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.     

Porous structure and adsorptive properties of pineapple peel based activated carbons prepared via microwave assisted KOH and K2CO3 activation

The present research explores the feasibility of microwave irradiation for preparation of high surface area activated carbon from pineapple peel (PPAC), an agricultural effluent emitted from the food can processing industries via KOH and K₂CO₃ activation. The activation process was performed at the microwave power of 600 W and irradiation time of 6 min. The equilibrium behavior of PPAC was investigated by performing batch adsorption experiments using methylene blue as adsorbate. Nonlinear adsorption isotherm models, Langmuir, Freundlich and Temkin were used to simulate the equilibrium data. KOH activated sample demonstrated a better development of pore structure, with the BET surface area, total pore volume and average pore size of 1006 m²/g, 0.59 m³/g and 23.44 Å, respectively, while the monolayer adsorption capacity of methylene blue was determined to be 462.10 mg/g. The findings support the potential use of microwave assisted KOH and K₂CO₃ activation as a promising activation technique.     

Post-synthesis modifications of SBA-15 carbon replicas: Improving hydrogen storage by increasing microporous volume

SBA-15 carbon replicas were synthesized with a sucrose solution as carbon source, carrying out carbonization at two different temperatures (800 and 1000 °C). Carbon pyrolised at 800 °C showed higher BET surface area and was chosen for further post-synthesis activation treatments (physical via CO₂ or chemical via KOH), with the aim of improving hydrogen adsorption capacity. For comparison, an amorphous carbon was also synthesized, by direct carbonization of the carbon source, without any inorganic template: on this material a chemical activation was also performed. H₂ adsorption isotherms at the temperature of liquid nitrogen and sub-atmospheric pressure were measured. A linear correlation was found between hydrogen uptake and microporous volume of the different carbons, rather than with BET specific surface area. Surprisingly, the sample prepared in the absence of inorganic template resulted the most effective one.     

Nanoporous rice husk derived carbon for gas storage and high performance electrochemical energy storage

We report on the gas storage behaviour and electrochemical charge storage properties of high surface area activated nanoporous carbon obtained from rice husk through low temperature chemical activation approach. Rice husk derived porous carbon (RHDPC) exhibits varying porous characteristics upon activation at different temperatures and we observed high gas uptake and efficient energy storage properties for nanoporous carbon materials activated even at a moderate activation temperature of 500 °C. Various experimental techniques including Fourier transform-infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and pore size analyser are employed to characterise the samples. Detailed studies on gas adsorption behaviour of CO₂, H₂ and CH₄ on RHDPCs have been performed at different temperatures using a volumetric gas analyser. High adsorption capacities of ~9.4 mmol g^?1 (298 K, 20 bar), 1.8 wt% (77 K, 10 bar) and ~5 mmol g^?1 (298 K, 40 bar) were obtained respectively for CO₂, H₂ and CH₄, superior to many other carbon based physical adsorbents reported so far. In addition, these nanoporous carbon materials exhibit good electrochemical performance as supercapacitor electrodes and a maximum specific capacitance of 112 F g^?1 has been obtained using aqueous 1 M Na₂SO₄ as electrolyte. Our studies thus demonstrate that nanoporous carbon with high porosity and surface area, obtained through an efficient approach, can act as effective materials for gas storage and electrochemical energy storage applications.     

Preparation of a highly microporous carbon from a carpet material and its application as CO2 sorbent

In order to increase the use of carpet wastes (pre- and/or post-consumer wastes), this work studies for the first time the preparation and characterisation of a microporous material from a commercial carpet (pile fiber content: 80% wool/20% nylon; primary and secondary backings: woven polypropylene; binder: polyethylene) and its application for CO₂ capture. The porous material was prepared from an entire carpet material using a standard chemical activation with KOH and then, characterised in terms of their porous structure and surface functional groups. Adsorption of CO₂ was studied using a thermogravimetric analyser at several temperatures (25-100 °C) and under different CO₂ partial pressures (i.e. pure CO₂ flow and a ternary mixture of 15% CO₂, 5% O₂ and 80% N₂). In order to examine the adsorbent regenerability, multiple CO₂ adsorption/desorption cycles were also carried out. The surface area and micropore volume of the porous adsorbent were found to be 1910.17 m² g^− 1 and 0.85 cm³ g^− 1, respectively. The CO₂ adsorption profiles illustrate that the maximum CO₂ capture on the sample was reached in less than 10 min. CO₂ adsorption capacities up to 8.41 wt.% and 3.37 wt.% were achieved at 25 and 70 °C, respectively. Thermal swing regeneration studies showed that the prepared adsorbent has good cyclic regeneration capacities.     

Conversion of Poly(Ethylene Terephthalate) Waste into Activated Carbon: Chemical Activation and Characterization

Due to its high carbon content, low impurities, low cost and easy availability, poly(ethylene terephthalate) (PET) waste is considered as a suitable precursor for the production of activated carbon. The chemical activation of PET wastes using different chemical agents such as H₃PO₄, H₂SO₄, ZnCl₂, and KOH was investigated. KOH‐ and ZnCl₂‐activated PET were found to be the best choices for the adsorption of small and large molecules. The capacities of the adsorbents towards I₂, methylene blue, N₂, CH₄, and CO₂ followed the order KOH‐PET >H₃PO₄‐PET > ZnCl₂‐PET > H₂SO₄‐PET; however, in the molasses uptake and selective adsorption of CO₂ compared to CH₄, ZnCl₂‐PET performed better than the other adsorbents.     

In situ nitrogen enriched carbon for carbon dioxide capture

In situ nitrogen enriched carbon was synthesized from locally available low cost soybean as the proteinaceous source. The material was synthesized by chemical activation using zinc chloride followed by physical activation using CO₂. The surface area of synthesized nitrogen enriched carbon was found to be 811 m²/g which is comparable with commercially available activated carbon. The nitrogen enriched carbon was having a breakthrough adsorption capacity of 23 mg/g at 120 °C which was almost three times higher in comparison with the commercially available activated carbon for a gas mixture comprising 15% CO₂ balanced with helium. This high adsorption capacity was attributed to the presence of nitrogen group within the carbon matrix, which was estimated to be about 0.64% as determined using the Kjeldahl’s method. The presence of different nitrogen containing groups assisting the adsorption of CO₂ in the synthesized sample was also confirmed by infrared analysis. For checking the consistent performance of the synthesized carbon, multi-cycle adsorption-desorption studies were carried out at 30 and 75 °C in binary mixture of CO₂/N₂.     

Preparation and characteristics of rice-straw-based porous carbons with high adsorption capacity

To prepare porous carbons with high adsorption capacity from rice straws, two different kinds of precursors, i.e. one as the raw rice straws (one-stage process) and the other as pre-carbonized rice straws (two-stage process), were activated with KOH of various impregnation ratios. The two-stage process was found very effective for manufacturing porous carbons with high surface area and adsorption capacities for MB and I₂. For example, the porous carbon that was carbonized at 700°C and subsequently activated at 900°C exhibited the surface area of 2410 m²/g, the adsorption capacities of 800 and 1720 mg/g for MB and I₂, respectively, and the total pore volume of 1.4 ml/g. In the two-stage method, there was a preferential optimum impregnation ratio of KOH to a precursor carbon, i.e. 4:1, with which high surface area of porous carbons could be achieved. The formation of uni- and bidentate carboxylic salt structure, induced by reaction between KOH and oxygen containing carbon, that facilitates the formation of azo group (-NN-) on a subsequent heat treatment was considered as one of the key factors for the presence of optimum impregnation ratio of KOH. In contrast, the porous carbons of only moderate adsorption capacity could be obtained from the one-stage method. The original morphology of rice straw was sustained during the two-stage process, yet not during the one-stage process.     

Activation of coal tar pitch carbon fibres: Physical activation vs. chemical activation

Activated carbon fibres (ACF) are obtained mainly by physical activation with steam or carbon dioxide. Additionally, there are many papers dealing with chemical activation of carbon fibres, or a polymeric raw material, with several chemical agents like for example, phosphoric acid, zinc chloride, aluminium chloride,… Nevertheless, although it is well known that hydroxides are good activating agents, there are few papers about the activation of carbon fibres with KOH or NaOH. In the present work, ACF with high surface area are obtained by chemical activation with KOH and NaOH. Both chemical agents present different behaviour; thus, NaOH developed the highest value of porosity and KOH developed samples with narrower micropore size distribution. In order to compare the results with those obtained by physical activation, some ACF have been prepared using CO₂ activation. The main conclusion of this work is that by using chemical activation it is possible to obtain similar, or even higher, porosity (∼1 ml/g, ∼3000 m²/g) than by physical activation. However, chemical activation presents two important advantages: (1) a much higher yield (27-47% for chemical activation and 6% physical activation for ∼2500 m²/g activated carbon fibres) and (2) the surface of the fibres prepared by chemical activation is less damaged than by physical activation.     

Amine modified mesocellular siliceous foam (MCF) as a sorbent for CO2

Adsorption is considered a promising method for carbon capture. CO₂ adsorbents take a variety of forms - but one approach is to fill mesoporous substrates with a polymeric CO₂ selective sorbent. SBA-15 and mesocellular siliceous foam (MCF) are high pore volume, high surface area ordered mesoporous materials for which modification with amine should result in high capacity, highly selective adsorbents. SBA-15 and MCF were separately loaded with approximately one pore volume equivalent of linear polyethyleneimine (PEI) (M_w = 2500) or branched PEI (M_n = 1200). CO₂ adsorption/desorption isotherms under dry CO₂ were obtained at 75, 105 and 115 °C. The CO₂ adsorption/desorption kinetics were improved with temperature, though the CO₂ capacities generally decreased. The adsorption capacity for MCF loaded with branched PEI at 105 and 115 °C were 151 and 133 mg/g adsorbent, respectively (in 50% CO₂/Ar, 20 min adsorption time). These are significantly higher than the adsorption capacity observed for SBA-15 loaded with branched PEI under same conditions, which were 107 and 83 mg/g adsorbent, respectively. Thus the results indicate that, on a unit mass basis, amine modified MCF's are potentially better adsorbents than amine modified SBA-15 for CO₂ capture at modestly elevated temperature in a vacuum swing adsorption process.     

Production and adsorption characteristics of MAXSORB: High-surface-area active carbon

High-surface-area (over 3000 m² g⁻¹) active carbon has been developed with an extremely large adsorption capacity. Various kinds of petroleum coke were mixed with an excess amount of KOH and dehydrated at 400°C, followed by activation at 600–900°C in an inert atmosphere. The remaining KOH was removed by washing with water after the activation. Pore analysis indicated that this active carbon has a large portion of mesopores (1.0–1.5 ml g⁻¹) with radii between 10 and 20 Å, whereas micropores are as numerous as in conventional steam activated carbon (0.5 ml g⁻¹). Since considerable amounts of K₂CO₃ and hydrogen were formed, the majority of the carbon consumption was due to the transformation of K₂O into K₂CO₃ by CO₂. Potassium metal was also formed from the hydroxide by dehydration and reduction by hydrogen or carbon. Reversible adsorption of gasoline vapour, and isotherms of methylene blue and iodine in solution were obtained. Regardless of the kind of adsorbent tested, the adsorption capacity increased proportionally to the BET surface area. The fact that the surface area exceeds the geometric maximum was explained by introducing the concept of associated adsorption. This product is now commercially available from our company under the brand name of MAXSORB.     

Effect of activation on the carbon fibers from phenol–formaldehyde resins for electrochemical supercapacitors

Activated carbon fibers (ACF) are prepared from phenol–formaldehyde resin fibers through chemical activation and physical activation methods. The chemical activation process consisted of KOH, whereas the physical activation was performed by activation in CO₂. The characteristics of the electrochemical supercapacitors with carbon fibers without activation (CF), carbon fibers activated by CO₂ (ACF-CO₂), and carbon fibers activated by KOH (ACF-KOH) have been compared. The activated carbon fibers from phenol–formaldehyde resins present a broader potential range in aqueous electrolytes than activated carbon and other carbon fibers. Activation does not produce any important change in the shape of starting fibers. However, activation leads to surface roughness and larger surface areas as well as an adapted pore size distribution. The higher surface areas of fibers treated by KOH exhibited higher specific capacitances (214 and 116 F g⁻¹ in aqueous and organic electrolytes, respectively) and good rate capability. Results of this study suggest that the activated carbon fiber prepared by chemical activation is a suitable electrode material for high performance electrochemical supercapacitors.     

Effects of chemical modification of petroleum cokes on the properties of the resulting activated carbon

Activated carbons have been prepared from petroleum cokes by the combination of a chemical treatment with HClO₄ or H₂O₂ and a chemical activation with KOH at a constant KOH/coke ratio of 3/1. The influence of different chemical treatments on the properties of the activated carbon precursors and final carbons activated with KOH was invested by using XRD, FTIR, and BET techniques. XRD results indicated that the value of interplanar distance d₀₀₂ increased by chemical treatment and the disappearance of the peak corresponding to 0 0 2 faces correlated to high specific surface area. FTIR studies showed that chemical modification promoted the formation of surface oxygen functionalities. Significant effects on BET surface area, pore texture and iodine adsorption capacity were evidenced. The results show that chemical modification prior to activation dramatically increased the BET surface area and total pore volume of the resulting activated carbon. Modified petroleum coke based activated carbon with chemical activation had higher specific surface area (2336 m²/g) and better iodine adsorption value (1998 mg/g).     

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.     

A comparison of physical activation of carbon xerogels with carbon dioxide with chemical activation using hydroxides

Carbon xerogels synthesized with a fixed resorcinol/sodium carbonate molar ratio (R/C) were physically activated using CO₂. The effect of activation temperature and activation time on the final properties of the activated carbon xerogels was evaluated. The specific surface area increases from ∼600 m² g⁻¹ to 2000 m² g⁻¹ and more by increasing the temperature and duration of the activation step. A comparison between physical activation with CO₂ and chemical activation with hydroxides was also performed: it was found that both processes produce an increase of the micropore volume and specific surface area without altering the mesoporosity developed during the synthesis. However, chemical activation can lead to the development of the narrow microporosity mainly whereas, in physical activation, the widening of the narrow micropores takes place whatever the process conditions.     

Hydrogen adsorption in different carbon nanostructures

Hydrogen adsorption in different carbonaceous materials with optimized structure was investigated at room temperature and 77 K. Activated carbon, amorphous carbon nanotubes, SWCNTs and porous carbon samples all show the same adsorption properties. The fast kinetics and complete reversibility of the process indicate that the interaction between hydrogen molecules and the carbon nanostructure is due to physisorption. At 77 K the adsorption isotherm of all samples can be explained with the Langmuir model, while at room temperature the storage capacity is a linear function of the pressure. The surface area and pore size of the carbon materials were characterized by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. A linear relation between hydrogen uptake and specific surface area (SSA) is obtained for all samples independent of the nature of the carbon material. The best material with a SSA of 2560 m²/g shows a storage capacity of 4.5 wt% at 77 K.     

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.     

Hydrogen sorption characteristics of Zonguldak region coal activated by physical and chemical methods

Hydrogen sorption characteristics of activated carbons (ACs) produced by physical and chemical activations from two coal mines (Kilimli and Armutcuk) in the Zonguldak region, Turkey were investigated by a volumetric technique at 77 K. H₂ adsorption isotherms were obtained on the samples exposed to pyrolytic thermal treatments in a temperature range of 600–900 °C under N₂ flow and chemical activation using different chemical agents such as KOH, NH₄Cl, ZnCl₂ from the two mines. Experimental hydrogen adsorption isotherm data at 77 K were used for the evaluation of the adsorption isotherm constants of the Brunauer-Emmett-Teller (BET) and the Langmuir models, and also the amount of hydrogen adsorbed on the various samples was evaluated by using the adsorption isotherm data. Higher hydrogen adsorption capacity values were obtained for all the heat and the chemically treated activated carbon samples from the Kilimli coal samples than Armutcuk. The amount of H₂ adsorbed on the original Kilimli coal samples was 0.020 wt%, and it was increased to 0.89 wt% on the samples pyrolyzed at 800 °C. The highest value of hydrogen adsorption obtained was 1.2 wt% for the samples treated with KOH+NH₄Cl mixture at 750 °C followed by oxidation with ZnCl₂. It was shown that chemical activations were much more effective than physical activations in increasing the surface area, pore volume and the hydrogen sorption capacities of the samples.     

A novel carbonized polydopamine (C‐PDA) adsorbent with high CO2 adsorption capacity and water vapor resistance

Novel carbonized polydopamine adsorbents (C‐PDAs) with high surface area, high CO₂ adsorption capacity and superior moisture resistance performance were prepared by one‐step synthesis method using polydopamine as carbon precursor at different KOH/C ratios, and then characterized. CO₂ and water vapor adsorption performances of C‐PDAs were examined separately by static adsorption and fixed‐bed experiments. Results showed that BET area and pore volume of C‐PDA‐4 were up to 3342 m²/g and 2.01 cm³/g, respectively. Its CO₂ adsorption capacity reached up to 30.5 mmol/g at 25 bar, much higher than many other adsorbents including metal‐organic frameworks (MOFs). C‐PDAs prepared with high KOH/C ratios had low surface element concentrations of O and N resulting in low surface hydrophilic property. H₂O(g) isotherm of C‐PDA was much lower than those on Mg‐MOF‐74, Cu‐BTC, and MIL‐101(Cr). Fixed‐bed experiments showed that co‐presence of water vapor in feed stream with 30% RH had negligible impact on CO₂ working capacity of C‐PDA. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3730–3738, 2016     

Effect of various porous nanotextures on the reversible electrochemical sorption of hydrogen in activated carbons

The reversible hydrogen storage capacity of three series of activated carbons (ACs) prepared from different precursors by KOH, CO₂ and steam activation is determined by electrodecomposition of an alkaline water solution and is correlated with the nanotextural parameters of ACs. Galvanostatic charge/discharge appears as a precise quantitative method for estimating the hydrogen sorption capacity, whereas, cyclic voltammetry supplies a very useful information on the electrosorption mechanism. For the ACs studied, the hydrogen sorption capacity is not linearly related with any of the porosity parameters commonly used in other publications, such as the Dubinin-Radushkevich micropore volumes determined by nitrogen or carbon dioxide adsorption, VDR N₂ and VDR CO₂. In particular, an important discrepancy is observed for the KOH activated materials, suggesting that this treatment may provoke changes of pore shape. A better correlation is found considering the nanopore size distribution obtained from CO₂ adsorption by the DFT method. The amount of hydrogen reversibly adsorbed demonstrates a proportional trend with the volume of micropores smaller than 0.6-0.7 nm. However, in all cases, a part of the micropore volume estimated by CO₂ adsorption is ineffective, suggesting that some ultramicropores are involved in irreversible trapping of hydrogen.