Determination of model parameters for zinc (II) ion biosorption onto powdered waste sludge (PWS) in a fed-batch system

Biosorption of zinc (II) ions onto pre-treated powdered waste sludge (PWS) was investigated using a completely mixed tank operating in fed-batch mode instead of an adsorption column. Experiments with variable feed flow rate (0.05-0.5 L h(-1)), feed Zn(II) ion concentrations (37.5-275 mg L(-1)) and amount of adsorbent (1-6 g PWS) were performed using fed-batch operation at pH 5 and room temperature (20-25 degrees C). Break-through curves describing variations of aqueous (effluent) zinc ion concentrations with time were determined for different operating conditions. Percent zinc removal from the aqueous phase decreased, but the biosorbed (solid phase) zinc ion concentration increased with increasing feed flow rate and zinc concentration. A modified Bohart-Adams equation was used to determine the biosorption capacity of PWS (q'(s)) and the rate constant (K) for zinc ion biosorption. Biosorption capacity (q'(s)=57.7 g Zn kg(-1) PWS) of PWS in fed-batch operation was found to be comparable with powdered activated carbon (PAC) in column operations. However, the adsorption rate constant (K=9.17 m(3) kg(-1) h(-1)) in fed-batch operation was an order of magnitude larger than those obtained in adsorption columns because of elimination of mass transfer limitations encountered in the column operations. Therefore, a completely mixed tank operated in fed-batch mode was proven to be more advantageous as compared to adsorption columns due to better contact between the phases yielding faster adsorption rates.     

Removal of basic dye (Astrazon Blue FGRL) using macroalga Caulerpa lentillifera

The macroalga Caulerpa lentillifera was found to have adsorption capacity for a basic dye, Astrazon Blue FGRL. For the whole range of concentrations employed in this work (20-1280 mgl(-1)), the adsorption reached equilibrium within the first hour. The kinetic data corresponded well with the pseudo second-order kinetic model where the rate constants decreased as initial dye concentrations increased. At low dye concentrations (20-80 mgl(-1)), an increase in the adsorbent dosage resulted in a higher removal percentage of the dye, but a lower amount of dye adsorbed per unit mass (q). The adsorption isotherm followed both the Langmuir and Freundlich models within the temperature range employed in this work (18-70 degrees C). The highest maximum adsorption capacity (q(m)) was obtained at 50 degrees C. The enthalpy of adsorption was estimated at 14.87 kJmol(-1) suggesting a chemical adsorption mechanism.     

Adsorption of basic dye from aqueous solution onto fly ash

The fly ash treated by H₂SO₄ was used as a low-cost adsorbent for the removal of a typical dye, methylene blue, from aqueous solution. An increase in the specific surface area and dye-adsorption capacity was observed after the acid treatment. The adsorption isotherm and kinetics of the treated fly ash were studied. The experimental results were fitted using Langmuir and Freundlich isotherms. It shows that the Freundlich isotherm is better in describing the adsorption process. Two kinetic models, pseudo-first order and pseudo-second order, were employed to analyze the kinetic data. It was found that the pseudo-second-order model is the better choice to describe the adsorption behavior. The thermodynamic study reveals that the enthalpy (ΔH⁰) value is positive (5.63 kJ/mol), suggesting an endothermic nature of the adsorption.     

A comparative study on the properties,mechanisms and process designs for the adsorption of non-ionic or anionic dyes onto cationic-polymer/bentonite

The adsorption properties and mechanisms of a cationic-polymer/bentonite complex (EPI-DMA/bentonite), prepared from polyepicholorohydrin-dimethylamine and bentonite, for non-ionic dyes (Disperse Blue SBL and Vat Scarlet R) and anionic dyes (Reactive Violet K-3R and Acid Dark Blue 2G) were investigated in this study. The solution pH, presence of salt and surfactant can significantly affect the dye removal efficiency. The equilibrium data were analyzed using the Langmuir and Freundlich models. The Langmuir model is the most suitable to describe non-ionic dye adsorption, but for anionic dyes the Freundlich model is best. The kinetic data for the adsorption of different dyes were analyzed using pseudo first- and second-order equations, and the experimental data conformed to the pseudo second-order kinetic model better. The possibility of intraparticle diffusion was also examined by using the intraparticle diffusion equation. The single-stage batch adsorber design for the adsorption of both types of dyes onto EPI-DMA/bentonite was studied based on the Langmuir isotherm model for non-ionic dyes and the Freundlich isotherm model for anionic dyes. The results showed that the required amount of EPI-DMA/bentonite for 95% dye removal in 5 L dye solution with a concentration of 50 mg/L is 378.0 g for DB SBL, 126.5 g for VS R, 9.7 g for RV K-3R and 15.5 g for ADB 2G.     

A two stage batch adsorber design for methylene blue removal to minimize contact time

The adsorption of methylene blue onto bentonite in a batch adsorber has been studied. Three kinetic models, the intraparticle diffusion equation and the pseudo first and second order equations, were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption of methylene blue onto bentonite could be described by the pseudo second order equation. Adsorption of methylene blue onto bentonite followed the Langmuir isotherm. A model has been developed for the design of a two stage batch adsorber based on pseudo second order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total contact time to achieve a specified amount of methylene blue removal using a fixed mass of adsorbent. The results of two stage batch adsorber design studies showed that the required times for specified amounts of methylene blue removal significantly decreased. This design is particularly suitable for low-cost adsorbents/adsorption systems when minimising contact time is a major operational and design criterion and a significant volume of effluent needs to be treated in the minimum amount of time.     

Development of activated carbon from Nerium oleander flower and their rapid adsorption of direct and reactive dyes

The present study investigates the thermally activated carbon derived from Nerium oleander flower which was used an adsorbent. Physicochemical properties of Nerium oleander flower carbon (NOFC) were characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared for the removal of DTB (Direct Turquoise Blue) and RR-HE7B (Reactive red–HE7B) dyes from aqueous solution. Adsorption studies were carried out with different pH, adsorbent dose, contact time, and initial concentration dye solution. Optimum conditions for maximum removal of DTB and RR-HE7B was achieved to be pH 2 for both dyes, adsorbent dose of 100 mg and equilibrium time of 35 and 60 min, respectively, for NOFC. The maximum adsorption capacity of NOFC was found to be 33.33 and 19.60 mg g^?1, respectively, for the removal of dye solution. The mechanism of adsorption was studied by using different kinetic models and isotherms. The results clearly showed that the NOFC adsorption was fitted to pseudo–first-order for DTB and pseudo–second-order for RR-HE7B. Equilibrium data were well fitted with both isotherm models. According to the results, NOFC can effectively remove DTB and RR-HE7B from aqueous solutions.     

草木灰对亚甲基蓝的吸附研究

本实验目的是研究草木灰对吸附亚甲基蓝的去除效果,探讨了亚甲基蓝初始量、吸附时间、pH值等对吸附效果的影响,并运用伪一级、伪二级反应动力学模型和Laugmuir、Freundlich等温线模型进行拟合。结果表明,草木灰对亚甲基蓝溶液的吸附在5 min~30 min速率比较快,约在65 min内达到吸附平衡,pH越大越有利于吸附,浓度在5mg/L时草木灰对亚甲基蓝的吸附最佳。与伪二级动力学曲线模型拟合效果较好,由Laugmuir等温线模型计算得出理论最大吸附容量Qm为2.275 mg/g,吸附性能优异。     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Possible Utilization of Silica Gel Sludge for the Removal of Phenol from Aqueous Solutions: Laboratory Studies

This paper discusses the adsorption capacity of silica gel sludge for phenol removal from aqueous solution. Kinetic experiments showed that phenol adsorption was completed after 2 h. Adsorption isotherms were measured for phenol from aqueous solution onto silica gel sludge under various pHs and temperatures. Results showed that the adsorption capacities for phenol was increased as pH decreased from 6.5 to 2. Temperature also was found to affect the adsorption isotherm. As temperature increases from 30 to 50°C, the adsorption capacity increases. The adsorption equilibrium of phenol on silica gel sludge was described by the linear Freundlich and Langmuir models. Furthermore, results showed that the isotherm parameters fit both linearized Langmuir and Freundlich adsorption isotherms. The Freundlich and Langmuir parameters at optimum pH was found as K _f=2.89, 1/n=0.23 and K _d=22.0, q _m=7.98, respectively. Whereas, for those at optimum temperature it was observed as K _f=2.87, 1/n=0.16 and K _d=20.93, q _m=7.91, respectively.     

Removal of phosphorus from aqueous solutions using chemically modified sawdust of Aleppo pine (<Emphasis Type="Italic">Pinus halepensis Miller</Emphasis>): kinetics and isotherm studies

In the present study, chemically modified Aleppo pine (Pinus halepensis Miller) sawdust was used for the removal of phosphate from water. Biosorbent preparation process included size fractionation, extraction for surface activation, acid prehydrolysis, and treatment with urea. Sorption of phosphate ions onto biosorbent was studied using the batch technique. The effect of different parameters such as contact time, adsorbate concentration, and temperature was investigated. The adsorption kinetics data were best described by the pseudo-second-order rate equation, and equilibrium was achieved after 40 and 80 min for modified and unmodified sawdust, respectively. The Langmuir and Freundlich equations for describing adsorption equilibrium were applied to data. The constants and correlation coefficients of these isotherm models were calculated and compared. The adsorption isotherms obey the Freundlich equation. The thermodynamic parameters like free energy, enthalpy, and entropy changes for the adsorption of phosphate ions have been evaluated, and it has been found that the reaction was spontaneous and endothermic in nature. The low value of activated energy of adsorption, 3.088–3.540 kJ mol⁻¹, indicates that the phosphate ions are easily adsorbed on the sawdust. Results suggest that the prepared chemically modified Aleppo pine sawdust has potential in remediation of contaminated waters by phosphate.     

Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Kinetic and equilibrium isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk ash

The present study deals with the adsorption of Brilliant Green (BG) on rice husk ash (RHA). RHA is a solid waste obtained from the particulate collection equipment attached to the flue gas lines of rice husk fired boilers. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH0), contact time, adsorbent dose and initial concentration (C0) on the removal of BG. Optimum conditions for BG removal were found to be pH0 approximately 3.0, adsorbent dose approximately 6 g L(-1) of solution and equilibrium time approximately 5 h for the C0 range of 50-300 mg L(-1). Adsorption of BG followed pseudo-second-order kinetics. Intra-particle diffusion does not seem to control the BG removal process. Equilibrium isotherms for the adsorption of BG on RHA were analyzed by Freundlich, Langmuir, Redlich-Peterson (R-P), Dubnin-Radushkevich (D-R), and Temkin isotherm models using a non-linear regression technique. Langmuir and R-P isotherms were found to best represent the data for BG adsorption onto RHA. Adsorption of BG on RHA is favourably influenced by an increase in the temperature of the operation. Values of the change in entropy (DeltaS0) and heat of adsorption (DeltaH0) for BG adsorption on RHA were positive. The high negative value of change in Gibbs free energy (DeltaG0) indicates the feasible and spontaneous adsorption of BG on RHA.     

Physicochemical characterization of hydroxyapatite and its application towards removal of nitrate from water

A laboratory study was conducted to investigate the efficiency of hydroxyapatite (HAP) towards removal of nitrate from synthetic nitrate solution. In the present research HAP synthesized from egg-shell was characterized using SEM, XRD, FTIR and TGA–DSC. The removal of nitrate was 96% under neutral conditions, using 0.3 g of adsorbent in 100 mL of nitrate solution having an initial concentration of 100 mg/L. An adsorption kinetic study revealed that the adsorption process followed first order kinetics. Adsorption data were fitted to a linearly transformed Langmuir isotherm with correlation coefficient (R²) > 0.98. Thermodynamic parameters were also calculated to study the effect of temperature on the removal process. In order to understand the adsorption type, equilibrium data were tested with the Dubinin–Radushkevich isotherm. The process was rapid and equilibrium was established within the first 40 min.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.     

Application of cupuassu shell as biosorbent for the removal of textile dyes from aqueous solution

The cupuassu shell (Theobroma grandiflorum) which is a food residue was used in its natural form as biosorbent for the removal of C.I. Reactive Red 194 and C.I. Direct Blue 53 dyes from aqueous solutions. This biosorbent was characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption/desorption curves. The effects of pH, biosorbent dosage and shaking time on biosorption capacities were studied. In acidic pH region (pH 2.0) the biosorption of the dyes were favorable. The contact time required to obtain the equilibrium was 8 and 18 h at 298 K, for Reactive Red 194 and Direct Blue 53, respectively. The Avrami fractionary-order kinetic model provided the best fit to experimental data compared with pseudo-first-order, pseudo-second-order and chemisorption kinetic adsorption models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Radke-Prausnitz isotherm models. For both dyes the equilibrium data were best fitted to the Sips isotherm model.     

Removal of phenol from aqueous solutions by adsorption

Experiments have been conducted to examine the liquid-phase adsorption of phenol from water by silica gel, HiSiv 3000, activated alumina, activated carbon, Filtrasorb-400, and HiSiv 1000. Experiments were carried out for the analysis of adsorption equilibrium capacities and kinetics. The adsorption isotherm model of the Langmuir-Freundlich type was the best to describe adsorption equilibrium data for phenol for the adsorbents studied. Results of kinetic experiments indicated that HiSiv 1000 had the highest rate of adsorption among the adsorbents studied and therefore more detailed studies were carried out with this adsorbent. The influence of particle size, temperature, and thermal regeneration on adsorption of phenol by HiSiv 1000 was evaluated. From particle size experiments it appeared that adsorption capacity of HiSiv 1000 did not change by changing the particle size, but the rate of adsorption decreased considerably by increasing the particle size. The effect of temperature on adsorption was studied by determining equilibrium isotherms for HiSiv 1000 at 25, 40, and 55 degrees C. The results showed that adsorption capacity decreased with increasing temperature. Thermal regeneration of HiSiv 1000 was performed at 360 degrees C. It was observed that adsorption capacity of HiSiv 1000 did not change after 14 regeneration cycles. Equilibrium experiments showed that the adsorption capacities of activated carbon and Filtrasorb-400 were several times higher than that of HiSiv 1000.     

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.     

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic,equilibrium, and thermodynamic studies

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4 h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.     

电化学反应器吸附去除氟离子的研究

采用改性活性炭粉末对用纯净水加氟化钠配制而成的含氟水溶液进行动态电吸附去除实验.研究不同电压、电吸附时间,以及Cl-和SO2-4对氟离子去除的影响,并探讨吸附动力学和吸附方程.实验结果表明:活性炭对氟离子的吸附等温方程符合Freundlich方程,吸附动力学符合一级动力学方程;活性炭对氟离子去除与所施加的电位、吸附时间等因素有关,施加的电位越大,去除效果越好;随着吸附去除时间的延长,氟离子浓度下降趋缓;Cl-对氟离子去除影响很小,而SO2-4对氟离子去除有显著的不利影响.     

Fly ash for the treatment of Zn(II) rich effluents

Summary The ability of fly ash to remove Zn(II) from water by adsorption has been tested at different concentrations, temperatures and pH of the solution. It was found that low adsorbate concentration, small particle size of adsorbent and higher temperature favoured the removal of Zn(II) from aqueous solution. The Langmuir isotherm was used to represent the equilibrium data at different temperatures. The apparent heat of adsorption has been found to be 17.325 Kcal mol^–1, which indicates the process to be endothermic. The uptake of Zn(II) is diffusion controlled and the mass transfer coefficient is 3.56 × 10^–5 cm s ^–1.The maximum removal was noted at pH 7.5. Dr V.N. Singh is Professor and Head of the Department of Applied Chemistry, Dr A.K. and Prof. D.P. Singh are members of the Department of Mining Engineering; all are situated in the Institute of Technology at Banaras Hindu University.