Permeation and Separation Characteristics of Acetic Acid‐Water Mixtures by Pervaporation through Acrylonitrile and Hydroxy Ethyl Methacrylate Grafted Poly(vinyl alcohol) Membrane

Abstract

In this study, acrylonitrile (AN) and hydroxyl ethyl methacrylate (HEMA) were grafted onto poly(vinyl alcohol) (PVA) using cerium (IV) ammonium nitrate as initiator at 30°C. The graft copolymer was characterized using the Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The grafted PVA membranes (PVA‐g‐AN/HEMA) were prepared by a casting method, and used in the separation of acetic acid‐water mixtures by pervaporation. The effects of the membrane thickness, operating temperature, and feed composition on the permeation rate and separation factor for acetic acid‐water mixtures were studied. Depending on the membrane thickness, the temperature and feed composition PVA‐g‐AN/HEMA membranes gave separation factors 2.26–14.60 and permeation rates of 0.18–2.07 kg/m²h. It was also determined that grafted membranes gave lower permeation rates and greater separation factors than PVA membranes. Diffusion coefficients of acetic acid‐water mixtures were calculated from permeation rate values. The Arrhenius activation parameters were calculated for the 20 wt.% acetic acid content in the feed using the permeation rate and the diffusion data obtained at between 25–50°C.     

Ultrafiltration of Aqueous Solutions of PVA‐Cu(II) Macromolecular Complex

Abstract

The hydrodynamic behavior of aqueous solutions of poly(vinyl alcohol) and poly(vinyl alcohol)–cupric complex and its effect on the performance in the concentration of the macromolecular cupric complex by ultrafiltration is considered in this study which implements various synthetic membranes in polyethersulfone. The polyelectrolyte–like behavior of poly(vinyl alcohol) is highlighted. This behavior disappears in the case of the macromolecular complex. The disappearance of the polyelectrolyte–like effect is explained by the modification of the macromolecular conformation induced by the formation of the complex which takes up a tightly packed conformation. The study of the effect of the variation of the pH and the ionic strength made it possible to observe that the increase of the pH is accompanied by the reduction of the medium viscosity and the increase of the flux through the ultrafilters and the increase of the ionic strength of the medium is accompanied by the increase of the thickness of the adsorbed solute layer. The study of the effect of the nature of the ionic species in solution on the hydrodynamic behavior of the aqueous solutions of the macrocomplex leads to the conclusion that the use of the cupric chloride salt, instead of the nitrate or the sulphate salts, in the preparation of the macrocomplex improves the hydrodynamic properties of the solution and enhances the performance of its treatment by means of the ultrafiltration process.     

Recovery of Plutonium(IV) from Aqueous Solutions Using Emulsion Liquid Membrane Containing 2‐Ethylhexyl Phosphonic Acid Mono‐2‐Ethylhexyl Ester as Ion Transporter

Abstract

An emulsion liquid membranes (ELMs) containing 2‐ethylhexyl phosphonic acid mono‐2‐ethylhexyl ester (H₂A₂) was tested for the extraction of plutonium(IV) from aqueous nitrate solutions of different compositions. Span 80 was used as the surface‐active agent and a mixture of 0.05 mol dm^?3 HNO₃+0.3 mol dm^?3 H₂C₂O₄ was used as the internal phase. Influence of some important experimental parameters such as exterior phase nitric acid concentration, ionic impurities in the exterior phase, concentration of H₂A₂ in ELM phase, and organic solvents on the ELM permeation process were systematically studied. The maximum efficiency of Pu extraction among group of experiments was 98% with permeability coefficient=0.508 min^?1, and the corresponding concentration factor of Pu in the receiving phase was ca. 10. The stability of the emulsions was tested in the presence of different organic solvents and at different concentrations of Span 80 in LM phase. The extractions of Pu by ELM from actual and simulated waste solutions as well as in presence of some added ionic impurities were investigated. Rate of Pu extraction by ELM was studied at different treatment ratios and under repeat extractions by the same emulsion. The repeat extraction experiments showed that a concentration factor of more than 80 for Pu could be achieved.     

Synthesis and Characterization of Poly(Ethyleneimine)-Modified Poly(Acrylic Acid)-Grafted Nanocellulose/Nanobentonite Superabsorbent Hydrogel for the Selective Recovery of β-Casein From Aqueous Solutions

A novel adsorbent, poly(ethyleneimine)-modified poly(acrylic acid)-grafted nanocellulose/nanobentonite superabsorbent hydrogel (PEI-PAA-g-NC/NB) was prepared by free radical graft copolymerization technique and well characterized. Swelling behavior of adsorbent was studied under different pH and temperatures. The various adsorption parameters for the adsorption of the protein, β-Casein (βCN) onto the PEI-PAA-g-NC/NB were investigated. Sips adsorption isotherm and pseudo-first-order kinetic model were best suited for the present adsorbent. The adsorption-desorption experiments were conducted with 0.1 M NaSCN for four cycles. The results of the present investigation proved that PEI-PAA-g-NC/NB is highly effective for the separation of βCN from aqueous solutions.     

Pervaporation of Methanol/Methyl‐t‐Butyl Ether Mixtures Through Poly(Vinyl Alcohol)/Poly(Acrylic Acid) Blend Membranes

Abstract

Membranes obtained by blending poly(vinyl alcohol) (PVOH) and poly(acrylic acid) (PAA) have been investigated for the separation of methanol and methyl‐t‐butyl ether (MTBE) liquid mixtures through a pervaporation process. Experiments were performed by contacting one side of a polymer dense film with the liquid mixture and removing the vapor on the other side with an inert gas flux, a setup for a process with sweeping gas. The blend membranes, with a COOH/OH ratio in the 0.5–2.5 range, are permeated by methanol preferentially. Higher values of flux and lower values of selectivity are observed when the methanol content in the feed increases. The ratio PAA/PVOH of the membrane influences both flux and selectivity in the same way. A maximum of both flux and selectivity is observed at a COOH/OH ratio of about 2. The swelling of membranes of different composition in the presence of different liquid composition explains the flux behavior in the pervaporation experiments. The observed membrane swelling has been explained on the basis of the solubility parameters of the components of the system.     

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.     

Ion Exchange of the Organometallic Aqua‐Ion fac‐[99mTc(CO)3(H2O)3]+ from Aqueous Solutions

Dynamic (column) studies on the ion exchange of triaquatricarbonyltechnetium(I) cation, fac‐[^99mTc(CO)₃(H₂O)₃]⁺ (1), in the system: amphoteric ion exchange resin (Purolite S‐950) ‐ aqueous HNO₃ solutions (0.05–2 M) corroborate the +1 charge of 1. Stability constants of fac‐[^99mTc(CO)₃(H₂O)_3?nCl_n]^1?n complexes, determined from the distribution coefficients in the system anion exchanger (Dowex 1X4) ‐ aqueous HCl solutions (0.1–12 M) differ from the literature values determined at a constant ionic strength. This difference, resulting from the decrease in the activity of water with increasing HCl concentration, may be a measure of the effect of non‐constant ionic strength on ion‐exchange equilibria. Weak acidic properties of 1 in aqueous solution at n.c.a. (no carrier added) level (pK_a ?9) have been demonstrated by paper electrophoresis.     

Functionalized Multi-Walled Carbon Nanotubes with Vitamin C Structures: Characterization and Fabrication of Thiazole Containing Poly(amide–imide)-based Composites

The functionalization of multi-walled carbon nanotubes by ascorbic acid (vitamin C) was carried out. Then, functionalized multi-walled carbon nanotubes were dispersed throughout a poly(amide–imide) matrix by ex situ technique with 5, 10, and 15% loading by weight. The composite hybrid films were prepared by a solvent casting method. It was found that the functionalization of multi-walled carbon nanotubes could improve their dispersion and interfacial adhesion to the poly(amide–imide) matrix as proved by field emission scanning and transmission electron microscopy techniques. The modulus, tensile strength, and the thermal stability of the composites were improved in spite of excellent multi-walled carbon nanotube dispersion in the matrix.     

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.     

Studies on Permeation of Nd (III) through Supported Liquid Membrane Using DNPPA + TOPO as Carrier

The transport behavior of Nd (III) through a supported liquid membrane (SLM) containing PTFE as support with organophosphorus extractant dinonyl phenyl phosphoric acid (DNPPA) carrier has been studied. The effect of neutral donors such as TOPO (tri-n-octyl phosphine oxide) TBP (tri-n-butyl phosphate), TEHP (tris 2-ethylhexyl phosphate) and Cyanex 923 (a mixture of four trialkyl phosphine oxides) in combination with DNPPA on transport of Nd (III) from HCl across SLM has been examined and the following trend was observed: TOPO > Cyanex 923 > TBP > TEHP. The effect of experimental variables such as feed acidity (0.5 to 5 M HCl), neodymium metal ion concentration (6.94 × 10^?4 to 6.94 × 10^?3 M), DNPPA concentration (0.2 to 0.6 M), stripping reagents in the receiving phase on Nd (III) transport across SLM were investigated. The percentage transport of Nd (III) was 97% after 6 hr run with 0.6 MDNPPA + 0.13 MTOPO as carrier. The permeability of Nd (III) decreased with increase in HCl and Nd (III) concentration in the feed solution. The transport of Nd (III) decreased with increase in membrane thickness as well as with decrease in pore size. Under optimized conditions transport behavior of other rare earths was also investigated independently, the trend observed was: La > Pr ≥ Nd > Sm > Eu > Gd > Tb > Dy > Ho > Er > Tm > Lu ≥ Y.     

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).     

Morphology and Properties of Poly(γ-benzyl L-glutamate)-block-poly(ethylene glycol)/Poly(L-lactic acid) Blend Membrane

A series of poly(γ-benzyl L-glutamate)-block-poly(ethylene glycol) (PBLG-block-PEG)/poly(L-lactic acid) (PLLA) blend membranes were prepared by casting the polymer blend solution in chloroform. Surface morphologies of the PBLG-block-PEG/PLLA blend membranes were investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Thermal, mechanical, and chemical properties of PBLG-block-PEG/PLLA blend membranes were studied by thermogravimetric analysis (TGA), tensile tests, and contact angle testing. It was found that the introduction of PLLA could exert outstanding effects on the morphology and the properties of polypeptide copolymer membrane.     

Aggregation and Adsorption at the Air–Solution Interface of the Cetyltrimethyl Ammonium Tosylate With Two Poly(oxyethylene)–Poly(oxypropylene)–Poly(oxyethylene) Block Copolymers Aqueous Mixtures

The aqueous mixed systems (EO₇₆PO₃₀EO₇₆) (TBCP8400)—cetyltrimethyl ammonium tosylate (CTAT), and (EO₉₇PO₆₉EO₉₇) (TBCP12600)—CTAT were studied to determine both the bulk aggregation and the adsorbed monolayer at the air/water interface. Results were interpreted with the pseudophase separation model plus the regular solution theory for aggregates and monolayers. The behavior is different for TBCP8400–CTAT and TBCP12600–CTAT mixtures, but it is strongly non-ideal in both cases. In bulk, TBCP8400–CTAT mixtures produce aggregates more close to CTAT micelles having TBCP8400 as a solubilizate than the inverse. At low CTAT content, the interaction is repulsive becoming attractive at high TBCP8400 content. The TBCP12600–CTAT aggregates strongly differ from the structure of both pure component micelles, and the interaction is always repulsive. In both cases, the interaction seems not to be cooperative but gradual. CTAT effect on copolymers aggregates seems to be more similar to that of a zwitterionic surfactant than to that of an ionic one. However, CTAT is not included in the aggregates as an ion pair, as revealed by the ionization degree results. It seems that cetyltrimethyl ammonium and tosylate ions have different effects on aggregates which in part are opposite. The adsorbed monolayers also show different behavior. In TBCP8400–CTAT system, the monolayer is mainly a CTAT one with inclusion of TBCP8400 as a monolayer-soluble impurity. However, the inclusion of the non-ionic surfactant alters the structure of the monolayer, which differs from that of the pure CTAT one. The area per adsorbed molecule (A₀) is systematically higher than the ideal and computed ones. The system TBCP12600–CTAT shows a monolayer composition which is almost the same that the overall surfactant mixture composition, and the monolayer structure differs from both the pure-TBCP12600 and the pure-CTAT monolayers ones. The experimental A₀ values are systematically lower than the ideal and the computed ones. Then, in both cases the A₀ values for the pure components do not remain invariable in the mixed monolayer. The phenomenon is interpreted on the basis of the conformation of the copolymers adsorbed at the air/solution interface.     

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.     

Surface Morphology and Properties of Rigid Poly(γ-benzyl L-glutamate) Membrane Modified by Flexible Poly(Vinyl Chloride)

Rigid poly(γ-benzyl L-glutamate)/flexible poly(vinyl chloride) (PBLG/PVC) blend membranes were prepared by casting the polymer blend solution in dichloroethane. Structure and morphologies of the PBLG/PVC blend membranes were investigated by Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Thermal, mechanical, and chemical properties of PBLG/PVC blend membranes were studied by differential scanning calorimetry (DSC), tensile tests, and other physical methods. It was found that the introduction of PVC could exert marked effects on the morphology and the properties of PBLG membrane.     

Preparation,structure, and pervaporation performance of poly(amide–imide)-sulfonated polyimide composites

Poly{[4,4′-bisdiphenyl-2,2′-disulfonic acid]imide-1,3-bis(3,4-dicarboxyphenoxy)benzene} was synthesized via polycondensation and subsequent thermal imidization in m-cresol:triethylamine. The obtained polymer and its composites with aromatic poly(amide–imide) obtained through polycondensation of 4-chloroformyl-(N-p-chloroformylphenyl)phthalimide and 4,4′-diaminodiphenyl ether were investigated by use of nuclear magnetic resonance, thermogravimetric analysis, dynamic mechanical analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis. Transport properties of composite films were studied during pervaporation of water–alcohol mixtures. On the basis of the data obtained, suggestions on the structure of materials and its influence on transport and other physical properties were made. The addition of 30 wt % of sulfonated polyimide to the poly(amide–imide) matrix enhances its separation factor in the process of separation of an azeotrope water/ethanol mixture by four times while permeability remains unchanged. The methanol permeability increases with an increase of the mass fraction of sulfonated polyimide in the composite film. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48197.     

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.     

Recovery of 1,4‐Dimethyl Piperazine from Aqueous Solutions Using Polymeric Adsorbent and Ion‐Exchange Resins

Abstract

Strong and weakly acidic ion exchange resins and polymeric adsorbents are used for recovery of 1,4‐dimethyl piperazine (DMP) from aqueous solutions. Sorption of the amine in undissociated form is the primary mechanism of uptake of DMP on the ion‐exchange resins. Equilibrium adsorption data for DMP on the resins, at various temperatures, are fitted in Langmuir adsorption isotherm. Kinetic studies show that intraparticle diffusional resistance controls the sorption of DMP into the resin matrix. A mathematical model based on intraparticle diffusion and external mass transfer is used for simulating breakthrough profiles and compared with the experimental results for a fixed bed of weakly acidic Indion‐652 resin. The DMP loaded bed of the resin was effectively regenerated with methanol.     

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.     

Separation of Acetic Acid/Water Mixtures by Pervaporation through Poly(Vinyl Alcohol)–Sodium Alginate Blend Membranes

Abstract

Dense pervaporation (PV) membranes were prepared by blending hydrophilic polymers, poly(vinyl alcohol) (PVA), and sodium alginate (SA), which were then crosslinked with glutaraldehyde (GA) for the separation of acetic acid/water mixtures. These membranes (PVA‐SA) were characterized for morphology, intermolecular interactions, thermal stability, and physico‐mechanical properties using XRD, FTIR, TGA and tensile testing respectively. The effect of experimental parameters such as feed composition and permeate pressure on separation performance of the crosslinked membranes was determined. Sorption studies and porosity measurement were carried out to evaluate the extent of interaction and degree of swelling of the polyion membranes, in acetic acid and water as well as in mixtures of acetic acid and water. Further the results were compared with the commercial membrane (Sulzer pervap 2205). The membrane appears to have a good potential for dehydrating 90 wt% acetic acid with a reasonably high selectivity of 21.5 and a substantial water flux of 0.24 kg/m²/h/10 µm. Separation factor was found to improve with decreasing feed water concentration whereas the corresponding flux decreased. Higher permeate pressures caused a reduction in both flux and selectivity.