Oxygen-containing functional group-facilitated CO2 capture by carbide-derived carbons

A series of carbide-derived carbons (CDCs) with different surface oxygen contents were prepared from TiC powder by chlorination and followed by HNO₃ oxidation. The CDCs were characterized systematically by a variety of means such as Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultimate analysis, energy dispersive spectroscopy, N₂ adsorption, and transmission electron microscopy. CO₂ adsorption measurements showed that the oxidation process led to an increase in CO₂ adsorption capacity of the porous carbons. Structural characterizations indicated that the adsorbability of the CDCs is not directly associated with its microporosity and specific surface area. As evidenced by elemental analysis, X-ray photoelectron spectroscopy, and energy dispersive spectroscopy, the adsorbability of the CDCs has a linear correlation with their surface oxygen content. The adsorption mechanism was studied using quantum chemical calculation. It is found that the introduction of O atoms into the carbon surface facilitates the hydrogen bonding interactions between the carbon surface and CO₂ molecules. This new finding demonstrated that not only the basic N-containing groups but also the acidic O-containing groups can enhance the CO₂ adsorbability of porous carbon, thus providing a new approach to design porous materials with superior CO₂ adsorption capacity.     

CO2 Adsorption capacity of activated N‐doping porous carbons prepared from graphite nanofibers/polypyrrole

In this study, N‐doping porous carbons (NPCs) with a 3D aperiodic hierarchical and layered structure were prepared by the sodium hydride (NaOH) activation of graphite nanofibers (GNFs)/polypyrrole (PPY) composites. The effects of the N groups and structural features on the CO₂ adsorption capacity of NPCs were investigated by N₂ full isotherms, XRD, SEM, and TEM. The CO₂ adsorption capacity was measured by the CO₂ isothermal adsorption at 25°C and 1 atm. It was found that GNFs served as a substrate and layered graphitic carbons were formed by the thermal annealing of PPY. The content of N groups and textural properties of NPCs were enhanced with increasing activation temperature, resulting in improved CO₂ adsorption capacity. The CO₂ adsorption isotherms showed that GPK‐600 exhibited the best CO₂ adsorption capacity of 88.8 mg/g when the activation temperature was 600°C. The result indicates that the pore size and its distribution of NPCs lead to feasible contact CO₂, and the presence of high N groups on the NPCs could have resulted in further stabilization of the surface effect. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40517.     

The Characterization of the Micropore Structures of Some Activated Carbons of Plant Origin by N2 and CO2 Adsorptions

Abstract

In this study, active carbons prepared from almond and hazelnut shells under various experimental conditions were investigated. Merck-2514 and Merck-2184 active carbons were used for comparison. N₂ (77 K) gas and CO₂ (273 and 195 K) gas adsorptions were determined as comparison criteria. Regarding the specific surface area and micropore volume results obtained from these adsorption data, it is concluded that N₂ (77 K) adsorption by itself is inadequate in the characterization of active carbons which are low-sized microporous dominated. In addition, it is concluded that it would be useful to investigate CO₂ (195 and 273 K) adsorption. The iodine and methylene blue tests at 298 K were also applied for the characterization of the carbon adsorbents mentioned. From these data it was seen that the iodine test can be applied as a total porosity indicator and that the methylene blue test can be used as a developed microporosity indicator. These results indicate that the best adsorbents were those prepared from hazelnut shells. Depending on the preparation conditions, the physically activated carbon has an activation time up to 4 hours and has adsorption properties on the level of Merck commercial carbons.     

Enhanced mercury adsorption in activated carbons from biomass materials and waste tires

Agricultural residues and waste tires constitute an important source of precursors for activated carbon production. Activated carbons offer a potential tool for mercury emissions control. In this work, pine and oak wood, olive seed and tire wastes have been used for the preparation of activated carbons, in order to be examined for their mercury removal capacity. In the case of activated carbons produced from pine/oak woods and tire wastes, a two stage physical activation procedure was applied. Activated carbons derived from olive seeds were prepared by chemical activation using KOH. Pore structure of the samples was characterized by N₂ and CO₂ adsorption, while TPD-IR experiments were performed in order to determine surface oxygen groups. Hg° adsorption experiments were realized in a bench-scale adsorption unit consisting of a fixed-bed reactor. The influence of activation technique and conditions on the resulted activated carbon properties was examined. The effects of pore structure and surface chemistry of activated carbons were also investigated. Activated carbons produced from olive seeds with chemical activation possessed the highest BET surface area with well-developed micropore structure, and the highest Hg° adsorptive capacity. Oxygen surface functional groups (mainly lactones) seem to be involved in Hg° adsorption mechanism.     

Microporous phenol-formaldehyde resin-based adsorbents for pre-combustion CO2 capture

Different types of phenolic resins were used as precursor materials to prepare adsorbents for the separation of CO₂ in pre-combustion processes. In order to obtain highly microporous carbons with suitable characteristics for the separation of CO₂ and H₂ under high pressure conditions, phenol-formaldehyde resins were synthesised under different conditions. Resol resins were obtained by using an alkaline environment while Novolac resins were synthesised in the presence of acid catalysts. In addition, two organic additives, ethylene glycol (E) and polyethylene glycol (PE) were included in the synthesis. The phenolic resins thus prepared were carbonised at different temperatures and then physically activated with CO₂. The carbons produced were characterised in terms of texture, chemical composition and surface chemistry. Maximum CO₂ adsorption capacities at atmospheric pressure were determined in a thermogravimetric analyser. Values of up to 10.8 wt.% were achieved. The high-pressure adsorption of CO₂ at room temperature was determined in a high-pressure magnetic suspension balance. The carbons tested showed enhanced CO₂ uptakes at high pressures (up to 44.7 wt.% at 25 bar). In addition, it was confirmed that capture capacities depend highly on the microporosity of the samples, the narrow micropores (pore widths of less than 0.7 nm) being the most active in CO₂ adsorption at atmospheric pressure. The results presented in this work suggest that phenol-formaldehyde resin-derived activated carbons, particularly those prepared with the addition of ethylene glycol, show great potential as adsorbents for pre-combustion CO₂ capture.     

Porous carbonaceous materials from hydrothermal carbonization and KOH activation of corn stover for highly efficient CO2 capture

Sustainable biomass-derived carbon materials were produced by hydrothermal carbonization of corn stover that was followed by chemical activation with KOH. The prepared carbon materials were used for CO₂ adsorption and had a CO₂ uptake of 7.14?mmol/g at a pressure of 1?bar and at 0°C that was much higher than CO₂ uptake by activated carbon that was prepared from direct activation of corn stover (2.78?mmol/g). The porous corn stover-derived carbonaceous material had high surface area (2442?m²/g) and large pore volume (1.55?cm³/g). Product yields obtained by the activation of hydrothermally carbonized corn stover were significantly higher than those obtained by the direct activation of corn stover (36–75?vs. 8%). The prepared corn stover-derived porous carbon had a high CO₂/N₂ selectivity of 15.5 and exhibited constant CO₂ uptake for five successive reuse cycles. The hydrothermal carbonization step plays an important role for producing porous carbons from biomass that have high and specific adsorption properties.     

Preparation of activated carbons by utilizing solid wastes from palm oil processing mills

Feasibility of producing activated carbons by utilizing solid wastes (extracted flesh fibre and seed shell) from palm oil processing mills was investigated. The effects of activation conditions (CO₂ flow rate, activation temperature and retention time) on the characteristics of the activated carbons, i.e. density, porosity, BET surface area, pore size distribution and surface chemistry were studied. In this study, the optimum conditions for activation were an activation temperature of 800 °C and a retention time of 30 min for fiber or 50 min for shell, which gave the maximum BET surface area. Pore size distribution revealed that the shell-based activated carbons were predominantly microporous whilst fiber activated carbon had predominant mesopores and macropores, suggesting the application of shell and fiber activated carbon as adsorbents for gas-phase and liquid-phase adsorption, respectively. This was confirmed by further gas- and liquid-phase adsorption tests.     

Chemical modification of carbon powders with aminophenyl and aryl-aliphatic amine groups by reduction of in situ generated diazonium cations: Applicability of the grafted powder towards CO2 capture

Aminophenyl, p-aminobenzyl and p-aminoethylphenyl groups were grafted at the surface of carbon Vulcan XC72R by spontaneous reduction of the in situ generated diazonium cations from the corresponding amine. X-ray photoelectron spectroscopy and elemental analysis confirmed an amine loading of about 1 mmol/g. The grafting of amine functionalities leads to a decrease of specific surface area from 223 to about 110 m²/g with a drastic loss of microporosity. Acid-base properties of the surface are also affected by the modification. Aminophenyl grafted groups make the surface more acidic while aryl-aliphatic amines groups tends to render it more basic. The grafted layer shows in each case a good thermal stability up to 250 °C. The affinity of the modified powder towards CO₂ and N₂ has been evaluated by thermal swing adsorption. The maximum adsorption capacity of CO₂ of modified carbons is lower than the unmodified carbon but the presence of the amine functionalities involves a better selectivity of the material towards CO₂ adsorption in comparison of N₂ adsorption.     

Preparation and Phosphine Adsorption of Activated Carbon Prepared from Walnut Shells by KOH Chemical Activation

Walnut-shell activated carbons (WSACs) with high surface area and predominant micropore development were prepared by KOH chemical activation. The effects of carbonization temperature, activation temperature, and ratio of KOH to chars on the pore development of WSACs and PH₃ adsorption performance of the modified walnut-shell activated carbons (MWSACs) were studied. Criteria for determining the optimum preparation conditions were pore development of WSACs and PH₃ breakthrough adsorption capacity of MWSAC adsorbents. The result shows that the optimum preparation conditions are a carbonization temperature of 700°C, an activation temperature of 700°C, and a mass ratio of 3. The BET surface area and the micropore volume of the optimal WASC are 1636m²/g and 0.641cm³/g, respectively. The micropore volume percentage of WSAC plays an important role in PH₃ adsorption when there is a slight difference in BET surface areas. High-surface-area WSACs with predominant micropores are suitable for PH₃ adsorption removal. The MWSAC adsorbent owns the biggest PH₃ breakthrough adsorption capacity (284.12mg/g) due to the biggest specific surface area, total pore volume, and micropore volume percentage. The MWSAC adsorbent will be a potential adsorbent for PH₃ adsorption removal from yellow phosphorus tail gas.     

Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

Enhancement of CO2 adsorption on phenolic resin-based mesoporous carbons by KOH activation

Carbons with high surface area and large volume of ultramicropores were synthesized for CO₂ adsorption. First, mesoporous carbons were produced by soft-templating method using triblock copolymer Pluronic F127 as a structure directing agent and formaldehyde and either phloroglucinol or resorcinol as carbon precursors. The resulting carbons were mainly mesoporous with well-developed surface area, large total pore volume, and only moderate CO₂ uptake. To improve CO₂ adsorption, these carbons were subjected to KOH activation to enhance their microporosity. Activated carbons showed 2–3-fold increase in the specific surface area, resulting from substantial development of microporosity (3–5-fold increase in the micropore volume). KOH activation resulted in enhanced CO₂ adsorption at 760 mmHg pressure: 4.4 mmol g⁻¹ at 25 °C, and 7 mmol g⁻¹ at 0 °C. This substantial increase in the CO₂ uptake was achieved due to the development of ultramicroporosity, which was shown to be beneficial for CO₂ physisorption at low pressures. The resulting materials were investigated using low-temperature nitrogen physisorption, CO₂ sorption, and small-angle powder X-ray diffraction. High CO₂ uptake and good cyclability (without noticeable loss in CO₂ uptake after five runs) render ultramicroporous carbons as efficient CO₂ adsorbents at ambient conditions.     

Superior carbon-based CO2 adsorbents prepared from poplar anthers

A series of renewable nitrogen-containing granular porous carbons with developed porosities and controlled surface chemical properties were prepared from poplar anthers. The preparation conditions such as pre-carbonization and activation temperatures and KOH amount significantly influence the structures and chemical compositions of the porous carbons, the CO₂ adsorption capacities of which are highly dependent on their pore structures, surface areas, nitrogen contents and adsorption conditions. The sample with developed microporosity, especially with the pores between 0.43 and 1 nm and high nitrogen content shows high CO₂ adsorption capacity at 1 bar and 25 °C. In contrast, when the adsorption pressure is higher than 5 bar, its CO₂ adsorption capacity is dominated by its surface area, and more accurately by its pore volume. Irrespective of this, if the pressure was decreased to 0.1 bar, its CO₂ capture ability is closely correlated to its nitrogen content but not to its porosity. By optimizing the preparation conditions, a porous carbon with a surface area of 3322 m² g⁻¹ and a CO₂ adsorption capacity as high as 51.3 mmol g⁻¹ at 50 bar and 25 °C was prepared.     

Importance of activated carbon's oxygen surface functional groups on elemental mercury adsorption

The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury (Hg⁰) was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N₂), air oxidation (693 K), and nitric acid (6N HNO₃) treatment of two activated carbons (BPL, WPL) were conducted to vary their surface oxygen functional groups. Adsorption experiments of Hg⁰ by the activated carbons were conducted using a fixed-bed reactor at a temperature of 398 K and under N₂ atmosphere. The pore structures of the samples were characterized by N₂ and carbon dioxide (CO₂) adsorption. Temperature-programmed desorption (TPD) and base-acid titration experiments were conducted to determine the chemical characteristics of the carbon samples. Characterization of the physical and chemical properties of activated carbons in relation to their Hg⁰ adsorption capacity provides important mechanistic information on Hg⁰ adsorption. Results suggest that oxygen surface complexes, possibly lactone and carbonyl groups, are the active sites for Hg⁰ capture. The carbons that have a lower carbon monoxide (CO)/CO₂ ratio and a low phenol group concentration tend to have a higher Hg⁰ adsorption capacity, suggesting that phenol groups may inhibit Hg⁰ adsorption. The high Hg⁰ adsorption capacity of a carbon sample is also found to be associated with a low ratio of the phenol/carbonyl groups. A possible Hg⁰ adsorption mechanism, which is likely to involve an electron transfer process during Hg⁰ adsorption in which the carbon surfaces may act as an electrode for Hg⁰ oxidation, is also discussed.     

CO2 Adsorption by Modified Palm Shell Activated Carbon (PSAC) Via Chemical and Physical Activation and Metal Impregnation

The aim of this study was to verify the ability of nickel-impregnated palm shell activated carbon (PSAC) for CO₂ adsorption and compare its performance with the chemically and physically activated PSAC. Sodium hydroxide and CO₂ were used as activating agents for chemical and physical activation, respectively. Nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) was used as a precursor for metal impregnation. The effect of different chemical loadings (NaOH: 20–50 wt%), metal impregnation (Ni(NO₃)₂·6H₂O: 16–28 wt%), and heat treatment time (1–4 h) was studied as parameters. Adsorption capacity was calculated using breakthrough graphs. The effect of humidity on CO₂ adsorption and desorption of CO₂ was also investigated in this study. The results revealed that chemically modified PSAC yields the highest adsorption capacity (48.2 mg/g) compared to other methods of activation. Interestingly, it was found that the adsorption capacity of nickel-impregnated PSAC was similar to other types of metal-impregnated activated carbon. Humidity gave a negative effect on CO₂ adsorption. In summary, results showed that chemical activation is an efficient technique to modify PSAC for CO₂ adsorption.     

Adsorption of carbon dioxide on ionic liquids-modified active carbons and amino-modified polymer

Active carbons with various particle sizes (38–150, 300–500 and 800–1,200 μm) were modified by ionic liquids (ILs), and organic polymer was modified by acrylamide using a simple procedure, and these materials were applied to capture carbon dioxide (CO₂). The CO₂ adsorption amounts were calculated using a mass balance equation at three different temperatures (298.15, 308.15 and 318.15 K), respectively, and the influences of gas pressure, particle size and temperature on adsorption were discussed. Experimental results showed that the CO₂ adsorption capacity of ILs-modified active carbons was better than amino-modified polymer, and the smaller particle size (38–150 μm) ILsmodified active carbons had the largest adsorption capacity at 298.15 K. Compared with previous research about polyethyleneimine (PEI)-modified silica gel, the adsorption amount of CO₂ on ILs-modified active carbons has been greatly improved with lower cost.     

Activation of carbon nanofibres for hydrogen storage

The present study was aimed to investigate different methods of activation of carbon nanofibres, CNF, in order to determine the beneficial effect on the hydrogen sorption capacities of increasing the surface area. Two activation systems were used: physical activation with CO₂ and chemical activation with KOH. A range of potential adsorbents were thus prepared by varying the temperature and time of activation. The structure of the CNF proved more suitable to activation by KOH than by CO₂, with the former yielding higher surface area carbons (up to 1000 m² g⁻¹). The increased surface area, however, did not correspond directly with a proportional increase in hydrogen adsorption capacity. Although high surface areas are important for hydrogen storage by adsorption on solids, it would appear that it is essential that not only the physical, but also the chemical, properties of the adsorbents have to be considered in the quest for carbon based materials, with high hydrogen storage capacities.     

Development of low-cost biomass-based adsorbents for postcombustion CO2 capture

In this work a series of carbon adsorbents were prepared from a low-cost biomass residue, olive stones. Two different approaches were studied: activation with CO₂ and heat treatment with gaseous ammonia. The results showed that both methods are suitable for the production of adsorbents with a high CO₂ adsorption capacity, and their potential application in VSA or TSA systems for postcombustion CO₂ capture. It was found that the presence of nitrogen functionalities enhances CO₂ adsorption capacity, especially at low partial pressures.     

The effect of activation method on the properties of pecan shell‐activated carbons

Pecan shell chars were activated using steam, carbon dioxide (CO₂), or phosphoric acid (H₃PO₄) to produce granular activated carbons (GACs). The GACs were characterized for select physical, chemical and adsorption properties. Air oxidation of the GACs was used to increase copper ion (Cu²⁺) adsorption. BET surface areas of pecan carbons were equal to or greater than commercial GACs. Carbon dioxide activation favored microporosity, while the other activations increased both mesoporosity and microporosity. Bulk densities and particle attrition of the pecan shell GACs were generally similar to the commercial carbons. Air oxidation of steam‐and CO₂‐activated GACs increased copper ion adsorption, although not to the same extent as GACs made by H₃PO₄ activation. Copper ion adsorption and the amount of titratable functional groups greatly exceeded the values for the commercial GACs. Steam‐and CO₂‐activated pecan shell carbons were similar to but in some cases exceeded the ability of commercial GACs to remove certain organic compounds from water. GACs from pecan shells showed considerable commercial potential to remove metal ions and organic contaminants from water. © 1999 Society of Chemical Industry     

Comparative study of the textural characteristics of oil palm shell activated carbon produced by chemical and physical activation for methane adsorption

The objective of this study is to relate textural and surface characteristics of microporous activated carbon to their methane adsorption capacity. Oil palm shell was used as a raw material for the preparation of pore size controlled activated carbon adsorbents. The chemical treatment was followed by further physical activation with CO₂. Samples were treated with CO₂ flow at 850 °C by varying activation time to achieve different burn-off activated carbon. H₃PO₄ chemically activated samples under CO₂ blanket showed higher activation rates, surface area and micropore volume compared to other activation methods, though this sample did not present high methane adsorption. Moreover, it was shown that using small proportion of ZnCl₂ and H₃PO₄ creates an initial narrow microporosity. Further physical activation grantees better development of pore structure. In terms of pore size distribution the combined preparation method resulted in a better and more homogenous pore size distribution than the conventional physical activation method. Controlling the pore size of activated carbon by this combined activation technique can be utilized for tuning the pore size distribution. It was concluded that the high surface area and micropore volume of activated carbons do not unequivocally determine methane capacities.     

Highly selective CO2 capture by S-doped microporous carbon materials

S-doped microporous carbon materials were synthesized by the chemical activation of a reduced-graphene-oxide/poly-thiophene material. The material displayed a large CO₂ adsorption capacity of 4.5 mmol g⁻¹ at 298 K and 1 atm, as well as an impressive CO₂ adsorption selectivity over N₂, CH₄ and H₂. The material was shown to exhibit a stable recycling adsorption capacity of 4.0 mmol g⁻¹. The synthesized material showed a maximum specific surface area of 1567 m² g⁻¹ and an optimal CO₂ adsorption pore size of 0.6 nm. The microporosity, surface area and oxidized S content of the material were found to be the determining factors for CO₂ adsorption. These properties show that the as synthesized S-doped microporous carbon material can be more effective than similarly prepared N-doped microporous carbons in CO₂ capture.