Possible errors in microporosity in chemically activated carbon deduced from immersion calorimetry

The microporosity of granular and disc-shaped activated carbons prepared by both ZnCl₂ and H₃PO₄ activation has been evaluated by adsorption of nitrogen at −196 °C and immersion calorimetry into liquids of different molecular dimensions (dichloromethane, benzene, 2,2-dimethylbutane, carbon tetrachloride and α-pinene). Experimental results show that immersion calorimetry into dichloromethane provides values of surface area more similar to nitrogen adsorption (BET equation) than benzene. No such effect is found for physically activated carbon. Some apparent anomalies have also been detected for the enthalpy of immersion of carbons activated with H₃PO₄ into α-pinene due to a small amount of phosphorous remaining in the carbon after washing. This is not the case for carbons activated with ZnCl₂, because the washing was more effective in the removal of the chemical.     

High selectivity of TiC-CDC for CO2/N2 separation

A series of carbide-derived carbons (CDC) have been prepared starting from TiC and using different chlorine treatment temperatures (500–1200 °C). Contrary to N₂ adsorption measurements at −196 °C, CO₂ adsorption measurements at room temperature and high pressure (up to 1 MPa) together with immersion calorimetry measurements into dichloromethane suggest that the synthesized CDC exhibit a similar porous structure, in terms of narrow pore volume, independently of the temperature of the reactive extraction treatment used (samples synthesized below 1000 °C). Apparently, these carbide-derived carbons exhibit narrow constrictions were CO₂ adsorption under standard conditions (0 °C and atmospheric pressure) is kinetically restricted. The same accounts for a slightly larger molecule as N₂ at a lower adsorption temperature (−196 °C), i.e. textural parameters obtained from N₂ adsorption measurements on CDC must be underestimated. Furthermore, here we show experimentally that nitrogen exhibits an unusual behavior, poor affinity, on these carbide-derived carbons. CH₄ with a slightly larger diameter (0.39 nm) is able to partially access the inner porous structure whereas N₂, with a slightly smaller diameter (0.36 nm), does not. Consequently, these CDC can be envisaged as excellent sorbent for selective CO₂ capture in flue-gas streams.     

Microporosity and mesoporosity of PPTA-derived carbons. Effect of PPTA thermal pretreatment

Isothermal treatments of the polyaramid fiber, [poly(p-phenylene terephthalamide)] (PPTA) in an inert atmosphere below its decomposition temperature are known to induce an important increase in char yield and modify the chemical composition and some other properties of the resulting chars. The objective of this work was to study the effect of this isothermal stage on the porous texture of chars and activated carbon fibers (ACFs) produced from PPTA. To this end, chars and ACFs were prepared by PPTA pyrolysis to 850 °C followed by CO₂ activation at 800 °C to various burn-offs (BOs), introducing or not an intermediate isothermal pre-treatment under the conditions (500 °C, 200 min) known to lead to a maximum increase in char yield. The porosity characteristics of the resulting chars and ACFs were comparatively investigated by adsorption of CO₂ (0 °C), and N₂ (−196 °C). The isothermal stage led to a char with enhanced micropore volume and wider micropores. The ACFs prepared from this char exhibited larger amounts of wide micropores and mesopores than those prepared from PPTA pyrolyzed at a constant heating rate.     

Molybdenum carbide-derived carbon for hydrogen storage

Physisorption of hydrogen in microporous molybdenum carbide (Mo₂C)-derived carbons has been studied as a function of synthesis conditions. Changes in local structure induced by varying the chlorination temperature afford controllable variations in average pore size and specific surface area. Optimal hydrogen storage capacity of 4.3 wt%, measured at −196 °C and 35 bar pressure, is obtained from a sample chlorinated at 660 °C for 3 h. This optimum correlates with the largest fraction of total pore volume having average pore sizes in the 0.6–0.8 nm range.     

The controlled reaction of active carbons with air at 350°C—I: Reactivity and changes in surface area

Two activated carbons prepared from almond shells and olive stones were reacted with air at 350°C to different percentages burn-off. The reactivity was studied in the temperature range 350–500°C where the reaction is relatively slow. The activated carbon from almond shells is more resistant to the reaction with air and the activation energy of that reaction is 101 kJ mol⁻¹. The adsorption of N₂ at 77 K has been used to characterize the adsorptive properties and surface area of all the obtained products, which have high surface areas (around or above 1000 m² g⁻¹). The gas adsorption results, together with mercury porosimetry have allowed a study of the variation of surface area and porosity as a function of the burn-off. In any case, the exposure of the active carbons to air at 350°C for several days does not considerably affect their adsorptive properties even for a weight loss up to 50%.     

The adsorption of water by active carbons, in relation to the enthalpy of immersion

It is shown that there exists a simple relation between the enthalpy of immersion of pure active carbons into water, and the number of so-called primary adsorption sites a₀ derived from the water adsorption isotherm by using the new Dubinin-Serpinsky equation. The adsorption sites left on the surface after outgassing near 400°C, probably of the carbonyl type, contribute to the enthalpy of immersion by −25 kJ/mole, vs −0.6 kJ/mole for the bulk of the water filling the micropores at 307 K.     

The factors affecting the performance of activated carbon prepared from oil palm empty fruit bunches for adsorption of phenol

Powdered activated carbons (PACs) were produced from oil palm empty fruit bunches (EFB) by varying the operating parameters of temperatures, CO₂ gas flow rates and activation times using 2-level full factorial experimental design. The EFB samples were first carbonized for 30 min using nitrogen gas followed by physical activation using CO₂ to optimize best production conditions. The optimum conditions for PACs produced were investigated through adsorption tests on aqueous solution of phenol. The results of this study demonstrated that the activation temperature with the range of 800–900 °C had the most significant effect on the adsorption characteristics as well as the yield of the activated carbon produced. Based on the analysis of variance (ANOVA) and model equation developed, the optimum production conditions for the EFB PAC were found to be at the activation temperature of 900 °C with CO₂ gas flow rate of 0.1 L/min and activation time of 15 min. Characterization of PAC produced showed that the activation conditions would find good-quality adsorbent with the BTE surface area of 345.1 m²/g and well forming pores distribution.     

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.     

Catalytic treating of gas pollutants over cobalt catalyst supported on porous carbons derived from rice husk and carbon nanotube

Porous carbons were prepared from rice husks, commercial coconut-shell-derived carbon, and carbon nanotube (CNT) by activation with CO₂, KOH, and ZnCl₂. Cobalt catalysts were supported on the six different porous carbons by excess-solution impregnation, and were used to carry out reactions with different constituents such as NO + CO, toluene, NO + toluene, and NO + CO + toluene in the presence of 6% O₂ at 250 °C to evaluate the activity of porous catalysts. The properties of the catalysts were analyzed by X-ray powder diffractometer (XRD), a field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), and an X-ray energy dispersive spectrometer (EDS). The cobalt catalysts supported on rice-husk-based carbon activated by CO₂ and those on commercial-activated-carbon re-treated by KOH showed 100% conversion on toluene oxidation. CNT-cobalt catalyst showed 63% NO conversion with CO and 46% with toluene at 250 °C. Among the six porous supported catalysts, the cobalt catalysts prepared with CNT and rice-husk-derived carbon by using CO₂ showed the best catalytic activity and thermal stability when compared to the others.     

Preparation and characterization of active carbons from olive stones

Olive stones have been carbonized under a flow of nitogen in the temperature range from 700 to 900°C and activated in a CO₂ flow in the range from 675 to 875°C. ZnCl₂ was used in some of the activation processes. The adsoptive characteristics of the carbonized and activated samples have been determined by adsorption of nitrogen (77 and 90 K), carbon dioxide (195 and 273 K), n-butane (273 K) and methylene blue (aqueous solution at 298 K). Meso and macroporosity have been followed by mercury porosimetry. The resulting activated carbons have very large surface areas as well as a highly developed microporosity. The most adequate experimental conditions for the preparation of active carbons, highly microporous but with a well developed meso and macroporosity, are discussed. All active carbons prepared have a very low ash content and complete absence of sulphur, both very attractive characteristics.     

Bimetallic catalysts for the catalytic combustion of methane using microreactor technology

Pt–W and Pt–Mo based catalysts were evaluated for methane combustion using a sandwich-type microreactor. Alumina washcoated microchannels were impregnated with platinum in combination with and promoted with tungsten and molybdenum and compared with commercially available Pt/Al₂O₃ catalysts. Catalysts were tested in the range of 300–700 °C with flow rates adjusted to GHSV of 74,000 h⁻¹ and WHSV of 316 L h⁻¹ g⁻¹. Catalysts containing tungsten were found to be the most active and the most stable possibly due to a metal interaction effect. A Pt–W/γ-Al₂O₃ containing 4.6 wt% Pt and 9 wt% W displayed the highest activity with full conversion at 600 °C and a selectivity to CO₂ of 99%.     

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.     

Effect of Pd additive on the activity of monolithic LaMnO3-based catalysts for methane combustion

When the perovskites are calcined at 750 °C, the incorporation of Pd into LaMnO₃ enhances the activity of the catalyst in methane combustion at temperatures below 750 °C upon substitution of 0.1 mol La with Pd, and at temperatures below 600 °C when Pd is substituted for 0.1–0.15 mol Mn. Monolith catalysts based on La_1−xPd_xMnO₃ (x = 0.1, 0.15) display a higher activity in methane combustion than do LaMn_1−xPd_xO₃-based catalysts, which is due to the higher Pd/(Pd + Mn + La) ratio. The activities of the two perovskite types increase when calcination temperature is raised from 650 to 800 °C. With the increase in calcination temperature, an increase in the Pd content and a decrease in the La content is observed on the surfaces (X-ray photoelectron spectroscopy (XPS)). The rise in the temperature of perovskite calcination to 850 °C produces sintering which leads to the lowering in both the Pd content on the surfaces and the specific surface areas (SSAs) of the perovskites and, consequently, decreases catalytic activity.     

The adsorptive properties of carbonised olive stones

Olive stones were carbonised to 1120°K and activated in carbon dioxide at 1100°K to 20% burn-off. Adsorptive properties were measured by adsorption of nitrogen (77°K) and carbon dioxide (195°K, 273°K) using the Langmuir and Dubinin equations of adsorption to deduce effective surface areas. The extents of development, with activation of meso- and macro-porosity were monitored by mercury porosimetry; the surface textures of the parent olive stones, and carbonised and activated products were described by scanning electron microscopy. The carbonised stones had a surface area of 500 k(m)² kg⁻¹ in microporosity increasing to 1500 k(m)² kg⁻¹ at twenty per cent burn-off. This sample had a micropore volume of 600 cm³ kg⁻¹ and 600 cm³ kg⁻¹ in the meso- and macro-porosity. The activation process did not occur evenly, but selectivity. There was no strong evidence for catalytic initiation of the selective gasification. The activated carbons were pseudomorphs of the parent olive stones and did not abraid easily. Their purity (0·21% ash) and low sulphur content (less than 0·1%) may make these active carbons commercially attractive.     

Activated carbon from jackfruit peel waste by H3PO4 chemical activation: Pore structure and surface chemistry characterization

The effects of activation temperature and impregnation ratio on the pore structure and surface chemistry of activated carbons derived from jackfruit peel with chemical activation method using phosphoric acid as activating agent were studied. Activated carbons with well-developed pore sizes were produced at activation temperatures of 450 and 550 °C. The BET surface areas and total pore volumes of the carbons produced at these temperatures are in the range of 907–1260 m²/g and 0.525–0.733 cm³/g, respectively.     

Nano-gold supported on Fe2O3: A highly active catalyst for low temperature oxidative destruction of methane green house gas from exhaust/waste gases

A number of nano-gold catalysts were prepared by depositing gold on different metal oxides (viz. Fe₂O₃, Al₂O₃, Co₃O₄, MnO₂, CeO₂, MgO, Ga₂O₃ and TiO₂), using the homogeneous deposition precipitation (HDP) technique. The catalysts were evaluated for their performance in the combustion of methane (1 mol% in air) at different temperatures (300–600 °C) for a GHSV of 51,000 h⁻¹. The supported nano-gold catalysts have been characterized for their gold loading (by ICP) and gold particle size (by TEM/HRTEM or XRD peak broadening). Among these nano-gold catalysts, the Au/Fe₂O₃ (Au loading = 6.1% and Au particle size = 8.5 nm) showed excellent performance. For this catalyst, temperature required for half the methane combustion was 387 °C, which is lower than that required for Pd(1%)/Al₂O₃ (400 °C) and Pt(1%)/Al₂O₃ (500 °C) under identical conditions. A detailed investigation on the influence of space velocity (GHSV = 10,000–100,000 cm³ g⁻¹ h⁻¹) at different temperatures (200–600 °C) on the oxidative destruction of methane over the Au/Fe₂O₃ catalyst has also been carried out. The Au/Fe₂O₃ catalyst prepared by the HDP method showed much higher methane combustion activity than that prepared by the conventional deposition precipitation (DP) method. The XPS analysis showed the presence of Au in the different oxidation states (Au⁰, Au¹⁺ and Au³⁺) in the catalyst.     

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).     

The phenol steam reforming reaction towards H2 production on natural calcite

The steam reforming of phenol towards H₂ production was studied in the 650–800 °C range over a natural pre-calcined (air, 850 °C) calcite material. The effects of reaction temperature, water, hydrogen, and carbon dioxide feed concentrations, and gas hourly space velocity (GHSV, h⁻¹) were investigated. The increase of reaction temperature in the 650–800 °C range and water feed concentration in the 40–50 vol% range were found to be beneficial for catalyst activity and H₂-yield. A similar result was also obtained in the case of decreasing the GHSV from 85,000 to 30,000 h⁻¹. The effect of concentration of carbon dioxide and hydrogen in the phenol/water feed stream was found to significantly decrease the rate of phenol steam reforming reaction. The latter was probed to be related to the reduction in the rate of water dissociation as evidenced by the significant decrease in the concentration of adsorbed bicarbonate and OH species on the surface of CaO according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)-CO₂ adsorption experiments in the presence of water and hydrogen in the feed stream. Details of the CO₂ adsorption on the CaO surface at different reaction temperatures and gas atmospheres using in situ DRIFTS and transient isothermal adsorption experiments with mass spectrometry were obtained. Bridged, bicarbonate and unidentate carbonate species were formed under CO₂/H₂O/He gas mixtures at 600 °C with the latter being the most populated. A substantial decrease in the surface concentration of bicarbonate and OH species was observed when the CaO surface was exposed to CO₂/H₂O/H₂/He gas mixtures at 600 °C, result that probes for the inhibiting effect of H₂ on the phenol steam reforming activity. Phenol steam reforming reaction followed by isothermal oxygen titration allowed the measurement of accumulated “carbonaceous” species formed during phenol steam reforming as a function of reaction temperature and short time on stream. An increase in the amount of “carbonaceous” species with reaction time (650–800 °C range) was evidenced, in particular at 800 °C (4.7 vs. 6.7 mg C/g solid after 5 and 20 min on stream, respectively).     

Activated carbon from cherry stones

Fruit stones constitute a significant waste disposal problem for the fruit-processing industry. High-quality activated carbon can be produced from waste cherry stones: the activated carbon is low in impurities and has an adsorption capacity that compares favorably with commercial activated carbons. Activation at 800°C in steam for 2–3 hours, following initial carbonization, produces an activated carbon in about 10% yield (by weight) of the initial cherry stone. The activated carbons produced have surface areas (CO₂ adsorption) as high as 1200 m²/g and CCl₄ numbers of 70–80. Activation in carbon dioxide requires higher temperatures (900°C) and gives a carbon of slightly lower activity. Carbon from the hull, or hard outer portion of the fruit stone, provides essentially all of the adsorption capacity; the inner kernel does not form a microporous material. The hull structure is dominated by 0.4-micron pores which facilitate access to internal microporosity. This structure requires that the carbon be ground to less than 75 micron particles to achieve reasonable adsorption rates.