Porous properties of activated carbon produced from Eucalyptus and Wattle wood by carbon dioxide activation

This work focused on the preparation of activated carbon from eucalyptus and wattle wood by physical activation with CO₂. The preparation process consisted of carbonization of the wood samples under the flow of N₂ at 400°C and 60 min followed by activating the derived chars with CO₂. The activation temperature was varied from 600 to 900°C and activation time from 60 to 300 min, giving char burn-off in the range of 20/2-83%. The effect of CO₂ concentration during activation was also studied. The porous properties of the resultant activated carbons were characterized based on the analysis of N2 adsorption isotherms at −196°C. Experimental results showed that surface area, micropore volume and total pore volume of the activated carbon increased with the increase in activation time and temperature with temperature exerting the larger effect. The activated carbons produced from eucalyptus and wattle wood had the BET surface area ranging from 460 to 1,490 m²/g and 430 to 1,030 m²/g, respectively. The optimum activation conditions that gave the maximum in surface area and total pore volume occurred at 900°C and 60 min for eucalyptus and 800°C and 300 min for wattle wood. Under the conditions tested, the obtained activated carbons were dominated with micropore structure (∼80% of total pore volume).     

Influence of preparation conditions on porous structures of olive stone activated by H3PO4

An olive factory residue was used as a precursor in the preparation of granular activated carbon by chemical activation with H₃PO₄. Effects of final activation temperature, time, and H₃PO₄ concentration used in the impregnation stage on the porous development were investigated. SO₂ adsorption experiments were also performed for some of the activated carbon samples to represent their adsorption performance. Activation at low temperature represented that micropores were developed first at early stages of the temperatures. Mesoporosity developed at around 250 °C, enhanced up to 400 °C, and then started to decrease due to possibly shrinking of pores. The optimum temperature for olive stone was found to be around 400 °C on the basis of total pore volume and BET surface area. It was clearly demonstrated that H₃PO₄ concentration used in the impregnation stage was not only effective for development of surface area and pore volumes but also an effective tool for tailoring the pore structure and size distribution.     

CO2 capture capacities of activated carbon fibre-phenolic resin composites

The potential of activated carbon fibre-phenolic resin composites for CO₂ capture has been evaluated in this work. A number of composites were fabricated using different types of carbon fibre under various conditions. The effect of a range of variables such as the type of carbon fibre, mass ratio of carbon fibre to phenolic resin, activation temperature and duration on the CO₂ adsorption capacity was investigated. Activated carbon derived from powdered phenolic resin demonstrates its capability to capture CO₂ and it plays a significant role in the low burn-off range. An apparent optimal degree of activation for CO₂ adsorption capacity was identified which was coincident with the maximum micropore volume measured by CO₂ physical adsorption. Micropore volume by CO₂ has been identified as a potential design parameter for the development of activated carbon fibre-phenolic resin composites for CO₂ capture. The existence of a cross-over regime is confirmed and lower burn-off samples are found to capture more CO₂ at ambient conditions. This is attributed to a narrow microporosity and a large contribution of micropore volume from smaller pores in the microporosity range of the composites. The optimal pore size for CO₂ capture becomes smaller when the relative pressure of CO₂ goes lower.     

Textural Characterization of Activated Carbons Prepared from Oil-palm Stones Pre-treated with Various Impregnating Agents

Activated carbons with relatively high densities and well-developed porosities were prepared from oil-palm stones which were pre-treated with different types of impregnating agents (ZnCl₂, H₃PO₄ or KOH). The benefits derived from impregnation in terms of higher BET surface areas were generally in the following order: 20% ZnCl₂ > 40% H₃PO₄ > 10% KOH. The textural properties such as density and total porosity, overall yield, BET and micropore surface areas and pore size distributions of the activated carbon were related to the concentration of the impregnating solution and the activation conditions (activation temperature and hold time). For the highest BET surface area obtained in this study, the optimum conditions for CO₂ activation were found to be at an activation temperature of 750°C for 1 hour from oil-palm stones pre-treated with 20% ZnCl₂ for 24 hours. Pore size distribution suggests the application of oil-palm-stone activated carbons as gas-phase adsorbents for air pollution control.     

Analysis of the microporous texture of a glassy carbon by adsorption measurements and Monte Carlo simulation. Evolution with chemical and physical activation

A mesoporous glassy carbon has been chemically (KOH) and physically (CO₂) activated in order to improve its micropore volume while preserving the well-defined mesopore network. The microporosity of the glassy carbon and the evolution of the micropore texture with activation have been studied by means of Monte Carlo simulation and gas adsorption. Micropore size distributions obtained from simulated adsorption isotherms on slit-shaped pores revealed different accessibilities of methane and nitrogen to the microporous texture of the original sample, indicating the presence of constrictions in the micropore network. Both activating agents are able to increase the micropore volume generating new micropores, although KOH showed to be more effective. While CO₂ treatment preserved some hindrances to the access of nitrogen molecules to the micropores, KOH activation generates a more accessible micropore network. Therefore, chemical activation by KOH is a suitable way to increase the adsorption capacity of glassy carbons while preserving the mesoporous structure. Molecular simulation of adsorption linked to experimental adsorption of different gases, has proven to give very satisfactory results in analysing the evolution of the micropore texture and accessibility of carbon materials by different activation treatments.     

Preparation and characterization of activated carbons for SO<Subscript>2</Subscript> adsorption from Taixi anthracite by physical activation with steam

Taixi anthracite was used as a precursor to prepare activated carbons (AC) for SO₂ adsorption from flue gas. In this work the activated carbons were prepared by physical activation with steam. Specifically, the effects of activation temperature and burn-off degree on the physico-chemical properties of the resulting AC samples were comparatively studied. The different types of pore volumes, pore size distributions and surface chemistries of the activated carbons on the SO₂ adsorption were also analyzed. The results show that the increasing burn-off leads to samples with continuous evolution of all types of pores except ultramicropore. The ultramicropore volume increases to a maximum of 0.169 cm³/g at around 50% burn-off and then decreases for 850 °C activation. At higher activation temperature, the micropore volume decreases and the mesopore structure develops to a certain extent. For all the resulting AC samples, the quantities of the basic surface sites always appear much higher than the amount of the acidic sites. The activated carbon prepared with higher micropore volume, smaller median pore diameter and higher quantities of the basic surface sites represents better SO₂ sorption property.     

Synthetic carbons activated with phosphoric acid: II. Porous structure

Synthetic activated carbons were prepared by H₃PO₄ activation of a chloromethylated and sulfonated copolymer of styrene and divinylbenzene, using an impregnation weight ratio of 0.75 and carbonization temperatures in the 400-1000 °C range. Other impregnation ratios (0.93 and 1.11) were also used at a carbonization temperature of 800 °C. The porous texture of the resulting carbons was characterized by N₂ adsorption at −196 °C and CO₂ adsorption at 0 °C. All carbons exhibited a multimodal pore size distribution with maxima in the micropore and meso/macropore regions. Maxima in pore volume were attained at 900 °C for micropores and at 500 and 900 °C for mesopores. The mesopore volume was less sensitive than the micropore volume to changes in the impregnation ratio. It is concluded that the porous texture is not a prime factor in determining the outstanding cation exchange capacities of these carbons.     

Synthesis and characterization of mesoporous electrospun carbon fibers derived from silica template

In our study, mesoporous carbon fibers were prepared by using electrospinning and physical activation. In order to develop mesoporous structure, silica was used as a physical activation agent due to meso-size of particle. The diameter of activated carbon fibers increased and surface became rougher after physical activation. Textural properties of carbon fibers were evaluated by using surface pore structure analysis apparatus. The specific surface area increased 12 times and total pore volume increased about 57 times through physical activation using silica. The development of mesoporous structure was confirmed by pore size distribution and fraction of micropore volume. From the DFT pore size distribution, it is sure that broad meso-sized porous carbon fibers were obtained from physical activation in our experiment. The fact that fractions of micropore volume are too low showing less than 2% by the results of total pore volume and HK pore volume concedes that silica activated CFs are pretty mesoporous. Eventually activated carbon fibers having broad meso-sized pores were obtained successfully.     

On the methane adsorption capacity of activated carbons: in search of a correlation with adsorbent properties

BACKGROUND: There exists now a widely held view that the methane storage capacity on an activated carbon is not related to any of the routinely determined properties of the adsorbent, such as surface area or micropore volume. This has been confirmed and a correlation pursued with other physical and/or chemical properties of both commercially available carbons and those prepared in the laboratory. Textural characteristics (from nitrogen adsorption isotherms at 77 K) considered were BET‐equivalent specific surface area, DR micropore volume and Horvath–Kawazoe micropore size distribution. Chemical properties were evaluated using Fourier transform infrared (FTIR) spectroscopy, thermal programmed decomposition (TPD) and Boehm titrations. Both kinetic and equilibrium methane adsorption experiments were performed at 273 and 298 K and up to 3.5 MPa. RESULTS: Using phosphoric acid to activate peach stones together with additional thermal treatment enabled the production of activated carbons with 137 v/v methane adsorption capacity at 298 K. CONCLUSIONS: The presence of acidic surface functional groups has a detrimental influence on methane uptake, due to the chemical inertness of the adsorbate and/or to pore blockage of the adsorbent. Basic surface functional groups (pyrone), together with a desirable pore size distribution centered at ca 0.8 nm, are thought to be responsible for improved methane adsorption capacity on such activated carbons. Copyright © 2009 Society of Chemical Industry     

Activated carbon from cherry stones by chemical activation: Influence of the impregnation method on porous structure

Cherry stones are utilized as a precursor for the preparation of activated carbons by chemical activation with phosphoric acid (H₃PO₄). The activation process typically consists of successive impregnation, carbonization, and washing stages. Here, several impregnation variables are comprehensively studied, including H₃PO₄ concentration, number of soaking steps, H₃PO₄ recycling, washing of the impregnated material, and previous semi-carbonization. The choice of a suitable impregnation methodology opens up additional possibilities for the preparation of a wide variety of activated carbons with high yields and tailored porous structures. Microporous activated carbons with specific surface areas of ～800 m² g^?1 are produced, in which > 60% of the total pore volume is due to micropores. High surface areas of ～1500 m² g^?1 can be also developed, with micropore volumes being a 26% of the total pore volume. Interestingly, using the same amount of H₃PO₄, either carbons with surface areas of 791 and 337 m² g^?1 or only one carbon with a surface area of 640 m² g^?1 can be prepared. The pore volumes range very widely between 0.07–0.55, 0.01–0.90, and 0.09–0.79 cm³ g^?1 for micropores, mesopores, and macropores, respectively.     

油茶壳微孔活性炭的制备及表征

以油茶壳为原料,经炭化、KOH活化,制备微孔活性炭。考查了活化温度、活化时间和碱炭比对微孔活性炭碘吸附值和产率的影响,并采用正交试验优化了制备条件。研究结果表明：活化温度800℃、活化时间180 min、碱炭质量比3.5：1时,活性炭的碘吸附值达3 221 mg/g,产率51.2%。采用比表面积孔隙分析仪测定了氮气吸附/脱附等温线,计算得BET比表面积为1 755.72 m²/g,平均孔径为2.15 nm,总孔容为0.328 cm³/g,微孔孔容占总孔容的55.8%;SEM分析可见活性炭表面具有大量孔隙结构;FT-IR分析表明活化促进了—CH₃、—OH热解,活性炭中仍保存含氧官能团。     

Advances in the study of methane storage in porous carbonaceous materials

This paper presents an overview of the results of our research group in methane storage, in which the behaviour of different carbon materials in methane storage has been studied. These materials include physically activated carbon fibres (ACFs), chemically activated carbons (ACs) and activated carbon monoliths (ACMs), all of them prepared in our laboratories. These results have been compared with those corresponding to commercial ACFs, commercial activated carbon cloths and felts, and a commercial activated carbon.An in depth analysis (different raw materials, activating agent and preparation variables) has been done in order to obtain the carbon material with the best methane adsorption capacity by unit volume of adsorbent. The important effect of the micropore volume, micropore size distribution (MPSD) and packing density of the carbon materials in the methane adsorption capacity and delivery has been analysed. After this study, activated carbons with volumetric methane uptake as high as 166 v/v and delivery of 145 v/v have been prepared. In addition, ACM with methane uptake of 140 v/v and a delivery of 126 v/v has also been obtained.Moreover, the results corresponding to preliminary in situ small angle neutron scattering (SANS) study of CD₄ adsorption under pressure in different porous carbons and a zeolite are also included. These experiments have established SANS as a viable technique to investigate high-pressure methane adsorption. CD₄ adsorption at supercritical conditions produces changes in the SANS curves. The changes observed are in agreement with theoretical speculations that the density of the adsorbed phase depends upon the pore size.     

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.     

Synthesizing activated carbons from resins by chemical activation with K2CO3

We prepared activated carbons from phenol-formaldehyde (PF) and urea-formaldehyde (UF) resins by chemical activation with K₂CO₃ with impregnation during the synthesis of the resins. The influence of carbonization temperature (773-1173 K) on the pore structure (specific surface area and pore volume) and the temperature range at which K₂CO₃ worked effectively as an activation reagent, were investigated. The specific surface area and micropore volume of PF-AC and UF-AC increased with an increase of carbonization temperature in the range of 773-1173 K. We prepared activated carbon with well-developed micropores from PF, and activated carbon with high specific surface area (>3000 m²/g) and large meso-pore volume from UF. We deduced the activation mechanism with thermogravimetry and X-ray diffraction. In preparing activated carbon from PF, K₂CO₃ was reduced by carbon in the PF char. The carbon was removed as CO gas resulting in increased specific surface area and pore volume above 1000 K. In preparing AC from UF, above 900 K the carbon in UF char was consumed during the K₂CO₃ reduction step.     

Characterization of accessible and inaccessible pores in microporous carbons by a combination of adsorption and small angle neutron scattering

We determine the pore size distribution for five activated carbons (comprising carbide derived as well as commercial activated carbon samples) by the interpretation of experimental small angle neutron scattering (SANS) intensity profiles, based on the primary assumption of an infinitely dilute solution of hollow spherical particles. The interpretation yields the pore size distribution of the carbon samples that have predominantly micropore populations (size <20 Å), but not for carbons which have significant mesopore populations of sizes up to 48 Å and high mass fractal degrees. The pore size distribution (PSD) results based on SANS data reveal significant populations of micropores of size <6.1 Å, and mesopores of size >20 Å, which are not present in the PSD results based on adsorption isotherms of either Ar at 87 K or CO₂ 273 K. This inaccessible porosity becomes accessible to CO₂ and Ar on heat treatment, leading to increase in the adsorption based pore volume. However, the surface area does not commensurately increase, indicating the inaccessible microporosity to predominantly comprise surface defects and roughness that are removed on heat treatment or activation. This finding sheds the light onto the evolution of porosity of activated carbons during gasification or post synthesis-treatment.     

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.     

Experimental and Kinetic Studies on Pore Development During CO2 Activation of Oil-Palm-Shell Char

The results of experimental and kinetic studies on pore development during CO₂ activation of char derived from oil-palm shell, an abundant solid waste in some tropical countries, were presented in this paper. CO₂ was used as an activating agent instead of air because the 21% oxygen content in air would cause severe burn-off of carbon contents, resulting in detrimental effects on pore development. In preparing the activated carbon from oil-palm shell by CO₂ activation, size of the starting material and CO₂ gas flow rate were identified to minimize the effects of gas diffusion. Under a kinetic-controlled condition, the effects of char characteristics and activation temperature on BET and micropore surface areas, porosity and pore size distribution were investigated. For the char prepared from oil-palm shell at a low carbonization temperature of 873 K, the activated carbon with a reasonably high pore surface area and predominant microporosity was obtained.Its applications are in gas-adsorbing processes such as air pollutant removal and gas separation. A random pore model was developed to describe pore development during the carbon-CO₂ reaction process. Model predictions were compared with data from thermogravimetric analyses. Kinetic study showed that the activation reaction rate was dependent on both the initial pore structure of the char and the transient pore structure which was developed progressively during the activation process.     

Pore structures of multi-walled carbon nanotubes activated by air, CO2 and KOH

Multi-walled carbon nanotubes (MWNTs) synthesized by the catalytic decomposition of benzene were activated by KOH, CO₂ or air. The adsorption isotherms of the activated MWNTs were analyzed and their pore size distributions were obtained. The results showed that the specific surface areas of the MWNTs activated by KOH, CO₂ and air were increased to 785 m²/g, 429 m²/g and 270 m²/g, respectively. The MWNTs activated by KOH were rich in micropores and mesopores, especially high mesopores having volumes up to 1.04 cm³/g. The CO₂-activated MWNTs also had many micropores while the air-activated MWNTs had a much smaller micropore volume. The morphologies of the activated MWNTs were examined by transmission electron microscopy and high resolution transmission electron microscopy, and the activation mechanisms were discussed.     

Molecular probe technique for the assessment of the carbon molecular sieve structure

Nitrogen adsorption at 77 K is the most common technique for defining the surface area and pore volume of a porous material. However it is not adequate to assess the microporosity of carbon molecular sieves (CMS), because of activated diffusion effects. In this paper, a molecular probe technique was used to defining the pore size of CMS materials. Adsorption of gases (vapors) with different molecular sizes, were measured by a gravimetric method using a spring balance. The amount adsorbed at room temperature was recorded over a 24-h period. The following molecular probes were chosen: CO₂ (0.33 nm), C₂H₆ (0.4 nm), n-C₄H₁₀ (0.43 nm), i-C₅H₁₁₂ (0.5 nm), and CCl₄ (0.6 nm). The micropore volumes were estimated by the Dubinin-Raduhkevich (DR) equation. Assuming that the diameters of the micropores are larger than those of the adsorbed molecules, the micropore volume distribution of each sample was estimated. The results demonstrated that the main pore size of the studied CMSs are less than 0.5 nm. One of the samples had a narrow pore size distribution in the range of 0.33–0.43 nm, which is the critical pore size for kinetic separation of oxygen from nitrogen. It is concluded that the molecular probe technique is an effective mean to assess the CMS adsorbents structure, which is not currently possible using conventional approaches with a single adsorbate, such as nitrogen or argon.     

Preparation and pore characterization of activated carbon from Ma bamboo (Dendrocalamus latiflorus) by H3PO4 chemical activation

High specific surface area activated carbon materials have been produced from the naturally occurring Ma bamboo (Dendrocalamus latiflorus) using phosphoric acid (H₃PO₄) as the activating agent. The effects of different sizes of raw materials, H₃PO₄ concentrations, and activation temperatures on the specific surface area, pore morphology, and mass yield of activated carbon are presented. A high specific surface area for activated carbon derived from Ma bamboo was achieved under the optimized conditions of 45 wt% H₃PO₄ impregnation concentration, activation temperature of 400 °C, and a holding time of 120 min. Chemical activation of Ma bamboo by H₃PO₄ is a useful technique for obtaining activated carbon with desired pore size distributions and pore morphologies from low cost precursors and at low activation temperatures.