Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons

The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution.     

Kinetic and calorimetric study of the adsorption of dyes on mesoporous activated carbon prepared from coconut coir dust

Mesoporous activated carbon has been prepared from coconut coir dust as support for adsorption of some model dye molecules from aqueous solutions. The methylene blue (MB) and remazol yellow (RY) molecules were chosen for study of the adsorption capacity of cationic and anionic dyes onto prepared activated carbon. The adsorption kinetics was studied with the Lagergren first- and pseudo-second-order kinetic models as well as the intraparticle diffusion model. The results for both dyes suggested a multimechanism sorption process. The adsorption mechanisms in the systems dyes/AC follow pseudo-second-order kinetics with a significant contribution of intraparticle diffusion. The samples simultaneously present acidic and basic sites able to act as anchoring sites for basic and acidic dyes, respectively. Calorimetric studies reveal that dyes/AC interaction forces are correlated with the pH of the solution, which can be related to the charge distribution on the AC surface. These AC samples also exhibited very short equilibrium times for the adsorption of both dyes, which is an economically favorable requisite for the activated carbon described in this work, in addition to the local abundance of the raw material.     

Removal of Congo red from aqueous solutions by neem saw dust carbon

Neem sawdust was used to develop an effective carbon adsorbent. This adsorbent was used for the removal of Congo Red (CR) from aqueous solution. The data suggest that the pH of aqueous solutions influences CR removal due to the decrease of removal efficiency with increasing pH. An optimal pH < 3 for the adsorption of CR onto neem sawdust carbon (NSDC) was determined. The experimental data were analysed by the Langmuir, Freundlich, Redlich-Peterson, Toth, Temkin, Sips and Dubinin-Radushkevich models of adsorption. Three simplified kinetic models based on pseudo-first-order, pseudo-second-order and intraparticle diffusion equations were used to describe the adsorption process. It was shown that the adsorption of CR could be described by the pseudo-second-order equation, suggesting that the adsorption occurs as a chemisorption process. The results indicate that the NSDC can be used as a low cost adsorbent alternative to commercial activated carbon for the removal of dyes from wastewaters.     

Mesoporous activated carbon from <Emphasis Type="Italic">Pentace</Emphasis> species sawdust via microwave-induced KOH activation: optimization and methylene blue adsorption

This work studied the optimization of preparation conditions of Pentace species sawdust activated carbon (PSAC) via microwave-induced KOH activation for the adsorption of methylene blue (MB) dye from aqueous solutions. The produced activated carbon was characterised through Brunauer–Emmett–Teller (BET) surface area and pore structural analysis, proximate and ultimate, scanning electron microscopy, and Fourier transform infrared spectroscopy. Response surface methodology technique was used to optimize the radiation power, radiation time and impregnation ratio for MB removal and PSAC yield through central composite design. The optimum preparation conditions for PSAC were obtained at a radiation power of 418 W, radiation time of 6.4 min, and an impregnation ratio of 0.5, which resulted in 27% PSAC yield and 93.74% MB removal. A mesoporous structure of PSAC was formed, with a BET surface area, total pore volume and average pore diameter of 914.15 m²/g, 0.52 cm³/g, and 3.19 nm, respectively. The experimental kinetic data were well described by a pseudo-second-order model and intraparticle diffusion. Adsorption data fitted the Redlich–Peterson equation better than the Langmuir, Freundlich, Temkin, Dubinin–Radushkevich and Sips equations. However, the exponential value of Redlich–Peterson approached unity, hence, resulting in the original Langmuir equation, with adsorption capacity of 357.14 mg/g. The adsorption performance was effectively preserved even after four consecutive cycles, demonstrating good regeneration ability.     

Modeling adsorption rate of organic micropollutants present in landfill leachates onto granular activated carbon

The overall adsorption rate of single micropollutants present in landfill leachates such as phthalic acid (PA), bisphenol A (BPA), diphenolic acid (DPA), 2,4-dichlorophenoxy-acetic acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid (MCPA) on two commercial activated carbons was studied. The experimental data obtained were interpreted by using a diffusional model (PVSDM) that considers external mass transport, intraparticle diffusion, and adsorption on an active site. Furthermore, the concentration decay data were interpreted by using kinetics models. Results revealed that PVSDM model satisfactorily fitted the experimental data of adsorption rate on activated carbon. The tortuosity factor of the activated carbons used ranged from 2 to 4. The contribution of pore volume diffusion represented more than 92% of intraparticle diffusion confirming that pore volume diffusion is the controlling mechanism of the overall rate of adsorption and surface diffusion can be neglected. The experimental data were satisfactorily fitted the kinetic models. The second-order kinetic model was better fitted the experimental adsorption data than the first-order model.     

Valorization of two waste streams into activated carbon and studying its adsorption kinetics,equilibrium isotherms and thermodynamics for methylene blue removal

Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC) with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB) onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g) of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.     

Removal of Cr (VI) from aqueous solutions by the nonliving biomass of Alligator weed: kinetics and equilibrium

The removal of Cr (VI) from aqueous solutions using Alligator weed, a freshwater macrophyte, was investigated in batch studies. Various factors including solution pH, Cr (VI) concentrations, agitation time, and temperature were taken into account and promising results obtained. An initial solution pH of 1.0 was most favorable for Cr (VI) removal. The kinetic data were analyzed using several models, including the pseudo-second-order equation, external diffusion model, and intraparticle diffusion model. The comparison gave insight about the mechanism of adsorption and potential rate controlling step. The results suggested that the Cr (VI) adsorption at all temperatures was best represented by the pseudo-second-order equation. The external film diffusion played an important role in the adsorption mechanism. The Freundlich, Langmuir and Langmuir-Freundlich isotherms for the present system were analyzed. The best interpretation for the equilibrium data at different temperatures was given by the Langmuir-Freundlich isotherm. The Alligator weed could serve as low-cost adsorbent to remove Cr (VI) from aqueous solutions.     

Removal of methylene blue by seed-watermelon pulp-based low-cost adsorbent: Study of adsorption isotherms and kinetic models

Based on the abundance of seed-watermelon pulp (SWP) in Xinjiang, China, SWP was employed to prepare low-cost adsorbent toward the removal of methylene blue (MB). The effects of contact time at different initial concentration were studied. The widely used adsorption isotherm models including Langmuir, Freundlich, and Temkin isotherms were employed to depict the adsorption process. The Langmuir isotherm was best fitted to the experimental data. Batch kinetic studies showed that an equilibrium time of 300 minutes was needed for the adsorption. The adsorption properties can be well described by pseudo-second-order kinetic model and the MB uptake was not controlled by intraparticle diffusion mechanism.     

Kinetic modeling of liquid-phase adsorption of reactive dyes on activated carbon

In this paper, adsorption equilibrium and kinetics of three reactive dyes from their single-component aqueous solutions onto activated carbon were studied in a batch reactor. Effects of the initial concentration and adsorbent particle size on adsorption rate were investigated Adsorption equilibrium data were then correlated with several well-known equilibrium isotherm models. The kinetic data were fitted using the pseudo-first-order equation, the pseudo-second-order equation, and the intraparticle diffusion model. The respective characteristic rate constants were presented. A new adsorption rate model based on the pseudo-first-order equation has been proposed to describe the experimental data over the whole adsorption process. The results show that the modified pseudo-first-order kinetic model generates the best agreement with the experimental data for the three single-component adsorption systems.     

Sorption characteristics of an economical sorbent material used for removal radioisotopes of cesium and europium

Application study for the evaluation of sorption characteristics of sawdust as an economical sorbent material used for decontamination of radioisotopes cesium and europium from aqueous solution has been carried out in the present work. In this respect, sawdust (untreated and treated by HNO₃) has been prepared from the commercial processing of wood for furniture production. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N₂ adsorption and DFT software. Radiotracer method onto sawdust from aqueous solutions was studied in a batch technique with respect to pH, contact time, temperature. The kinetics of adsorption of Eu³⁺ and Cs⁺ have been discussed using five kinetic models namely, pseudo-first-order model, pseudo-second-order model, Elovich equation, intraparticle diffusion model, and modified Freundlich equation that have been tested in order to analysis the experimental data. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the sorption kinetics for two metal ions. The metal uptake process was found to be controlled by intraparticle diffusion. Thermodynamic parameters, such as ΔH, ΔG and ΔS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures. The obtained results indicated that endothermic nature of sorption process for both ^152+154Eu and ¹³⁴Cs onto sawdust.     

Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite

The adsorption of two dyes, namely, Acid Red 57 (AR57) and Acid Blue 294 (AB294), onto acid-activated bentonite in aqueous solution was studied in a batch system with respect to contact time, pH, and temperature. Acidic pH was favorable for the adsorption of these dyes. The surface characterization of acid-activated bentonite was performed using the FTIR technique. The pseudo-first-order and pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamic data fitted the pseudo-second-order kinetic model well and also followed the intraparticle diffusion model up to 90 min, but diffusion is not the only rate controlling step. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were determined. The Freundlich model agrees very well with experimental data. The activation energies of adsorption were also evaluated for the adsorption of AR57 and AB294 onto activated bentonite.     

Activated carbon blended with grape stalks powder: Properties modification and its application in a dye adsorption

In this study, activated carbon was blended with grape stalks powder to adsorb methylene blue (MB) dye with various concentrations from a wastewater. For this purpose, five independent variables involving pH (2–13), contact time (5–270 min), grape stalks powder dosage (0.1–10 g/l), methylene blue initial concentration (20–300 mg/l), and activated carbon dosage (0.1–10 g/l) for methylene blue adsorption were studied. The Central Composite Design (CCD) under Response Surface Methodology (RSM) was applied to estimate the independent variables effects on the methylene blue adsorption. The pseudo- first order, pseudo-second order, Elovich and intraparticle diffusion models were employed to study the adsorption kinetics and isotherm. The Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models were applied to investigate the adsorption isotherm. It was concluded that the intraparticle diffusion isotherm and pseudo-second order kinetic models could show the best results. Furthermore, some data such as physical adsorption (by analyzing FTR and applying some standard equations) and mean free energy (E) were discovered in this research. Finally, activated carbon blended with grape stalks powder as an effective bio-adsorbent for the methylene blue reduction from a wastewater was introduced.     

ZnO/C纳米球的亚甲基蓝单吸附特性:平衡、动力学及机理

采用电弧放电法制备了ZnO/C纳米球,利用FESEM、XRD和N₂吸附/脱附测试进行了表征。在避光条件下研究了复合材料对亚甲基蓝的吸附性能。研究结果表明,随着亚甲基蓝的浓度及接触时间的增长吸附量明显上升,在吸附时间为150 min时达到吸附平衡。采用Langmuir、Freundlich及Temkin等温吸附模式对吸附平衡进行了研究。结果表明,吸附等温线符合Langmuir等温吸附模式,单层吸附饱和容量可达188.68 mg·g^-1。利用动力学模型、内扩散模型和外扩散速率控制模型拟合实验数据,拟合数据表明其动力学符合伪二级动力学模型;内扩散机理不是吸附速率的唯一限制机理,亚甲基蓝的总吸附速率受膜扩散控制。     

ZnO/C纳米球的亚甲基蓝单吸附特性:平衡、动力学及机理

采用电弧放电法制备了ZnO/C纳米球,利用FESEM、XRD和N₂吸附/脱附测试进行了表征。在避光条件下研究了复合材料对亚甲基蓝的吸附性能。研究结果表明,随着亚甲基蓝的浓度及接触时间的增长吸附量明显上升,在吸附时间为150 min时达到吸附平衡。采用Langmuir、Freundlich及Temkin等温吸附模式对吸附平衡进行了研究。结果表明,吸附等温线符合Langmuir等温吸附模式,单层吸附饱和容量可达188.68 mg·g^-1。利用动力学模型、内扩散模型和外扩散速率控制模型拟合实验数据,拟合数据表明其动力学符合伪二级动力学模型;内扩散机理不是吸附速率的唯一限制机理,亚甲基蓝的总吸附速率受膜扩散控制。     

Slow adsorption reaction between arsenic species and goethite (alpha-FeOOH): diffusion or heterogeneous surface reaction control

The slow stage of phosphate or arsenate adsorption on hydrous metal oxides frequently follows an Elovich equation. The equation can be derived by assuming kinetic control by either a diffusion process (either interparticle or intraparticle) or a heterogeneous surface reaction. The aim of this study is to determine whether the slow stage of arsenic adsorption on goethite is more consistent with diffusion or heterogeneous surface reaction control. Adsorption kinetics of arsenate and dimethylarsinate (DMA) on goethite (alpha-FeOOH) were investigated at different pH values and inert electrolyte concentrations. Their adsorption kinetics was described and compared using Elovich (Gamma vs ln time) plots. Desorption of arsenate and DMA was studied by increasing the pH of the suspension from pH 4.0 to pH 10.0 or 12.0. The effective particle sizes and zeta-potential of goethite were also determined. Effective particle size increased rapidly as the pH approached pH(IEP), both in the absence and presence of arsenic. Inert electrolyte concentrations and pH had no effect on the slow stage of arsenate adsorption on goethite, while the kinetics of DMA adsorption on goethite was influenced by both parameters. The slow stage of arsenate adsorption on goethite follows an Elovich equation. Since effective particle size changes with both pH and inert electrolyte concentrations, and effective particle size influences interparticle diffusion, the arsenate adsorption kinetics indicate that the slow adsorption step is not due to interparticle diffusion. DMA also has complex adsorption kinetics with a slow adsorption stage. DMA desorbed completely and rapidly when the pH was raised, in contrast to the slow adsorption kinetics, indicating that the slow adsorption step is not due to intraparticle diffusion. The slow adsorption is not the result of diffusion, but rather is due either to the heterogeneity of the surface site bonding energy or to other reactions controlling arsenic removal from solution.     

Adsorption of methylene blue dye from aqueous solution by agricultural waste: Equilibrium,thermodynamics, kinetics,mechanism and process design

The adsorption of methylene blue (MB) dye from aqueous solution onto a cashew nut shell (CNS) was investigated as a function of parameters such as solution pH, CNS dose, contact time, initial MB dye concentration and temperature. The CNS was shown to be effective for the quantitative removal of MB dye, and the equilibrium was reached in 60 min. The experimental data were analysed by two-parameter isotherms (Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models) using nonlinear regression analysis. The characteristic parameters for each isotherm and the related correlation coefficients were determined. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were also evaluated, the sorption process was found to be spontaneous and exothermic. Pseudo-first-order, pseudo-second-order and Elovich kinetic models were used to analyze the adsorption process. The results of the kinetic study suggest that the adsorption of MB dye matches the pseudo-second-order equation, suggesting that the adsorption process is presumably chemisorption. The adsorption process was found to be controlled by both surface and pore diffusion. Analysis of adsorption data using a Boyd kinetic plot confirmed that the external mass transfer is a rate determining step in the sorption process. A single-stage batch adsorber was designed for different CNS doses to effluent volume ratios using the Freundlich equation. The results indicated that the CNS could be used effectively to adsorb MB dye from aqueous solutions.     

Influence of Initial pH Value on the Adsorption of Reactive Black 5 Dye on Powdered Activated Carbon: Kinetics,Mechanisms, and Thermodynamics

The aim of this work was to investigate the influence of initial pH value (pH₀) on the isothermal adsorption of Reactive Black 5 (RB5) dye on commercial powdered activated carbon. Four initial pH values were chosen for this experiment: pH₀ = 2.00, 4.00, 8.00, and 10.00. In order to investigate the mechanism of adsorption kinetic, studies have been performed using pseudo-first-order and pseudo-second-order kinetic models as well as an intraparticle diffusion model. In addition, thermodynamic parameters of adsorption were determined for pH₀ = 4.00. Results of this research showed that the initial pH value significantly influences the adsorption of RB5 dye onto activated carbon. The highest adsorption capacities (q_e) and efficiencies of decolouration were observed for initial pH values of pH₀ = 2.00 (q_e = 246.0 mg g⁻¹) and 10.00 (q_e = 239.1 mg g⁻¹) due to strong electrostatic interactions and attractive π···π interactions, respectively. It was also shown that the adsorption of RB5 dye on activated carbon at all initial pH values is kinetically controlled, assuming a pseudo-second-order model, and that intraparticle diffusion is not the only process that influences on the adsorption rate.     

Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite

Adsorptive removal of dichloromethane, chloroform, and carbon tetrachloride from aqueous solutions at 25 °C by activated carbon (AC) that was loaded with cerium oxide nanoparticles (CeO₂-NP/AC) was investigated. The developed adsorbent was characterized by scanning electron microscope (SEM), FTIR spectrophotometer, X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The effect of contact time, initial concentration, and the adsorbent dosage were also studied. The equilibrium and kinetics of adsorption were studied in a batch-type adsorption system, and the equilibrium experimental data were analyzed using Langmuir, Freundlich, and Temkin isotherm models. Freundlich adsorption isotherm showed the best fit for the equilibrium adsorption data. Three adsorption kinetic models, pseudo first- and second-order, and intraparticle diffusion models were applied to test the kinetic data. Kinetic characterization of the adsorption process onto CeO₂-NP/AC is well-described by the pseudo second-order model, and the adsorption best-fit by the intraparticle diffusion model. Our study shows that at optimum conditions, 82.72%, 99.40% and 89.42% of dichloromethane, chloroform, and tetrachloride, respectively, were removed by CeO₂-NP/AC, at concentration between 0.25 and 5.00 g/L.     

Kinetics of solute adsorption at solid/aqueous interfaces: searching for the theoretical background of the modified pseudo-first-order kinetic equation

It is shown that the modified pseudo-first-order (MPFO) kinetic equation proposed recently by Yang and Al-Duri simulates well the behavior of the kinetics governed by the rate of surface reaction and described by our general kinetic equation, based on the statistical rate theory. The linear representation with respect to time, offered by the MPFO equation seems to be a convenient tool for distinguishing between the surface reaction and the diffusional kinetics. Also, a method of distinguishing between the surface reaction and the intraparticle diffusion model based on analyzing the initial kinetic isotherms of sorption is proposed. The applicability of these procedures is demonstrated by the analysis of adsorption kinetics of the reactive yellow dye onto an activated carbon.