation
500/1k
700/1.4 (3)
840
n/a
n/a
n/a
0.2
0.19
0.55
‒
25
1.34
‒
‒
(Shahkarami et al., 2015a)
CO2 Activation
500/1k
890/1.6 (3)
820
n/a
n/a
n/a
0.17
0.13
0.45
‒
25
1.43
‒
‒
(Shahkarami et al., 2015a)
KOH Activation
500/1k
775/2 (3)
1400
n/a
n/a
n/a
0.40
0
0.62
‒
25
1.77
‒
‒
(Shahkarami et al., 2015a)
93
Sawdust
KOH Activation
500 (7)
775/2 (3)
1268
n/a
n/a
0.43
0.36
0
0.43
‒
25
1.77
‒
‒
94
Flax Straw
KOH Activation
500 (7)
775/2 (3)
1281
n/a
n/a
0.45
0.25
0
0.45
‒
25
1.64
‒
‒
95
Wheat Straw
KOH Activation
500 (7)
775/2 (3)
1212
n/a
n/a
0.40
0.24
0.04
0.44
‒
25
1.60
‒
‒
96
Willow Ring
KOH Activation
500 (7)
775/2 (3)
1563
n/a
n/a
0.57
0.31
0.03
0.62
‒
25
1.70
‒
‒
28
(Shahkarami et al., 2015b) (Shahkarami et al., 2015b) (Shahkarami et al., 2015b) (Shahkarami et al., 2015b)
97
Corn Stalk
CO2 Activation + HNO3 Treatment
98
Silk Fiber
KOH Activation
99
Coconut Shell
100
London Plane Leaves
101
Pili Nut Shell
102
Olive Stone
103
800/0.5
639
457
n/a
0.211
n/a
0.11
n/a
2n
25
1.68
‒
‒
(Song et al., 2015)
300/4 & 600/1
700/1
3000
n/a
n/a
n/a
n/a
n/a
1.38
1
25
4.8
‒
9.96
(Wang et al., 2015)
500/2 (5)
650/2 (5)
1483
n/a
n/a
0.66
0.61
n/a
0.66
1
25
4.26
42.5
10.22
(Yang et al., 2015)
600/1 (3)
700/1 (3)
1600
1550
n/a
0.54
n/a
n/a
0.65
1
25
4.43
28.5
12.34
(Zhu et al., 2015)
400/0.5
750/1
85
n/a
n/a
0.21
n/a
n/a
0.10
1
25
2.62
‒
12.60
(Yao et al., 2015)
CO2 Activation
800/2
800/7
1479
1667
n/a
0.59
0.34
0.08
0.73
1
25
3.05
‒
6.16
(Calvo-Muñoz et al., 2016)
Plywood
Water Vapor Activation + C4H6BaO4 Impregnation
800/2
800/2
708
805
n/a
0.28
0.72
0.16
0.45
1
25
1.98
‒
6.85
(Calvo-Muñoz et al., 2016)
104
Coffee Waste
K2CO3 Activation
800/1 (20)
700/1 (20)
189
n/a
n/a
0.07
n/a
0.02
0.09
2n
60
0.6
‒
‒
(Chaiw et al., 2016)
105
Coconut Shell
Urea Treatment + KOH Activation
500/2 (5)
650/1 (5)
1535
n/a
n/a
0.56
0.73
n/a
0.60
1
25
4.8
33.0
12.07
(Chen et al., 2016)
106
Jujun Grass
KOH Activation
250/2
700/1 (5)
3144
2753
n/a
1.23
n/a
n/a
1.56
1
25
4.1
‒
6.07
(Coromina et al., 2016)
107
Camellia Japonica
KOH Activation
250/2
700/1 (5)
1353
1283
n/a
0.56
n/a
n/a
0.67
1
25
5.0
‒
10.49
(Coromina et al., 2016)
108
Microcrystalline Cellulose
CO2 Activation
400/2 (1) & 800/3 (5)
850/4 (5)
753
n/a
0.9
0.27
n/a
n/a
0.43
1
25
3.34
‒
10.29
(Dassanayake et al., 2016)
109
Olive Stone
Water Vapor Activation
550 (5)
800/1 (5)
910
n/a
n/a
0.33
n/a
0.09
0.63
0.3
30
0.8
‒
‒
(Erto et al., 2016)
110
Apricot Stone
Water Vapor Activation
550 (5)
800/1 (5)
830
n/a
n/a
0.36
n/a
0.04
0.50
0.3
30
1.2
‒
‒
(Erto et al., 2016)
111
Peach Stone
Water Vapor Activation
550 (5)
800/1 (5)
820
n/a
n/a
0.27
n/a
0.08
0.41
0.3
30
1.1
‒
‒
(Erto et al., 2016)
112
Yellow Mombin Stone
KOH Activation
400/4 (3)
500 (3)
1384
1523
n/a
0.49
0.44
‒
0.62
1
25
7.3
27.5
12.38
(Fiuza-Jr et al., 2016)
113
Corncob particles
NH3 Activation
400 (5)
800/3 (5)
1154
n/a
n/a
n/a
n/a
n/a
0.57
1
25
2.81
55.1
20.76
(Geng et al., 2016)
Ammoxidation + KOH Activation KOH Activation NaOH Activation + HNO3 Modification
29
114
Wheat Flour
KOH Activation
900/2 (5)
Steam Activation + DEAf Impregnation Steam Activation + MEAc Impregnation
700/1 (5)
1438
n/a
n/a
0.58
0.38
n/a
0.65
1
25
3.48
28.1
7.54
(Hong et al., 2016)
Commercial
652
525
2.34
n/a
n/a
n/a
0.38
4
70
5.3
‒
‒
(Kongnoo et al., 2016)
Commercial
392
280
2.42
n/a
n/a
n/a
0.24
4
70
4.75
‒
‒
(Kongnoo et al., 2016)
115
Palm Shell
116
Palm Shell
117
Mesquite Biochar
KOH Activation
450/4
800/0.75 (25)
3167
n/a
n/a
n/a
n/a
n/a
1.65
30
25
26.0
21.0
‒
(Li et al., 2016c)
118
Pine Cone Shell
KOH Activation
500/2 (5)
650/1 (3)
3135
n/a
n/a
n/a
n/a
n/a
n/a
1
25
4.73
27.2
9.13
(Li et al., 2016b)
119
Popcorn
KOH Activation
400/1 (5)
800/1
867
794
n/a
0.37
n/a
n/a
0.40
1
25
4.60
24.3
16.40
(Liang et al., 2016)
‒
‒
n/a
n/a
n/a
n/a
n/a
n/a
n/a
2n
‒
5.01
‒
‒
(Luo et al., 2016)
850
‒
3.17
n/a
n/a
n/a
n/a
n/a
0.007
‒
30
1.01
‒
‒
‒
850
‒
182
n/a
n/a
n/a
n/a
n/a
0.003
‒
30
1.07
‒
‒
120
121 122
Sugarcane Bagasse Sawdust Biochar Sawdust Biochar
NaOH Treatment + Acrylamide Grafting + TETAg Impregnation MEAc Impregnation
(Madzaki et al., 2016) (Madzaki et al., 2016)
123
Walnut Shell
H3PO4 Treatment + KOH Activation
‒
700/1 (5)
2642
n/a
n/a
0.46
n/a
0.93
1.39
10
17
12.25
‒
‒
(Rashidi et al., 2016)
124
Chestnut Tannin
NH3 Activation
600/2 (5)
800/0.33 (20)
n/a
561
n/a
n/a
n/a
n/a
n/a
1
25
2.27
22.9
11.01
(Nelson et al., 2016)
125
Olive Stone
CO2 Activation
1248
1112
1.09
0.48
0.44
n/a
0.53
1
30
2.75
‒
‒
(Querejeta et al., 2016)
126
Potato Starch
KOH Activation
250/2
800/1 (3)
3000
n/a
n/a
1.09
n/a
0.32
1.41
1
25
2.8
‒
‒
(Sevilla et al., 2016)
127
Cellulose
KOH Activation
250/2
800/1 (3)
3100
n/a
n/a
1.05
n/a
0.41
1.46
1
25
2.8
21.0
‒
(Sevilla et al., 2016)
128
Eucalyptus Sawdust
Melamine + KOH Activation
250/2
800/1 (3)
3420
n/a
n/a
1.16
n/a
1.14
2.30
1
25
2.2
19.0
‒
(Sevilla et al., 2016)
129
White Wood
Steam Activation + MgO Impregnation
‒
700/1.4 (3)
615
n/a
n/a
0.14
0.12
0.33
0.49
0.24n
25
1.11
‒
‒
(Shahkarami et al., 2016)
130
Algae
Freeze-drying
‒
‒
416
117
n/a
n/a
n/a
n/a
0.38
1
25
2.03
‒
‒
(Tian et al., 2016)
131
Black Locust
KOH Activation
650/3 (2)
830/1.5 (3)
2511
2160
2.15
1.16
n/a
n/a
1.35
1
25
5.05
33.1
14.50
(Zhang et al., 2016)
132
Pinecone
KOH Activation
600/1 (3)
700/1 (3)
1680
1670
n/a
0.56
n/a
n/a
0.61
1
25
4.8
29.8
25.80
(Zhu et al., 2016)
800/6 (5)
30
847
n/a
n/a
n/a
0.28
n/a
n/a
1
25
2.75
25.72
9.73
(Álvarez-Gutiérrez et al., 2017b)
563
n/a
n/a
n/a
0.28
n/a
n/a
1
25
2.88
27.93
9.46
(Álvarez-Gutiérrez et al., 2017b)
1575
1535
ns/a
0.7
n/a
n/a
0.8
1
25
4.6
‒
8.67
(Balahmar et al., 2017)
1557
1294
n/a
0.53
n/a
n/a
0.75
1
25
4.6
‒
10.41
(Balahmar et al., 2017)
2349
1915
n/a
0.86
n/a
n/a
1.48
1
25
3.9
‒
6.85
(Balahmar et al., 2017)
600/1 (5)
1034
923
n/a
0.37
n/a
n/a
0.46
1
25
3.8
‒
‒
(Balahmar et al., 2017)
700/2 (0.5)
900/2 (5)
773
710
n/a
0.37
0.76
0.08
0.45
1
25
1.9
‒
‒
(Botomé et al., 2017)
CO2 Activation
700/2 (0.5)
900/4 (5)
949
856
n/a
0.44
0.20
0.13
0.58
1
25
1.7
‒
‒
(Botomé et al., 2017)
133
Almond Shell
CO2 Activation
134
Macadamia Nut Shell
CO2 Activation
135
Eucalyptus Sawdust
KOH Activation
136
Eucalyptus Sawdust
KOH Activation
137
Paeonia Lactiflora
KOH Activation
138
Sargassum fusiforme
KOH Activation
250/2
H3PO4 Treatment + CO2 Activation
139
140
Chromated Copper Arsenate-treated Wood Chromated Copper Arsenate-treated Wood
750/4 (10) 600/1
900/0.5 700/1 (5)
250/2
700/1 (5) 800/1 (5)
141
Walnut Shell
KOH Activation
520/2
800/1
2000
n/a
0.95
0.8
n/a
n/a
n/a
1
25
2.9
‒
‒
(Chomiak et al., 2017)
142
Camphor Leaves
KOH Activation
240/5 (5)
800/1 (3)
1633
1083
2.41
0.58
n/a
n/a
0.98
1
25
0.8
‒
‒
(Guangzhi et al., 2017)
143
Micro Algae
K2CO3 Activation
180/10
700/2 (5)
1396
1118
n/a
0.59
n/a
n/a
0.75
1
25
4.2
29.0
8.23
(Guo et al., 2017)
144
Micro Algae
K2CO3 Activation
180/10
800/4 (5)
1904
849
n/a
0.46
n/a
n/a
1.08
1
25
3.5
24.0
5.64
(Guo et al., 2017)
145
Chitosan Char
KOH Activation
550/0.5
600/1.5 (10)
728
n/a
n/a
0.31
0.12
n/a
0.33
1
25
4.17
39.0
27.79
(Li et al., 2017)
350/0.5
800/1 (10j)
1098
n/a
2.33
0.52
n/a
0.11
0.64
1
25
3.20
29.7
‒
(Mehrvarz et al., 2017)
350/0.5
800/1 (10j)
614
n/a
2.49
0.27
n/a
0.10
0.38
1
25
2.33
26.0
‒
(Mehrvarz et al., 2017)
KOH & H3PO4 Activation + TETAg Treatment KOH & H3PO4 Activation + Urea Treatment
146
Broom Sorghum Stalk
147
Broom Sorghum Stalk
148
Olive Stone
KOH Activation
300/1
850/3 (10)
n/a
1173
n/a
n/a
0.26
n/a
n/a
1
0
5.6
4.1
‒
149
Olive Stone
K2CO3 Activation
300/1
900/2 (5)
n/a
989
n/a
n/a
0.41
n/a
n/a
1
0
3.8
6.0
‒
150
Persian Ironwood
H3PO4 Treatment
‒
700
1904
n/a
n/a
0.81
n/a
0.77
1.58
1
30
5.05
18.0
‒
151
Persian Ironwood
KOH Activation
‒
800
1935
n/a
n/a
0.80
n/a
0.02
0.82
1
30
3.77
41.52
‒
152
Date Seed
CO2 Activation
800
900/1 (15)
723
678
n/a
0.26
n/a
n/a
n/a
n/a
20
3.2
‒
‒
31
(Moussa et al., 2017) (Moussa et al., 2017) (Nowrouzi et al., 2017) (Nowrouzi et al., 2017) (Ogungbenro et al., 2017)
153
Soya
NaOH Treatment
154
Palm Kernel Shell
CO2 Activation
155
Pomegranate Peels
156 157 158 159
1072
n/a
1.2
n/a
n/a
n/a
0.45
1
25
3.2
‒
‒
(Rana et al., 2017)
850/1 (5)
367
n/a
n/a
n/a
n/a
n/a
0.21
1
25
2.0
31.25
9.04
(Rashidi and Yusup, 2017)
KOH Activation
700/1
585
n/a
n/a
0.20
n/a
n/a
0.28
1
25
4.11
21.25
11.07
(Serafin et al., 2017)
Piptoporus Betulinus
KOH Activation
700/1
1267
n/a
n/a
0.40
n/a
n/a
0.45
1
25
3.5
‒
8.25
(Serafin et al., 2017)
Lioyd
KOH Activation
700/1
1346
n/a
n/a
0.46
n/a
n/a
0.57
1
25
3.25
‒
5.80
(Serafin et al., 2017)
KOH Activation
700/1
1699
n/a
n/a
0.48
n/a
n/a
0.80
1
25
2.0
‒
4.46
(Serafin et al., 2017)
KOH Activation
700/1
1111
n/a
n/a
0.33
n/a
n/a
0.55
1
25
2.5
‒
6.64
(Serafin et al., 2017)
Mistletoe Leaves Mistletoe Branches
300/3
1000/2 (5)
160
Kiwi Fruit Peel
KOH Activation
700/1
1381
n/a
n/a
0.49
n/a
n/a
0.62
1
25
2.75
‒
6.12
(Serafin et al., 2017)
161
Carrot Peel
KOH Activation
700/1
1379
n/a
n/a
0.51
n/a
n/a
0.58
1
25
4.18
‒
9.10
(Serafin et al., 2017)
162
Fern Leaves
KOH Activation
700/1
1593
n/a
n/a
0.54
n/a
n/a
0.74
1
25
4.12
‒
5.69
(Serafin et al., 2017)
163
Sugar Beet Pulp
KOH Activation
700/1
1263
n/a
n/a
0.41
n/a
n/a
0.62
1
25
2.80
‒
6.65
(Serafin et al., 2017)
164
Arundo Donax
KOH Activation
600/2
1122
n/a
0.56
0.5
n/a
n/a
0.59
1
25
3.6
31.0
‒
(Singh et al., 2017b)
165
Arundo Donax
500/2 (10)
1863
33
2.1
n/a
n/a
n/a
1.00
1
25
2.1
32.2
‒
(Singh et al., 2017a)
166
Arundo Donax
167
Coconut Shell
Chitosan + ZnCl2 Activation ZnCl2 Activation
500 (10)
3298
4
n/a
0
n/a
100
1.9
30
25
24.2
21.8
‒
(Singh et al., 2017c)
CO2 Activation
900/2.33 (10j)
1452
n/a
n/a
0.60
n/a
n/a
0.65
1
20
2.43
‒
‒
(Vilella et al., 2017)
168
Babassu Coconut
CO2 Activation
(10j)
809
n/a
n/a
0.32
n/a
n/a
0.39
1
20
2.20
‒
‒
(Vilella et al., 2017)
169
Pine Wood Pellet
CO2 Activation
561
n/a
n/a
0.22
0.31
n/a
0.1
10
30
4
28.4
‒
(Vivo-Vilches et al., 2017)
170
Stalks of Rice and Wheat Ash
TEPAh Impregnation
‒
‒
0.54
n/a
4.02
n/a
n/a
n/a
0.73×10‒3
138k
60
2.02
‒
‒
(Wang et al., 2017b)
171
Longan Shell
KOH Activation + Carbamide Modification
500/2 (5)
800/2 (5)
3260
2670
4.2
1.3×106
n/a
n/a
2.6×106
1
25
4.3
55.0
4.20
(Wei et al., 2017)
172
Coconut Shell
KOH Activation
500/2 (5)
600/1 (5)
1172
n/a
n/a
0.43
0.58
n/a
0.44
1
25
4.23
37.0
13.72
(Yang et al., 2017)
173
Rotten Strawberries
KOH Activation
180/12
650
1117
n/a
n/a
0.39
0.63
n/a
0.52
1
25
4.49
41.0
12.85
(Yue et al., 2017)
174
Argan Fruit Shell
KOH Activation
700/1 (10)
850/1 (5)
1889
1581
n/a
0.8
0.15
0.07
0.87
1
25
5.63
‒
11.75
(Boujibar et al., 2018)
175
Argan Fruit Shell
NaOH Activation
700/1 (10)
850/1 (5)
1826
1428
n/a
0.73
0.10
0.23
0.96
1
25
3.73
‒
6.71
(Boujibar et al., 2018)
900/2.33
900/5 (10)
32
Mg(NO3)2.6H2O Impregnation KOH Activation Ammoxidation + KOH Activation H3PO4 Activation + Cu(NO3)2:3H2O Impregnation H3PO4 Activation
176
Walnut Shell
177
Fir Bark
178
Coffee Grounds
179
Persian Ironwood
180
Olive Stone
181
Olive Stone
CO2 Activation
600/1 (5)
182
Olive Stone
H2O Activation
183
Vine Shoots
184
Vine Shoots
185
Walnut Shell
186
Walnut Shell
187
Arundo Donax
188
Arundo Donax
189
Water Chestnut
190
Lotus Stem
191
(Lahijani et al., 2018) (Luo et al., 2018)
900/1.5
500/0.25
292
n/a
n/a
0.11
n/a
n/a
0.15
1n
25
1.86
‒
‒
450/1 (5)
700/2 (3) 400/1 + 600/1
1377
n/a
n/a
0.51
0.07
0.12
0.74
1
25
5.2
22.47
30.15
990
n/a
n/a
0.45
n/a
n/a
0.55
-
35
2.67
49.9
‒
(Liu and Huang, 2018)
500
1954
n/a
n/a
1.60
n/a
0.02
1.63
1
30
6.78
‒
‒
(Nowrouzi et al., 2018)
170/0.5 (5j)
1178
n/a
n/a
0.45
n/a
0.04
0.49
32
30
10.87
‒
‒
(Peredo-Mancilla et al., 2018)
600/1 (5j)
757
n/a
n/a
0.3
n/a
0.02
0.32
32
30
5.87
‒
‒
(Peredo-Mancilla et al., 2018)
600/1 (5)
600/1 (5j)
754
n/a
n/a
0.28
n/a
0.3
0.58
32
30
7.96
8.5
‒
(Peredo-Mancilla et al., 2018)
CO2 Activation
600/1 (5)
800/3 (10)
767
526
n/a
0.24
0.10
0.04
0.37
1
25
3.00
27.5
13.63
(Manyà et al., 2018)
KOH Activation
600/1 (5)
700/1 (10)
1439
861
n/a
0.49
0.13
0.02
0.67
1
25
4.00
25.8
9.94
(Manyà et al., 2018)
600/1 (5)
600/2 (7.5)
1315
1121
1.99
0.48
n/a
n/a
0.65
1
25
7.42
7.0
‒
(Rouzitalab et al., 2018)
600/1 (5)
750/1.5 (7.5)
4230
611
2.30
0.24
n/a
n/a
2.43
10
25
14.03
4.0
‒
(Rouzitalab et al., 2018)
600 (3)
982
n/a
n/a
n/a
n/a
n/a
0.62
1
25
2.2
39.0
‒
(Singh et al., 2018b)
600/2
2232
n/a
n/a
n/a
n/a
n/a
1.01
1
25
3.2
15.4
‒
(Singh et al., 2018a)
Urea Treatment + KOH Activation Urea Treatment + KOH Activation Urea Treatment + KOH Activation H2SO4 Treatment + KOH Activation Melamine Treatment + KOH Activation
400/1
500/2 (5)
700/2 (5)
3401
3049
2.94
1.87
n/a
n/a
2.50
1
25
4.7
‒
20.54
(Wei et al., 2018)
KOH Activation
180/24
800/1 (2)
2091
n/a
1.67
0.65
n/a
n/a
0.87
1
25
3.85
36.0
6.68
(Wu et al., 2018b)
Camphor Leaves
KOH Activation
500/2
600/1 (5)
1146
n/a
n/a
0.47
0.27
n/a
0.54
1
25
3.74
24.0
8.87
(Xu et al., 2018)
192
Coconut Shell
K2CO3 Activation + Urea Modification
500/2 (5)
600/1 (5)
1082
n/a
n/a
n/a
0.49
n/a
0.39
1
25
3.71
29.0
9.72
(Yue et al., 2018)
193
Pine Wood
KOH Activation
906
n/a
n/a
n/a
n/a
n/a
n/a
1
15
3.86
39.7
‒
(Ahmed et al., 2019)
194
Pine Wood
ZnCl2 Activation
1122
n/a
n/a
n/a
n/a
n/a
1
15
3.20
29.6
‒
(Ahmed et al., 2019)
853/2 (10j)
633/1
853/2 (10j)
33
195
Sugarcane Bagasse
Urea Treatment + KOH Activation
600/0.5 (10)
600/1 (10)
1113
n/a
n/a
n/a
0.50
n/a
0.57
1
25
4.8
32.5
13.26
(Han et al., 2019)
196
Garlic Peel
KOH Activation
360/2 (4)
700/1 (2)
1248
919
2.19
0.52
n/a
n/a
0.68
1
25
4.1
17.0
7.85
(Huang et al., 2019b)
197
Garlic Peel
KOH Activation
200/24 + 400/2 (4)
600/1 (2)
947
928
n/a
0.50
n/a
n/a
0.51
1
25
4.22
40.0
10.92
(Huang et al., 2019a)
198
Date Sheet
KOH Activation
800/2 (10)
800/1 (10)
2367
2059
0.54
0.83
n/a
n/a
1.14
1
25
4.36
17.60
7.02
(Li et al., 2019)
199
Rice Husk
KOH Activation + PEIa Impregnation
200/6
700 /1 (5)
1190
n/a
n/a
0.42
0.17
n/a
0.77
1
25
4.48
36.0
24.18
(Liu et al., 2019b)
200
Lotus Leaf
NaNH2 Activation
500/1
550/1 (5)
1087
n/a
n/a
0.45
0.54
n/a
0.54
1
25
3.50
32.0
10.30
(Liu et al., 2019a)
201
Palm Kernel Shell
500/1 (10)
140 (0.16)
1700
1352
n/a
0.56
n/a
n/a
0.89
1
25
5.29
43.11
‒
(Ma et al., 2019)
202
Water Chestnut Shell
Urea Treatment + Steam Activation NaNH2 Activation
500/1 (5)
1416
n/a
n/a
0.53
0.62
n/a
0.58
1
25
4.50
37.0
10.12
(Rao et al., 2019)
203
Lumpy Bracket
KOH Activation
850/1
1968
n/a
n/a
0.55
0.40
n/a
1.14
1
25
4.62
26.5
16.73
(Serafin et al., 2019)
204 205 206 207 208
Walnut Shell Pineapple Waste Pineapple Waste Pineapple Waste Waste Tea
NaNH2 Activation K2C2O4 Activation Na2C2O4 Activation Li2C2O4 Activation KOH Activation + EDAi Treatment
500/1 (10)
450
1687
n/a
n/a
0.77
n/a
n/a
0.92
1
25
3.06
38.0
4.22
(Yang et al., 2019)
210/10
700/2 (5)
1076
n/a
n/a
n/a
0.92
n/a
0.08
1
25
4.25
‒
10.76
(Zhu et al., 2019)
210/10
700/2 (5)
397.3
n/a
n/a
n/a
0.09
n/a
0.26
1
25
1.59
22.0
6.01
(Zhu et al., 2019)
210/10
600/2 (5)
302.7
n/a
n/a
n/a
0.06
n/a
0.49
1
25
1.59
27.0
9.77
(Zhu et al., 2019)
11.80
n/a
n/a
n/a
n/a
n/a
n/a
‒
30
2.47
‒
‒
(Rattanaphan et al., 2020)
500/2
123 124
a
Polyethylenimine (PEI), b N-(2-aminoethyl)-3-aminopropylmethyldimethoxsilane (AEAPDMS), c Monoethanolamine (MEA), d 2-amino-2-methyl-1-propanol
125
(AMP), e 3-Aminopropylmethyldiethoxsilane (APDES), f Diethanolamine (DEA), g Triethylenetetramine (TETA), h Tetraethylenepentamine (TEPA), i
126
Ethylenediamine (EDA), j K/min, k s, m not analyzed (n/a), n h, p ml/g, q %CO2/g carbon.
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4. Key Factors Controlling CO2 Adsorption onto Lignocellulose-based Adsorbents
128
4.1. Adsorbent Features
129
It is generally believed that the performance of AC is closely associated with adsorbent porosity
130
and specific surface area (SSA); however, surface chemistry is another important factor
131
influencing CO2 adsorption capacity (Shafeeyan et al., 2010; Vargas et al., 2013; Tan et al.,
132
2017).
133
4.1.1. Surface Area
134
High surface area is an important driving force to have a larger uptake of CO2, as it provides
135
sites for the adsorption process (Yang et al., 2017; Wu et al., 2018b). Fig. 8 shows the CO2
136
adsorption capacity at 1 bar and 25 ℃ versus the specific surface area of the reported adsorbents
137
in Table 3. Boonpoke et al. reported that unmodified Bagasse-based activated carbon (BAC)
138
showed better CO2 adsorption than the amine-modified BAC due to its higher surface area
139
(Boonpoke et al., 2012). On the other hand, Li et al. observed the reverse influence of SSA on
140
the CO2 adsorption. A higher surface area of pine cone shell-derived ACs did not lead to higher
141
CO2 adsorption capacity. This was attributed to the unique pore size distribution (PSD) of the
142
adsorbent with unavailable regions for CO2 adsorption (Li et al., 2016b). Yang et al. summarized
143
the CO2 adsorption capacities of various carbonaceous materials in which coconut shells were
144
used as carbon precursors and CO2 adsorption was measured at 25°C and 0‒200 kPa. The results
145
showed that the micropore shape and size distribution affected the adsorption properties (Yang et
146
al., 2011). Similarly, Fiuza Jr. et al. prepared various ACs from the stones of yellow mombin
147
using KOH as activating agent. The prepared samples were tested as adsorbents in post-
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combustion capture conditions and observed that the activated sample at 700 ℃ had a lower CO2
149
uptake (8.6 mmol/g) compared to the samples with lower surface area, indicating a transference
150
of PSD to mesopore range (Fiuza-Jr et al., 2016). It can be noticed that there is an apparent
151
discrepancy with the physisorption concept, which denotes that the a higher surface area would
152
result in a higher CO2 adsorption (Yang et al., 2015).
153
Fig. 8 CO2 adsorption capacity (at 1 bar and 25 ℃) versus the surface area (data are from Table 3). 154
155
4.1.2. Pore Structure
156
As reported in the literature, materials with high surface area tend to possess large
157
micropores/small mesopores and exhibit high CO2 uptake at an elevated pressure (20 bar and
158
above) because in this case, the uptake mechanism is likely to occur by surface coverage 36
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(Coromina et al., 2016; Li et al., 2016b; Li et al., 2016c; Rashidi et al., 2016). While the
160
governing mechanism under low pressure adsorption (up to 1 bar) is pore filling (driven by the
161
gas molecules and pore walls interactions) in which the overlapping of the potential fields from
162
the neighboring walls would enhance CO2 adsorption, and therefore, small micropores become
163
more relevant (Banisheykholeslami et al., 2015; Coromina et al., 2016). Still, meso/macropores
164
facilitate the mass transport of CO2 within the skeleton of carbons (Sun and Webley, 2011; Bae
165
and Su, 2013).
166
Some earlier studies in the literature have suggested that pores smaller than five times of CO2
167
molecular size (pores lower than 1 nm) would provide the highest CO2 adsorption capacity at the
168
ambient atmospheric pressure (Maroto-Valer et al., 2005). A comparison of the porosity data and
169
CO2 uptake by Coromina et al. onto Jujun grass and Camellia japonica-derived ACs shows that
170
narrow micropores are the key determinant of CO2 uptake at pressures up to 1 bar (Coromina et
171
al., 2016). This observation was supported by earlier studies performed by Ello et al., who
172
produced ACs using African palm shells through carbonization and KOH activation and revealed
173
that ultramicropores ( ≤ 0.7 nm) intensified CO2 adsorption and the adsorbent interaction energy
174
in these narrow pores (Ello et al., 2013b). Similar observations have been reported for various
175
carbons (Deng et al., 2014; Deng et al., 2015; Li et al., 2015a; Coromina et al., 2016; Rashidi and
176
Yusup, 2017; Serafin et al., 2017). Fig. 9 shows the variation of the optimal micropore size with
177
CO2 adsorption at 0 and 25 °C under (a) sub-atmospheric (Deng et al., 2015; Li et al., 2015b;
178
Chomiak et al., 2017; Serafin et al., 2017) and (b) atmospheric pressures (Boonpoke et al., 2011;
179
Sevilla and Fuertes, 2011; Sevilla et al., 2012; Wei et al., 2012; Rashidi et al., 2013; David and
180
Kopac, 2014; Deng et al., 2014; Hong et al., 2016; Chomiak et al., 2017; Serafin et al., 2017;
181
Luo et al., 2018; Li et al., 2019). 37
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Fig. 9 The variation of the optimal micropore size with CO2 adsorption under (a) subatmospheric and (b) atmospheric pressures at 0 and 25 °C from different references. 183 184
Erto et al. carbonized a series of agricultural wastes (peach stones, olive stones, and apricot
185
stones) followed by water vapor activation to examine their CO2 adsorption capacity. Based on
186
the results, all the ACs exhibited pore sizes higher than CO2 molecule dimensions and the peach
187
stone-derived AC sample showed the highest CO2 adsorption capacity owing to its high
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188
micropore volume, mostly formed by ultramicropore, narrower PSD and its comparative higher
189
basic character of the surface (Erto et al., 2016). Besides, Yue et al. confirmed their results and
190
suggested that the highest CO2 adsorption for the AC derived from rotten strawberries, thanks to
191
high nitrogen content, narrow micropore volume and also adequate narrow micropore size (Yue
192
et al., 2017). Moreover, Heo and Park investigated the CO2 sorption capacities of steam-
193
activated cellulose fibers and proposed micropore volume fraction and ultramicropore size
194
distribution as two key factors in improving CO2 adsorption capacity under ambient conditions
195
(Heo and Park, 2015).
196
4.1.3. Surface Chemistry
197
In addition to the textural properties of ACs, numerous studies have been conducted to verify the
198
significance of surface chemistry in CO2 adsorption capacity (Shafeeyan et al., 2010; Fiuza-Jr et
199
al., 2016). As CO2 has an acidic character (Plaza et al., 2009b), surface modification of AC
200
through removing/neutralizing the acidic functionalities or replacing them with proper basic
201
groups is the common way to increase the adsorption capacity of AC toward CO2 (David and
202
Kopac, 2014).
203
Heteroatom (N, B, P, S, and O) doping plays an important role in CO2 adsorption as well (Luo
204
et al., 2018). The introduction of nitrogen-containing functional groups on the AC surface is the
205
most common type of functionalization due to the improvement of electrical conductivity
206
(Braghiroli et al., 2012; Sevilla et al., 2012), oxidation reduction (Xu et al., 2010) and surface
207
properties (surface polarity and base sites) (Sevilla et al., 2012; Creamer et al., 2014; Fiuza et al.,
208
2015; Han et al., 2019), as well as the electron-donor ability of the carbon matrix (Wang et al.,
209
2013; Sha et al., 2015). Moreover, Xing et al. have reported that the incorporation of N atoms 39
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210
into the carbon would facilitate the hydrogen bonding interactions of CO2 molecules with carbon
211
surface hydrogen atoms (from CH and NH), which is the reason for the superior CO2 adsorption
212
capacity (Xing et al., 2012; Song et al., 2014). Consequently, it remarkably provides a large
213
number of chemically active sites and boosts their potential applications (Rana et al., 2017; Wei
214
et al., 2018; Rattanaphan et al., 2020). Indeed, this increase depends on the precursor used and
215
the surface modification methodology (Plaza et al., 2009a; Sha et al., 2015; Xu et al., 2018).
216
There are mainly two methods for the synthesis of nitrogen-doped porous carbon materials,
217
namely: in-situ modification and post-modification. In-situ modification includes (i) the
218
carbonization of nitrogen-containing precursors such as agricultural residues or commercially
219
available monomers (Song et al., 2014; Sha et al., 2015; Zhu et al., 2015; Liang et al., 2016;
220
Yang et al., 2017; Xu et al., 2018), and (ii) the co-carbonization of nitrogen-containing and
221
nitrogen-free compounds (Chen et al., 2016; Rouzitalab et al., 2018; Han et al., 2019). Post-
222
modification comprises (i) thermal treatment of porous carbons with nitrogen-containing gases,
223
for instance, ammonia in the presence or absence of oxygen (Plaza et al., 2011a; Shafeeyan et al.,
224
2011; Heidari et al., 2014a; Geng et al., 2016; Nelson et al., 2016; Zhang et al., 2016) or
225
nitrogen-containing organic compounds, e.g. urea (Mehrvarz et al., 2017; Yue et al., 2018), and
226
(ii) impregnation with amine-functional groups (Plaza et al., 2009a; Boonpoke et al., 2012;
227
Calvo-Muñoz et al., 2016; Kongnoo et al., 2016; Luo et al., 2016; Wang et al., 2017a). The post-
228
modification technique demands high temperatures, and may cause the blockage of porous
229
structure, which consequently decreases the adsorption capacity; therefore, this method is not
230
preferred (Pevida et al., 2008; Mehrvarz et al., 2017; Rouzitalab et al., 2018).
231
In light of the above considerations, any lignocellulose-based activated carbon will exhibit
232
high CO2 adsorption performance as long as it has a high surface area, micropore volume, and 40
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basic surface functionalities simultaneously. Yang et al. demonstrated that the CO2 capture
234
capacity of carbonaceous adsorbents made by walnut shell and treated by NaNH2 can be
235
improved by doping a certain amount of nitrogen in conjunction with the adequate porous
236
texture. The best CO2 adsorption capacity of these one-step nitrogen-doped carbons, activated at
237
450 °C with a KOH to precursor ratio of 2.5:1, reached a high value of 3.06 mmol/g at 25 °C and
238
1 bar (Yang et al., 2019). This result is in good agreement with further studies reported by other
239
researchers (Heidari et al., 2014b; Yang et al., 2015; Chen et al., 2016; Rouzitalab et al., 2018).
240
Contrary to the previous reports in which CO2 adsorption under ambient conditions depends on
241
narrow micropores, Yue et al. demonstrated that nitrogen incorporation is indeed advantageous
242
for the enhancement of CO2 capture (Yue et al., 2018), which agrees with the results reported by
243
Xing et al. (Xing et al., 2012), Yao et al. (Yao et al., 2015), and Yang et al. (Yang et al., 2017).
244
Moreover, Li et al. suggested that the dominant parameter at very low pressure of CO2
245
adsorption is the nitrogen content, not the surface area or pore volume, which is in agreement
246
with Song et al.’s observation (Song et al., 2014; Li et al., 2015b). In addition, it was observed
247
that even if two samples have a comparable surface area or small micropore volume, the
248
nitrogen-enriched carbon would exhibit higher CO2 capture (Thote et al., 2010; Xu et al., 2018).
249
Furthermore, it was found that the CO2 adsorbent affinity is highly dependent on both a high
250
amount of nitrogen content and the type of N-functionalities introduced, allowing chemisorption
251
to operate predominantly, thus capturing more CO2 (Pevida et al., 2008; Sevilla et al., 2012;
252
Shafeeyan et al., 2012; Yao et al., 2015; Rashidi and Yusup, 2017), which is different from the
253
temperature of treatment (Shafeeyan et al., 2012).
254
Similarly, the presence of metal particles will affect the mechanism and effectiveness of CO2
255
adsorption (Hidayu and Muda, 2016; Shahkarami et al., 2016; Zhu et al., 2016; Botomé et al., 41
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256
2017). Hidayu and Muda studied the adsorption of several metal oxides (BaO, MgO, CuO, TiO2
257
and CeCO2) loading on the best physical and chemical AC from coconut and palm kernel shell.
258
The impregnation process can block access to fine microporosity through positioning metal
259
particles in the most internal part of the pores, thereby decreasing the adsorption. It was found
260
that irrespective of the adsorbent, the CO2 adsorption depends mainly on surface area, pore
261
volume and the reaction occurring between the CO2 and the loaded AC. Before any interaction
262
between CO2 and the surface of carbon occurs, the fixed impregnant provides active sites
263
through chemical bonds forming between metal oxides and carbon surface. Among the used
264
metal oxides, high basicity of BaO leads to strong reactivity, enabling it to transfer charge to the
265
adsorbed CO2 (Hidayu and Muda, 2016). Another study was conducted by Shahkarami et al. on
266
the MgO impregnated whitewood ACs made by different preparation techniques and MgO
267
contents as two governing factors. As observed by the authors, an increase in Mg content
268
enhances the CO2 adsorption, although the surface area becomes smaller (Shahkarami et al.,
269
2016). In this case, Lahijani et al. suggested that the contribution of chemisorption was more
270
than the share of physisorption (Lahijani et al., 2018), and even low metal contents are enough to
271
satisfy the improvement of CO2 adsorption capacity (Botomé et al., 2017).
272
4.1.4. Other Factors
273
The pyrolytic decomposition of the non-carbon elements, hydrogen, nitrogen, and oxygen,
274
namely volatile products, through carbonization process results in a solid residue rich in carbon
275
(Boujibar et al., 2018; Luo et al., 2018). As more volatile contents are removed, enhanced
276
reactivity of carbon would improve pore development on the carbonaceous material (Nasri et al.,
277
2014). The effect of carbon and ash contents of the rice husk-based AC and bagasse-based AC
278
was investigated by Boonpoke et al. The authors pointed out that with a comparable surface area 42
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279
and pore characteristics, bagasse-derived AC had a higher CO2 adsorption capacity in
280
comparison with rice husk-derived AC, owing to the low inorganic contents (Boonpoke et al.,
281
2012). Indeed, different laboratory studies indicated that the CO2 adsorption capacity is closely
282
related to low organic volatile content, high elementary carbon, and low ash of any carbonaceous
283
material (Bae and Su, 2013; Rashidi et al., 2013; David and Kopac, 2014).
284
4.2. Preparation Conditions
285
4.2.1. Carbonization Condition
286
A vital consideration in the evolution of primary pores within the carbon structure is
287
carbonization parameters, owing to the fact that volatile matters will be released from the matrix
288
of carbon during the carbonization process. As the textural properties of the produced carbon are
289
significantly affected by the pore development of the char, carbonization parameters need to be
290
brought up in calculations before the carbon production.
291
4.2.1.1. Carbonization Type
292
Lignocellulose-based materials convert to activatable carbonaceous matter through two main
293
processes, i.e. hydrothermal carbonization (HTC) and direct thermal pyrolysis. Hydrothermal
294
carbonization is a process of thermochemical decomposition of lignocellulose-based materials in
295
the presence of superheated water, which results in a so-called hydrochar, while direct pyrolysis
296
proceeds via a rise in the carbon content of lignocellulose-based materials precursors during
297
heating in the absence of oxygen (Coromina et al., 2016; Balahmar et al., 2017). Operating at a
298
relatively low temperature (typically up to 250 °C) and handling biomass without drying pre-
299
treatment are the advantages of HTC in comparison with the direct pyrolysis method (Coromina
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300
et al., 2016; Wu et al., 2018b). For example, Guangzhi et al. prepared N-doped camphor leaves-
301
derived porous biocarbons using HTC at different temperatures (180 to 270 °C) followed by
302
KOH activation at a constant condition (AHTCs). The AHTC-240 had the highest specific
303
surface area (up to 1633.71 m2/g) and microporosity ratio, both of which are adsorption-
304
enhancing factors (6.63 mmol/g at 25 °C under 4 bar) (Guangzhi et al., 2017).
305
It is noteworthy that there are two types of thermal direct pyrolysis process, namely fast and
306
slow. Comparative research was conducted by Shahkarami et al. to investigate the changes
307
occurring during fast and slow pyrolysis of forest and agriculture residue-based precursors
308
followed by chemical activation using KOH as a chemical agent. Apart from the precursor type,
309
the fast pyrolysis resulted in a higher surface area and total pore volume, smaller particle size
310
and ultra-pore volume, in addition to a large contribution of carboxylic and phenolic/ketone
311
groups. However, the slow pyrolysis process causes the formation of aromatic regions with
312
lower contribution of C=O on the surface. Furthermore, the maximum CO2 sorption (1.77
313
mmol/g in N2) was found to take place through the application of slow pyrolyzed sawdust based
314
AC with the highest ultramicropore volume (up to 0.36 cm3/g); however, the presence of oxygen
315
functional groups on its surface leads to a low selectivity (2.8) over O2. The obtained results
316
illustrate that the ultramicropores and surface chemistry of adsorbents play a crucial role in the
317
adsorption of CO2 rather than the internal surface area, total pore volume, and the particle size
318
(Shahkarami et al., 2015b).
319
Microwave-assisted pyrolysis (MWP) is a feasible alternative to conventional pyrolysis,
320
which supplies a temperature gradient from the center to the outer surface of lignocellulose-
321
based materials. Microwave heating (MWH) provides a non-contact, fast, volumetric, uniform
322
heating, resulting in a shorter processing time and better energy savings. It is a safe, 44
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323
environmentally friendly technique due to its low hazardous product formation and emission
324
pollutants. Moreover, the yield and quality of the products of microwave torrefaction are very
325
high (Huang et al., 2016; Li et al., 2016a; Ao et al., 2018). As an example, Huang et al.
326
investigated the effect of microwave pyrolysis of rice straw on CO2 adsorption capacity and
327
observed that the resultant biochar showed a 14-percent higher CO2 adsorption capacity
328
compared to the derived biochar from conventional pyrolysis (Huang et al., 2015).
329
4.2.1.2. Carbonization Temperature
330
It is generally agreed that defining optimal carbonization temperature is critical in controlling the
331
decomposition and release of volatile matters between 250 ℃ to 600 ℃, or their recombination
332
above 600 ℃, and consequently optimizing char yield (Collard and Blin, 2014; Boujibar et al.,
333
2018). Moreover, improving the graphitization degree of the carbon samples upon higher
334
carbonization temperature is confirmed by high resistance to the destruction of pores (Rashidi et
335
al., 2012; Song et al., 2014; Fiuza-Jr et al., 2016) and also higher surface area (Creamer et al.,
336
2014; Nelson et al., 2016; Li et al., 2019).
337
4.2.1.3. Carbonization Flow Rate
338
The inert gas flow rate during the carbonization process also affects the CO2 adsorption of the
339
adsorbents. The results reported by Chaiw et al. reveal that too high flow rate leads to incomplete
340
removal of volatile matter as a result of low surface temperature of the sample. Accordingly, the
341
pore structure development is probably limited owing to the high flow rate of gases. This
342
eventually results in the low surface area of the produced sample. Contrariwise, a low flow rate
343
of gases causes the released volatile matter not to be fully removed during the thermal reaction,
344
consequently resulting in the volatile matter’s re-deposition to the surface of the sample, which 45
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345
gives rise to pore blockage and impedes the forming of a more porous structure within the
346
sample. As a result, the optimization of the flow rate is a key factor in developing appropriate
347
carbonized lignocellulose-based material (Chaiw et al., 2016).
348
4.2.2. Activation Condition
349
Different activation methods and activation conditions lead to differences in both the physical
350
characteristics and the chemical properties of the resultant ACs (Sevilla and Fuertes, 2011;
351
Rashidi et al., 2012; Wei et al., 2012; González et al., 2013; Heidari et al., 2014a; Plaza et al.,
352
2014a; Álvarez-Gutiérrez et al., 2015; Li et al., 2016b; Madzaki et al., 2016; Nowrouzi et al.,
353
2017; Singh et al., 2017b; Peredo-Mancilla et al., 2018; Wu et al., 2018b).
354
4.2.2.1. Number of Activation Steps
355
In search of sustainable, cheaper ACs, simplifying the synthesis process and omitting the HTC or
356
direct carbonization step before activation are desirable; in other words, it is preferred to form
357
ACs with similar or improved yield and/or properties via direct activation process instead of the
358
conventional, longer, two-step routes (Balahmar et al., 2017).
359
Eucalyptus wood sawdust, seaweed (Sargassum Fusiforme), and the flowering plant Paeonia
360
Lactiflora-based ACs were produced by Balahmar et al. through a direct activation using KOH
361
as an activating agent, without any need for HTC or direct pyrolysis. Different characterization
362
techniques confirmed that the directly activated carbons offer a greener and easier route at a
363
lower cost and comparable to or higher features than those derived from conventional methods.
364
Furthermore, the degree of graphitic ordering and the textural properties of both directly and
365
conventionally generated ACs were found to be similar (Balahmar et al., 2017). Also, Singh et
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366
al. applied the resulting Arundo donax AC from a single step activation using KOH to remove
367
CO2 from gas stream. Compared with typical two-step carbonization and activation procedure,
368
the single step product (using similar temperature and activation conditions) has a higher surface
369
area and micropore volume and save energy better. Single step activated carbon with a KOH/C
370
ratio of 2:1 shows the highest CO2 adsorption capacity (up to 6.3 mmol/g at 1 bar and at 0 °C)
371
among the as-synthesized ACs (Singh et al., 2017b). Single step activation has been reported for
372
various precursors (Plaza et al., 2014a; Rashidi and Yusup, 2017; Vilella et al., 2017)
373
4.2.2.2. Activating Agent
374
The commonly used gases and chemicals for the activation of lignocellulose-based carbon
375
include CO2, steam, H3PO4, ZnCl2, K2CO3, and KOH among others (Shahkarami et al., 2015a;
376
Moussa et al., 2017; Manyà et al., 2018; Sevilla et al., 2018; Li et al., 2019).
377
It has been reported by Alvarez et al. that the CO2 activation of cherry-stone leads to
378
microporous ACs while steam activation results in newly developed pores and a larger
379
micropore widening (Álvarez-Gutiérrez et al., 2015; Heo and Park, 2015). Although physical
380
activation is less expensive and more eco-friendly, nowadays, the chemical activation process is
381
receiving more attention due to its superior ability to create highly developed porous structure
382
and increase the specific surface area at much lower temperatures and with a higher carbon yield
383
(Deng et al., 2015; Heo and Park, 2015).
384
Heidari et al. investigated the effect of two different activating chemicals (H3PO4 and ZnCl2)
385
on to the pore structure of activated carbon produced from eucalyptus camaldulensis wood and
386
observed a degree of macroporosity along with a high incidence of microporosity. Compared to
387
ZnCl2, H3PO4 provided larger mesopores and even macropores (Heidari et al., 2014a). Although 47
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388
H3PO4 is an acid, it supplies a high influential surface area in comparison with its negative effect
389
on the interactions between the basic surface groups and CO2 molecules (Peredo-Mancilla et al.,
390
2018). In another study, the effects of KOH and K2CO3 activation were compared on the olive
391
pomace-derived ACs by Moussa et al. Higher surface area and larger porosity as well as higher
392
CO2 adsorption capacity were obtained through KOH activation of the raw precursor (Moussa et
393
al., 2017).
394
Of the different activation approaches, activation by KOH is one of the most constraining
395
techniques for the development of highly microporous structure and functional groups on the
396
surface of carbons owing to the intercalation of potassium compounds between the carbon
397
lattices, integration of carbon oxidation and in-situ physical activation (with CO2) in high
398
temperature processes (Li et al., 2015b; Zhang et al., 2016; Singh et al., 2017b). It is worth
399
noting that ACs’ porosity is well-controlled by varying the activation conditions (Singh et al.,
400
2017b). In spite of the fact that KOH is a highly-effective activator that can create developed
401
porous structure advantageous for CO2 capture on different kinds of carbon precursor, its
402
corrosive effect and high temperature operation are two inherent disadvantages (Yue et al., 2018;
403
Rao et al., 2019). Rao et al. activated water chestnut shell via NaNH2 and demonstrated that
404
NaNH2 has great potential as an activating agent, since its corrosive effect is much less than that
405
of KOH, and thus simultaneous pore forming and nitrogen doping will reduce sample
406
preparation costs (Rao et al., 2019). Furthermore, Sevilla et al. suggested using potassium
407
oxalate (C2K2O4) as a versatile and less corrosive activating chemical agent rather than the
408
widely used KOH (Sevilla et al., 2018). Correspondingly, Zhu et al. synthesized a series of
409
pineapple-derived ACs using three different alkali metal oxalates (K2C2O4, LiC2O4, and NaC2O4)
410
and activation temperatures (500, 600, and 700 ℃). They found that the microporous structure of 48
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411
ACs activated by K2C2O4 led to remarkable CO2 adsorption performance in comparison with
412
non-porous and meso/macroporous carbons activated by LiC2O4 and NaC2O4 at a certain
413
temperature (Zhu et al., 2019). In addition, Yalcin and Sevinc found that besides the type of the
414
activating agent, its concentration influenced the textural parameters (Yalçın and Sevinç, 2000;
415
Mehrvarz et al., 2017).
416
4.2.2.3. Activating Agent Dosage
417
Luo et al. studied the effect of different KOH to carbon mass ratios of 0.5‒6 on heteroatom self-
418
doped activated carbons derived from fir bark. Although the higher weight ratio enhances the
419
surface area, micropore volume and micropore size distribution, excessive KOH treatment will
420
destroy pore walls or result in aggressive chemical reaction between KOH and the
421
lignocellulose-based adsorbent, thus promoting pore widening and reducing the surface area
422
(Wang et al., 2012a; Wei et al., 2012; Lee et al., 2014; Deng et al., 2015; Li et al., 2015a; Chaiw
423
et al., 2016; Luo et al., 2018; Wu et al., 2018b; Xu et al., 2018; Rao et al., 2019).
424
In another study, Rouzitalab et al. fabricated a series of highly nanoporous N-doped carbons
425
with walnut shell as the starting material through a combination of in-situ urea modification
426
coupled with KOH activation (mass ratios of 2-6), and pointed out that mild activation condition
427
(KOH/C mass ratio of 2) exhibited higher CO2 adsorption capacity (7.42 mmol/g under room
428
temperature) under atmospheric pressure than that prepared in severe condition (KOH/C mass
429
ratio of 6), which is favorable for CO2 adsorption under high pressures (14.03 mmol/g under 10
430
bar at room temperature) (Sevilla and Fuertes, 2011; Rouzitalab et al., 2018). As previously
431
reported, residual urea can react with KOH and promote its penetration into deep layers of the N-
432
doped samples to develop a highly porous structure (Chen et al., 2016; Rouzitalab et al., 2018). 49
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433
4.2.2.4. Activation Temperature
434
In 2015, Parshetti et al. examined a series of carbonaceous adsorbents, which were prepared
435
from empty palm fruit bunch by HTC coupled with KOH activation at two different temperatures
436
(600 °C and 800 °C) for CO2 capture. They concluded that regardless of the precursor, higher
437
activation temperature leads to a remarkable enhancement of the specific surface area, the total
438
pore volume and the micropore volume of the ACs. This development of adsorbents’ textural
439
properties can be ascribed to the removal of volatile matters and impurities in gaseous form
440
during thermal decomposition process (David and Kopac, 2014; Heo and Park, 2015; Parshetti et
441
al., 2015; Rashidi and Suzana, 2015; Geng et al., 2016). Moreover, Sun and Webley reported that
442
the pore widening begins to dominate at severe activation temperature and accordingly mesopore
443
surface area and mesopore volume increase (Sun and Webley, 2011; Plaza et al., 2012; Song et
444
al., 2014), which may cause structural collapse under over-intense activation conditions
445
(Rouzitalab et al., 2018).
446
It is mentioned in the literature that nitrogen groups incorporated into the carbon structure
447
have low thermal stability and tend to decrease by an increase in activation temperature (Xing et
448
al., 2012; Rashidi and Suzana, 2015; Yang et al., 2015; Xu et al., 2018; Han et al., 2019).
449
Nevertheless, Geng et al. utilized ammonia treatment as both the activating agent and nitrogen
450
source without preliminary oxidation to produce corncob-derived adsorbents and demonstrated
451
inconsistent results with literature. They observed that the increasing trend of N doping with
452
increasing temperature indicated a dynamic balance between N doping and removal during the
453
reactions and finally N doping extended beyond N removal (Geng et al., 2016). Furthermore,
454
Xing et al. proved that either low activation temperature or low KOH dosage will result in more
455
H atoms with more hydrogen bonding interactions between CO2 molecules and consequently 50
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456
higher CO2 uptakes than the carbons prepared at high temperature or high KOH dosage (Xing et
457
al., 2012).
458
4.2.2.5. Activation Time
459
David and Kopac used rapeseed oil cake and walnut shell as a precursor to prepare activated
460
carbon using CO2 as activating agent by similar pyrolysis and activation temperature and
461
variable activation time (0.5-3.5 h). With a short activation time, the applicable pores are not
462
developed due to an insufficient devolatilization reaction. Meanwhile, severe reactions between
463
CO2 and carbon surface will take place during prolonged activation time that causes
464
simultaneous pore opening and pore widening with a subsequent pore collapse and development
465
of mesopores or macropores, which are not suitable for CO2 adsorption under atmospheric
466
conditions. Further, more ash residues may form through intensified activation time and block
467
the existing pores with no more CO2 capture (Plaza et al., 2009b; Bhati et al., 2013; Ello et al.,
468
2013a; González et al., 2013; David and Kopac, 2014; Rashidi and Suzana, 2015; Ogungbenro et
469
al., 2017).
470
Li et al. also investigated the effect of activation time (1, 1.5 and 2 h) on the porosity
471
improvement of peanut shell-derived AC using KOH with an impregnation ratio of 2 at 780 °C.
472
They found that increasing activation time could not promote the elimination of char elements,
473
so ultramicropore volume hardly varied while ultramicropore fraction (V<0.7
474
decreased and then increased as prolonged activation time caused pore wall collapse and reduced
475
Vtot (Li et al., 2015a). According to both Ello et al. and David and Kopac, higher burn-off degree
476
through the activation time enhancement reduces the carbon yield (Ello et al., 2013a; David and
477
Kopac, 2014). 51
nm/Vtot)
first
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478
4.2.2.6. Activation Flow Rate
479
Rashidi et al. prepared a series of activated carbons simply by activating different agricultural
480
waste materials (palm shell, palm mesocarp fiber, coconut shell, coconut fiber, rice husk) in a
481
varied CO2 atmosphere flow rate. They observed that the variable CO2 flow rate did not present
482
any effective change in the porosity development and adsorption capacity of the adsorbents
483
(Rashidi and Suzana, 2015). On the contrary, Li et al. varied the protective-gas (N2) flow rate
484
(100, 450, 800 or 1040 mL/min) during the activation of chitosan derived ACs using KOH with
485
the impregnation ratio of 1:1. They demonstrated that the CO2 uptake as well as CO2/N2
486
selectivity of ACs could significantly increase owing to the significant effect of N/C ratio of
487
adsorbent surface, the flow rate on ultramicropore volume, and the nature of N-containing
488
species of the materials (Li et al., 2017).
489
4.2.2.7. Activation Heating Rate
490
Alvarez et al. studied the effect of heating rate on the CO2 adsorption capacity of cherry stone-
491
derived ACs prepared by physical activation (CO2/steam). They found that variable heating rate
492
(10.00 °C/min-1, 12.03 °C/min-1, 15.00 °C/min-1, 17.97 °C/min-1 and 20.00 °C/min-1) was
493
considerably ineffective in the CO2 capture capacity of any studied material, CO2 or steam
494
activated adsorbents (Álvarez-Gutiérrez et al., 2015). A similar finding was reported by Rashidi
495
and Suzana (Rashidi and Suzana, 2015).
52
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496
4.3. Adsorption Conditions
497
4.3.1. Temperature
498
According to the conclusions drawn by previous reports, as a typical process of physical
499
adsorption, during the enhancement of adsorption temperature the adsorption capacity reduces
500
through the desorption of the adsorbed gases on the AC surface. Nevertheless, lignocellulose-
501
based adsorbents have sufficient CO2 adsorption capacity under ambient condition (Maroto-
502
Valer et al., 2005; Huang et al., 2011; Shafeeyan et al., 2011; Boonpoke et al., 2012; David and
503
Kopac, 2014; Heidari et al., 2014b; Moussa et al., 2017; Rashidi and Yusup, 2017). Chemical
504
modification provides an effective approach to suppress this occurrence at high temperatures by
505
introducing base sites on the surface of lignocellulose-based adsorbents (Shafeeyan et al., 2011;
506
Xiong et al., 2013). Fig. 10 shows the essence of adsorption at low and high temperatures,
507
derived from the study by Xiong et al.
508
Fig. 10 The relationship between the CO2 adsorption capacity of the modified char and (a) the micropore volume, and (b) the nitrogen content. Reprinted from reference (Xiong et al., 2013), 53
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with permission from Springer Nature, license number: 4732400985852. 509 510
To explain this, fundamental thermodynamic concepts should be discussed. Quantification of
511
the isosteric heat of adsorption (Qst) is a pivotal factor for the design and development of CO2
512
adsorbents (Parshetti et al., 2015). For adsorption, Qst is negative since heat is released when the
513
molecules are adsorbed and as it is known, when the surface is energetically homogenous, no
514
interaction occurs between adsorbed molecules and Qst is independent of the surface coverage.
515
However, when the surface is heterogeneous, because of strong binding sites and the filling
516
ultramicropores, followed by the adsorption onto weak binding sites and the filling of larger
517
pores, Qst varies with the surface loading (Shafeeyan et al., 2015; Li et al., 2017). It decreases
518
gradually with increase in CO2 adsorption capacity, which is due to the disappearance of
519
favorable adsorption sites. However, the adsorbate/adsorbate interaction, which occurs mainly
520
after the complete surface coverage of porous sorbent, must not be ignored (Guan et al., 2018),
521
which may lead to the enhancement of Qst value along with increase in the CO2 adsorption
522
capacity owing to strong lateral interactions of CO2 molecules onto second and higher layers
523
(Rouzitalab et al., 2018).
524
It is a common hypothesis that the isosteric heat of adsorption is temperature-independent or
525
only slightly dependent on temperature; however, this hypothesis is not always confirmed.
526
Earlier studies focused their attention on the dispersion force, which is the interaction between
527
the solid and gas, and neglected the adsorbate-adsorbate interactions, or more precisely, the force
528
among the gas molecules, involving both the adsorbed phase and bulk phase (Guan et al., 2018).
529
In order to compare the effect of temperature on the CO2 adsorption of ZIF-8, in 2011, Grand
530
Canonical Monte Carlo (GCMC) simulations were conducted by Huang et al. They separated the 54
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531
overall isosteric heat of adsorption into the adsorbate-adsorbent (Qst-F-MOF) as well as the
532
adsorbate-adsorbate (Qst-F-F) isosteric heat of adsorption. The simulation outcomes prove that the
533
effect of temperature on Qst-F-MOF is not very large, while for Qst-F-F is much larger. Therefore,
534
high fluctuations of the interaction energy among adsorbate molecules caused by temperature
535
variations result in more significant temperature dependence (Huang et al., 2011). In other
536
words, at high temperatures, the molecules of gases have sufficient kinetic energy to overcome
537
the effects of intermolecular forces between adsorbate and adsorbent (Do, 1998). Recently, Guan
538
et al. defined a “critical temperature point” at which increasing adsorption temperature does not
539
change the adsorption capacity anymore and even makes similar isotherms above this point since
540
the kinetic energy of CO2 molecules cannot overcome the higher energy barriers that the
541
adsorbed molecules possess (Guan et al., 2018). As shown in Fig. 11, all the injection pressures
542
exhibit a linear decrease in CO2 capture up to 323.15 K coupled with an inclination of near zero
543
beyond that point.
544
Fig. 11 The relationship between the CO2 adsorption capacity and temperature with a critical
55
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temperature point of 323.15 K. Reprinted from reference (Guan et al., 2018), with permission from Elsevier, license number: 4731710708179. 545 546
The effect of basic surface functional groups on the Qst is another important factor that should
547
be discussed. Singh et al. prepared a series of nitrogen functionalized porous carbons from Giant
548
reed (Arundo donax) and the chitosan through single-step chemical activation. Their synthesized
549
samples, which consisted of lower nitrogen content (3.5 - 4.1 wt%) showed a low isosteric heat
550
of adsorption (26.5 kJ/mol and 24.6 kJ/mol); however, an increase in nitrogen content (5.41
551
wt%) resulted in a further enhancement of isosteric heat of adsorption (32.2 kJ/mol) (Singh et al.,
552
2017a). The higher isosteric heat of functionalized ACs is mainly due to strong electrostatic
553
interaction between polarizable CO2 and electronegative heteroatoms, hydrogen bonding and
554
acid-base interactions between acidic CO2 and nitrogen-containing basic functional groups rather
555
than relatively weak dispersion forces (Shafeeyan et al., 2015; Ashourirad et al., 2016).
556
Lim et al. investigated the impact of nitrogen-containing functional groups in carbon-based
557
adsorbents on CO2 adsorption as well as the surface interactions with CO2 using computational
558
calculation. The energy of adsorption (Eads), which is profoundly analogous to the isosteric heat,
559
was calculated for CO2 molecules in six different initial configurations (Inglezakis and Zorpas,
560
2012). Functionalization, irrespective of the type of nitrogen-containing functional group,
561
enhances binding energies with CO2 as follow: pyridone (21.58 kJ/mol) > pyridine (21.00
562
kJ/mol) > amine (14.16 kJ/mol) > quaternary nitrogen (12.04 kJ/mol) > pyridine nitrogen-oxide
563
(11.65 kJ/mol) > cyanide (10.79 kJ/mol) > pyrrole (10.60 kJ/mol). An adsorption process is
564
considered as physical, chemical or ion exchange regarding the adsorption energy when it is
565
respectively below 8 kJ/mol, over 16 kJ/mol and between 8-16 kJ/mol. For the pyridone group, 56
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566
the hydrogen bond between the negatively charged oxygen atom of CO2 and the positively
567
charged hydrogen of the hydroxyl group in pyridone group governs the CO2 adsorption behavior.
568
Regarding a pyridine-functionalized surface, adsorption energy, Eads, is approximately the same
569
as that of the pyridone-functionalized surface. Pyridinic-nitrogen is more appropriate for CO2
570
adsorption owing to its stronger electronegativity as compared to carbon atoms, even in the
571
absence of a hydroxyl group. Although the grafted amine group provides strong basicity, its
572
adsorption energy reduction, in comparison with pyridine group, is due to the basicity decrease
573
of the nitrogen atom in addition to steric hindrance by the hydrogen atom existing in amine
574
group. Moreover, quaternary nitrogen, pyridine nitrogen-oxide, pyrrole, and cyanide groups are
575
not effective enough in enhancing CO2 adsorption strength owing to the less discrepancy
576
between their Eads and pristine surface Eads (9.44 kJ/mol). The weak interaction in quaternary
577
nitrogen as well as cyanide groups can result from the lowest basicity of nitrogen atom.
578
Furthermore, the weaker bonding interactions of pyrrole group and pyridine nitrogen-oxide
579
group with CO2 molecule (‒NH⋯O and ‒NO⋯C, respectively) as compared to the hydrogen
580
bonding of pyridone group and the Lewis acid-base interaction of pyridine group result in lower
581
CO2 adsorption energy (Lim et al., 2016).
582
The Henry’s law constant (KH), which characterize adsorbent heterogeneity and adsorption
583
affinity toward CO2 molecule at low pressure (Henry’s law region) was calculated using Virial
584
model according to the equation that has been recorded elsewhere (Parshetti et al., 2015) in order
585
to have another quantitative estimate of CO2 adsorption. In this region, gas molecules can
586
separately explore the entire adsorbent surface, owing to the fact that adsorbate-adsorbate
587
molecule interactions are insignificant due to low densities (Schindler, 2008). The higher the
588
value of the constant was, the stronger affinity between adsorption pair would be. As shown in 57
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589
Table 3, heteroatom self-doped activated carbon from fir bark showed superior Henry constant
590
(30.15 mmol/g.bar) and consequently high CO2 adsorption capacity (5.2 mmol/g at 1 bar and
591
25℃) due to the strong dispersion forces between CO2 and fir bark-derived AC which arise from
592
suitable pore size and the presence of N- and O- containing groups on adsorbent surface (Luo et
593
al., 2018). Notwithstanding thermodynamics suggestion that Henry constant always exist, Do et
594
al. dismisses this issue with the fact that sometimes the linear portion of the isotherm will occur
595
at far too low pressure, and far too low in capacity owing to the few number of strong sites and
596
their considerable strength that makes KH unmeasurable (Do et al., 2008).
597
4.3.2. Humidity
598
Water vapor is one of flue gas components alongside CO2 and N2. The perpetual dipole moment
599
belonging to the molecules of water makes it adsorb a great deal of adsorbents (Plaza et al.,
600
2014b). Activated carbon hygroscopicity at low levels of relative humidity (RH) can come from
601
the affinity of hydrophilic surface oxygen functional groups to water and the linking of water
602
molecules to surface functional group and adsorbate water molecules via hydrogen bonds (Pego
603
et al., 2019), and at high RH capillary condensation begins to take place and adsorb significant
604
amounts of water (Plaza et al., 2016; You and Liu, 2019). The results can have a negative effect
605
on the CO2 adsorption capacity through partial closure of pore mouth and consequent reduction
606
of beneficial CO2 adsorption sites as well as enhancement of diffusion resistance of CO2
607
conveyance to the active sites of carbon (Cen et al., 2013). Thermal treatment under a flow of
608
hydrogen or inert gas, different types of coatings as well as different acid treatments are several
609
techniques to limit water vapor adsorption (Querejeta et al., 2016).
610
A restricted number of investigations have been carried out into the effect of wet flue gas on
611
the CO2 adsorption using activated carbons. Plaza et al. employed the single step activation 58
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612
method to produce an olive-derived microporous AC using rarefied air (3% O2, balance N2) at
613
650 °C. They suggested that overlapped CO2 breakthrough curves under dry and humid (RH =
614
65%) conditions reveal the fact that water vapor is not an impediment factor for CO2 adsorption
615
on a short time scale owing to the much slower adsorption kinetics of H2O (Plaza et al., 2014b).
616
Two years later they took a fresh look at adsorption behavior of ternary N2/CO2/H2O mixture
617
through wet flue gas on their previous adsorbent. Using the IAS theory, based on the Toth model
618
for CO2 and N2 adsorption and the extended Cooperative Multimolecular Sorption (CMMS)
619
model for H2O adsorption, they predicted a reduction in the CO2 adsorption capacity up to a
620
level of 64% for the inlet gas stream with RH value of 95% (Plaza et al., 2016). In another study
621
by Luo et al., the existence of water vapor promoted the CO2 chemisorption on the amine-
622
functionalized sugarcane bagasse (SB-AM-TETA) and resulted in a superior CO2 adsorption
623
amount (Luo et al., 2016). In a recent study, the CO2 adsorption and recovery from wet flue gas
624
were simulated on a fixed bed of AC by You and Liu. The Langmuir model and arc-tangent
625
expression were applied in order to justify the amount of water vapor adsorption instigated by
626
the presence of hydrophilic groups as well as the amount adsorbed due to capillary condensation,
627
respectively. Moreover, the multi-component Langmuir model was used with the assumption of
628
competitive adsorption equilibrium occurrence between H2O, CO2 and N2. They reported a large
629
prohibitive influence on the adsorption and recovery of CO2 with the enhancement of humidity
630
(50.00%-100.00%). Nevertheless, the competitive adsorption of H2O and CO2 is comparatively
631
minor, mainly because of the bed temperature variation produced by the heat of H2O
632
adsorption/desorption (You and Liu, 2019).
59
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633
4.3.3. Multicomponent Adsorption
634
It has been reported that the adsorption capacity of AC is contingent on the molecular size of
635
adsorbate, i.e. a decrease in the molecular size leads to an increase in the adsorbability (Zhang et
636
al., 2017). For instance, when N2 (molecular diameter of ~3.64 Å) interacts with the surface of
637
an adsorbent with a smaller pore size, the opportunity of its molecules to be ensnared in the
638
adsorbent pores is diminished, whereas for smaller molecules like CO2 (molecular diameter of
639
~3.30 Å) this chance is higher (Banisheykholeslami et al., 2015). Nonetheless, providing that the
640
microporosity in a sample is large enough to disregard shape selectivity impacts on the basis of
641
the kinetic diameter of gas molecules (molecular diameter of ~3.80 Å for CH4), the larger
642
quadrupolar moment of CO2 (CO2, 13.4 × 10‒40 C m2; N2, 4.7 × 10‒40 C m2; CH4, does not hold a
643
quadrupole moment) may be responsible for such a distinct adsorption capacity. The quadrupole
644
moment, yields a robust attraction to the surface of adsorbent, which results in an improved
645
uptake. The adsorption performance may also be affected by the polarizability (CO2, 29.1 × 10‒25
646
cm‒3; N2, 17.4 × 10‒25 cm‒3; CH4, 26 × 10‒25 cm‒3). As the polarizability as well as the
647
quadrupole moment of CO2 are superior to those of N2, a surpassing selectivity is expected
648
owing to a higher affinity of the pore surface for CO2 (Álvarez-Gutiérrez et al., 2015; Parshetti et
649
al., 2015). Although both CO2 and CH4 have high polarizability, the quadrupole moment is much
650
more powerful than this attraction force (Álvarez-Gutiérrez et al., 2015).
651
The flue gas produced from combustion of carbon-rich fuels also contains oxygen (O2), NOX
652
and SOX compounds as a result of reactions between oxygen and available nitrogen and sulfur,
653
as well as hydrogen sulfide (H2S) (Sass et al., 2005).
654
Notwithstanding the great potential of adsorbent materials in applications of CO2 capture, the
655
presence of SOX, NOx and H2S impurity gases and their negative impact on lifetime of the 60
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656
adsorbents remains a significant challenge. Prevalent CO2 capture processes, which are based on
657
adsorption, depend entirely on applying a pretreatment stage to eliminate the aforementioned
658
impurities, which noticeably increases the production cost, owing to their permanent adsorption
659
potential, falloff total available active sites and conveyance limitation through the porous
660
network. The higher acidity and permanent dipole moment of SO2 in conjunction with higher
661
polarity and adsorption strength of NO2 would not comply with the adsorption of CO2 (Rezaei et
662
al., 2015). Moreover, H2S parasitically affect CO2 adsorption with its chemisorption and the
663
consequent reduction of porous volume and surface area, which alter both physisorption and
664
chemisorption of CO2 (de Oliveira et al., 2019).
665
Furthermore, Boonpoke et al. (Boonpoke et al., 2012), Fiuza-Jr et al. (Fiuza-Jr et al., 2016),
666
and Erto et al. (Erto et al., 2016) investigated the CO2 sorption capacities of different biomass-
667
derived ACs as a function of influent CO2 concentration (balanced with N2). They concluded that
668
CO2 adsorption capacity is strongly enhanced through CO2 inlet concentration enhancement due
669
to an improvement in the partial pressure of CO2, faster mass transfer and also a more rapid solid
670
coverage and saturation occurrence.
671
672
5. Conclusion and Future Research Needs
673
Carbon dioxide is an inert gas that has no heating value of combustion. It is believed that CO2 is
674
the most potent GHG and contributes to global warming more than other GHGs. Thus, not only
675
is it an environmental concern but it is also crucial for developing a practicable implementation
676
strategy of GHG control, which can cover industrial facilities as well as power plants. For this
677
purpose, varied technologies have been developed for CO2 capture and storage. Despite the fact 61
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678
that every technology has its strengths and limitations, CCS from point source emissions has
679
appeared as one of the possible remedies for stabilizing the CO2 level in the environment. To
680
decrease CO2 capture and separation costs, as well as make CCS obtainable for concrete
681
application, gas-solid adsorption has been considered as a possible solution as it reveals several
682
advantages, such as cost/ease of adsorbent synthesis, enhancement of CO2 adsorption capacity,
683
regeneration facility, rapid reaction rated and the simplicity of practicability over a wide variety
684
of operating temperatures and pressures. If renewable resources are used as materials and the
685
costs of CO2 capture are reduced, lignocellulose-based nanomaterials can be a promising
686
precursor. A review of the lignocellulose-based adsorbents for CO2 capture was made, with a
687
focus on the key factors governing CO2 adsorption. Overall, the results showed that the
688
synergetic effect of the physical characteristics and surface chemistry of adsorbents determines
689
the CO2 adsorption capacity. In general, high specific surface area, ultramicropore volume and
690
alkalinity result in high CO2 adsorption capacity. Nevertheless, the aforementioned factors were
691
not the entire parameters determining adsorption capacities. Synthetic parameters such as
692
carbonization temperature, inert gases flow rate, activating agent type and dosage, activation
693
time and temperature can simply be changed to fulfill the requirements for CO2 adsorption at
694
various operating pressures. Moreover, incorporating nitrogen groups in the ACs structures is
695
one of the most feasible approaches for high temperature CO2 adsorption. Furthermore, almost
696
all ACs are hydrophobic and the presence of water not only does not reduce their adsorption but
697
also in some cases leads to higher adsorption.
698 699
Another important part of this review is the investigation into the health and environmental effects of CO2 and different techniques for its reduction.
62
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700
In summary, many practical solid sorbents are available for CO2 capture but future technology
701
should focus on promising solid sorbent candidates with high CO2 selectivity and adsorption
702
capacity, high cycle lifetime and multicycle durability, low price as well as environmental
703
friendliness to serve as a tool for CO2 adsorption in real scale application. This review
704
demonstrates that the use of lignocellulose-based materials can be a practical option for the
705
development of low-cost adsorbents and, as a result, it is suggested that more investigations
706
should be carried out on lignocellulose-based adsorbents for CO2 capture. While it can be the
707
first step for CO2 reduction, it may not be the comprehensive solution to climate change.
708 709
710
Compliance with Ethical Standards
711
Conflict of Interest: The authors declare that they have no conflict of interest.
712 713
References
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Ahmed, M.B., Hasan Johir, M.A., Zhou, J.L., Ngo, H.H., Nghiem, L.D., Richardson, C., Moni, M.A., Bryant, M.R., 2019. Activated carbon preparation from biomass feedstock: Clean production and carbon dioxide adsorption. Journal of Cleaner Production 225, 405-413. Ainsworth, E.A., Long, S.P., 2005. What have we learned from 15 years of free-air CO2 enrichment (FACE)? A meta-analytic review of the responses of photosynthesis, canopy properties and plant production to rising CO2. The New phytologist 165, 351-371. Alabadi, A., Razzaque, S., Yang, Y., Chen, S., Tan, B., 2015. Highly porous activated carbon materials from carbonized biomass with high CO2 capturing capacity. Chemical Engineering Journal 281, 606-612. Álvarez-Gutiérrez, N., Gil, M.V., Rubiera, F., Pevida, C., 2017a. Kinetics of CO2 adsorption on cherry stone-based carbons in CO2/CH4 separations. Chemical Engineering Journal 307, 249-257. Álvarez-Gutiérrez, N., Rubiera, F., Pevida, C., Jin, Y., Bae, J., Su, S., 2017b. Adsorption Performance Indicator to Screen Carbon Adsorbents for Post-combustion CO2 Capture. Energy Procedia 114, 23622371.
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Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
Journal Pre-proof Highlights
Lignocellulose is a feasible substitute for development of low-cost sorbents. Key factors controlling CO2 adsorption onto lignocellulose-based adsorbents are reviewed. Synthesis conditions change consequent adsorbent features. Prospective research challenges of lignocellulose-based adsorbents are summarized.