Equilibrium and Kinetic Modelling of Adsorption of Phosphorus on Calcined Alunite

The adsorption of phosphorus onto calcined alunite has been studied. Its equilibrium isotherm has been measured. The isotherm was determined by shaking 1.0 g calcined alunite, particle size range 90–150 m, with 100 mL phosphorus solution of initial concentrations from 0.5 to 2.5 mmol/L. The water bath shaking a constant rate of 200-rpm was used and the temperature maintained at 298 ± 2 K. A contact time of 120 min was required to achieve equilibrium. The experimental isotherm data were analyzed using the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich equations. The monolayer adsorption capacity is 1.355 mmol P per g calcined alunite. Three simplified kinetic models including a pseudo first-order equation, pseudo second-order equation and intraparticle diffusion equation were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium sorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the adsorption of phosphorus could be described by the pseudo second-order equation.     

New insights into pseudo-second-order kinetic equation for adsorption

This study looked into the theoretical basis of the most commonly used pseudo-second-order kinetic equation for adsorption. It was demonstrated that the pseudo-second-order kinetic equation for adsorption indeed is in line with the universal rate law for a chemical reaction, while the same principle can also be applied to the pseudo-first-order kinetic equation for adsorption. This in turn offers a theoretical basis for the pseudo-second-order equation. If the second-order equation is applicable, the rate of adsorption was found to be subject to a second-order rate law with respect to the availability of adsorption sites on the surface of adsorbent rather than adsorbate concentration in bulk solution as proposed in the literature. Based on the rate law for the second-order adsorption process, the original complex second-order kinetic equation can be transformed to a simple hyperbolic form with clearly defined mathematical structure: Q_t = Q_e(t/t + t_r) in which t_r is relaxation time representing time required for adsorption to reach half-saturation state of adsorbent under given experimental conditions, i.e., Q_t = 0.5Q_e.     

Adsorption of 2-methylbenzoic acid onto MCM-41 mesoporous material: kinetics and equilibrium studies

Ordered mesoporous molecular sieves are widely studied as alternative materials in areas where sorptive and catalytic applications are required. MCM-41 type mesoporous material was tested as sorbent of 2-methylbenzoic acid (MBA), an aromatic carboxylic acid selected as model molecule for adsorption studies on mesoporous silicas. Adsorption kinetic studies of MBA on MCM-41 type materials were carried out using ethanol solutions at different MBA concentrations. Experimental results followed Langmuir isotherm model showing large adsorption capacity (3.5?g/g). Two kinetic models, the pseudo first- and second-order, were selected to describe the adsorption process and to determine the best model fitting with the experimental data. Kinetic parameters for each kinetic equation were calculated and discussed. It was shown that the MBA adsorption process onto MCM-41 material could be described by the pseudo-second-order equation and that the MCM-41 performs as a suitable adsorbent material.     

多胺型阴离子交换纤维吸附铬(VI)的动力学

以聚丙烯腈纤维为原料, 采用化学改性法, 制备了多胺型阴离子交换纤维. 研究该纤维对Cr(VI)的吸附特性. 在研究的温度及浓度范围内, 该纤维对Cr(VI)吸附的平衡数据符合Langmuir和Freundlich吸附等温方程, 对Cr(VI)有较强的亲和力, 吸附反应易于进行. 重点研究了该纤维对Cr(VI)的吸附动力学特性, 分别采用Lagergren一级动力学方程、修正伪一级动力学方程、伪二级动力学方程和颗粒内扩散方程进行拟合, 计算相应的速率常数. 研究表明, 该吸附是一个快速吸附过程, 20 min即可接近吸附平衡, 吸附过程符合伪二级动力学方程, 以化学吸附为主, 该纤维能够多次反复对Cr(VI)进行吸附.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES:ADSORPTION EQUILIBRIUM OF IRON(Ⅲ)ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 KJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.     

PREPARATION AND CHARACTERIZATION OF NOVEL CHITOSAN DERIVATIVES: ADSORPTION EQUILIBRIUM OF IRON(Ⅲ) ION

The adsorption of Fe(Ⅲ)ions from aqueous solution by chitosan alpha-ketoglutaric acid(KCTS)and hydroxamated chitosan alpha-ketoglutaric acid(HKCTS)was studied in a batch adsorption system.Experiments were carried out as function of pH,temperature,agitation rate and concentration of Fe(Ⅲ)ions.The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and isotherm constants were determined.The Langmuir model agrees very well with experimental data.The pseudo-first-order and second-order kinetic models were used to describe the kinetic data and the rate constants were evaluated.The dynamical data fit well with the second-order kinetic model.The pseudo second-order kinetic model was indicated with the activation energy of 19.61 and 7.98 kJ/mol for KCTS and HKCTS,respectively.It is suggested that the overall rate of Fe(Ⅲ)adsorption is likely to be controlled by the chemical process.Results also showed that novel chitosan derivatives(KCTS and HKCTS)were favorable adsorbents.     

HPD-100树脂吸附小檗碱的热力学及动力学研究

研究了小檗碱在HPD-100树脂上的吸附热力学和动力学行为。考察了小檗碱在HPD-100树脂上的吸附等温曲线和吸附动力学曲线,确定了吸附过程的热力学及动力学参数。结果表明,HPD-100树脂对小檗碱的等温吸附可采用Langmuir方程描述、吸附为自发进行的放热型物理吸附过程;Dunwald–Wagnen内扩散方程能较好地拟合吸附动力学数据,吸附过程以颗粒内扩散为主要控制步骤,该吸附过程的表观活化能为29.11kJ/mol。本文为HPD-100树脂分离富集小檗碱类生物碱的实际应用提供基础数据及指导。     

Adsorption of U(VI) onto kaolin studied by batch method

Adsorption of U(VI) on purified kaolin was studied by batch methods under ambient conditions, including contact time, pH, fulvic acid, etc. Three kinetic models were used to model the kinetic adsorption which was very well described by the pseudo-second-order rate equation, and the activation energy of adsorption was 52.20 kJ/mol. The Freundlich and Dubinin–Radushkevich models fitted the experimental data better than the Langmuir model for the adsorption and desorption isotherms. The thermodynamic parameters indicated that the adsorption of U(VI) on kaolin was an endothermic and spontaneous process.     

Biosorption of nickel from aqueous solutions by Acacia leucocephala bark: Kinetics and equilibrium studies

The biosorption of nickel(II) ions from aqueous solution by Acacia leucocephala bark was studied in a batch adsorption system as a function of pH, initial metal ion concentration, adsorbent dosage, contact time and temperature. The maximum Ni(II) adsorption was obtained at pH 5. Further, the biosorbents were characterized by Fourier Transformer Infrared Spectroscopy (FTIR). The experimental data were analysed using three sorption kinetic models viz., the pseudo-first- and second-order equations and the intraparticle diffusion model. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process. The equilibrium nature of Ni(II) adsorption at different temperatures of 30, 40 and 50 °C have been described by the Langmuir and Freundlich isotherm models. The equilibrium data fit well Langmuir isotherm. The monolayer adsorption capacity of A. leucocephala bark as obtained from Langmuir isotherm at 30 °C was found to be 294.1 mg/g. The Chi-square (χ²) and Sum of the square errors (SSE) tests were also carried out to find the best fit adsorption isotherm and kinetic model. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were calculated indicating that this system was a spontaneous and endothermic process. Present investigation emphasized that A. leucocephala bark may be utilized as a low cost adsorbent for nickel removal.     

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.     

Kinetics and adsorption equilibrium in the system aqueous solution of copper ions—granulated activated carbon

The feasibility of using granulated activated carbon for adsorption removal of copper from aqueous solution was studied. The influence of pH, amount of the adsorbent, contact time, and copper concentration on adsorption of copper was investigated. The single-component equilibrium data on copper adsorption were analyzed using the Langmuir, Freundlich, Redlich—Peterson, Temkin, and Toth adsorption isotherms. The adsorption process was followed by two simplified kinetic models including pseudo-first- and pseudo-second-order equations. Kinetic parameters, rate constants, equilibrium sorption capacities, and the corresponding correlation coefficients were calculated and examined for each kinetic model. It was shown that copper adsorption can be described by the pseudo-second-order equation.     

The kinetics of ethanol adsorption from the aqueous phase onto zeolite NaZSM-5

The kinetics of the isothermal adsorption of ethanol from an aqueous solution onto a hydrophobic zeolite of the NaZSM-5 type in the temperature range 298–333 K was investigated. Specific shape parameters of the adsorption degree curves were determined. The changes in the specific shape parameters of the adsorption degree curves with temperature were determined. The kinetic parameters of ethanol adsorption (E_a,ln A) were determined by the initial rate, the saturation rate and the maximum rate methods as well as from the Johnson, Mehl and Avramy equation. The kinetic model of ethanol adsorption kt=[1−(1−α)^1/3] was determined by the “model fitting” method. Ethanol adsorption from aqueous solution onto NaZSM-5 is a kinetically controlled process limited by the rate of three-dimensional movement of the boundary layer of the adsorption phase. A model for the mechanism of ethanol adsorption onto NaZSM-5 is suggested on the basis of the kinetic model. Ethanol molecules in aqueous solution are associated in clusters. The activation energy of the adsorption process corresponds to the energy required for the detachment of an ethanol molecule from a cluster and its adsorption onto the zeolite.     

纳米γ-Al_2O_3吸附Ge(Ⅳ)的机理及性能

研究了纳米γ-Al2O3吸附剂对Ge(Ⅳ)的吸附行为,考察了吸附平衡时间、温度和溶液的pH值等因素对吸附过程的影响.结果表明,纳米Al2O3对Ge(Ⅳ)的吸附在2min时基本达到平衡,在pH=4～11范围内,Ge(Ⅳ)可以被纳米Al2O3定量富集,吸附率大于95%;吸附于纳米Al2O3上的Ge(Ⅳ)可以用0.3mol/LK3PO4和1mol/LH2SO4混合溶液洗脱,5min后基本达到解析平衡,解析率能达到97%;该吸附过程符合准二级反应动力学模型,计算了不同温度下的吸附速率常数,并求得纳米Al2O3对Ge(Ⅳ)的吸附活化能(Ea)为11.63kJ/mol;该体系的吸附过程符合Freundlich等温式,由D-R等温式求得常温下纳米Al2O3对Ge(Ⅳ)的平均吸附能为10.87kJ/mol.Ge(Ⅳ)吸附反应的ΔG0为负值,焓变ΔH0为正值,说明该吸附过程是自发的吸热反应.     

乙酰苯胺修饰的吸附树脂对苯酚和对氯苯酚的吸附研究

通过Friedel-Crafts后交联及化学修饰反应,合成了乙酰苯胺基修饰的超高交联吸附树脂ZH-05,通过红外光谱(IR)和比表面及孔径分析(BET)对其结构进行表征.以Amberlite XAD-4树脂作为参照,通过等温吸附实验和吸附动力学实验探讨了ZH-05树脂对水溶液中苯酚和对氯苯酚的吸附性能和机理.结果表明,与XAD-4树脂相比,ZH-05树脂对苯酚和对氯苯酚均具有更佳的吸附性能.Langmuir和Freundlich方程均能较好拟合ZH-05树脂对苯酚和对氯苯酚的吸附等温线.ZH-05树脂对苯酚和对氯苯酚的吸附以焓推动的自发物理吸附过程为主,吸附过程放热;吸附符合准一级动力学吸附方程,颗粒内扩散是吸附过程的主要控制步骤.     

Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds: Kinetics,isotherms, mass transfer,thermodynamics and process design

The adsorption of Basic Magenta II onto H₂SO₄ activated immature Gossypium hirsutum seeds was analysed using Ho, modified Freundlich, Sobkowsk–Czerwi, Blanchard, Elovich, Avrami, and modified Ritchie kinetic models by nonlinear regression-sum of normalized errors analysis. The goodness of fit was evaluated with coefficient of determination and root mean square error. The good agreement of experimental data to Avrami second-order model indicated that the mechanism of adsorption followed multiple kinetic orders. The Avrami second-order mechanism was applied to predict the rate constant of sorption and the equilibrium capacity and subsequently the obtained equilibrium adsorption capacities were utilized to find the equilibrium concentrations. Langmuir, Freundlich, Temkin, Sips and Hill isotherms were investigated to understand the nature of adsorption with the help of nonlinear regression analysis. Both Sips and Hill isotherms were best fit to the adsorption equilibrium data showing the homogeneous adsorption on the heterogeneous surface of carbon and the positive co-operative manifestations of the Basic Magenta II molecules. The mass transfer study depicted the details such as mass transfer coefficient, intra-particle diffusion rate, pore diffusion coefficient, and film diffusion coefficient. The adsorption process was found to be controlled by film diffusion. The thermodynamic parameters like, Gibbs free energy change, enthalpy change, entropy change and isosteric heat of adsorption confirmed the endothermic, feasible and spontaneous nature of adsorption. A single stage batch adsorber was designed using Sips isotherm constants to estimate the amount of carbon required for desired purification.     

Conversion of biomass residual to acid-modified bio-chars for efficient adsorption of organic pollutants from industrial phosphoric acid: an experimental,kinetic and thermodynamic study

ABSTRACT

This study reports the removal of organic matters from phosphoric acid using waste-produced bio-charcoal structures. Particularly, the freshly made bio-char species via pyrolysis and two sub-driven acids activated charcoals were applied during the removal process. The treated charcoal with hydrochloric and nitric acids had attained a higher adsorption rate for organic matters than that of the non-treated one. Removal percentages of 70% and 60% were, respectively, attained by acid-modified chars. The kinetics of the adsorption process was fitted via pseudo-first/second-order and Morris–Weber models. The thermodynamic parameters of the presented sorption process indicate that organic matter removal has been endothermic, physical and spontaneous.     

Determination of kinetic parameters of Cu(II) interaction with chemically modified thin chitosan membranes

In this work, vanillin-modified thin chitosan membranes were utilized as adsorbents for the removal of Cu(II) from aqueous solutions. A rise of temperature accelerates mass transfer of Cu(II) to the membranes surfaces. The kinetic data did present a rough fit to the traditional Lagergren adsorption kinetic equations. An alternative Avrami kinetic equation was successfully fitted to the kinetic adsorption quantities. From this new equation, from one to three regions presenting distinct kinetic parameters were found, and the use of the parameter n was also related to the determination of the kinetic orders. Variations of the adsorption rate in relation to the contact time and the temperature were also calculated and are discussed.     

Kinetic of Adsorption of Urea Nitrogen onto Chitosan Coated Dialdehyde Cellulose under Catalysis of Immobilized Urease

The adsorption of urea nitrogen onto chitosan coated dialdehyde cellulose (CDAC) under catalysis of immobilized urease in gelatin membrane (IE) was studied in batch system. The pseudo first-order and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model.     

An alternative Avrami equation to evaluate kinetic parameters of the interaction of Hg(II) with thin chitosan membranes

In this work, thin chitosan membranes were utilized as an adsorbent for the removal of Hg(II) from aqueous solutions. A rise of temperature accelerates the mass transfer of Hg(II) to the membranes, surfaces. The kinetic data did not present a good fitting to the traditional Lagergren adsorption kinetic equations. An alternative Avrami kinetic equation was employed and successfully fitted to the kinetic adsorption quantities. From this new equation, two regions presenting distinct kinectic parameters were found, and the use of the parameter n was also relationed to the determination of the kinetic order. Variations of the adsorption kinetic rate in relation to the time, the initial Hg(II) concentration, and the temperature were also calculated and are discussed.     

Lignin from Agro-Industrial Waste to an Efficient Magnetic Adsorbent for Hazardous Crystal Violet Removal

The presence of cationic dyes, even in a tiny amount, is harmful to aquatic life and pollutes the environment. Therefore, it is essential to remove these hazardous dyes to protect the life of marine creatures from these pollutants. In this research, crystal violet (CV) dye elimination was performed using a lignin copper ferrite (LCF) adsorbent. The adsorbent was synthesized and characterized using FTIR, Raman, SEM, EDX with mapping, and VSM, which proved the successful formation of magnetic LCF. Adsorption experiments were performed using different effective parameters. The highest adsorption potential (97%) was executed at mild operating conditions, with a 5 min contact time at room temperature and pH 8. The adsorption kinetic study utilized four kinetic models: first-order, second-order, intraparticle diffusion, and Elovich. The results revealed that the adsorption process complies with the pseudo-first-order with a maximum adsorption capacity of 34.129 mg/g, proving that the adsorption process mechanism is a physical adsorption process. Three isotherm models, Langmuir, Freundlich, and Temkin, were examined. The adsorption mechanism of CV onto LCF was also followed by the Langmuir and Freundlich models. The thermodynamic parameters were examined and revealed that the adsorption onto LCF was an exothermic process. It was proposed that the adsorption process is a spontaneous exothermic process. LCF appears to forcefully remove toxic CV dye from textile wastewater.