Adsorption characteristics of aniline and 4-methylaniline onto bifunctional polymeric adsorbent modified by sulfonic groups

In this paper a new bifunctional polymeric resin (LS-2) was synthesized by introducing sulfonic groups onto the surface of the resin during the post-crossing of chloromethyl low crosslinking macroporous poly-styrene resin, and the comparison of the adsorption properties of LS-2 with Amberlite XAD-4 toward aniline and 4-methylaniline in aqueous solutions was made. The study focuses on the static equilibrium adsorption behaviors, the adsorption thermodynamics, and the column dynamic adsorption and desorption profiles. Freundlich model gives a perfect fitting to the isotherm data. Although the specific surface area of LS-2 is lower than that of Amberlite XAD-4, the adsorbing capacities for these two adsorbates on LS-2 are higher than those on Amberlite XAD-4 within the temperature range 288-318 K, which is contributed to microporous structure and the polar groups on the network of LS-2 resins. The adsorption for aniline or 4-methylaniline on LS-2 was proved to be an endothermic process and increasing temperature was favorable. From the studies on the adsorption thermodynamics, static equilibrium adsorption, and the desorption conditions, an important conclusion can be drawn that the adsorption for aniline or 4-methylaniline on the LS-2 is a coexistence process of physical adsorption and chemical transition.     

乙酰苯胺和水杨酸修饰的两种吸附树脂对对氯苯酚的吸附行为

分别用乙酰苯胺、水杨酸化学修饰氯甲基化低交联大孔苯乙烯-二乙烯苯聚合物,合成超高交联吸附树脂FZH03、FZH04。与Amberlite XAD-4对照,研究了这两种树脂在不同温度下对水溶液中对氯苯酚的静态吸附和动态吸附行为。结果表明,两种树脂的等温吸附数据可被Langmuir和Freundlich等温吸附方程很好地进行拟合,对对氯苯酚的吸附量明显高于XAD-4,是焓推动的吸附过程,对对氯苯酚吸附动力学均符合一级动力学方程,有两个独立的动力学过程,颗粒内扩散是该吸附过程的速控步骤。     

Biosorption of Pb(II) ions by modified quebracho tannin resin

In this study, the effect of temperature, pH and initial metal concentration on Pb(II) biosorption on modified quebracho tannin resin (QTR) was investigated. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to investigate QTR structure and morphology. Besides, the specific BET surface area and zeta-potential of the QTR were analysed. Thermodynamic functions, the change of free energy (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) of Pb adsorption on modified tannin resin were calculated as -5.43 kJ mol(-1) (at 296+/-2K), 31.84 kJ mol(-1) and 0.127 J mmol(-1) K(-1), respectively, indicating the spontaneous, endothermic and the increased randomness nature of Pb(2+) adsorption. The kinetic data was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion model. The results suggested that the pseudo-second-order model (R(2)>0.999) was the best choice among all the kinetic models to describe the adsorption behavior of Pb(II) onto QTR. Langmuir, Freundlich and Tempkin adsorption models were used to represent the equilibrium data. The best interpretation for the experimental data was given by the Langmuir isotherm and the maximum adsorption capacity (86.207 mg g(-1)) of Pb(II) was obtained at pH 5 and 296 K.     

Removal of malachite green by using an invasive marine alga Caulerpa racemosa var. cylindracea

The biosorption of a cationic dye, malachite green oxalate (MG) from aqueous solution onto an invasive marine alga Caulerpa racemosa var. cylindracea (CRC) was investigated at different temperatures (298, 308 and 318 K). The dye adsorption onto CRC was confirmed by FTIR analysis. Equilibrium data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (DR) equations. All of the isotherm parameters were calculated. The Freundlich model gave a better conformity than Langmuir equation. The mean free energy values (E) from DR isotherm were also estimated. In order to clarify the sorption kinetic, the fit of pseudo-first-order kinetic model, second-order kinetic model and intraparticle diffusion model were investigated. It was obtained that the biosorption process followed the pseudo-second-order rate kinetics. From thermodynamic studies the free energy changes were found to be -7.078, -9.848 and -10.864 kJ mol(-1) for 298, 308 and 318 K, respectively. This implied the spontaneous nature of biosorption and the type of adsorption as physisorption. Activation energy value for MG sorption (E(a)) was found to be 37.14 kJ mol(-1). It could be also derived that this result supported physisorption as a type of adsorption.     

邻羧基苯甲酰基修饰的吸附树脂对水中2-萘酚的吸附

采用邻羧基苯甲酰基修饰的吸附树脂FZH5,以Amberlite XAD-4作为参照,探讨了对水溶液中2-萘酚的吸附热力学和吸附动力学。分别用Langmuir等温方程和Freundlich等温方程对吸附等温线进行拟合,并采用动力学准一级和二级方程对两种树脂进行了动态吸附拟合。结果表明,经过修饰的FZH5对水中2-萘酚的吸附效率高于Amberlite XAD-4,对2-萘酚的吸附过程在温度较高时化学吸附为主导,吸附速率主要受控于颗粒内扩散过程。     

Adsorption of phenol and p-chlorophenol from their single and bisolute aqueous solutions on Amberlite XAD-16 resin

Removal of phenol and p-chlorophenol from synthetic single and bisolute aqueous solutions at 303.15 K through adsorption on Amberlite XAD-16 resin under batch equilibrium and dynamic column experimental conditions was investigated. The equilibrium adsorption data from single component solutions were fitted to Langmuir and Freundlich adsorption isotherm models to evaluate the model parameters and the parameters in turn were used to predict the extent of adsorption from bisolute aqueous solutions using Ideal Solution Adsorption (IAS) model. The effect of pH on removal of phenol and p-chlorophenol from single and bisolute systems was studied. The breakthrough capacity and total capacity of the resin for the adsorbates at different concentrations were evaluated through column adsorption studies. Attempts were made to regenerate the resin by solvent washing using methanol as an eluent. The limited number of adsorption-desorption cycles indicated that the adsorption capacity of the resin remained unchanged.     

Biosorption of Cu(II) from aqueous solutions by mimosa tannin gel

The biosorption of Cu(II) from aqueous solutions by mimosa tannin resin (MTR) was investigated as a function of particle size, initial pH, contact time and initial metal ion concentration. The aim of this study was to understand the mechanisms that govern copper removal and find a suitable equilibrium isotherm and kinetic model for the copper removal in a batch reactor. The experimental isotherm data were analysed using the Langmuir, Freundlich and Temkin equations. The equilibrium data fit well in the Langmiur isotherm. The experimental data were analysed using four sorption kinetic models -- the pseudo-first- and second-order equations, and the Elovich and the intraparticle diffusion equation -- to determine the best fit equation for the biosorption of copper ions onto mimosa tannin resin. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process, whereas the Elovich equation also fits the experimental data well. Thermodynamic parameters such as the entropy change, enthalpy change and Gibb's free energy change were found out to be 153.0 J mol(-1)K(-1), 42.09 kJ mol(-1) and -2.47 kJ mol(-1), respectively.     

Adsorption equilibrium and kinetics of polyvinyl alcohol from aqueous solution on powdered activated carbon

In this study, powdered activated carbon (PAC) was used to remove polyvinyl alcohol (PVA) from the aqueous PVA solution. The adsorption kinetics has been studied pertaining to various initial PVA concentration and PAC dosage. The rates of adsorption were found to conform to the second-order kinetics with good correlation. Boyd plot confirmed that external mass transfer was the rate-limiting step in the sorption process. The adsorption isotherm obtained resembled with H-type of isotherm, which indicated a high affinity of the solute for the sorption sites. The Freundlich model appeared to fit the isotherm data better than the Langmuir model. The thermodynamic parameters such as Delta H degrees , Delta S degrees and Delta G degrees were evaluated from the slope and intercept of linear plot of log Kc against (1/T) x 1000. The change in entropy (DeltaS degrees ) and heat of adsorption (Delta H degrees ) of PAC was estimated as 1.45 kJ mol(-1)K(-1) and 365 kJ mol(-1), respectively. The free energy of the adsorption at all temperatures was negative indicating a spontaneous process. The maximum PVA removal of 92% was obtained at a pH of 6.3 and contact time of 30 min for an adsorbent dose of 5 g/L.     

Investigation kinetics mechanisms of adsorption malachite green onto activated carbon

Lignite was used to prepare activated carbon (T3K618) by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N2 adsorption isotherm. BET surface area of activated carbon is determined as 1000 m2/g. Adsorption capacity of malachite green (MG) onto T3K618 activated carbon was investigated in a batch system by considering the effects of various parameters like initial concentration (100, 150 and 200 mg/L) and temperature (25, 40 and 50 degrees C). The adsorption process was relatively fast and equilibrium was reached after about 20 min for 100, 150 mg/L at all adsorption temperature. Equilibrium time for 200 mg/L was determined as 20 min and 40 min at 298, 313 and 323 K, respectively. Simple mass and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate controlling steps such as external mass transfer, intraparticle diffusion. Pseudo second-order model was found to explain the kinetics of MG adsorption most effectively. It was found that both mass transfer and pore diffusion are important in determining the adsorption rates. The intraparticle diffusion rate constant, external mass transfer coefficient, film and pore diffusion coefficient at various temperatures were evaluated. The activation energy (Ea) was determined as 48.56, 63.16, 67.93 kJ/mol for 100, 150, 200 mg/L, respectively. The Langmiur and Freundlich isotherm were used to describe the adsorption equilibrium studies at different temperatures. Langmiur isotherm shows better fit than Freundlich isotherm in the temperature range studied. The thermodynamic parameters, such as DeltaG degrees, DeltaS and DeltaH degrees were calculated. The thermodynamics of dyes-T3K618 system indicates endothermic process.     

香草醛改性壳聚糖对镉离子的吸附热力学和动力学

研究了微波辐射条件下香草醛改性壳聚糖(V-CTS)对Cd2+离子的吸附性能,测定了吸附等温线和吸附动力学曲线。结果表明,该吸附剂对Cd2+离子的吸附行为符合Freundlich吸附等温式,在298～318K温度范围内,焓变ΔH=24.22kJ/mol,表明吸附是吸热过程。吸附动力学符合Lagergren二级吸附速率方程,反应活化能为25.58kJ/moL,表明V-CTS对金属离子的吸附由化学反应控制,而非扩散控制。吸附剂解吸再生循环使用4次后,镉离子的吸附容量仅减少18.9%,该吸附剂具有较好地再生使用性。     

Equilibrium, kinetic and thermodynamic studies on the adsorption of m-cresol onto micro- and mesoporous carbon

Investigations were conducted in batch mode to study the adsorption behaviour of m-cresol on a porous carbon prepared from rice husk (RHAC) by varying the parameters such as agitation time, m-cresol concentration (50-300 mg/l), pH (2.5-10) and temperature (293-323 K). Studies showed that the adsorption decreased with increase in pH and temperature. The isotherm data were fitted to Langmuir, Freundlich, and Dubinin-Radushkevic (D-R) models. The kinetic models such as pseudo-first-order, pseudo-second-order and intraparticle diffusion models were selected to understand the reaction pathways and mechanism of adsorption process. The thermodynamic equilibrium coefficients obtained at different temperatures were used to evaluate the thermodynamic constants DeltaG degrees, DeltaH degrees and DeltaS degrees. The sorption process was found to be exothermic in nature (DeltaH degrees : -23.46 to -25.40 kJ/mol) with a decrease in entropy (DeltaS degrees: -19.44 to -35.87 J/(mol K)). The negative value of Gibbs free energy, DeltaG degrees indicates that the adsorption occurs via a spontaneous process. The decrease in the value of -DeltaG degrees from 17.70 to 13.54 kJ/mol with increase in pH and temperature indicates that the adsorption of m-cresol onto activated carbon is less favourable at higher temperature and pH range. The influence of mesopore and a possible mechanism of adsorption is also suggested.     

乙酰苯胺修饰的吸附树脂对对甲苯胺的吸附机理研究

合成了一种用乙酰苯胺修饰的新型超高交联吸附树脂ZH-05,并用Amberlite XAD-4作对照,比较了它们对水溶液中对甲苯胺的静态吸附和脱附行为。结果表明:经过乙酰苯胺修饰的吸附树脂ZH-05在一定温度下对对甲苯胺的吸附过程中存在化学吸附,ZH-05对对甲苯胺的吸附能力明显强于AmberliteXAD-4,两种树脂对甲苯胺的吸附均符合Freundlich方程。     

The adsorption kinetics and removal of cationic dye, Toluidine Blue O, from aqueous solution with Turkish zeolite

Clinoptilolite, a natural zeolite, was investigated as an inexpensive and effective adsorbent for the adsorption of Toluidine Blue O (TBO) from its aqueous solution. The effect of parameters such as the initial concentration of TBO, the solution of pH, contact time, temperature and particle size on the TBO adsorption was examined. The adsorption rate data were analysed according to the first and second-order kinetic models. Kinetic studies show that adsorption of TBO on clinoptilolite was fitted to the second-order adsorption model with two-step diffusion process. The activation energies for TBO adsorption on clinoptilolite for the first and second diffusion processes were 8.72 kJ mol(-1) and 19.02 kJ mol(-1), respectively. The adsorption isotherm was well fitted to both the Langmuir and Freundlich models. The maximum adsorption capacity of clinoptilolite for TBO was 2.1x10(-4) mol g(-1) at solution pH of 11.0.     

超高交联树脂对氯酚类化合物的吸附性能

通过静态吸附研究,比较了Am berlite XAD-4和ZH-01吸附树脂对水溶液中2-氯苯酚、2,4-二氯苯酚、2,4,6-三氯苯酚的吸附热力学特性。结果表明,在288 K~318 K和研究的浓度范围内,ZH-01、XAD-4对氯酚类化合物的吸附平衡数据符合F reund lich和L angm u ir吸附等温方程。2-氯苯酚在两树脂上的吸附为放热过程,是单分子层的物理吸附;而2,4-二氯苯酚和2,4,6-三氯苯酚在XAD-4吸附是单分子层物理吸附,在ZH-01的吸附属单分子层吸热过渡化学吸附,主要是毛细管凝聚和微孔填充作用造成的吸附。并计算了氯酚类化合物在两树脂上的吸附焓变、自由能变、吸附熵变,对吸附行为进行了合理的解释。     

Adsorption of reactive dye onto carbon nanotubes: equilibrium, kinetics and thermodynamics

The adsorption efficiency of carbon nanotubes for Procion Red MX-5B at various pHs and temperatures was examined. The amount adsorbed increased with the CNTs dosage; however, the adsorption capacity initially increased with the CNTs dosage (<0.25 g/l) and then declined as the CNTs dosage increased further (>0.25 g/l). The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined and the results revealed that Langmuir isotherm fitted the experimental results well. Kinetic analyses were conducted using pseudo first- and second-order models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics were more accurately represented by a pseudo second-order model. Changes in the free energy of adsorption (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees), as well as the activation energy (E(a)) were determined. DeltaH degrees and DeltaS degrees were 31.55 kJ/mol and 216.99J/molK, respectively, at pH 6.5 and 41.47 kJ/mol and 244.64 J/molK at pH 10. The activation energy was 33.35 kJ/mol at pH 6.5. DeltaH degrees, DeltaG degrees and E(a) all suggested that the adsorption of Procion Red MX-5B onto CNTs was by physisorption.     

非苯乙烯型超高交联树脂的修饰及对酚类化合物的吸附

分别通过4,4'-二氯甲基联苯与1,4'-二氟甲基苯的傅克烷基化聚合和胺化反应,制得一类比表面积可达1138 m2/g的胺基吸附树脂新材料.研究表明,这类非苯乙烯型胺基树脂对苯酚、对硝基苯酚的饱和吸附容量分别可达140 mg/g和331 mg/g,明显优于国内外用于酚类吸附的AmberliteXAD-4、H103等吸附...     

Removal of lanthanum and gadolinium from nitrate medium using Aliquat-336 impregnated onto Amberlite XAD-4

Aliquat-336 in benzene was supported on Amberlite XAD-4 crosslinked polystyrene resin. The use of XAD-4 impregnated with Aliquat-336 resin for removal of lanthanum(III) and gadolinium(III) from nitrate medium was carried out using batch technique. Various parameters affecting the uptake of these metal ions such as contact time, metal ion concentrations, V/m and pH value were separately studied. Effect of temperature on the equilibrium distribution values has been studied to evaluate the changes in standard thermodynamic quantities. A comparison of kinetic models applied to the adsorption rate data was evaluated for Lagergren first order, the pseudo second order and Morris-Weber kinetic models. From the results, both pseudo second order and intraparticle diffusion models were found to best correlate the experimental rate data. The capacity of the impregnated resin for both lanthanum(III) and gadolinium(III) was found to be 4.73 and 4.44 mg/g. From the results, impregnation of Aliquat-336 onto Amberlite XAD-4 provides an efficient impregnated resin for the removal of lanthanum(III) and gadolinium(III) from 0.1M nitrate aqueous solution.     

Equilibrium sorption isotherms for nitrate on resin Amberlite IRA 400

The adsorption isotherms of nitrate on resin Amberlite IRA 400 at various pH, in the range 2-12, were experimentally determined by batch tests. The experimental data have been analysed using the Langmuir, Freundlich, Redlich-Peterson and Sips isotherms models. In order to determine the best fit isotherm, two error analysis methods were used to evaluate the data: the regression correlation coefficient, and the statistic Chi-square test. In the range of pH tested, the Sips model was found to give the best fit of the adsorption isotherm data. The maximum adsorption capacity can be deduced from the obtained correlation coefficients and was found to decrease for increasing pH.     

Analysis of adsorption characteristics of 2,4-dichlorophenol from aqueous solutions by activated carbon fiber

In this study experiments were conducted to investigate the adsorption of 2,4-dichlorophenol (2,4-DCP) by activated carbon fiber (ACF) activated by static air. With the results of batch experiments at various temperatures, the adsorption isotherms, kinetics and thermodynamics of this adsorption process were evaluated. Four adsorption isotherm models, Langmuir, Freundlich, Redlich-Peterson and Toth equations, were used to fit the experimental data and the results reveal that the adsorption isotherm models fitted the data in the order of: Langmuir>Redlich-Peterson>Toth>Freundlich isotherms. A pseudo second-order adsorption model was better to describe the adsorption data than the pseudo first-order model and the Bangham model at the temperatures tested. The activation energy was calculated to be 40.90 kJ/mol, while the thermodynamic parameters DeltaH and DeltaS were estimated to be -5.82 kJ/mol and 0.07 kJ/(molK), respectively.     

Adsorption of Acid Blue 193 from aqueous solutions onto DEDMA-sepiolite

The adsorption of Acid Blue 193 (AB193) onto dodecylethyldimethylammonium (DEDMA)-sepiolite was investigated in aqueous solution in a batch system with respect to contact time, pH and temperature. The surface modification of DEDMA-sepiolite was examined by the FT-IR technique. The pseudo-first-order, pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted very well with the pseudo-second-order kinetic model and also followed the simple external diffusion model up to initial 10 min and then by intraparticle diffusion model up to 75 min, whereas diffusion is not only the rate-controlling step. The adsorption capacities of natural sepiolite and DEDMA-sepiolite at pH 1.5 and 20 degrees C were (1.19 and 2.57) x 10(-4) mol g(-1), respectively. The above results indicate that DEDMA-sepiolite has around two times higher adsorption capacity than natural sepiolite. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were also determined. The Freundlich model agrees with experimental data well. The activation energy, change of Gibbs free energy, enthalpy and entropy of adsorption were also evaluated for the adsorption of AB193 onto DEDMA-sepiolite.