Affinity of Clinoptilolite‐based Zeolites towards Removal of Cd from Aqueous Solutions

Abstract

Cd removal from aqueous solutions using as‐received and pretreated forms of two different clinoptilolite samples (denoted GC and BC) was investigated and dissimilar sorption affinities were revealed. Equilibrium behavior of systems were modeled using six different adsorption isotherms. The maximum sorption capacities, as obtained from the solubility‐normalized Dubinin‐Astakhov model for as‐received samples, were determined as 0.18 meq/g and 0.12 meq/g for GC and BC, whereas 0.72 meq/g and 0.41 meq Cd/g was determined for their pretreated forms, respectively. Examination of the release of exchangeable cations into the solution at equilibrium and the change of pH were discussed in terms of varying prevalence of ion exchange, dissolution of the sorbent and adsorption.     

Removal of Copper (II) Ions from Aqueous Solutions using Na‐mordenite

Abstract

The potential to remove copper (II) ions from aqueous solutions using Na‐mordenite, a common zeolite mineral, was thoroughly investigated. The effects of relevant parameters solution pH, adsorbent dose, ionic strength, and temperature on copper (II) adsorption capacity were examined. The sorption data followed the Langmuir, Freundlich, and Dubinin‐Radushkevich (D‐R) isotherms. The maximum sorption capacity was found to be 10.69 mg/g at pH 6, initial concentration of 40 mg/dm³, and temperature of 40°C. Different thermodynamic parameters viz., changes in standard free energy (ΔG⁰), enthalpy (ΔH⁰), and entropy (ΔS⁰) have also been evaluated and the results show that the sorption process was spontaneous and endothermic in nature. The dynamics of the sorption process were studied and the values of rate constant of adsorption, rate constant of intraparticle diffusion were calculated. The activation energy (E_a) was found to be 11.25 kJ/mol in the present study, indicating a chemical sorption process involving weak interactions between sorbent and sorbate. The interaction between copper (II) ions and Na‐mordenite is mainly attributable to ion exchange. The sorption capacity increased with the increase of solution pH and the decrease of ionic strength and adsorbent dose. The Na‐mordenite can be used to separate copper (II) ions from aqueous solutions.     

Centrifugal Polyelectrolyte Enhanced Ultrafiltration for Removal of Copper‐Citrate Complexes from Aqueous Solutions

Abstract

To replace the conventional dead‐end polyelectrolyte enhanced filtration (PEUF), which is a time consuming process in the optimization of process variables, centrifugal polyelectrolyte enhanced ultrafiltration was investigated to remove copper‐citrate complex in aqueous phase with a cationic polyelectrolyte, poly(diallydimethylammonium chloride) (PDADMAC). Effects of concentration ratios between polyelectrolyte, copper, and citrate and pH were observed. Below pH 3, copper was not removed by centrifugal PEUF. At the same concentration (1 mM) of citrate and copper, removal of copper at pH 5 was the highest value of 54%, 90%, and 98% with 5, 10, and 20 mM PDADMAC, respectively. Removal of copper decreased with the logarithmic ionic strength. Since the centrifugal PEUF is very economical in time compared with conventional dead‐end PEUF, the present method should be a valuable tool in the optimization of process variables.     

Applications of the Biosorption Process for Nickel Removal from Aqueous Solutions – A Review

Wastewaters and contaminants released to the aqueous environment increase due to developing industrialization and technology. These wastewaters should be treated before being discharged to water bodies. Also, reusable materials in wastewaters must be recovered by appropriate techniques. Discharge limits required by the authorities become more stringent with updated legislations. Nickel ions can be reusable by recovering it after the biosorption process. So, this will prevent the loss of raw materials in industries and it also affects the economy in a positive way. Conventional heavy metal removal processes may be costly and inadequate to meet the desired discharge limits and they exhibit low efficiencies. Eco-friendly and economical treatment technologies gain great importance in the removal and recovery of nickel from wastewaters. In this study, biosorption which is the subject of numerous studies and one of the heavy metal removal methods will be investigated, and nickel removal by this technique and the biosorption mechanism will also be elaborated with data from literature studies.     

Hybrid Properties of Alginate‐PEI Adsorbent for Chromium (VI) Removal from Aqueous Solutions

Abstract

An adsorbent consisting of polyethyleneimine (PEI) immobilized in calcium alginate gel beads was synthesized and evaluated for Cr⁶⁺ removal. An evaluation of the synthesis process showed the importance of the PEI molecular weight on the immobilization efficiency. Polyethyleneimine of 70,000 Da molecular weight displayed the highest immobilization percentage at 52%. Batch kinetics and equilibrium tests showed that alginate‐PEI (APEI) resin displayed considerable affinity for negatively charged Cr⁶⁺ complexes at low pH conditions ranging from pH 1.5‐pH 3. The results also indicated the reduction of Cr⁶⁺ to less toxic Cr³⁺ species by the APEI adsorbent. The column adsorption experiments showed the ability of APEI resin to treat a 10 mg/L Cr⁶⁺ solution with pH influent adjustment from pH 1.5 to pH 3 to concentrations that satisfy effluent standards for Cr⁶⁺ (<0.1 mg/L) and total Cr (<0.5 mg/L). Finally, comparisons with a highly aminated commercial resin Chitopearl CS‐03 highlighted the unique ability of the hybrid APEI beads with its amine and carboxylic groups for the adsorption of Cr⁶⁺ as well as the retention of generated Cr³⁺ ions.     

Sorption Potential of Styrene‐Divinylbenzene Copolymer Beads for the Decontamination of Lead from Aqueous Media

Abstract

The decontamination of lead ions from aqueous media has been investigated using styrene‐divinylbenzene copolymer beads (St‐DVB) as an adsorbent. Various physico‐chemical parameters such as selection of appropriate electrolyte, contact time, amount of adsorbent, concentration of adsorbate, effect of foreign ions, and temperature were optimized to simulate the best conditions which can be used to decontaminate lead from aqueous media using St‐DVB beads as an adsorbent. The atomic absorption spectrometric technique was used to determine the distribution of lead. Maximum adsorption was observed at 0.001 mol L^?1 acid solutions (HNO₃, HCl, H₂SO₄ and HClO₄) using 0.2 g of adsorbent for 4.83×10^?5 mol L^?1 lead concentration in two minutes equilibration time. The adsorption data followed the Freundlich, Langmuir, and Dubinin‐Radushkevich (D‐R) isotherms over the lead concentration range of 1.207×10^?3 to 2.413×10^?2 mol L^?1. The characteristic Freundlich constants i.e. 1/n=0.164±0.012 and A=2.345×10^?3±4.480×10^?5 mol g^?1 have been computed for the sorption system. Langmuir isotherm gave a saturated capacity of 0.971±0.011 mmol g^?1, which suggests monolayer coverage of the surface. The sorption mean free energy from D‐R isotherm was found to be 18.26±0.75 kJ mol^?1 indicating chemisorption involving chemical bonding for the adsorption process. The uptake of lead increases with the rise in temperature. Thermodynamic parameters i.e. ΔG, ΔH, and ΔS have also been calculated for the system. The sorption process was found to be exothermic. The developed procedure was successfully applied for the removal of lead ions from real battery wastewater samples.     

Fixed‐Bed Removal of Free and Complexed Ni from Synthetic and Industrial Aqueous Solutions

Abstract

This paper evaluates the application of several biosorbents for Ni removal from aqueous solutions in the absence and in the presence of EDTA. Fixed bed experiments were performed (Ni influent concentration, 2 mg dm^?3; EDTA doses, 0, 5, and 10 mg dm^?3; pH=7) to study the process feasibility as refining after conventional physicochemical treatment. In absence of EDTA, uptake capacity followed the order peat > Posidonia oceanica > chitosan > chitin ? Scharlau AC. Maximum uptakes of 8.95 mg g^?1 and 5.10 mg g^?1 were found for peat and Posidonia oceanica, respectively. In the presence of EDTA, removal capacity decreased for all biosorbents; Ni was detected in the effluent from the beginning of the operation, indicating low ability to retain Ni EDTA‐complexes. Activated carbon presented the ability to remove complexed Ni. Peat exhibited the best performance for the treatment of an industrial spill from a metal‐finishing facility, with effluent Ni concentration lower than 0.2 mg dm^?3 for more than two weeks of treatment (3500 pore volumes of treated wastewater).     

Kinetic Aspects of Copper‐LIX ® Extraction from Nitrate/Nitric Acid Aqueous Solutions

Abstract

A comparative kinetic study of the extraction of copper from nitrate/nitric acid aqueous solutions by different classes of LIX ^® reagents (LIX 984N, LIX 860N‐I, LIX 84‐I, LIX 65N) was performed. Using a Rotating Diffusion Cell, the rate constants of the chemical reactions (forward and reverse) were estimated and compared. In the case of the mixed extractant LIX 984N, a synergistic effect was observed. The values of the forward reaction constants of all the extractants were found to be an order of magnitude higher than those of the reverse reaction. The relatively low E _a ‐values prove the substantial influence of the diffusion on the extraction kinetics under the experimental conditions studied.     

Fluoride Removal from Aqueous Solutions by Magnesium,Nickel, and Cobalt Calcined Hydrotalcite‐like Compounds

Abstract

Magnesium, nickel and cobalt hydrotalcite‐like compounds (MgHT, NiHT, and CoHT), with similar M²⁺:Al³⁺ ratios were synthesized and characterized by XRD. It was confirmed from XRD that the materials have hydrotalcite‐like structure. MgHT, NiHT, and CoHT were calcined and treated with fluoride solutions in a batch system. F^? ions were determined in the remaining solutions using a fluoride ion selective electrode. The kinetics of the fluoride ions sorption on calcined hydrotalcite‐like compounds (CHT) was best described by the pseudo‐second order model and the equilibrium was reached in less than 300 minutes in all cases (MgCHT, NiCHT, and CoCHT). The sorption isotherms of the fluoride by hydrotalcite like compounds can be explained by the Langmuir‐Freundlich model and, the highest fluoride sorption capacity was obtained for NiCHT (1.202 mgF/gCHT). The fluoride removal from aqueous solutions by calcined hydrotalcite‐like compounds depends on the adsorption properties of the thermal decomposition products and the regeneration reaction mechanism of the hydrotalcite‐like compounds.     

Investigation of Selectivity and Kinetic Behavior of Strong‐Base Ion Exchange Resin Purolite A 520E for Nitrate Removal from Aqueous Solution

Abstract

The aim of this work is to present experimental results on the removal of nitrate by nitrate selective ion exchange resin, Purolite A 520E. The resin particle size, nitrate concentration, temperature, and stirring speed were investigated as experimental parameters and the optimum conditions for nitrate removal were determined. Nitrate removal by strong base anion exchange resin Purolite A 520E was carried out with the batch method in the presence of chloride and sulfate ions. The existence of a high concentration of competing ions in a solution resulted in a reduction of nitrate removal. Nitrate removal ratios decreased from 98% to 85% and 88%, respectively, in the presence of chloride and sulfate ions when the chloride and sulfate ratios were increased in solution. The process kinetics were predicted by using Homogenous Diffusion Models. It was seen that about 98% of nitrate in the aqueous solution could be removed using optimum conditions.     

Pseudo‐Hydroxide Extraction in the Separation of Sodium Hydroxide from Aqueous Solutions Using Alkyl Phenols

Abstract

Pseudo‐hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1‐octanol at 25°C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4‐tert‐octylphenol>3,5‐di‐tert‐butylphenol>2,4‐di‐tert‐butylphenol>2,6‐di‐tert‐butyl‐4‐methylphenol. A good correlation with phenol pK _a was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol –OH group. The effective partition ratios (P _eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1‐octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation‐exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for

1. Ion‐pair extraction to give Na⁺OH^? ion pairs and corresponding free ions in 1‐octanol the phase and

2. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic‐phase Na⁺A^? ion pairs and corresponding free organic‐phase ions.

Application of Layered Double Magnesium–Aluminum Oxides for the Purification of Aqueous Solutions from Dyes

Theoretical Foundations of Chemical Engineering - The possibility of purifying aqueous solutions from dyes with the use of layered double magnesium–aluminum oxides is studied. Using stamp ink...     

Removal of Copper and Lead from Aqueous Solution by Adsorption onto Cross-Linked Chitosan/Montmorillonite Nanocomposites in the Presence of Hydroxyl–Aluminum Oligomeric Cations: Equilibrium,Kinetic, and Thermodynamic Studies

Adsorption removal of Cu (II) and Pb (II) on cross-linked chitosan/Al₁₃-pillared montmorillonite (CCPM) was examined in solutions. The chitosan dosage was drastically reduced in the new nanocomposite, which is made from the treated clay (Al₁₃-pillared montmorillonite). Several important parameters that influenced the adsorption of Cu (II) and Pb (II) ions, such as cross-linked chitosan-to-clay ratio, pH, temperature, initial concentration, dosage, and contact time effect, were systematically investigated. Result showed that in the nanocomposite with cross-linked chitosan-to-clay ratio of 0.45:1, the maximum removal efficiencies of Cu (II) [pH 6.5, dosage 10 g/L, initial Cu (II) concentration 100 mg/L, contact time 2 h, 298 K] and Pb (II) [pH 6.0, dosage 5 g/L, initial Pb (II) concentration 100 mg/L, contact time 2 h, 298 K] were 96.0% and 99.5%, respectively. Kinetic and isotherm studies have indicated that the adsorption process of Cu (II) or Pb (II) nanocomposites was better fitted by the pseudo-second-order equation and the Freundlich equation, with chemical adsorptions as the rate-limiting step. The metal–ion affinity to the functional groups of CCPM followed the order Pb (II) > Cu (II). The thermodynamic parameters ΔH and ΔS values showed that the sorption process of Cu (II) or Pb (II) was spontaneous (ΔG < 0), was endothermic (ΔH < 0), and had decreased entropy (ΔS < 0). HNO₃ (0.1 M) could be a good desorbent in the recovery of metal ions after adsorption and regeneration of the adsorbent.     

High Performance of UiO-66 Metal–Organic Framework Modified with Melamine for Uptaking of Lead and Cadmium from Aqueous Solutions

Journal of Inorganic and Organometallic Polymers and Materials - In this paper, UiO-66 metal–organic framework (MOF) was prepared by a hydrothermal method and modified consequently with...     

Modification of Malonamide Ion-Exchange/Chelating Resins Using the Fields–Kabatschnik Reaction and Their Application to Metal Ion Removal from Aqueous Solutions

A resin containing 2-aminoethyl-substituted amides of malonic acid was modified in the Fields–Kabatschnik reaction using diethyl phosphite. The resultant ion-exchange/chelating resins have aminomethylphosphonate groups. Modification proceeds almost quantitatively, giving a resin with P=1.97 mmol/g, N=4.20 mmol/g, and water regain of 0.44 g/g. It can be selectively hydrolyzed by treatment with trimethylchlorosilane/potassium bromide in dry acetonitrile. Both acidic and ester forms of the resin were used in the removal of Cu(II), Cd(II), Ni(II), and Zn(II) from their diluted 1×10^–4 N solutions in 0.2 M acetate buffer at pH 3.7 and 5.6. The affinity of the resin in an acid form toward divalent metal cations is high, and at pH 5.6 the log K _d is 7.54, 3.97, 3.41, and 3.98, respectively. The resins are selective and the presence of an excess of sodium ions does not influence the uptake of metal ions. The type of complexes formed between the resins and Cu(II) ions was studied using EPR spectroscopy. The ester form of the resin was used in the removal of tetrachloroaurate anions from hydrochloric acid solution. It has been found that the log K _d is in the range of 3.14–3.94 for the uptake of AuCl^– ₄ from 5.0–0.5 M HCl solutions.     

Thermodynamic Data of 6-(4′-Aminobutylamino)-6-deoxycellulose Sorbent for Cation Removal from Aqueous Solutions

The natural biopolymer cellulose was first modified with thionyl chloride, followed by reaction with 1,4-diaminebutane to yield 6-(4′-aminobutylamino)-6-deoxycellulose. From 1.85% of nitrogen incorporated in the polysaccharide backbone, the amount of 0.66 ± 0.11 mmol of this molecule was anchored per gram of the chemically modified cellulose. The resulting chemically immobilized surface was characterized by elemental analysis, infrared spectroscopy, and nuclear magnetic resonance of the carbon nucleus in the solid state and thermogravimetry. The newly synthesized biopolymer gave maximum sorption capacities of 0.32 ± 0.03, 0.29 ± 0.01, 0.26 ± 0.03 and 0.25 ± 0.02 mmol g^?1 for divalent copper, cobalt, nickel, and zinc cations, using the batch method, whose data were fitted to different sorption models. The thermal effects obtained from a calorimetric titration procedure gave favorable thermodynamic data for cation sorption from aqueous solutions at the solid/liquid interface, suggesting the use of this anchored biopolymer for cation removal from the environment.     

Removal of Cr(VI) Oxy‐anions from Aqueous Solution by Sorption into Poly(Acrylamide‐Co‐Maleic Acid) Hydrogels

Abstract

The dynamic removal of hexavalent chromiuim by poly(acrylamide‐co‐maleic acid) hydrogels was studied by a batch equilibrium technique at 35°C. Various kinetic and adsorption parameters such as rate constant for sorption, intraparticle diffusion rate constant, Langmuir constant, and adsorption capacity have been evaluated. The sorption process follows the Langmuir‐type behavior and extent of sorption of Cr(VI) ions depends upon the composition of co‐polymeric gels, presence of other ions in the solution, and temperature of the system. Relatively higher temperature favors the sorption process. The activation energy was found to be ?20.369 kJ mol^?1. Finally, various thermodynamic parameters have also been calculated to elucidate the mechanism involved in the sorption process. The positive enthalpy change indicates the endothermic nature of the process. The presence of fluoride ions causes a decrease in the degree of sorption of Cr(VI). Finally, the sorption of Cr(VI) into the copolymeric sorbent has been explained on the basis of coordination between electron rich O and N atoms of sorbent molecules and the Cr(III) molecules. Moreover, H‐bonding interactions also seem to contribute to the sorption process.     

Flowsheet Modeling and Testing of Pseudohydroxide Extraction from Aqueous Sodium Hydroxide Solutions with 3,5‐di‐tert‐Butylphenol in Isopar® L Modified with Exxal® 8

Abstract

A conceptual counter‐current process flowsheet was developed for sodium hydroxide recovery from alkaline solutions via pseudohydroxide extraction (PHE). PHE relies on a simple sodium ion/proton exchange mechanism at elevated pH using a weak organic acid extractant. The contact of the sodium‐loaded organic phase with water results in the reconstitution of the extractant in the organic phase and sodium hydroxide in the aqueous phase. In this work, the 3,5‐di‐tert‐butylphenol (35‐DTBP) cation exchanger was used in the Isopar^® L diluent modified with isooctyl alcohol Exxal^® 8. Equilibrium isotherms determined for PHE from pure sodium hydroxide solutions and simulated radioactive waste leachate were used to develop a semi‐empirical model that could be used for designing PHE process flowsheets. Using this model, a conceptual PHE flowsheet was developed for recovering NaOH from solutions generated by caustic leaching of radioactive tank sludges. The flowsheet consists of the extraction, scrub, and strip processes, each employing four equilibrium stages. The modeling of this flowsheet indicates 97% recovery of the sodium hydroxide from the waste leachate feed solution. An experimental demonstration, performed with a simulated radioactive waste leachate using batch contacts in a co‐current analog of the counter‐current flowsheet, confirmed the potential for practical application of PHE technology.     

Effect of the Alkyl Chain Length in N,N‐Dialkylpyridine‐3‐carboxamides upon their Extraction of Copper(II) from Aqueous Chloride Solutions

Abstract

Three nicotinamide derivatives with two butyl, hexyl, or octyl alkyl chains at amide nitrogen were synthesized. These model individual compounds were used for copper(II) extraction from acidic chloride solutions at constant ionic strength I = 1.0. It was found that during the extraction N,N‐dialkylpyridine‐3‐carboxamides form two complexes with copper(II) and chloride ions; these can transfer into the organic phase. In these complexes the molar ratio of copper:chlorine:extractant = 1:2:2 or 1:2:3. The obtained stability constants of N,N‐dihexyl‐ and N,N‐dioctylpyridine‐3‐carboxamides complexes with copper(II) chloride in water are comparable, but N,N‐dibutylpyridine‐3‐carboxamide complexes stability constants are significantly lower. The partition constants of these complexes in toluene–water system depend on amide hydrophobicity, increasing with increasing carbon chain length in N,N‐dialkylpyridine‐3‐carboxamides.     

Removal of As(V) and Cr(VI) Ions from Aqueous Solution using a Continuous,Hybrid Field‐Gradient Magnetic Separation Device

Abstract

A continuous flow colloidal affinity magnetic separation device is used for the removal of As(V) and Cr(VI) from aqueous solutions. Langmuir isotherms fit the adsorption behavior of the individual ions on Orica MIEX^® ion exchange particles. In a mixture of equal weight percent As(V) and Cr(VI), the adsorption of As(V) begins only above a critical cut‐off concentration, implying preferential adsorption of the higher valence ion at the available sites. Cr(VI) is removed selectively from the mixture in the continuous flow device, consistent with the presence of a higher concentration of the higher valence ion in the proximity of a charged (anion‐exchange) surface.