Kinetics and retention characteristics of some nitrophenols onto polyurethane foams

The kinetics of sorption of the nitrophenols by the unloaded polyurethane foams (PUFs) were found fast, reached equilibrium in few minutes and followed a first-order rate equation with an overall rate constant k in the range (0.16-0.21)±0.01 min⁻¹. The retention of the tested nitrophenols by the unloaded foams is consistent with the “solvent extraction” mechanism. However, the sorption also followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The mean free sorption energy of the nitrophenols onto the PUF was found equal to 7.5±0.4 kJ/mol, which reflects physical sorption. Thus, a dual-mode involves both absorption related to solvent extraction and an added component for surface adsorption seems a more likely sorption mechanism model. While a dual-mode sorption model explains the observed retention behavior, the data suggest that, solvent extraction plays a much larger role than the added component for surface adsorption. The sorption and recovery percentages of the nitrophenols from fresh, natural and industrial wastewater by the proposed unloaded foam columns were quantitatively achieved. The height equivalent to theoretical plates (HETP), N, the breakthrough capacity and the critical capacity for the unloaded foam columns were found in the range of (0.8-1.1)±0.6 mm, (94-132)±3, 3.2-4.02 and 1.5-2.67 mg/g, respectively. The method was successfully applied for the retention and recovery of the tested nitrophenols spiked to fresh and industrial wastewaters.     

Kinetics, thermodynamic and chromatographic behaviour of the uranyl ions sorption from aqueous thiocyanate media onto polyurethane foams

The retention profile of uranyl ions from aqueous thiocyanate media by polyether-type based polyurethane foams (PUFs) has been studied to gain more information regarding the mechanism of extraction. The effect of pH, shaking time, surfactant type, extraction media, temperature and analyte concentration on the retention of uranyl ions onto PUFs has been studied. It has been found that, the sorption of uranyl ions involved in the formation of a ternary complex ion associate of uranyl ion, thiocyanate and PUFs is highly dependent on these parameters. The kinetics and thermodynamics of the uranyl ions sorption have been studied in more detail. The dependency of the extraction on the parameters can be explained via a “solvent extraction,” mechanism. However, owing to the complex nature of the PUFs a dual-mode sorption mechanism involving both absorptions related to “solvent extraction” and an added component for “surface adsorption” may be operated simultaneously. Attempts for quantitative retention and recovery of the uranyl ions in tap and industrial waste water samples by the proposed PUFs columns has been carried out and satisfactory results have been obtained. The cellular structure of the PUF sorbent offer unique advantages over a conventional bulk type sorbents in rapid, versatile effective separation and/or preconcentration of uranyl ions.     

Sorption profile and chromatographic separation of uranium (VI) ions from aqueous solutions onto date pits solid sorbent

The retention profile of uranium (VI) as uranyl ions (UO(2)(2+)) from the aqueous media onto the solid sorbent date pits has been investigated. The sorption of UO(2)(2+) ions onto the date pits was achieved quantitatively (98+/-3.4%, n=5) after 15 min of shaking at pH 6-7. The sorption of UO(2)(2+) onto the used sorbent was found fast, followed by a first order rate equation with an overall rate constant, k of 4.8+/-0.05 s(-1). The sorption data were explained in a manner consistent with a "solvent extraction" mechanism. The sorption data were also subjected to Freundlich isotherm model over a wide range of equilibrium concentration (1-20 microgmL(-1)) of UO(2)(2+). The results revealed that, a "dual-mode" of sorption mechanism involving absorption related to "solvent extraction" and an added component for "surface adsorption" is most likely operated simultaneously for uranyl ions uptaking the solid sorbent. The thermodynamic parameters (-DeltaH, DeltaS and DeltaG) of the uranyl ions uptake onto the date pits indicated that, the process is endothermic and proceeds spontaneously. The interference of some diverse ions on the sorption UO(2)(2+) from the aqueous media onto the date pits packed column was critically investigated and the data revealed quantitative collection of UO(2)(2+) at 5 mLmin(-1) flow rate. The retained UO(2)(2+) was recovered quantitatively with HCl (3.0 molL(-1)) from the column at 5 mLmin(-1) flow rate. The mode of binding of the date pits with UO(2)(2+) was determined from the IR spectral date bits before and after extraction of uranium (VI). The height equivalent (HETP) and the number (N) of theoretical plates of the date pits packed column were determined from the chromatograms. Complete retention and recovery of UO(2)(2+) spiked to wastewater samples by the date pits packed column was successfully achieved. The capacity of the used sorbent towards retention of uranium (VI) from aqueous solutions was much better than the most common sorbents.     

Gas sorption in polymers based on bisphenol-A

Equilibrium gas sorption measurements for CO₂, CH₄, and N₂ were made with three polymers based on bisphenol-A, namely a polyhydroxyether, a polyetherimide, and a polyarylate. These data plus previous results for two other bisphenol-A polymers, polycarhonate and polysulfone, were analyzed using the dual-mode sorption model and the more recent gas-polymer-matrix model. The models were compared on the basis of physical interpretations of the resulting parameters. The Langmuir capacity from the dual-model model was related to the unrelaxed volume of the glassy polymer. The Henry's law sorption parameter from the dual-mode model was related to the internal pressure of the polymer and to its tensile stress at yield. The work suggests a means for estimation of gas sorption levels from thermal and mechanical properties of the polymer.     

Kinetic and calorimetric study of the adsorption of dyes on mesoporous activated carbon prepared from coconut coir dust

Mesoporous activated carbon has been prepared from coconut coir dust as support for adsorption of some model dye molecules from aqueous solutions. The methylene blue (MB) and remazol yellow (RY) molecules were chosen for study of the adsorption capacity of cationic and anionic dyes onto prepared activated carbon. The adsorption kinetics was studied with the Lagergren first- and pseudo-second-order kinetic models as well as the intraparticle diffusion model. The results for both dyes suggested a multimechanism sorption process. The adsorption mechanisms in the systems dyes/AC follow pseudo-second-order kinetics with a significant contribution of intraparticle diffusion. The samples simultaneously present acidic and basic sites able to act as anchoring sites for basic and acidic dyes, respectively. Calorimetric studies reveal that dyes/AC interaction forces are correlated with the pH of the solution, which can be related to the charge distribution on the AC surface. These AC samples also exhibited very short equilibrium times for the adsorption of both dyes, which is an economically favorable requisite for the activated carbon described in this work, in addition to the local abundance of the raw material.     

Cesium removal from solution using PAN-based potassium nickel hexacyanoferrate (II) composite spheres

A polyacrylonitrile–potassium nickel hexacyanoferrates composite adsorbent was prepared to remove cesium ion in aqueous solution. The dual nozzle technique was applied to prepare a composite sphere. The physicochemical behavior of the ion exchanger was specified with different techniques including Fourier transform infrared spectroscopy, X-ray powder diffraction, specific surface analysis, scanning electron microscopy, and X-ray fluorescence spectroscopy analysis. The effects of contact time, solution initial pH, presence of various cations and initial cesium concentration on the adsorption was also investigated and the optimum conditions for separation of cesium were determined. In addition, adsorption kinetics and adsorption mechanism were studied by modeling the experimental data and related parameters were also evaluated, which showed that sorption data fitted to pseudo-second-order and film diffusion models. Adsorption isotherm in batch experiments showed that the sorption data were successfully fitted with Langmuir model. Finally the adsorption dynamic capacities of the synthesized composite in column experiments were evaluated at 139.925 and 119.539 mg/g for flow rate of 1 and 3 BV/min, respectively.     

Oxidative coupling and the irreversible adsorption of phenol by graphite

Uptake of phenol by graphite, and regeneration by methanol extraction, was measured to evaluate irreversible adsorption of phenols to carbon surfaces. The emphasis of this work was to identify the role of oxidative coupling, which has been invoked to explain irreversible phenol sorption by activated carbons. Graphite was chosen as a model carbon surface to eliminate potentially confounding effects of microporosity present in other types of carbonaceous sorbents. The isotherm data were well described by the Langmuir-Freundlich isotherm from pH 3 to 9. At pH 12, measured uptakes were higher than expected based on model predictions, suggesting the occurrence of an adsorption mechanism besides physisorption. One oxidative coupling product, 2,2'-dihydroxybiphenyl, was obtained exclusively after adsorption at pH values above 7, and appeared both in aqueous solution and in the methanol regenerant solution. The fraction of total uptake that was not recoverable by methanol extraction decreased with increasing phenol concentration in solution, suggesting preferential sorption by high-energy sites. However, absolute irreversible adsorption increased with phenol concentration in solution. Both fractional irreversible adsorption and 2,2'-dihydroxybiphenyl oxidative coupling product recovery as a function of pH and contact time demonstrated that irreversible sorption of phenol by graphite could not be explained by an oxidative coupling mechanism alone.     

A Film-Pore-Surface Diffusion Model for the Adsorption of Acid Dyes on Activated Carbon

The sorption of acid dyes from aqueous effluents onto activated carbon has been studied. The effects of initial dye concentration and activated carbon mass on the rate of Acid Blue 80, Acid Red 114 and Acid Yellow 117 removal have been investigated. A three-resistance mass transport model based on film, pore and surface diffusion control has been applied to model the concentration decay curves. The model incorporates an effective diffusion coefficient D _eff, which is dependant on the equilibrium solid phase concentration or fractional surface coverage. The results of the film-pore-surface diffusion model are compared with the data obtained from the basic film-pore diffusion model. It has been found that the film-pore-surface diffusion model provides a major improvement over the data correlated by the film-pore diffusion model. Also, the relationship between surface diffusion and fractional surface coverage has been investigated for the adsorption of acid dyes on activated carbon.     

A Film-Pore-Surface Diffusion Model for the Adsorption of Acid Dyes on Activated Carbon

The sorption of acid dyes from aqueous effluents onto activated carbon has been studied. The effects of initial dye concentration and activated carbon mass on the rate of Acid Blue 80, Acid Red 114 and Acid Yellow 117 removal have been investigated. A three-resistance mass transport model based on film, pore and surface diffusion control has been applied to model the concentration decay curves. The model incorporates an effective diffusion coefficient D _eff, which is dependant on the equilibrium solid phase concentration or fractional surface coverage. The results of the film-pore-surface diffusion model are compared with the data obtained from the basic film-pore diffusion model. It has been found that the film-pore-surface diffusion model provides a major improvement over the data correlated by the film-pore diffusion model. Also, the relationship between surface diffusion and fractional surface coverage has been investigated for the adsorption of acid dyes on activated carbon.     

Retention profile, kinetics and sequential determination of selenium(IV) and (VI) employing 4,4'-dichlorodithizone immobilized-polyurethane foams

Polyurethane foams (PUFs) loaded with the chromogenic reagent 4,4′-dichlorodithizone (Cl₂H₂D_Z) have been investigated for the quantitative retention, chemical speciation and sequential determination of traces of inorganic selenium(IV) and (VI) from aqueous media containing bromide ions. The retention profile of selenium(IV) onto the reagent loaded foam followed a dual-mode sorption mechanism involving both absorption related to “solvent extraction” and an added component for surface adsorption. The kinetics and thermodynamic characteristics of selenium(IV) uptake onto PUFs have been studied. The kinetics of selenium(IV) sorption onto PUFs was found fast, reached equilibrium in few minutes and followed a first-order rate constant in presence of bromide ions in the extraction media. The thermodynamic parameters, ΔH, ΔS and ΔG, indicated the exothermic and spontaneous nature of the sorption process. The sorption and the recovery percentages of inorganic selenium(IV) from fresh water by the proposed loaded foam columns were achieved quantitatively. The height equivalent to theoretical plate (HETP), the number of layers (N), breakthrough capacity and the critical capacity for selenium(IV) uptake onto Cl₂H₂D_Z loaded foams columns were found to be 1.3, 103, 8.6 and 7.2 mg/g, respectively. The method was successfully applied for the chemical speciation and sequential determination of inorganic selenium(IV) and/or (VI) species spiked to fresh and industrial wastewaters.     

一步法制备聚脲多孔材料及其对染料的吸附

以甲苯二异氰酸酯为单体, 在水和丙酮混合溶剂中不用致孔剂且无需任何高分子改性一步法合成了聚脲多孔材料(PPU), 通过扫描电镜和BET氮气吸附法对其表面形貌和孔参数进行了表征. 以酸品红(AF)溶液模拟染料废水, 对其在PPU上的吸附进行了研究, 讨论了pH、 吸附时间、 AF初始浓度及吸附剂用量对吸附过程的影响, 优化了吸附条件. 结果表明, PPU对染料AF具有优异的吸附效果. PPU在30℃, pH=3时对AF的最大吸附量为44.60 mg/g. PPU对AF的吸附过程更接近于Langmuir等温吸附的单分子层吸附机理. PPU对水溶性染料刚果红(CR)也有很好的吸附能力. 使用水、 乙醇和水混合溶剂以及NaOH水溶液对染料吸附后的解吸附结果表明, 乙醇和水混合溶剂对吸附染料的解吸效率最高, 对2种染料的解吸附都达90%以上. 解吸后PPU的再吸附能力略有下降, 但第三次吸附量仍达到首次吸附的80%以上.     

Mechanism of sorption of phenols from aqueous solutions onto surfactant-modified montmorillonite

Equilibrium and kinetic studies on the sorption of phenol, m-nitrophenol (m-NP), and o-cresol from water onto montmorillonite modified with cetyltrimethylammounium bromide (CTAB) were conducted. Experiments were carried out as a function of solution pH, sorbate concentration, and temperature (25-55 degrees C). It was shown that the sorption capacity decreased in the order phenol>o-cresol>m-NP. The Langmuir, dual-mode sorption, and Redlich-Peterson models were tested to fit the sorption isotherms of single-solute systems, whereas the Langmuir competitive model was used to describe bisolute sorption equilibria. Thermodynamic parameters (DeltaH degrees and DeltaS degrees ) and the mean free energy (E) for the sorption of phenols were determined from the temperature dependence of the distribution constant and the Dubinin-Radushkevick equation, respectively. A simplified kinetic model was proposed to confirm the sorption mechanism.     

Effect of quaternary ammonium cations on dye sorption to fly ash from aqueous media

The efficacy of the surface modification of fly ash by quarternary ammonium cations in the removal of dyes from aqueous solution is demonstrated. A series of organo-fly ash materials were synthesized by treating fly ash with quarternary ammonium cations such as tetraethylammonium, hexadecyltrimethylammonium, and benzyldimethyltetradecylammonium (TEA, HDTMA, and BDTDA). Two types of dyes were used for the investigation, disperse and anionic dyes. The effects of initial dye concentration, contact time, temperature, and the mechanism of dye sorption were investigated. The sorption was found to be affected by the structure and size of the quaternary ammonium cations as well as that of the dyes. Sorption of dyes was considerably enhanced by the surface modification. Thermodynamic parameters such as free energy (DeltaG0), enthalpy (DeltaH0), and entropy (DeltaS0) for the sorption process were also calculated.     

A Mechanistic Approach to Tributyltin (TBT) Sorption by Marine Microflagellated Alga Pavlova lutheri

The sorption of tributyltin (TBT) by phytoplankton cells was studied by exposing the marine microflagellated alga Pavlova lutheri grown in batch culture to TBT chloride concentrations ranging from 0.37 to 74 nM (0.1 to 21 μg l⁻¹) for a 24-hour period. The phytotoxicity of TBT was indicated by a decrease in cell density at all TBT concentrations used. TBT was tightly bound to the surface cell and was only washed out by a strong acidic solution (pH⩽3) while inner cell-absorbed TBT was only recovered by means of an organic solvent. The sorption of TBT by P. lutheri occurred via two mechanisms: a passive ionic surface adsorption followed by a facilitated intracellular absorption. The coupling/uncoupling of these two mechanisms was dependent upon the contamination level used. The cell surface adsorption of TBT was best described by the Freundlich adsorption model whereas the obstruction of the facilitated absorption mechanism was apparently related to the toxic activity of TBT towards cell components. © 1997 John Wiley & Sons, Ltd.     

Sorption of basic dyes onto granulated pillared clays: thermodynamic and kinetic studies

Effect of the granulation process onto the thermodynamic and kinetic sorption parameters of two basic dyes (Basic Yellow 28-BY 28 and Basic Green 4-BG 4) was evaluated in the present work. The charge surface properties of the surfactant-modified aluminium-pillared clay (CTAB-Al-Mont-PILC) particles were not modified, and the isoelectric point remains constant after high shear wet granulation. The Gibbs free energy of both BY 28 and BG 4 sorption was negative and decreased with the granulation; the endothermic nature of the sorption process was confirmed by the positive values of ΔH°. Adsorption kinetics of the two dyes, studied at pH 6 and 150 mg L(-1), follow the pseudo-first order kinetic model with observed rate constants of 2.5-4.2×10(-2) min(-1). The intraparticle diffusion model, proposed by Weber and Morris, was applied, and the intraparticle plots revealed three distinct sections representing external mass transfer, intraparticle diffusion and adsorption/desorption equilibrium. Diffusion coefficients, calculated from the Boyd kinetic equation, increased with the granulation and the particle size. Pseudo-first order kinetic constants, intraparticle diffusion rate constants and diffusion coefficients were determined for two other initial concentrations (50 and 100 mg L(-1)) and include in a statistical study to evaluate the impact of granulation and initial concentration on the kinetic parameters. Kruskal-Wallis tests, Spearman's rank order correlation and factor analysis revealed a correlation between (i) the diffusion coefficients and granulation, and between (ii) the intraparticle diffusion rate constants and initial concentration.     

循环伏安法研究光谱增感染料在溴化银上的吸附

用循环伏安法和电子显微镜研究了不同类型的染料在溴化银上的吸附,使用了电沉积在铂上的溴化银电极作为照相乳剂的模型,证明了由于染料电荷的不同,其在AgBr/Br^-表面上的吸附也不同,正性染料被吸附时,形成难溶的表面络合物,和负性染料相作用时,形成易溶的表面络合物,而当AgBr与非菁负性染料作用时,则由于负电排斥而不形成络合物。因此,利用循环伏安法可以判断不同染料的吸附情况。本文还研完了超增感及Riester提出的‘强色增感’中的吸附情况。实验结果表明在AgBr上染料的排列次序取决于其吸附强度。本工作还证明了Reister所提出的‘强色增感剂’的作用机理是可信的。     

Sorption of some azo-dyes on wool fiber from aqueous solutions

Sorption of some azo-dyes (acid violet 17, acid blue 90, acid red 1 and direct red 80) on locally available wool fiber from aqueous solution has been investigated as a function of shaking time, pH and dyes concentration as a function of temperature. Sorption isotherms for dyes on wool fiber were obtained. It was found that the increasing temperature induces positive effect on the sorption process. Isosteric heat of adsorption (q_st) have also been calculated at different surface coverage indicating that wool fiber used possessed heterogeneous surface with site of different activity. The results also indicate that initial sorption whether chemical or physical means, occurs first on the most active sites and then, as the concentration of dyes is increased, on sites of lesser activity.     

Removal of dyes from colored textile wastewater by orange peel adsorbent: equilibrium and kinetic studies

The use of low-cost and ecofriendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. Orange peel was collected from the fields of orange trees in the north of Iran and converted into a low-cost adsorbent. This paper deals with the removal of textile dyes from aqueous solutions by orange peel. Direct Red 23 (DR23) and Direct Red 80 (DR80) were used as model compounds. The adsorption capacity Q0 was 10.72 and 21.05 mg/g at initial pH 2. The effects of initial dye concentration (50, 75, 100, 125 mg/l), pH, mixing rate, contact time, and quantity of orange peel have been studied at 25 degrees C. The Langmuir and Freundlich models were used for this study. It was found that the experimental results show that the Langmuir equation fit better than the Freundlich equation. The results indicate that acidic pH supported the adsorption of both dyes on the adsorbent. Orange peel with concentrations of 8 and 4 g/l has shown adsorption efficiencies of about 92 and 91% for DR23 and DR80, respectively. Furthermore, adsorption kinetics of both dyes was studied and the rates of sorption were found to conform to pseudo-second-order kinetics with a good correlation (R > or = 0.998). Maximum desorption of 97.7% for DR23 and 93% for DR80 were achieved in aqueous solution at pH 2. Finally, the effect of adsorbent surface was analyzed by scanning electron microscope (SEM). SEM images showed reasonable agreement with adsorption measurements.     

Adsorption of polymers at the solution–solid interface. IX. Solution adsorption of nitrile rubbers on silicas

The adsorption of three acrylonitrile–butadiene random copolymers from two solvents has been studied: two pyrogenic silicas of differing surface areas, which had received several surface modifications, were used as adsorbents. Infrared spectroscopic studies confirm that the nitrile groups bond to the silica surface. The amount of copolymer adsorbed is related to the acrylonitrile content, which also controls the copolymer solubility: adsorptions are higher from benzene than from a better solvent, trichloroethylene. Vapor sorption of model compounds indicate how the adsorbent surface area and surface composition affect monolayer capacities: heats of adsorption are not markedly altered by the adsorbent modifications.