Adsorptive removal of Auramine-O: kinetic and equilibrium study

Present study deals with the adsorption of Auramine-O (AO) dye by bagasse fly ash (BFA) and activated carbon-commercial grade (ACC) and laboratory grade (ACL). BFA is a solid waste obtained from the particulate collection equipment attached to the flue gas line of the bagasse fired boilers of cane sugar mills. Batch studies were performed to evaluate the influences of various experimental parameters like initial pH (pH(0)), contact time, adsorbent dose and initial concentration (C(0)) for the removal of AO. Optimum conditions for AO removal were found to be pH(0) approximately 7.0 and equilibrium time approximately 30 min for BFA and approximately 120 min for activated carbons. Optimum BFA, ACC and ACL dosages were found to be 1, 20 and 2g/l, respectively. Adsorption of AO followed pseudo-second order kinetics with the initial sorption rate for adsorption on BFA being the highest followed by those on ACL and ACC. The sorption process was found to be controlled by both film and pore diffusion with film diffusion at the earlier stages followed by pore diffusion at the later stages. Equilibrium isotherms for the adsorption of AO on BFA, ACC and ACL were analyzed by Freundlich, Langmuir, Dubinin-Radushkevich, and Temkin isotherm equations using linear correlation coefficient. Langmuir isotherm gave the best correlation of adsorption for all the adsorbents studied. Thermodynamic study showed that adsorption of AO on ACC (with a more negative Gibbs free energy value) is more favoured. BFA which was used without any pretreatment showed high surface area, pore volume and pore size exhibiting its potential to be used as an adsorbent for the removal of AO.     

Investigation of nickel(II) biosorption on Enteromorpha prolifera: optimization using response surface analysis

In this study, the biosorption of nickel(II) ions on Enteromorpha prolifera, a green algae, was investigated in a batch system. The single and combined effects of operating parameters such as initial pH, temperature, initial metal ion concentration and biosorbent concentration on the biosorption of nickel(II) ions on E. prolifera were analyzed using response surface methodology (RSM). The optimum biosorption conditions were determined as initial pH 4.3, temperature 27 degrees C, biosorbent concentration 1.2 g/L and initial nickel(II) ion concentration 100 mg/L. At optimum biosorption conditions, the biosorption capacity of E. prolifera for nickel(II) ions was found to be 36.8 mg/g after 120 min biosorption. The Langmuir and Freundlich isotherm models were applied to the equilibrium data and defined very well both isotherm models. The monolayer coverage capacity of E. prolifera for nickel(II) ions was found as 65.7 mg/g. In order to examine the rate limiting step of nickel(II) biosorption, such as the mass transfer and chemical reaction kinetics, the intraparticle diffusion model, external diffusion model and the pseudo second order kinetic model were tested with the experimental data. It was found that for both contributes to the actual biosorption process. The pseudo second order kinetic model described the nickel(II) biosorption process with a good fitting.     

Removal of copper(II) and lead(II) from aqueous solution by manganese oxide coated sand II. Equilibrium study and competitive adsorption

The adsorption equilibrium of MOCS and the Cu(II) and Pb(II) ions removal capacity by MOCS in single-(non-competitive) and binary-(competitive) component sorption systems from aqueous solutions were investigated. The equilibrium data were analyzed using the Langmuir, Freundlich, Temkin and Redlich-Peterson isotherms. The characteristic parameters for each isotherm were determined. The Langmuir and Redlich-Peterson isotherms provided the best correlation for both Cu(II) and Pb(II) onto MOCS. From the Langmuir isotherms, maximum adsorption capacities of MOCS towards Cu(II) and Pb(II) are determined at different temperature. The maximum adsorption capacity of Cu(II) and Pb(II) per gram MOCS in single component sorption systems were from 5.91 and 7.71 micromol to 7.56 and 9.22 micromol for the temperature range of 288-318 K, respectively. The order of affinity based on a weight uptake by MOCS was as follows: Pb(II)>Cu(II). The same behavior was observed during competitive adsorption that is in the case of adsorption from their binary solution. The thermodynamic parameters (DeltaG degrees , DeltaH degrees , and DeltaS degrees) for Cu(II) and Pb(II) sorption on MOCS were also determined from the temperature dependence. This competitive adsorption showed that the uptake of each metal was considerably reduced with an increasing concentration of the other, the adsorption of Cu(II) being more strongly influenced by Pb(II) than vice versa due to the higher affinity of MOCS for the latter.     

Kinetic and equilibrium study for the sorption of cadmium(II) ions from aqueous phase by eucalyptus bark

The efficiency of eucalyptus bark as a low cost sorbent for removing cadmium ions from aqueous solution has been investigated in batch mode. The equilibrium data could be well described by the Langmuir isotherm but a worse fit was obtained by the Freundlich model. The five linearized forms of the Langmuir equation as well as the non-linear curve fitting analysis method were discussed. Results show that the non-linear method may be a better way to obtain the Langmuir parameters. Maximum cadmium uptake obtained at a temperature of 20 degrees C was 14.53mgg(-1). The influence of temperature on the sorption isotherms of cadmium has been also studied. The monolayer sorption capacity increased from 14.53 to 16.47 when the temperature was raised from 20 to 50 degrees C. The DeltaG degrees values were negative, which indicates that the sorption was spontaneous in nature. The effect of experimental parameters such as contact time, cadmium initial concentration, sorbent dose, temperature, solution initial pH, agitation speed, and ionic strength on the sorption kinetics of cadmium was investigated. Pseudo-second-order model was evaluated using the six linear forms as well as the non-linear curve fitting analysis method. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model using the non-linear method. The pseudo-second-order model parameters were function of the initial concentration, the sorbent dose, the solution pH, the agitation speed, the temperature, and the ionic strength.     

Synthesis of some ferromagnetic composite resins and their metal removal characteristics in aqueous solutions

In this study, a procedure for synthesis of new organic-inorganic magnetic composite resins was established. The procedure was based upon immobilization of magnetite (Mag) as a ferromagnetic material within the polymer poly(acrylic acid acrylonitrile) P(AA-AN) and the ion exchange resin (Amberlite IR120). The produced magnetic resins, IR120-PAN-Mag (R1) and P(AA-AN)-Mag (R2) were assessed as sorbents for Cr(VI). Various factors influencing the sorption of Cr(VI), e.g., pH, equilibrium time, initial concentration and temperature were studied. The sorption process was very fast initially and maximum sorption was achieved within 3 h and pH 5.1. The kinetic of the system has been evaluated with pseudo first order model, second order model, Elovich model, intra-particle diffusion model and liquid film diffusion model. Chromium interaction with composite particles followed second-order kinetics with a correlation coefficient extremely high and closer to unity and rate constant (k_s) has the values 1.68 × 10⁻⁴ and 1.9 × 10⁻⁴ g (mg⁻¹ min⁻¹) for R1 and R2, respectively. The values of equilibrium sorption capacity (q_e) are consistent with the modeled data and attain the range 893–951 mg g⁻¹. Kinetically, both pore diffusion and film diffusion are participating in ruling the diffusion of Cr(VI) ions. The sorption data gave good fits with Temkin and Flory–Huggins isotherm models. The isotherm parameters related to the heat of sorption are in the range 8–16 kJ mol⁻¹ which is the range of bonding energy for ion exchange interactions and so suggest an ion exchange mechanism for removal of Cr(VI) by the composite sorbents. The adsorption process was exothermic with ΔH in the range of −73 to −97 kJ mol⁻¹. The negative values of Gibbs free energy confirm the feasibility and the spontaneous nature of Cr(VI) removal with these novel composites.     

Batch sorption dynamics and equilibrium for the removal of cadmium ions from aqueous phase using wheat bran

Studies on a batch sorption process using wheat bran as a low cost sorbent was investigated to remove cadmium ions from aqueous solution. The influence of operational conditions such as contact time, cadmium initial concentration, sorbent mass, temperature, solution initial pH, agitation speed and ionic strength on the sorption kinetics of cadmium was studied. Pseudo-second-order model was evaluated using the six linear forms as well as the non-linear curve fitting analysis method. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model using the non-linear method. The sorption of cadmium was found to be dependent on initial concentration, sorbent mass, solution pH, agitation speed, temperature, ionic strength and contact time. The value of activation energy (12.38 kJ mol(-1)) indicates that sorption has a low potential barrier corresponding to a physical process. Sorption equilibrium isotherms at different temperatures was determined and correlated with common isotherm equations such as Langmuir and Freundlich models. It was found that the Langmuir model appears to well fit the isotherm data but a worse correlation was obtained by the Freundlich model. The five Langmuir linear equations as well as the non-linear curve fitting analysis method were discussed. Results show that the non-linear method may be a better way to obtain the Langmuir parameters. Thermodynamic parameters such as DeltaH degrees, DeltaS degrees and DeltaG degrees were calculated. These parameters indicate that the sorption of cadmium by wheat bran is a spontaneous process and physical in nature involving weak forces of attraction and is also endothermic.     

Metal sorption on soils as affected by the dissolved organic matter in sewage sludge and the relative calculation of sewage sludge application

To evaluate the influences of sewage sludge-derived organic matters on metal sorption and on the resultant sludge loading estimates, a batch experiment was conducted to compare the sorption of Ni, Cu and Pb in sewage sludge filtrates (1:20 sewage sludge to water) on eight soils and the adsorption of metals in a reference solution which had the same matrix as the sewage sludge filtrate except dissolved organic material (henceforth referred to as reference solution). Metal sorption could be well fitted by linear isotherm and the dissolved organic matter in sludge significantly depressed the sorption (p<0.01). The main factor controlling sorption of Ni on different soils was dominated by soil cation exchange capacity (CEC) and sorption of Cu and Pb was by soil organic matter (SOM). The parameters obtained from the sorption isotherm equations were then used to estimate sludge loadings into the soils. When the sorption parameters derived from the reference solution were used for calculation, that is the effect of dissolved organic matter was not considered, the calculated safe application rates are approximately 47.8, 51.4, 34.2, 31.3, 21.7, 46.3, 187.1 and 27.6 t-sludge/ha for the Beijing, Jiangxi, Xiamen, Jilin, Guangdong, Wuhan, Gansu and Xinjiang soils, respectively. However, when the sorption parameters derived from the dissolved organo-metallic complexes are used for calculation, the corresponding application rates are reduced to approximately 6.0, 3.4, 1.9, 10.0, 6.3, 3.6, 7.3 and 3.5 t-sludge/ha, respectively. By this study we can get a conclusion that the effect of sewage sludge derived dissolved organic matter on heavy metal sorption and soil properties should be considered in the course of regulating the safe application rates of sewage sludge to soil.     

分散剂CTAB对碳纳米管悬浮液分散性能的影响

以十六烷基三甲基溴化铵(CTAB)为分散剂, 制备了分散性能良好的碳纳米管悬浮液. 通过测定等温吸附曲线和悬浮液的Zeta电位, 研究了CTAB对碳纳米管表面性质的影响. 结果表明, CTAB的加入使Zeta电位由-29mV变为65mV左右; 等温吸附曲线表明,CTAB在碳纳米管表面为“两阶段吸附”, CTAB浓度为9×10^-4 mol·L^-1时, 在碳纳米管表面达到饱和吸附. 通过悬浮碳纳米管浓度测定确定了所需最佳CTAB的用量为9×10^-4 mol·L^-1左右, 同时对CTAB的吸附分散机理进行了分析和讨论.     

Sorption characteristics of Cu(II) ions onto silica gel-immobilized calix[4]arene polymer in aqueous solutions: batch and column studies

In the present study, Cu(II) removal from aqueous solutions by sorption was investigated. Aminopropyl silica gel-immobilized calix[4]arene polymer (APSIC[4]P) was used in sorption as sorbent. During the experimental part of this study, the effect of parameters, such as pH, initial Cu(II) concentration, temperature on Cu(II) removal was observed. In addition, sorption isotherm studies and column studies were made. Maximum Cu(II) removal was obtained at pH 6 and 25 degrees C. In the isotherm studies, Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data confirmed to Langmuir isotherm model. Batch sorption capacity (q0) was calculated as 5.08 mg/g. The capacity value for column study was obtained by graphical integration as 1.14 mg/g. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design.     

A comparative study of two chelating ion-exchange resins for the removal of chromium(III) from aqueous solution

Macroporous resins containing iminodiacetic acid (IDA) groups (Lewatit TP 207 and Chelex-100) were investigated as a function of concentration, temperature and pH for their sorption properties towards chromium(III). The chromium(III) ions sorbed onto the resin and in the equilibrium concentration were determined by inductively coupled plasma spectrophotometer. The maximum sorption for chromium ions was observed at pH 4.5. Solution pH had a strong effect on the equilibrium constant of Cr(III). The equilibrium constants were 320 and 7 at pH value 4.5 for Lewatit TP 207 and Chelex-100 resin, respectively. The Langmuir isotherm was used to describe observed sorption phenomena. Both the sorbents had high bonding constants with Lewatit TP 207 showing stronger binding. The equilibrium related to adsorption capacity and energy of adsorption was obtained by using plots of Langmuir adsorption isotherm. It was observed that the maximum adsorption capacity of 0.288 mmol of Cr(III)/g for Chelex-100 and 0.341 mmol of Cr(III)/g for Lewatit TP 207 was achieved at pH of 4.5. The rise in temperature caused a slight increase in the value of the equilibrium constant (K_c) for the sorption of chromium(III) ion.     

纳米碳纤维表面修饰及其在水溶液中的分散

为了研究纳米碳纤维(CNFs)在水溶液中的分散情况,对其进行高温纯化处理,以甲基纤维素(MC)为分散剂,制备分散良好的CNFs悬浮液.采用差热分析(DTA)和热重分析(TGA)研究了高温处理对CNFs的影响,通过测定悬浮液的紫外可见光吸光度、等温吸附曲线、zeta电位及表面张力等方法研究了MC对CNFs分散性能的影响,并讨论分析了MC对CNFs的分散机理.结果表明:MC的加入使CNFs悬浮液的zeta电位由-15.4 mV升至0,表面张力由38.87 mN/m降至36.54 mN/m;等温吸附曲线表明MC在CNFs的表面为"单阶段吸附",当MC的质量浓度达到0.4 g/L时,MC在CNFs表面饱和吸附;当CNFs达到最佳分散状态时,MC与CNFs的质量比为2∶1.     

Response Surface Modeling and Optimization in Multiresponse Experiments Using Seemingly Unrelated Regressions

Response surface methodology (RSM) is widely used for optimizing manufacturing processes and product designs. Most applications of RSM involve several response variables. In a typical RSM study, the experimenter will build an empirical model such as the second-order model to each response and use these models to determine settings on the design variables that produce optimal or at least acceptable values for the responses. In most multiple-response RSM problems, the experimenter fits a model to each response using ordinary least squares (OLS). This article illustrates another estimation technique useful in multiple-response RSM problems, seemingly unrelated regressions (SUR). This technique can be very useful when response variables in a multiple-response RSM problem are correlated. Essentially, SUR produces more precise estimates of the model parameters than OLS when responses are correlated. This improved precision of estimation can lead to a more precise estimate of the optimum operating conditions on the process.     

有机-无机复合材料壳聚糖/氧化钇对Cr(Ⅵ)的吸附动力学与热力学研究

以壳聚糖为包覆材料,采用花状Y2O3颗粒作为内核,制备有机-无机复合材料壳聚糖-氧化钇复合吸附剂。并通过扫描电镜(SEM)、透射电镜(TEM)、红外光谱(IR)的方法对复合材料进行表征。考察了pH值对吸附行为的影响并对吸附机理进行了分析。相关系数表明,拟二级模型可以更准确地模拟吸附动力学,说明该吸附过程主要由化学吸附控制。Langmuir等温线与实验数据拟合度较高。通过对吸附热力学参数进行分析,发现该吸附过程可以自发进行,是吸热反应。     

An Efficient Adaptive Sequential Methodology for Expensive Response Surface Optimization

The preset response surface methodology (RSM) designs are commonly used in a wide range of process and design optimization applications. Although they offer ease of implementation and good performance, they are not sufficiently adaptive to reduce the required number of experiments and thus are not cost effective for applications with high cost of experimentation. We propose an efficient adaptive sequential methodology based on optimal design and experiments ranking for response surface optimization (O‐ASRSM) for industrial experiments with high experimentation cost, limited experimental resources, and requiring high design optimization performance. The proposed approach combines the concepts from optimal design of experiments, nonlinear optimization, and RSM. By using the information gained from the previous experiments, O‐ASRSM designs the subsequent experiment by simultaneously reducing the region of interest and by identifying factor combinations for new experiments. Given a given response target, O‐ASRSM identifies the input factor combination in less number of experiments than the classical single‐shot RSM designs. We conducted extensive simulated experiments involving quadratic and nonlinear response functions. The results show that the O‐ASRSM method outperforms the popular central composite design, the Box–Behnken design, and the optimal designs and is competitive with other sequential response surface methods in the literature. Furthermore, results indicate that O‐ASRSM's performance is robust with respect to the increasing number of factors. Copyright © 2012 John Wiley & Sons, Ltd.     

Optimization of Welding Process Parameters for 9Cr-1Mo Steel Using RSM and GA

Optimization of A-TIG welding process parameters for 9Cr-1Mo steel has been carried out using response surface methodology (RSM) and genetic algorithm (GA). RSM has been used to obtain the design matrix for generating data on the influence of process parameters on the response variables. A second-order response surface model was developed for predicting the response for the set of given input variables. Then, numerical and graphical optimization was performed using RSM to obtain the target depth of penetration (DOP) and heat-affected zone (HAZ) width using desirability approach. Multiple regression models were developed based on the generated data, and then the models were used in GA to determine the optimum process parameters for achieving the target DOP and HAZ width. GA-based models employed two different selection processes. Both the RSM- and GA-based models suggested a number of solutions in terms of process parameters, and the identified solutions were validated by experiments. GA-based model employing tournament selection has been found to be a more accurate method for determining the optimum A-TIG welding process parameters.     

Kinetic and equilibrium studies in removing lead ions from aqueous solutions by natural sepiolite

The capacity of sepiolite for the removal of lead ions from aqueous solution was investigated under different experimental conditions. The Langmuir and Freundlich equations, which are in common use for describing sorption equilibrium for wastewater-treatment applications, were applied to data. The constants and correlation coefficients of these isotherm models for the present system at different conditions such as pH, temperature and particle size were calculated and compared. The equilibrium process was well described by the Langmuir isotherm model and the maximum sorption capacity was found to be 93.4 mg/g for the optimal experimental condition. The thermodynamic parameters (DeltaG(o), DeltaH(o) and DeltaS(o)) for lead sorption on the sepiolite were also determined from the temperature dependence. The influences of specific parameters such as the agitation speed, particle size and initial concentration for the kinetic studies were also examined. The sorption kinetics were tested for first order reversible, pseudo-first order and pseudo-second order reaction and the rate constants of kinetic models were calculated. The best correlation coefficients were obtained using the pseudo-second order kinetic model, indicating that lead uptake process followed the pseudo-second order rate expression.     

Equilibrium and kinetic studies for the sorption of 3-methoxybenzaldehyde on activated kaolinites

The sorption of 3-methoxybenzaldehyde on activated kaolinites has been investigated at different temperatures. Two types of activation tests were performed. The sorption equilibrium was studied by sorption isotherms in the temperature range 303-333K for natural (untreated), thermally and acid activated kaolinites. It was shown that the isotherm shapes were not affected by temperature and activation types of kaolinite. The absorbance data at 312nm were fitted reasonably well with the Langmuir and Freundlich isotherm models and the model parameters were determined for different temperatures. Thermodynamic quantities such as Gibbs free energy (DeltaG), the enthalpy (DeltaH) and the entropy change of sorption (DeltaS) were determined for natural, thermally and acid activated kaolinites. It was shown that the sorption processes were an endothermic reactions, controlled by physical mechanisms and spontaneously. Adsorption capacity of acid activated kaolinite for 3-methoxybenzaldehyde was higher compared to that of natural and thermally activated kaolinites at various temperatures. The adsorption and desorption rate constants (k(a) and k(d)) were obtained separately by applying a geometric approach to the first order Langmuir model. This method provided good conformity between the K from Langmuir parameters and K(geo) (k(a)/k(d)) from geometric approach.     

The use of anionic gum arabic as a dispersant for multi-walled carbon nanotubes in an aqueous solution

Stable homogeneous suspensions of multi-walled carbon nanotubes (MWCNTs) were prepared using gum arabic (GA) as a dispersant. By measuring adsorption isotherm, the surface chemical properties of the MWCNTs were investigated. The dispersion of MWCNTs in aqueous solution was examined with transmission electron microscopy and ultraviolet visible spectroscopy. The stabilization mechanism of the MWCNTs in aqueous solution using the GA surfactant was discussed. The isotherm of GA adsorption on MWCNTs indicates a typical two-step mechanism of adsorption (namely "SL"), and the adsorption isotherm reaches the saturation plateau at a GA concentration of 0.45 g x L(-1). The concentration measurement of MWCNTs shows that the optimum concentration of GA is 0.45 g x L(-1).     

An efficient method to estimate sorption isotherm curve coefficients

This paper aims at estimating the sorption isotherm coefficients of a wood fiber material using experimental data. First, the mathematical model, based on convective transport of moisture, the Optimal Experiment Design (OED) and the experimental set-up are presented. Then, measurements of relative humidity within the material are carried out, after searching the OED using the computation of the sensitivity functions and a priori values of the unknown parameters. It enables to plan the experimental conditions in terms of sensor positioning and boundary conditions out of 20 possible designs, ensuring the best accuracy for the identification method and, thus, for the estimated parameter. After the measurements, the parameter estimation problem is solved. The determined sorption isotherm coefficients calibrate the numerical model to fit better the experimental data. However, some discrepancies still appear since the hysteresis effects on the sorption capacity are not included in the model. Therefore, the latter is improved proposing an additional differential equation for the sorption capacity to consider the hysteresis effects. The OED approach is developed for the estimation of five of the coefficients involved in the hysteresis model. To conclude, the prediction of the model with hysteresis have better reliability when compared to the experimental observations.