Application of emulsion liquid membranes to recover cobalt ions from a dual-component sulphate solution containing nickel ions

Emulsion liquid membranes (ELMs) containing 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) have been applied to recover cobalt II ions from a dilute sulphate solution containing equal amounts of nickel II ions (0.16 g/l). We focused on the study to develop an effective technique to recover cobalt as a target metal. It is found that polyamine (PX 100) membranes allow better permeation rates of cobalt ions than sorbitan monooleate (Span 80) membranes. The separation factor (β_Co/Ni) in polyamine membranes averaged 70 at a carrier concentration of 12 mol/m³ and feed solution pH 5.5. The permeation rate of Co II was found to increase proportionately with feed pH while for Ni II it decreased substantially at pH above 5.5 indicative of slower interfacial reaction rate. We found that short contact time (4–6 min) of feed solution and emulsion improved separation factor (β_Co/Ni) at feed pH above 5.5 and also minimized chances of emulsion break up. We have also observed that Span 80 membranes are hydrolyzed readily in a moderate acidic sulphate solution (pH 4.0–5.5) to form viscous gels. Results have shown that excess carrier [(HR)₂] affects the stability of emulsion and thus the separation factor. The critical ratio of carrier to emulsifier [(HR)₂]/[C_sf] was found to be approximately 0.5. This paper concludes with a discussion on the prospects of ELM system in practical use.     

Separation and concentration of cobalt from ammoniacal solutions containing cobalt and nickel by emulsion liquid membranes using 5,7-dibromo-8-hydroxyquinoline (DBHQ)

The separation and concentration of cobalt from ammoniacal solutions containing nickel and cobalt by an emulsion liquid membranes (ELMs) using 5,7-dibromo-8-hydroxyquinoline as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (Span 80), a modifier (tributylphosphate), and an extractant (DBHQ). Very dilute sulphuric solution containing EDTA as complexing agent, buffered at pH 5.0, has been used as a stripping solution. pH of ammoniacal feed solution containing cobalt and nickel was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt have been studied. These variables are membrane composition, pH of the feed solution, cobalt and nickel concentrations of the feed solution, mixing speed, surfactant concentration, extractant concentration, EDTA concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively extract 99.0% of cobalt from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt with respect to nickel, based on initial feed concentration, have experimentally found to be of as high as 247.5 for about equimolar Co–Ni feed solutions.     

Gas-phase and liquid-phase pre-irradiation grafting of AAc onto LDPE and HDPE films for pervaporation membranes

A study has been made on gas-phase and liquid-phase pre-irradiation grafting of acrylic acid onto LDPE and HDPE films for pervaporation membranes of ethanol-water mixtures. It was found that the degree of grafting, percent volume change of grafted membranes and length of grafting chains depend on the methods of grafting, crystal state of substrate films and diffusion rate of the monomer in the films. The pervaporation characteristics of grafted membranes is influenced directly by the surface hydrophilicity of grafted membranes, temperature of the feed, degree of grafting, crosslinking of grafted chains and alkaline metal ions in the functional groups. The potassium ion exchange membrane of HDPE synthesized by gas-phase grafting has better pervaporation efficiency. At 80 wt% ethanol in the feed, 25°C feed temperature and 70% degree of grafting a grafted membrane has a 0.65 kg/m²h flux and a separation factor of 20.     

Radical and radiation-induced grafting of some synthetic high polymers within the temperature range of their glass transition

The temperature dependence of radiation-induced grafting onto poly(ethylene terephthalate), polyamides, polyacrylonitrile, and polypropylene has been investigated for several monomers. In all cases a maximum grafting yield is obtained when the reaction is performed in the temperature range of the glass transition T_g of the polymer used. This maximum yield does not only appear with radiation-induced simultaneous grafting. It also appears when the graft polymerization is induced by pre-irradiation or even by thermal decomposition of organic peroxides. It is assumed that the pronounced maximum of the reactivity at T_g is obtained because in the glassy state below T_g the radicals formed cannot react due to a reduced diffusion of the monomer, whereas above T_g the number of radicals available for polymerization will be reduced with increasing temperature.     

Grafted polymer membranes with extractive agents for the extraction process of VO2+ ions

To conduct experiments related to the facilitated extraction phenomenon and recovery of vanadium ions VO₂⁺, two grafted polymer membranes were prepared; containing respectively cholic acid and azithromycin as extractive agents and the obtained membranes were characterized. All experiments for the facilitated extraction phenomenon of these ions were carried out. Kinetic and thermodynamic models, based on the interaction of the substrate S (VO₂⁺) with the extractive agent T, and the diffusion of the formed entity (TS) through the membrane were developed, to determine the macroscopic parameters, permeability P and initial fluxes J₀, and the microscopic parameters, association constants K_ass and apparent diffusion coefficients D*, related to the formation of entities TS and their diffusion. A clear evolution of these parameters, depending on various factors (substrate concentration C₀, extractive agent concentration and feed and receiving phases temperature), and high permeabilities for this extraction phenomenon of VO₂⁺ ions were observed for this membrane type. Copyright © 2016 John Wiley & Sons, Ltd.     

Structural investigation of polystyrene grafted and sulfonated poly(tetrafluoroethylene) membranes

Structural investigation of polystyrene grafted and sulfonated poly(tetrafluoroethylene) (PTFE) membranes prepared by radiation-induced grafting of styrene onto commercial PTFE films and subsequent sulfonation was carried out by differential scanning calorimetry and X-ray diffraction. The effect of the structural changes taking place in the membranes during the preparation procedure (grafting and sulfonation) and the variation of the degree of grafting on melting temperature (T_m), glass transition temperature (T_g), heat of melting (ΔH_m), and degree of crystallinity was studied. The melting temperature (T_m) was found to be independent of the degree of grafting unlike glass transition temperature (T_g), which was found to be a function of the degree of grafting. Moreover, the degree of crystallinity of the membranes was found to decrease with the increase in the degree of grafting. The results of this work suggest that grafting takes place in the entire amorphous region without any significant disruption in the crystalline structure of PTFE film and the decrease in the degree of crystallinity is mainly attributed to the dilution effect.     

Radiation‐grafted solid polymer electrolyte membrane: studies of fluorinated ethylene propylene (FEP) copolymer‐g‐acrylic acid grafted membranes and their sulfonated derivatives

Acrylic acid was grafted onto FEP by simultaneous radiation technique and the resulting membranes were sulfonated. Results of dynamic mechanical properties of the membranes showed that storage modulus and temperature at tan δ_(max) increases on grafting. X‐ray diffraction (XRD) analysis of the grafted and sulfonated membranes showed decreasing trend in crystallinity with increase in degree of grafting. From scanning electron microscopy (SEM) studies it was confirmed that grafting takes place by the front mechanism. Copyright © 2004 John Wiley & Sons, Ltd.     

Extraction of cobalt (II) and nickel (II) by a solvent impregnated resin containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid

In the present work, studies have been conducted on the equilibrium distribution of cobalt (II) and nickel (II) between aqueous hydrochloric solution and macromolecular resin impregnated with bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex302, HL). Effects of extraction time, pH values, metal ion concentration, and temperature were investigated. Analysis of the results shows that the extraction of the two metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML ₂. An extraction reaction is proposed and the equilibrium constants of the complexes were determined. The Freundlich isotherm and thermodynamic quantities, i.e., ΔG, ΔH and ΔS were also obtained. Both of the extraction reactions of cobalt (II) and nickel (II) are endothermic ones. The efficiency of the resin in the separation of cobalt (II) and nickel (II) is provided according to the separation factors. Under the experimental conditions employed, pH₅₀ values for cobalt (II) and nickel (II) are 3.76, 5.01, respectively. The logarithmic value of separation factor was calculated as 2.50.     

Chemical modification of zeolite beta surface and its effect on gas permeation of mixed matrix membrane

Chemical modification of zeolite beta (BEA) with a series of organosilane compounds [R(CH₃)_nSiX_(3‐n), where X is a chloro or alkoxy group with n = 0 and 2, and R is an alkyl chain varying from CH₃ to C₁₈H₃₇] was investigated. The results of FT‐IR and ²⁹Si CP/MAS NMR indicated that the alkylsilyl species were covalently anchored onto the BEA surface. Grafting density of the alkylsilyl species was determined by CHN elemental analysis and thermogravimetric analysis (TGA). Evidently, it can be adjusted by varying the reaction time and organosilane concentration. The reaction kinetics was found to resemble the kinetics of the well‐known monolayer formation, i.e. SAMs. The kinetic plot illustrated two distinct regions, a rapid attachment followed by a gradual increase of grafting density. The degradation temperature at maximum rate (T_max) of the surface‐grafted BEA was observed in the range of 440–460°C. The modified BEA showed surface hydrophobic characteristic by having a strong affinity to the non‐polar n‐heptane. Good particle distribution and strong interfacial adhesion were observed in the mixed matrix membranes of the BEA grafted with C₃H₇ to C₁₈H₃₇. The grafted chain length was found to have an effect on gas permeability. Carbon dioxide, oxygen, and ethylene permeabilities of the membranes containing the unmodified BEA were comparable to those of the CH₃Si‐grafted BEA. Interestingly, the membranes containing the BEA grafted with C₃H₇ to C₁₈H₃₇ species showed enhancement of the carbon dioxide permeability. Affinity of the long alkyl chain to carbon dioxide probably caused the increase of carbon dioxide permeability. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,Characterization and Thermal Decomposition of p-iodo-phenylalanine Complexes of Cobalt or Nickel

New complexes of the non-natural amino acid (p-iodo-phenylalanine) with divalent cobalt and nickel ions have been synthesized. The composition of the complexes is [M(IC₆H₄CH₂CHNH₂COO)₂]×2.5H₂O (M=Co, Ni) and the crystal structure belongs to orthorhombic system. Infrared spectra indicate the nature of bonding in the complex. The first stage in the thermal decomposition process of the complex shows the presence of crystal water. The thermal decomposition process of cobalt complex differs from that of nickel. The intermediate and final residues in the thermal decomposition process have been analyzed to check the pyrolysis reactions. Thermal analysis indicates that the iodine atom of the ligand may coordinate to the metal ion in the lattice. This revised version was published online in August 2006 with corrections to the Cover Date.     

Graft Copolymerization on to Cellulose Using Binary Mixture of Monomers

The graft copolymerization of acrylonitrile (AN) and ethyl acrylate (EA) comonomers onto cellulose has been carried out using ceric ammonium nitrate (CAN) as an initiator in the presence of nitric acid at 35±0.1°C. The addition of ethyl acrylate as comonomer has shown a significant effect on overall and individual graft copolymerization of acrylonitrile on cellulose. The graft yield (%G_Y) and other grafting parameters viz. true grafting (%G_T), graft conversion (%C_G), cellulose number (Ng) and frequency of grafting (G_F) were evaluated on varying the concentration of comonomers from 6.0–30.0×10^?1 mol dm^?3 and ceric (IV) ions concentration from 2.5–25×10^?3 mol dm^?3 at constant feed composition (f_AN 0.6) and constant concentration of nitric acid (7.5×10^?2 mol dm^?3) in the reaction mixture. The graft yield (%G_Y) and other grafting parameters were optimal at 15×10^?1 mol dm^?3 concentration of comonomers and at 10×10^?3 mol dm^?3 concentration of ceric ammonium nitrate. The graft yield (%G_Y) and composition of grafted chains (F_AN) was optimal at a feed composition (f_AN) of 0.6. The energy of activation (Ea) for graft copolymerization has been found to be 16 kJ mol^?1. The molecular weight (Mw) and molecular weight distribution (Mw/Mn) of grafted chains was determined by GPC and found to be optimum at 15×10^?1 mol dm^?3 concentration of comonomer in the reaction mixture. The composition of grafted chains (F_AN) determined by IR method was used to calculate the reactivity ratios of monomers, which has been found to be 0.62 (r₁) and 1.52 (r₂), respectively for acrylonitrile (AN) and ethyl acrylate (EA) monomers used for graft copolymerization. The energy of activation for decomposition of cellulose and grafted cellulose was determining by using different models based on constant and different rate (β) of heating. Considering experimental observations, the reaction steps for graft copolymerization were proposed.     

Liquid–liquid extraction of Cu(II), Co(II) and Ni(II) with salicylidèneaniline from sulphate media

For a fundamental study on the development of novel extraction divalent metal, the extraction behaviour of copper(II), cobalt(II) and nickel(II) is studied with salicylidèneaniline (SAN). The phenol group in the Schiff base moiety leads to a large increase in the percentage of transition metal ions. SAN has both good reactivity towards metal ions and solubility in organic solvents. The solvent extraction of copper(II), cobalt(II) and nickel(II) with salicylidèneaniline from sulphate media is studied with the following parameters: pH, concentration of the extractant and the nature of diluent. The stoichiometry coefficients of the extracted species are determined by the slope analysis method. The extraction reaction proceeds by cation exchange mechanism and the extracted species are: CuL₂HL, CoL₂HL and NiL₂. The extaction constants are evaluated for the different diluents. Under suitable conditions of pH, the solvent extraction of cobalt(II) and nickel(II) in different diluents leads to third phase formation. This tendency is confirmed from numerical extraction constants for both metal cations (log?K _ex?=??15.10?±?0.03 for nickel(II) in CHCl₃) and (log?K _ex?=??12.56?±?0.04 for cobalt(II) in CHCl₃). The extraction efficiency is found to follow the order Cu(II)?>?Co(II)?>?Ni(II).     

Effect of conjugated linoleic acid grafting on the hemocompatibility of polyacrylonitrile membrane

Polyacrylonitrile (PAN) membrane was hydrolyzed with NaOH_(aq) and grafted with conjugated linoleic acid (CLA) via esterification with 1,3‐propanediol. The resulting CLA grafted PAN membranes were characterized using Fourier transform infrared spectrometry (FT‐IR) and X‐ray photoelectronic spectroscopy (XPS). The effects of CLA grafting on the blood coagulation, platelet aggregation, and oxidative stress were evaluated using human blood. The complete blood count (CBC) and coagulation time (CT) was evaluated in vitro for hemocompatibility. After CLA grafting, the proliferation of human umbilical vein endothelial cells (HUVECs) on the membranes were improved. In addition, the production of reactive oxygen species (ROS) was measured by the chemiluminescence (CL) method to evaluate the oxidative stress. The results showed that the CLA‐grafted PAN membrane could keep the CBC values more stable than unmodified PAN membrane. The CLA‐grafted PAN membranes also showed longer CT. CLA‐grafted PAN membrane could keep the CL counts of hydrogen peroxide and superoxide values more stable than unmodified PAN membrane. These results suggest that a CLA‐grafted PAN membrane could offer protection for patients against oxidative stress and would be helpful for reducing the dosage of anticoagulant during hemodialysis. Copyright © 2006 John Wiley & Sons, Ltd.     

Recovery of some metal ions using gamma-radiation induced grafted waste rubber powder

Waste rubber powder was grafted with different vinyl monomers by using gamma-radiation. The monomers used for grafting were acrylic acid, acrylamide and acrylonitrile. The sodium salt of grafted polyacrylic acid as well as the amidoxime derivative of grafted polycacrylonitrile were also obtained. Evaluation of the efficiency of the products obtained to the recovery of some metal ions such as cobalt and nickel as well as to phenol was carried out. It was found that the grafted waste rubber powder is able to recover cobalt and nickel ions from their corresponding salts depending on the type of monomers used. It was also found that phenol can be reasonably recovered by using rubber powder grafted with acrylamide and amidoxime derivative.     

Relations entre la structure et les proprietes des membranes de polytetrafluoroethylene greffe—III. Membranes non-ionisables contenant de la poly-n-vinylpyrrolidone

Equilibrium properties (swelling) and transport phenomena (dialysis) of non-ionizable membranes, obtained by radiation grafting of N-vinylpyrrolidone onto thin PTFE films, were studied. Grafting was conducted by the direct method with monomer solutions in benzene. The overall activation energy of grafting determined between 20 and 50° is high (12.5 kcal mol^?1): the reaction is controlled by the monomer diffusion into PTFE film. The length of grafted chains increases with temperature.The molality of the membranes decreases when the temperature of grafting increases; for a given grafting ratio, the swelling is higher for membranes containing a small number of long grafts than for membranes with numerous short branches. The transfer of both ions and water is a function of the free volume in the films, it depends on the grafting ratio and is not influenced by the preparation conditions.     

Preparation of cation-exchange membrane containing bi-functional groups by radiation induced grafting of acrylic acid and sodium styrene sulfonate onto HDPE: Influence of the synthesis conditions

Electron beam radiation induced grafting of acrylic acid (AA) and sodium styrene sulfonate (SSS) onto high-density polyethylene (HDPE) membranes was investigated by the pre-irradiation method, and a cation-exchange membrane containing bifunctional groups was synthesized. The effects of grafting conditions such as monomer concentration, radiation dose and temperature on grafting yield were studied. The dependence of grafting yield on pre-irradiation dose and monomer concentration was found to be 0.54 and 2.21, respectively. The activation energy for the grafting was calculated to be 22.2 kJ/mol. Infrared spectroscopy analysis of the grafted membrane confirmed the existence of sulfonate and carboxylic acid groups.     

Electrodialytic separation of cobalt(II) and nickel(II) using liquid membranes based on tri-n-octylamine and trialkylbenzylammonium chloride

Electrodialytic separation of Co(II) and Ni(II) in the course of their transfer from 3–4 M HCl solutions into dilute solutions of various acids using liquid membranes that contain anion-exchange carriers was studied. The influence exerted on the metal transport rate and separation efficiency by the compositions of the feed and receiving aqueous solutions and of liquid membranes and by the electrodialysis current density was examined. Under optimal conditions, in metal recovery from a solution containing an equimolar mixture of 0.01 M CoCl₂ and NiCl₂, the separation factor β_Co/Ni is 147; when nickel in the feed solution is in excess, it reaches 330, and when cobalt(II) is in excess, it exceeds 400.     

Graft copolymerization of methyl methacrylate onto curdlan

Graft copolymerization of methyl methacrylate onto curdlan was first investigated. In the graft copolymerization initiated by ammonium persulfate (APS) in DMSO under a homogeneous condition, the resulting graft copolymers had low molecular weights and low grafting percentages. However, the initiation by APS in water gave graft copolymers having relatively higher molecular weight ( ) and higher grafting percentage (548%) than those copolymers obtained by the homogeneous condition. When the graft copolymerization was carried out by cerium (IV) ammonium nitrate-HNO₃ initiation, the graft copolymer had the highest grafting percentage of 1620% without degradation of the curdlan backbone. The resulting graft copolymers were soluble in DMSO. The graft copolymers obtained by the cerium salt had narrow molecular weight distributions () compared with those by the APS catalyst in DMSO or water. The graft copolymers decomposed with sulfuric acid to isolate PMMAs, which molecular weights were larger than that of the corresponding homo-PMMAs. The structure of the grafted copolymers was characterized by IR, ¹³C NMR, DSC, and SEM. It was found that the graft copolymers exhibited the glass transition temperature (T_g), though curdlan had no T_g. As the grafting percentage increased, the T_g increased to reach 270°C, which was higher than the decomposition temperature of curdlan. The surface image of the grafted copolymers observed by SEM, showed smoothless compared with that of curdlan. It was also revealed that the graft copolymers having the grafting percentage of 1620% swelled in common organic solvents up to 4.5 times of the weight of the dry graft copolymer to form gels. © 1996 John Wiley & Sons, Inc.     

Spectral and thermal studies on new hydrazinium metal sulfite dihydrates

Some new hydrazinium transition metal sulfite dihydrate complexes of the formula (N₂H₅)₂M(SO₃)₂(H₂O)₂ where M=Fe, Co, Ni, Cu and Zn have been prepared and characterized by hydrazine and metal analyses, magnetic studies, electronic and infrared spectra and thermal analysis. The magnetic studies coupled with electronic spectra of iron, cobalt, nickel and copper complexes indicate their high spin octahedral nature. However the zinc complex is diamagnetic and show only the charge transfer transition. The infrared spectra shows that both the hydrazinium ions are coordinated to the metal ions, the sulfite ions are present as bidentate ligand. The simultaneous TG-DTA of these complexes were investigated in air and nitrogen atmospheres. In air, cobalt, nickel and zinc complexes give respective metal sulfate as the final residue while iron and copper complexes give the mixture of respective metal oxide and sulfate as the decomposition product. In nitrogen atmosphere respective metal sulfites are formed as the end residue.     

Simultaneous Determination of Tin,Nickel, Lead,Cadmium and Mercury in Tobacco and Tobacco Additives by Microwave Digestion and RP‐HPLC Followed by On‐Line Column Enrichment

A new method for the simultaneous determination of five heavy metal ions, tin, nickel, lead, cadmium and mercury ions as metal‐tetra‐(2‐aminophenyl)‐porphyrin (T₂APP) chelates was developed using reversed‐phase high performance liquid chromatography (RP‐HPLC) equipped with a photodiode array detector and combined with an on‐line enrichment technique. The tin, nickel, lead, cadmium and mercury ions were pre‐column derivatized with T₂APP to form color chelates. The Sn‐T₂APP, Ni‐T₂APP, Hg‐T₂APP, Cd‐T₂‐APP and Pb‐T₂APP chelates can be absorbed onto the front of the enrichment column when they are injected into the injector and sent to the enrichment column [Waters Xterra? RP₁₈(5μ, 3.9 × 20 mm)] with a buffer solution of 0.05 mol/L pyrrolidine‐acetic acid (pH = 10.0) as mobile phase. After the enrichment had finished, by switching the six‐port switching valves, the retained chelates were back‐flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column [Waters Xterra? RP₁₈ (5μ, 3.9 × 150 mm)] was satisfactory by gradient elution with methanol (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) and acetone (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) as mobile phase. The linearity range is 0.01?120 μg/L for each metal ion. The detection limits (S/N = 3) of tin, nickel, lead, cadmium and mercury are 4.0 ng/L, 3.5 ng/L, 2.5 ng/L, 3.0 ng/L and 3.0 ng/L, respectively. This method was applied to the determination of tin, nickel, lead, cadmium and mercury ions in tobacco and tobacco additives with good results.