Adsorption of hydrogen sulphide (H2S) by activated carbons derived from oil-palm shell

Adsorption of hydrogen sulphide (H₂S) onto activated carbons derived from oil palm shell, an abundant solid waste from palm oil processing mills, by thermal or chemical activation method was investigated in this paper. Dynamic adsorption in a fixed bed configuration showed that the palm-shell activated carbons prepared by chemical activation (KOH or H₂SO₄ impregnation) performed better than the palm-shell activated carbon by thermal activation and a coconut-shell-based commercial activated carbon. Static equilibrium adsorption studies confirmed this experimental result. An intra-particle Knudsen diffusion model based on a Freundlich isotherm was developed for predicting the amount of H₂S adsorbed. Desorption tests at the same temperature as adsorption (298 K) and at an elevated temperature (473 K) were carried out to confirm the occurrence of chemisorption and oxidation of H₂S on the activated carbon. Surface chemistries of the palm-shell activated carbons were characterized by Fourier transform infrared spectroscopy and Boehm titration. It was found that uptaking H₂S onto the palm-shell activated carbons was due to different mechanisms, e.g. physisorption, chemisorption and/or H₂S oxidation, depending on the activation agent and activation method.     

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     

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.     

Preparation and Characterization of Activated Carbon from Chestnut Shell and its Adsorption Characteristics for Lead

Activated carbons were prepared from chestnut shell by phosphoric acid activation and the prepared activated carbons were used to remove lead(II) from aqueous solutions. The effects of impregnation ratio (IR) and activation temperature on activated carbon production were investigated. The produced activated carbons were characterized by N₂ adsorption, scanning electron microscopy (SEM), and atomic force microscopy (AFM) techniques. The highest surface area (1611 m²/g) and total pore volume (0.7819 cm³/g) were obtained at a carbonization temperature of 500°C with an impregnation ratio of 3/1. The resulting activated carbon was used for removal of lead(II) from aqueous solution. The effects of temperature, contact time, and adsorbent dosage were investigated. The adsorption isotherm studies were carried out and the obtained data were analyzed by the Langmuir, Freundlich, and Temkin equations. The rate of adsorption was found to conform to the pseudo-second-order kinetic model. The Langmuir isotherm equation showed better fit for all temperatures and the maximum adsorption capacities of lead(II) was obtained as 138.88 mg/g at 45°C.     

Preparation of High Surface Area Mesoporous Activated Carbon: Kinetics and Equilibrium Isotherm

Activated carbon prepared from palm shell by phosphoric acid impregnation, at significantly favorable experimental conditions is characterized for the porous nature and adsorption of methylene blue dye molecules. The activation is carried out using a 2-stage activation process with the activation in a self-generated atmosphere. An activation temperature of 500°C, with an activation time of 75 minutes using a phosphoric acid impregnation ratio of 3 has yielded an activated carbon having unique characteristics. An activated carbon with a yield of 48%, total pore volume of 1.9 cm³/g, surface area of 1956 m²/g, an average pore diameter of 3.8 nm, with the ratio of the mesopore to the total surface area in excess of 75% has been prepared. The activated carbon exhibits a high methylene blue equilibrium adsorption capacity of 438 mg/g with the adsorption isotherm increasing with an increase in the adsorption temperature. Among the various adsorption isotherm models, the Langmuir model is able to explain the adsorption process well, evidenced by the proximity of the model with the experimental data. Among the different kinetic models tested with the experimental kinetic data, a pseudo-second-order model is found to fit the experimental data with close proximity.     

The effect of impregnation of activated carbon with SnCl2.2H2O on its porosity, surface composition and CO gas adsorption

Activated carbon was impregnated with different concentrations of SnCl₂.2H₂O. Unimpregnated and impregnated activated carbons were analysed by means of physical adsorption and XPS and were tested for CO gas adsorption in a PSA system. The adsorption isotherms of N₂ at 77 K were measured and showed a Type I isotherm indicating microporous carbon for all the samples. The surface area, pore volume and pore size distribution were reduced with impregnation. XPS analysis showed an increase in the intensity of Sn3d peak with impregnation. The impregnated activated carbon showed a very good adsorption ability of CO gas compared to the unimpregnated sample. The adsorptive species responsible for CO gas adsorption was confirmed to be SnO₂ instead of SnO due to the former’s comparative thermodynamic stability.     

Preparation of Activated Carbons from Tobacco Stems by Potassium Hydroxide Activation and Phosphine Adsorption

Activated carbon preparation from tobacco stems by KOH activation at different activation temperatures and KOH/char mass ratios were investigated in this study. The effects of preparation parameters on activated carbon pore structure, morphometrics, microcrystallinities, and surface functional groups were characterized by N₂ adsorption, SEM, XRD, and FTIR technologies, respectively. The optimum preparation condition of activated carbon was activation temperature of 850°C, and KOH/char mass ratio of 2. Under this condition, the BET surface area of 2215 m²/g, and the pore volume of 1.343 cm³/g can be obtained. Prepared activated carbon showed clearly honeycomb holes, and a predominated amorphous structure. With increase of activation temperature and KOH/char mass ratio, decrease of surface oxygen functional group, and aromatization of the carbon structure was found. The activated carbon was subject to PH₃ purification, and the maximum PH₃ adsorption capacity of 253 mg/g can be realized based on well prepared KOH-AC with modification of 2.5% Cu. It seems that the activated carbon produced from chemical activation of tobacco stem would be an effective and alternative adsorbent for PH₃ adsorption because of its high surface area, adsorption capacity, and low cost.     

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.     

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.     

The Sorption of Arsenic onto Activated Carbon Impregnated with Metallic Silver and Copper

Abstract

The adsorption of arsenic species in aqueous solutions onto activated carbon with and without chemical impregnation has been studied. The ability of activated carbon to adsorb arsenic depends on the arsenic oxidation state, the pH of the water, and the activity of the metal used for the activated carbon impregnation. The results of the investigations have shown that physical adsorption is effective only for the arsenic(V) species in water. Activated carbon adsorbs arsenic(V) with a saturation adsorption capacity of 0.27 mmol/g. The chemisorption process is effective for both arsenic species. By impregnation of activated carbon by copper, the sorption process for the arsenic(III) species is significantly improved. The saturation adsorption capacity of the activated carbon impregnated by copper is 0.41 and 0.23 mmol/g for the arsenic(III) and arsenic(V) species, respectively. The pH values of the water are important for both sorption processes because of the change in the ionic forms of both arsenic species. The optimal pH range is between 4 and 9, which is a consequence of the apparent affinity between the carbon surface and arsenic species H₃AsO₃ and H₂AsO₄ ^? that are predominant at this pH in water. Equilibrium isotherm analyses were undertaken using Langmuir and Freundlich equations.     

Preparation and characterizations of activated carbon from kenaf fiber for equilibrium adsorption studies of copper from wastewater

The potential of activated carbon prepared from kenaf fiber (KF) to remove copper (II) from aqueous effluents was investigated. The fibers were first semi-carbonized, then impregnated with potassium hydroxide (KOH) and finally activated by using carbon dioxide (CO₂) gas to produce activated carbon. Pore structure and physical characteristics of the prepared kenaf fiber activated carbon (KFAC) were determined. Adsorption studies for divalent copper (Cu) ions were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration on equilibrium adsorption capacity. The experimental data followed pseudo-second-order kinetics and Elovich Model than pseudo-first-order. Langmuir, Freundlich and Temkin models were implemented to analyze the parameters for adsorption at 30 °C, 50 °C and 70 °C. Thermodynamic parameters such as ??G ^o , ??H ^o and ??S ^o which represent Gibbs free energy, enthalpy and entropy, respectively, were evaluated. It was concluded that activated carbon from kenaf fiber (KFAC) can be used as an efficient adsorbent for removal of Cu (II) from synthetic wastewater.     

咖啡渣活性炭的制备、表征及其对Cr(Ⅵ)的吸附机制研究

以碘吸附值为评价指标,活化时间、活化温度和浸渍比为影响因素,采用响应面法试验设计对磷酸活化法制备咖啡渣活性炭的工艺条件进行优化,并通过静态吸附试验研究了不同吸附时间、溶液pH值和吸附温度条件下,活性炭对水溶液中Cr（Ⅵ）吸附性能的影响,最后利用Langmuir、Freundlich吸附等温方程、准一级动力学方程、准二级动力学方程和颗粒内部扩散方程进行拟合。试验结果表明,制备咖啡渣活性炭的最佳工艺条件为活化时间1 h、活化温度498℃、浸渍比1.72;在此条件下活性炭得率为30.4%,碘吸附值为（799±16）mg/g,比表面积为1 006 m²/g,孔容为0.779 cm³/g、微孔孔容为0.051 cm³/g、平均孔径为3.088 nm。较低pH值和较高温度能够促进活性炭对Cr（Ⅵ）的吸附;Langmuir等温方程能够更好地描述活性炭对Cr（Ⅵ）的吸附效果;活性炭对Cr（Ⅵ）的吸附分3个阶段：快速吸附阶段、慢速吸附阶段和吸附平衡阶段,10 min内可完成吸附总量的79%,360 min内达到吸附平衡,该吸附过程符合准二级吸附动力学方程。分析表明咖啡渣活性炭对Cr（Ⅵ）的吸附主要为单分子层的化学吸附。     

Effect of Preparation Conditions on the Property Cu/AC Adsorbents for Phosphine Adsorption

Copper-based activated carbon adsorbents (Cu/AC) were prepared and used to investigate the effects of various copper precursors, impregnation solution concentration, and calcination temperature on phosphine (PH₃) adsorption removal from yellow phosphorus tail gas. N₂ adsorption isotherm and X-ray Diffraction (XRD) were used for characterizing the Cu/AC adsorbents. It can be seen that the Cu(N)/AC adsorbent prepared from the Cu(NO₃)₂ precursor has higher PH₃ breakthrough adsorption capacity than other three adsorbent because the surface copper status of it is mainly CuO. Fresh activated carbon requires an optimal impregnation solution concentration (0.05 mol/L) to reach this optimal PH₃ breakthrough adsorption capacity (78.62 mg/g). The result shows that the surface chemical characteristics (Cu content) of activated carbon is more important than the physical ones (specific surface or pore volume) for the PH₃ adsorption performance. When the calcination temperature is 350°C, the Cu(N)/AC adsorbent has the biggest PH₃ breakthrough adsorbed amount of 112.38 mg/g. The present study confirmed that the Cu/AC adsorbents would be one of the candidates for PH₃ adsorption removal from yellow phosphorus tail gas.     

COD removal from landfill leachate using a high-performance and low-cost activated carbon synthesized from walnut shell

An activated carbon with high adsorption capacity was synthesized from walnut shell as a solid waste using different chemical reagents. It was used to mitigate chemical oxygen demand from municipal landfill leachate. The activated carbon synthesized with impregnation ratio of 4:1 (H₃PO₄ to char) at a temperature of 500°C (ACH4-500) demonstrated the best textural properties based on Brunauer–Emmett–Teller analysis, i.e., specific surface area of 1,851.1?m²/g, total pore volume of 1.03?cm³/g, and mean pore diameter of 2.24?nm and was selected for adsorption experiments. The maximum adsorption capacity and removal were 123.1?mg/g and 84.7% under optimum condition, respectively. The equilibrium data were fitted with different model isotherms and Redlich–Peterson model showed the best match with experimental data. Kinetic data were well described by pseudo-second-order equation. Study of adsorption thermodynamics revealed spontaneous and endothermic nature of adsorption. In addition, the adsorbent showed satisfactory results, e.g., 100% removal of Pb²⁺, Cd²⁺, and Mn²⁺, in diminishing heavy metals as hazardous materials from landfill leachate.     

Chemical Production of Activated Carbon from Nutshells and Date Stones

The effect of chemical reagent (H₃PO₄, KOH, and NaOH), temperature (400 °C, 475 °C, 550 °C), and impregnation ratio (100 %, 150 %, 200 %) was investigated on the specific surface area and iodine uptake of the carbons produced from almond, walnut, and pistachio‐nut shells and date stones. The effect of mesh size and holding time was also studied in the case of almond shell. While the alkali activation of the precursors resulted in such fine powders that purifying them of contaminants was almost impossible, the acid activation of the raw materials produced carbons with high iodine numbers (about 1000 mg I₂/g carbon). To further characterize their porosity, the almond‐based carbons underwent BET measurements, with the results showing comparatively high surface areas (about 1400 m²/g). The carbons were rather mesoporous, and thus more suitable for liquid applications, which was confirmed by using the carbons in chromium (VI) uptake in another study [1].     

Nano-sized carbon hollow spheres for abatement of ethylene

In this paper, the ethylene adsorption capacities of the nano-sized carbon hollow spheres (CNB) and active carbon (AC), the Pd (PdCl₂) impregnated CNB or AC (Pd/CNB, Pd/AC) and heat treatment under various conditions, were studied at different ethylene concentrations from 64 to 1060 ppm. The results indicated that AC had a good ethylene adsorption capacity at high ethylene concentration. Pd impregnation decreased the ethylene adsorption capacity of AC. Heat treatment and H₂ activation could increase the ethylene adsorption capacity, but also lowered than AC itself. CNB had lower ethylene adsorption capacity than AC, but heat treatment and H₂ activation could increase its ethylene adsorption capacity markedly. With activating condition from heat treatment in N₂ at 300 °C to activation in H₂/N₂ at 100 °C, to activation in H₂ at 200 °C, and to activation in H₂ at 300 °C, the ethylene adsorption capacity of Pd/CNB was increased regularly. At low ethylene concentration, viz., 64 ppm, the ethylene adsorption quantities (q _a) by Pd/CNB activated in H₂ at 200 or 300 °C were higher than any other adsorbents. So, activated in H₂ atmosphere at higher than 100 °C, Pd/CNB is particularly advantaged for adsorbing low concentration of ethylene. Amongst all the adsorbents used, Pd/CNB activated in H₂ atmosphere at 300 °C for 2 h has the highest ethylene adsorption capacity at lower concentration than 125 ppm. In addition, all the CNB, Pd/CNB, AC, and Pd/AC samples can be easily regenerated in airflow for more than 3 h.     

Phosphate Removal from Aqueous Solution Using Coir-Pith Activated Carbon

The present study deals with the removal of phosphates from aqueous solution using activated carbon developed from coir pith. Batch adsorption experiments were performed to delineate the effect of initial pH, contact time, adsorbent dose and temperature on the removal of phosphates by coir-pith activated carbon (CAC) (activated by H₂SO₄). The removal was found to be maximum in the pH range of 6–10. The kinetics of adsorption showed that the phosphate adsorption onto CAC was a gradual process with a quasi-equilibrium being attained in 3 h. The adsorption equilibrium data followed the Temkin isotherm. Thermodynamic parameters such as ΔG ^o , ΔH ^o , and ΔS ^o were evaluated by applying the Arrhenius and van't Hoff equations, and it was found that the adsorption of phosphate on CAC was spontaneous and endothermic.     

Oxidation of low concentrations of hydrogen sulphide: Process optimization and kinetic studies

Low concentrations (e.g. < 3) of H₂ S in natural gas can be selectively oxidized over an “granular Hydrodarco” activated carbon catalyst to elemental sulphur, water and a small fraction of by-product sulphur dioxide, SO₂. To optimize the H₂ S catalytic oxidation process, the process was conducted in the temperature range 125—200 °C, at pressures 230—3200 kPa, with the O/H₂ S ratio being varied from 1.05 to 1.20 and using different types of sour and acid gases as feed. The optimum temperature was determined to be approximately 175 °C for high H₂ S conversion and low SO₂ production with an O/H₂ S ratio 1.05 times the stoichiometric ratio. The life of the activated carbon catalyst has been extended by removing heavy hydrocarbons from the feed gas. The process has been performed at elevated pressures to increase H₂ S conversion, to maintain it for a longer period and to minimize SO₂ production. The process is not impeded by water vapour up to 10 mol% in the feed gas containing low concentrations of CO₂ (< 1.0). A decrease in H₂ S conversion and an increase in SO₂ production were obtained with an increase in water vapour in the feed gas containing a high percentage of CO₂. The process works well with “sour natural gas” containing approximately 1% H₂ S and with “acid gas” containing both H₂ S and CO₂. It gives somewhat higher H₂ S conversion and low SO₂ production with feed gas containing low concentrations of CO₂. A kinetics study to determine the rate-controlling step for the H₂ S catalytic oxidation reaction over “granular Hydrodarco” activated carbon has been conducted. It was concluded that either adsorption of O₂ or H₂ S from the bulk phase onto the catalyst surface is the rate-controlling step of the H₂ S catalytic oxidation reaction.     

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.     

Evaluating isotherm models for the prediction of flue gas adsorption equilibrium and dynamics

We evaluated isotherm models for the precise prediction of adsorption equilibrium and breakthrough dynamics. Adsorption experiments were performed using pure N₂, CO₂ and their binary mixture with an activated carbon (AC) material as an adsorbent. Both BET and breakthrough measurements were conducted at various conditions of temperature and pressure. The corresponding uptake amount of pure component adsorption was experimentally determined, and parameters of the four different isotherm models, Langmuir, Langmuir-Freundlich, Sips, and Toth, were calculated from the experimental data. The predictive capability of each isotherm model was also evaluated with the binary experimental results of binary N₂/CO₂ mixtures, by means of sum of square errors (SSE). As a result, the Toth model was the most precise isotherm model in describing CO₂ adsorption equilibrium on the AC. Based on the breakthrough experimental result from the binary mixture adsorption, non-isothermal modeling for the adsorption bed was performed. The breakthrough results with all of the isotherm models were examined by rigorous dynamic simulations, and the Toth model was also the most accurate model for describing the dynamics.