Adsorption of sulfur dioxide onto activated carbons prepared from oil‐palm shells impregnated with potassium hydroxide

Adsorption of sulfur dioxide (SO₂), a gaseous pollutant, onto activated carbons prepared from oil‐palm shells pre‐treated with potassium hydroxide (KOH) impregnation was studied. Experimental results showed that SO₂ concentration and adsorption temperature affected significantly the amount of SO₂ adsorbed and the equilibrium time. However, sample particle sizes influenced the equilibrium time (due to effect of diffusion rate) only. Desorption at the same temperature of adsorption and a higher temperature of 200 °C confirmed the presence of chemisorption due to pre‐impregnation. Impregnation with different activation agents was found to have limited effect on the inorganic components of the sample. Compared with the activated carbon pre‐treated with 30% phosphoric acid (H₃PO₄) that had larger BET and micropore surface areas, the sample impregnated with 10% KOH had a higher adsorptive capacity for SO₂, which was closely related to the surface organic functional groups of the sample. In general, the activated carbon prepared from oil‐palm shell impregnated with KOH was more effective for SO₂ adsorption and its adsorptive capacity was comparable to some commercial activated carbons. © 2000 Society of Chemical Industry     

Catalytic oxidative desulfurization of diesel utilizing hydrogen peroxide and functionalized-activated carbon in a biphasic diesel-acetonitrile system

This paper presents the development of granular functionalized-activated carbon as catalysts in the catalytic oxidative desulfurization (Cat-ODS) of commercial Malaysian diesel using hydrogen peroxide as oxidant. Granular functionalized-activated carbon was prepared from oil palm shell using phosphoric acid activation method and carbonized at 500 °C and 700 °C for 1 h. The activated carbons were characterized using various analytical techniques to study the chemistry underlying the preparation and calcination treatment. Nitrogen adsorption/desorption isotherms exhibited the characteristic of microporous structure with some contribution of mesopore property. The Fourier Transform Infrared Spectroscopy results showed that higher activation temperature leads to fewer surface functional groups due to thermal decomposition. Micrograph from Field Emission Scanning Electron Microscope showed that activation at 700 °C creates orderly and well developed pores. Furthermore, X-ray Diffraction patterns revealed that pyrolysis has converted crystalline cellulose structure of oil palm shell to amorphous carbon structure. The influence of the reaction temperature, the oxidation duration, the solvent, and the oxidant/sulfur molar ratio were examined. The rates of the catalytic oxidative desulfurization reaction were found to increase with the temperature, and H₂O₂/S molar ratio. Under the best operating condition for the catalytic oxidative desulfurization: temperature 50 °C, atmospheric pressure, 0.5 g activated carbon, 3 mol ratio of hydrogen peroxide to sulfur, 2 mol ratio of acetic acid to sulfur, 3 oxidation cycles with 1 h for each cycle using acetonitrile as extraction solvent, the sulfur content in diesel was reduced from 2189 ppm to 190 ppm with 91.3% of total sulfur removed.     

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.     

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.     

Oxidation of hydrogen sulfide over microporous carbons

Microporous carbon of high purity was produced by the carbonization of Saran at 900° followed by activation in either CO₂ at 900°, O₂ at 300°, or air at 425°. The activated carbons were characterized using N₂ adsorption at ?195° CO₂ adsorption at 25°, and mercury and helium displacements. Hydrogen sulfide oxidation (at H₂S pressures between 0.4–3.8 Torr) by O₂ (in excess of stoichiometric amount) was studied between 100–160° using a microbalance, that is by weighing the build-up of sulfur on the carbon. The predominant reaction, $\text{H}{}_2\text{S +}\text{1}\text{2}\text{O}{}_2\text{→}\text{1}\text{2}\text{S}{}_2\text{+ H}{}_2\text{O}$ was first order in H₂S concentration and independent of O₂ concentration. The rate was only slightly reduced by sulfur build-up to at least 36%, by weight, on the carbon. The oxidation rate was significantly higher over the O₂-activated carbon than over the CO₂-activated carbon. Throughout the studies, oxidation rates could be correlated with area active to O₂ chemisorption. It is concluded that H₂S oxidation proceeds via rapid dissociative chemisorption of oxygen on carbon sites followed by reaction with H₂S. Rates of H₂S oxidation were also studies over commercial, granular activated carbons of significant ash contents.     

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     

Production of microporous palm shell based activated carbon for methane adsorption: Modeling and optimization using response surface methodology

In this study, the optimization of the palm shell based activated carbon production using combination of chemical and physical activation for methane adsorption is investigated. response surface methodology (RSM) in combination with central composite design (CCD) was used to optimize the operating parameters of the production process. Physical activation temperature, chemical impregnation ratio and physical activation time were chosen as the main process variables and the amount of methane adsorption was selected as the investigated response. Phosphoric acid and carbon dioxide were used as chemical and physical agents, respectively. The optimum reaction conditions were found to be a physical activation temperature of 855 °C, H₃PO₄ impregnation ratio of 9.42 g of phosphorous per gram palm shell and physical activation time of 135 min. The results exhibited significant increase in methane adsorption after physio-chemical activation.     

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.     

Effect of KI and KOH Impregnations over Activated Carbon on H2S Adsorption Performance at Low and High Temperatures

In the present work, commercial-grade activated carbon was modified by steam activation to improve its surface properties for high temperature desulfurization. The modified sample was also further upgraded by impregnating with KOH and KI to promote the chemisorption with of H₂S. The H₂S adsorption performance was tested under the temperature range of 30–550°C using the temperature program adsorption technique to understand the effect of adsorption temperature on the material adsorption characteristic. It was found that at ambient temperature, the impregnation of activated carbon with KOH can promote the H₂S adsorption capacity of activated carbon, whereas the impregnation with KI does not provide a significant beneficial effect. At high adsorption temperature (upto 550°C), both KOH and KI impregnation considerably improve the H₂S adsorption performance of activated carbon in terms of the adsorption capacity and breakthrough time. It was revealed from N₂ adsorption, SEM and EDS measurement that the chemical reactions between H₂S and alkaline compounds (KOH and KI) are promoted at high temperature. Based on all experimental results, the equilibrium adsorption model using the linear isotherm was developed to predict the adsorption behavior of these sorbents in terms of equilibrium isotherm constant and mass transfer coefficient for later scaling-up process.     

Lead(II) adsorption onto the graphene layer of carbonaceous materials in aqueous solution

Lead(II) adsorption from an aqueous solution onto a graphene layer (Cπ electrons) was investigated using activated carbon and charcoal. The carbonaceous materials were treated by several steps to prepare ash free and acidic oxygen free graphite surface by washing with HCl and H₂F₂ solution followed by out gassing at 1273 K. Changes in Pb(II) adsorption capacity were checked at each step to maximize the area of the graphene layer. As received activated carbon and charcoal and their HNO₃ oxidized counterparts were also used for the adsorption experiments for comparison with the ash free and the acidic oxygen free carbons. Boehm titration and Langmuir isotherms were used to evaluate the Pb(II) adsorption onto the adsorbents. The experimental results indicate that an acidic oxygen free graphene layer exhibits a basic character caused by Cπ electrons. When only a small amount of acidic oxygen groups was present, the Pb(II) adsorption strength onto the graphene layer (Cπ electrons) significantly diminished, and the Pb(II) adsorption sites were switched from the graphene layer to carboxylic and lactonic groups on the carbons in the results.     

Hydrogen storage on chemically activated carbons and carbon nanomaterials at high pressures

Hydrogen adsorption measurements have been carried out at different temperatures (298 K and 77 K) and high pressure on a series of chemically activated carbons with a wide range of porosities and also on other types of carbon materials, such as activated carbon fibers, carbon nanotubes and carbon nanofibers. This paper provides a useful interpretation of hydrogen adsorption data according to the porosity of the materials and to the adsorption conditions, using the fundamentals of adsorption. At 298 K, the hydrogen adsorption capacity depends on both the micropore volume and the micropore size distribution. Values of hydrogen adsorption capacities at 298 K of 1.2 wt.% and 2.7 wt.% have been obtained at 20 MPa and 50 MPa, respectively, for a chemically activated carbon. At 77 K, hydrogen adsorption depends on the surface area and the total micropore volume of the activated carbon. Hydrogen adsorption capacity of 5.6 wt.% at 4 MPa and 77 K have been reached by a chemically activated carbon. The total hydrogen storage on the best activated carbon at 298 K is 16.7 g H₂/l and 37.2 g H₂/l at 20 MPa and 50 MPa, respectively (which correspond to 3.2 wt.% and 6.8 wt.%, excluding the tank weight) and 38.8 g H₂/l at 77 K and 4 MPa (8 wt.% excluding the tank weight).     

Production of fibrous activated carbons from natural cellulose (jute, coconut) fibers for water treatment applications

Different fibrous activated carbons were prepared from natural precursors (jute and coconut fibers) by physical and chemical activation. Physical activation consisted of the thermal treatment of raw fibers at 950 °C in an inert atmosphere followed by an activation step with CO₂ at the same temperature. In chemical activation, the raw fibers were impregnated in a solution of phosphoric acid and heated at 900 °C in an inert atmosphere. The characteristics of the fibrous activated carbons were determined in the following terms: elemental analysis, pore characteristics, SEM observation of the porous surface, and surface chemistry. As the objective of this study was the reuse of waste for industrial wastewater treatment, the adsorption properties of the activated carbons were tested towards pollutants representative of industrial effluents: phenol, the dye Acid Red 27 and Cu²⁺ ions. Chemical activation by phosphoric acid seems the most suitable process to produce fibrous activated carbon from cellulose fiber. This method leads to an interesting porosity (S_BET up to 1500 m² g⁻¹), which enables a high adsorption capacity for micropollutants like phenol (reaching 181 mg g⁻¹). Moreover, it produces numerous acidic surface groups, which are involved in the adsorption mechanisms of dyes and metal ions.     

Modeling the selectivity of activated carbons for efficient separation of hydrogen and carbon dioxide

Grand canonical Monte Carlo simulations (GCMC) are carried out to investigate the separation of hydrogen and carbon dioxide via adsorption in activated carbons. In the simulations, both hydrogen and carbon dioxide molecules are modeled as Lennard-Jones spheres, and the activated carbons are represented by a slit-pore model. At elevated temperatures (T = 505 and 923 K), the activated carbons exhibit essentially no preference over the two gases and the selectivity of carbon dioxide relative to hydrogen falls monotonically as the pore size increases. At room temperature, however, the selectivity of carbon dioxide relative to hydrogen reaches up to 90, indicating that hydrogen and carbon dioxide can be efficiently separated. Furthermore, the optimized pore sizes, of width H = 1.48 nm for the bulk mole fraction ratio of x_CO2/x_H2=1:2 and H = 1.18 nm for x_CO2/x_H2=1:8, are identified in which the activated carbons show the highest selectivity for the separation of hydrogen and carbon dioxide.     

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.     

Chemisorption of halogen on carbon—II Thermal reversibility of Cl2, HCl and H2 chemisorption

There are surface double bonds on carbons which differ from the graphitic surface π-bonds in their chemical reactivity. They may be created by degassing prechlorinated or prehydrogenated carbon samples, besides their natural occurrence in nontreated carbons.Cl₂, H₂ and HCl may be added to these double bonds and partially degassed by thermal cycling in presence of the gases. This indicates that at least part of these olefinic bonds are thermally labile and are, therefore, important for catalysis and surface chemical modifications of carbons. The surface concentration of the labile bonds is low, amounting to a few hundredths of meq/100m² of carbon surface area. Discrimination between physisorption and chemisorption of H₂ on carbon can be made by analysis of the dependence of adsorption on temperature. With Cl₂, considerable overlap between the two processes takes place.     

Surface modification and adsorption of eucalyptus wood-based activated carbons: Effects of oxidation treatment, carbon porous structure and activation method

The incorporation of oxygen functional groups onto the surface of eucalyptus activated carbon and its surface chemistry were investigated as a function of oxidation conditions, carbon porous properties and carbon preparation method. Under all treatment conditions of increasing time, temperature and oxidant concentration, liquid oxidation with HNO₃, H₂O₂ and (NH₄)₂S₂O₈ and air oxidation led to the increase of acidic group concentration, with carboxylic acid showing the largest percentage increase and air oxidation at the maximum allowable temperature of 350 °C produced the maximum content of both carboxylic acid and total acidic group. Nitric acid oxidation of chemically activated carbon produced higher total acidic content but a lower amount of carboxylic acid compared to the oxidized carbon from physical activation. The increased contents of acidic groups on oxidized carbons greatly enhanced the adsorption capacity of water vapor and heavy metal ions.     

Activated carbon catalyst for selective oxidation of hydrogen sulphide: On the influence of pore structure, surface characteristics, and catalytically-active nitrogen

The catalytic oxidation of hydrogen sulphide (H₂S) on various activated carbon materials was studied. The effects of pore structure, surface characteristics, and nitrogen content on the activity and selectivity of the carbons towards oxidation of H₂S were investigated. It was found that a high volume of both micropores and small mesopores, in combination with a relatively narrow pore size distribution, were crucial for the retention of sulphur dioxide (SO₂), a by-product of H₂S oxidation. For the retention of carbonyl sulphide (COS), another H₂S oxidation by-product, high surface reactivity with a significant amount of basic groups were found to be important. The only carbon with all these characteristics, and consequently the carbon that was able to retain both H₂S and COS for an extended period of time, was an experimental product, “WSC”. This carbon was found to be superior to the other carbons studied, exhibiting high activity and selectivity for oxidation of H₂S to sulphur. H₂S breakthrough capacities and selectivity values of the carbons were found to be dependent on the nitrogen content of the carbons. In a hydrogen stream, carbons possessing the highest nitrogen contents exhibited the greatest H₂S breakthrough capacities but, at the same time, the lowest selectivity with respect to sulphur formation. In reformate streams, the maximum breakthrough capacity and greatest selectivity were exhibited by carbons with a nitrogen content of about 1-1.5 wt%.     

Sorption of mercury by activated carbon in the presence of flue gas components

The purpose of the current study is to evaluate the mercury removal ability of F400 and Norit FGD activated carbons, through fixed bed adsorption tests at inert atmosphere (Hg° + N₂). Additionally, adsorption tests were realized on F400 activated carbon, in the presence of HCl, O₂, SO₂ and CO₂ in nitrogen flow. The obtained results, revealed that F400 activated carbon, with a high-developed micropore structure and increased BET area, exhibit larger Hg° adsorptive capacity compared to Norit. HCl and O₂, can strongly affect mercury adsorption, owing to heterogeneous oxidation and chemisorption reactions, which is in accordance with the assumptions of some researchers. Additionally, SO₂ presence enhances mercury adsorption, in contrast with the conclusions evaluated in other studies. The above result could be attributed to the possible formation of sulphur spaces on activated carbon surface and consist of a clarification for the role of SO₂ on mercury adsorption. On the contrary, the mercury adsorption efficiency of F400 activated carbon showed a decrease at about 25%, with increasing CO₂ concentration from 0 to 12%.     

Removal of elemental mercury from coal combustion flue gas by chloride-impregnated activated carbon

In this work, adsorption of vapour-phase elemental mercury (Hg⁰) from pulverised-coal combustion flue gas by commercially available granular activated carbons treated with zinc chloride (ZnCl₂) impregnation was investigated. The experiment results showed that ZnCl₂ impregnation significantly enhanced the adsorptive capacity for mercury vapour, but decreased the specific surface area of the activated carbon. This could be explained by the occurrence of chemisorption, which was confirmed by adsorption tests over a wide range of temperatures. The influence of ZnCl₂ solution concentration on the mercury removal performance was also studied. Mechanisms of mercury adsorption onto the Cl-impregnated activated carbon were proposed.     

Direct oxidation of hydrogen sulphide to sulphur using impregnated activated carbon catalysts

Low concentrations of H₂S were directly oxidized to sulphur and small quantities of SO₂, over seven different activated carbons with or without impregnation. The effectiveness of virgin activated carbon was tested at 175°C, 700 kPa, and O₂/H₂S ratio with 5% greater than stoichiometry. The conversion of H₂S was 99.9 mol% with SO₂ production of 3–6%, for 360 min runtime for Fisher coconut shell activated carbon and 648 min for Envirotrol bituminous (EB) activated carbon. Then the activated carbons became deactivated due to deposition of sulphur on the surface. Under these conditions mesoporous activated carbons such as EB and Hydrodarco had the longest breakthrough time. The addition of 5.5 wt% ammonium iodide, potassium iodide and potassium carbonate individually to EB decreased the production of SO₂ while having minimal effect on the overall H₂S conversion. The addition of 5.5 wt% NH₄I decreased the average SO₂ production from 2.5% to 0.9%. The activation energy for the H₂S oxidation on the 5.5 wt% NH₄I on EB activated carbon was determined to be 40 kJ/mol.