Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

棘孢曲霉(Aspergillus aculeatus)对Pb~(2+)和Cd~(2+)的吸附特征

为了研究棘孢曲霉(Aspergillus aculeatus)对溶液中Pb~(2+)和Cd~(2+)吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb~(2+)和Cd~(2+)最大吸附量分别为71.2 mg/g和59.8 mg/g;动力学实验数据很好的符合二级动力学方程,吸附达到平衡的时间为3 h;热力学实验数据显示该吸附过程为自发的、吸热的过程。     

棘孢曲霉（Aspergillus aculeatus）对Pb2＋和Cd2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71.2 mg/g和59.8 mg/g;动力学实验数据很好的符合二级     

Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.     

棘孢曲霉（Aspergillus aculeatus）对Pb^2＋和Cd^2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71．2mg／g和59．8mg／g;动力学实验数据很好的符合二级动力学方程,吸附达到平衡的时间为3h;热力学实验数据显示该吸附过程为自发的、吸热的过程。     

Modeling VOCs adsorption onto activated carbon

The activated carbon adsorption process is affected by the characteristics of adsorbent, adsorbate and environmental conditions. In this study, both adsorption and desorption processes are assumed to occur simultaneously and a numerical model was developed with a non-linear driving force in conjunction with the Langmuir model for predicting the overall adsorption process. The numerical model provides both adsorption and desorption rate constants and activation energies. The resultant equilibrium constants are of the same order of magnitude as reported by other studies. Results show that the model could well predict the adsorption isotherms and breakthrough curves under various conditions.     

Adsorption-oxidation of hydrogen sulfide on activated carbon fibers: effect of the composition and the relative humidity of the gas phase

The removal of hydrogen sulfide by oxidation-adsorption on two type carbon fibers, Actitex FC1201 and RS1301, was studied. Two kinetic steps where identified. During the first step, the degradation appears to be limited by the oxidation reaction. In the second kinetic step, the by-products inhibit the hydrogen sulfide degradation. This leads to a limitation in the carbon site's accessibility and to a lower kinetic. The Langmuir-Hinshelwood model was used to correlate the experimental results and to estimate the kinetic (k) and the Langmuir adsorption (K) constants. For FC1201 fibers, the kinetic constant (k) is five time higher and the adsorption constant is five time lower compared to the RS1301 fibers. The role of the humidity was found to be highly beneficial for the removal of hydrogen sulfide. Especially in the second kinetic step, where it removes the by-product formed and therefore delays the occurrence of this low kinetic step. The kinetic constant (k) is strongly influenced by humidity while the Langmuir adsorption constant (K) seems independent. The effect of the nature of the gas phase on the reaction kinetic was also studied. Under a dry atmosphere, we note that the oxidation-reaction occurs even if the gaseous oxygen is not present. This oxidation is due to the oxygen surface function of the carbon fibers. Moreover, the degradation kinetic is faster under a dry nitrogen atmosphere. The presence of water traces leads to the acidification of the carbon surface, under oxygen or carbon dioxide atmospheres, and hence limits the hydrogen sulfide dissociation. In a humid atmosphere, the oxygen or carbon dioxide leads to a faster reaction kinetic. The acidification of the carbon surface is largely counterbalanced by the dissolution of the by-products.     

一株产絮酵母菌废菌体对Cd2+的吸附特性

将一株产絮酵母菌(编号B-02号)发酵后的废菌体制成生物吸附剂,研究该生物吸附剂对废水中Cd2+的生物吸附特性。结果表明:(1)pH值对Cd2+会产生较大的影响,偏酸性(pH=4～6)条件利于吸附;该吸附剂对Cd2+吸附速率较快,8～10 min就可达到吸附平衡;(2)吸附剂的吸附动力学符合二级动力学模型,吸附Cd2+的实验数据对Langmuir等温式的拟合情况良好,吸附剂吸附Cd2+的最大吸附量为70.752 mg/g。用0.5 mol/L HNO3对吸附Cd2+的酵母菌进行解吸,解吸率可达89.7%。     

改性沸石吸附低浓度氨氮废水及其脱附的研究

采用氯化钠溶液对浙江某地天然沸石改性,以低浓度氨氮废水为处理对象,比较了天然沸石和改性沸石的吸附等温线、吸附动力学和动态吸附,并进行了改性沸石的动态脱附研究.结果表明,沸石的平衡吸附量随着平衡浓度的增大而增大;Freundlich方程比Langmuir方程更好地描述沸石吸附低浓度氨氮废水的行为,改性沸石比天然沸石具有更...     

Removal of 2,4-D from aqueous solution by the adsorbents from spent bleaching earth

The removal of 2,4-D (2,4-dichlorophenoxyacetic acid) from aqueous solutions by activated spent bleaching earths (SBE) was studied at 20 degrees C. Experiments were performed as a function of time, initial concentration, dose and particle size of the adsorbent. The Langmuir and Freundlich adsorption equations were fitted by the adsorption data obtained. The values of Langmuir and Freundlich constants were determined. The adsorption kinetic was found to follow Lagergren equation. Both the boundary layer and intraparticle diffusion played important roles in the adsorption rate of 2,4-D. As the size of the adsorbent increased, the time to reach equilibrium increased but adsorption capacity decreased.     

Studies on the adsorption and kinetics of photodegradation of a model compound for heterogeneous photocatalysis onto TiO(2)

An investigation was made on the adsorption and kinetics of photodegradation of potassium hydrogenphthalate in an aqueous suspension of TiO(2). Two models, Langmuir and Freundlich, were used to describe the adsorption process and the model proposed by Langmuir-Hinshelwood (L-H) was employed to describe the kinetics of the photodecomposition reactions of hydrogenphthalate. The results of the adsorptions were fitted to the models proposed by Langmuir and Freundlich. Adsorption was found to be a function of the temperature, with adsorption capacity increasing from 2.4 to 4.5 mg/g when the temperature rose from 20 to 30 degrees C. The kinetic model indicates that the rate constant, k, of the first order reaction, is high in the 10.0 to 100 mg/l interval, which is coherent with the low value of the adsorption constant, K. The results fitted to the L-H model led to an equation that, within the range of concentrations studied here, theoretically allows one to evaluate the photodegradation rate.     

磺胺类抗生素的活性炭吸附过程研究

采用煤质活性炭对3种磺胺类抗生素(浓度在1～2 mg/L之间)的吸附处理过程做了深入研究。结果表明,3种磺胺类抗生素在2～3 h之内可以达到吸附平衡;准一级动力学对其吸附动力学的模拟结果良好,且SMZ、SM1和SM2的一级吸附动力学常数k1分别为0.029、0.024和0.017 min-1,3种抗生素的平衡吸附容量分别为3.75、3.23和2.95 mg/g,SMZ的平衡吸附容量最大,最先达到吸附平衡,且平衡浓度也最低。3种磺胺类抗生素的吸附过程中,吸附前期的阻力主要是内扩散,而吸附后期较低浓度的抗生素吸附过程的阻力主要来自于膜扩散;采用Freundlich等温线方程描述3种磺胺类抗生素的吸附过程更为合理。     

一株产絮酵母菌废菌体对Cd~（2＋）的吸附特性

将一株产絮酵母菌（编号B-02号）发酵后的废菌体制成生物吸附剂,研究该生物吸附剂对废水中Cd2＋的生物吸附特性。结果表明：（1）pH值对Cd2＋会产生较大的影响,偏酸性（pH=4～6）条件利于吸附;该吸附剂对Cd2＋吸附速率较快,8～10 min就可达到吸附平衡;（2）吸附剂的吸附动力学符合二级动力学模型,吸附Cd2＋的实验数据对Langmuir等温式的拟合情况良好,吸附剂吸附Cd2＋的最大吸附量为70.752 mg/g。用0.5 mol/L HNO3对吸附Cd2＋的酵母菌进行解吸,解吸率可达89.7%。     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

The removal of reactive black 5 from aqueous solutions by cotton seed shell

This study investigated the removal of Reactive Black 5 (RB5) textile dye from aqueous solutions using cotton (Gossypium hirsutum) seed shell (CSS) as low cost adsorbents. The data were described according to the Freundlich and Langmuir isotherm models. Of these, the Langmuir model provided the best fit for the experimental data. The highest measured adsorption density was 12.19 mg/g at pH 2. An equilibrium adsorption rate of RB5 by CSS (q(e) = 11.879 mg/g) was observed at 30 minutes. In order to evaluate the adsorption kinetic mechanisms, pseudo first and second order rate kinetic models and an intraparticle diffusion model were applied, with the pseudo second order model providing an excellent fit for the data.     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid (2,4-D) from aqueous solution on powdered activated carbon

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D), one of the most commonly used phenoxy acid herbicides, from aqueous solution was studied by using acid-washed powdered activated carbon (PAC) as an adsorbent in a batch system. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and initial 2,4-D concentration. Powdered activated carbon exhibited the highest 2,4-D uptake capacity of 333.3 mg g(-1) at 25 degrees C and an initial pH value of 2.0. Freundlich, Langmuir, and Redlich-Peterson isotherm models were used to express the equilibrium data of 2,4-D depending on temperature. Equilibrium data fitted very well to the Freundlich equilibrium model in the studied concentration range of 2,4-D at all the temperatures studied. Three simplified models including pseudo-first-order, pseudo-second-order, and saturation-type kinetic models were used to test the adsorption kinetics. It was shown that the adsorption of 2,4-D on PAC at 25, 35, and 45 degrees C could be best fitted by the saturation-type kinetic model with film and intraparticle diffusions being the essential rate-controlling steps. The activation energy of adsorption (EA) was determined as--1.69 kJ mole(-1). Using the thermodynamic equilibrium coefficients obtained at different temperatures, the thermodynamic constants of adsorption (deltaG degrees, deltaH degrees, and deltaS degrees) were also evaluated.     

溴化十六烷基吡啶改性沸石对水中甲基橙的吸附

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性制备得到了CPB改性沸石,通过批量吸附实验考察了CPB改性沸石对水中阴离子染料甲基橙的去除作用。结果表明,天然沸石对水中甲基橙的吸附能力很差,而CPB改性沸石则可以有效吸附去除水中的甲基橙。CPB改性沸石对水中甲基橙的吸附能力随CPB负载量的增加而增加,CPB负载量最大的改性沸石对水中甲基橙的吸附能力最强。双分子层CPB改性沸石对水中甲基橙的去除率随吸附剂投加量的增加而增加,而CPB改性沸石对水中甲基橙的单位吸附量则随吸附剂投加量的增加而降低。双分子层CPB改性沸石对水中甲基橙的吸附平衡数据可以采用Langmuir等温吸附模型加以描述。根据Langmuir模型计算得到的CPB负载量为341 mmol/(kg沸石)的双分子层CPB改性沸石对水中甲基橙的最大吸附容量为63.7 mg/g(303 K和pH 7)。准二级动力学模型适合用于描述双分子层CPB改性沸石对水中甲基橙的吸附动力学过程。pH和反应温度对双分子层CPB改性沸石吸附水中甲基橙的影响较小。以上结果说明,双分子层CPB改性沸石适合作为一种吸附剂用于去除废水中的甲基橙。     

活性炭吸附处理电镀废水中的EDTA

采用颗粒活性炭对模拟废水中EDTA进行批式吸附实验,在实验中考察了恒温振荡器的振荡速度、温度、pH值等因素对吸附的影响,同时探讨了吸附等温线模型和吸附动力学模型。实验结果表明,在25％时活性炭对EDTA的吸附平衡时间为40h。在pH值为5．0、温度为25℃、振荡器振荡速度为200r／min、活性炭粒径为1～2mm、活性炭加入量为10g／L的情况下,EDTA的浓度在48h内由368．8mg／L降低至76．34mg／L,对应的COD值从305．9mg／L降低为67．21mg／L,去除率达到了79．3％。活性炭对EDTA的吸附符合Langmuir吸附等温线模型,其吸附行为可以用准二级吸附动力学模型来描述。     

Zn / Al 双金属氧化物对水中硫酸根离子的吸附性能简

研究了用Zn/Al水滑石制得的Zn/Al双金属氧化物（Zn/Al-300）吸附剂对水中硫酸根离子的吸附,考查了吸附剂投加量、初始pH等因素对硫酸根离子吸附的影响。结果表明,Zn/Al-300对水中硫酸根离子的吸附符合Langmuir吸附等温方程,理论最大吸附量为62.5 mg/g。运用动力学方程进行拟合,吸附过程符合准二级动力学方程;溶液的pH影响吸附剂对硫酸根的吸附,在pH=5.5时硫酸根的去除率最大;X射线衍射结果显示,水滑石经过焙烧后丧失了原有的构形,并在吸附硫酸根离子后重新恢复水滑石的部分层状结构。吸附机制主要为Zn/Al-300从溶液中获取阴离子以重建水滑石的晶体结构,即“记忆效应”。对吸附后的双金属氧化循环应用4此后,吸附容量几乎不变,说明双金属氧化物具有可循环型。通过将Zn/Al-300与其他几种吸附剂的经济性分析,表明此吸附剂在使用过程中具有一定优势。     

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m²/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin–Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.