New polymeric structures designed for the removal of Cu(II) ions from aqueous solutions

New polymeric structures obtained by chemical transformations of maleic anhydride/dicyclopentadiene copolymer with triethylenetetraamine, p‐aminobenzoic acid, and p‐aminophenylacetic acid were used for the removal Cu(II) ions from aqueous solutions. The experimental values prove the importance of the chelator nature and of the macromolecular chain geometry for the retention efficiency. The retention efficiency (η_r), the retention capacity (Q _e ), and the distribution coefficient of the metal ion into the polymer matrix (K _d ) are realized by evaluation of residual Cu(II) ions in the effluent waters, by atomic adsorption. Also are discussed the influence of pH, the thermal stability of the polymer, and their polymer–metal complex, as well as the particular aspects regarding the contact procedure and the batch time. Based on the polymers and polymer–metal complexes characterization a potential retention mechanism is proposed. All polymer supports as well theirs metal–complexes are characterized by ATD and FTIR measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1397–1405, 2007     

Recovery of Lithium from Seawater Using a New Type of Ion-Sieve Adsorbent Based on MgMn2O4

Abstract

A new type of ion-sieve manganese oxide, HMnO(Mg), was prepared by an acid treatment of MgMn₂O₄. The HMnO(Mg) showed a remarkably high selectivity for lithium ions among alkali metal and alkaline earth metal ions. The selectivity sequences were Na ? K ? Li for alkali metal ions and Mg ≤ Ca ≤ Sr ≤ Ba for alkaline earth metal ions at pH 8. The HMnO(Mg) showed a high selectivity for lithium ions in seawater. The lithium uptake increased with increasing solution pH and adsorption temperature. The maximum lithium uptake from native seawater reached 8.5 mg/g, corresponding to a lithium content of 1.8% in the form of Li₂O. The adsorbed lithium could easily be eluted with a dilute acid solution. The adsorptive capacity for lithium ions gradually decreased through repeated adsorption/elution cycles. The HMnO(Mg) after 4 cycles showed a lithium adsorptivity which was about 60% of the initial value.     

Preparation of Hollow Fiber Membranes by Nonsolvent Induced Phase Separation along with Hydrogen Gas Formation Using a Single Orifice Spinneret

Traditional nonsolvent induced phase separation (NIPS) process for fabrication of hollow fiber membranes (HFMs) faces challenges, like design and manufacture of spinneret with two concentric orifices to provide parallel and continuous feed of polymer solution and bore fluid at specific rates. These factors limit the use of traditional technique to produce HFMs. Here, a new direct spinning method for fabricating HFMs by feeding a polymer solution, containing a gas producing agent using single orifice spinneret is reported. Polysulfone‐dimethylacetamide solution containing NaBH₄ is extruded through a stainless‐steel needle (single orifice spinneret) into HCl aqueous solution (coagulation bath) at specific rates. Effects of polysulfone concentration, temperature, and pH of coagulant bath on structure and performance of the HFMs are investigated. Synergy between hydrogen from NaBH₄ hydrolysis and NIPS process benefits fabrication of HFMs with good hollow bore structure and high porous wall. The prepared HFMs show good dye separation.     

Synthesis of a polyacrylamidoxime chelating fiber and its efficiency in the retention of palladium ions

A chelating fibrous polymer with metal complexing ability was prepared by partial conversion of the nitrile groups of melana (an acrylonitrile‐based synthetic fiber) into amidoxime groups ? C(NH₂) = NOH using a solution of 3% hydroxylamine in methanol by refluxing at 80°C. The molar ratio of NH₂OH/CN and the reaction time were adjusted to values of 0.9 and 2 h, respectively. The amidoximated polyacrylonitrile fiber with a 2.89 meq/g ion‐exchange capacity functions as an efficient chelating adsorbent for palladium ions. The pH dependence, the contact time, and the temperature of palladium ion retention from a model solution on amidoximated acrylic fiber were studied. The fibrous chelating adsorbent exhibited high affinity for palladium ions in acidic solution (pH = 2–6) at high temperature (50–60°C). The values of parameters q_m and K_L (from the Langmuir equation) determined at different temperatures of adsorption and the thermodynamic quantities ΔG, ΔH, and ΔS were calculated. The adsorbed palladium ions can be quantitatively desorbed by elution with a 0.3% hydrochloric solution of thiourea. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3730–3735, 2004     

Thin-Film-Composite Gas Separation Membranes: On the Dynamics of Thin Film Formation Mechanism On Porous Substrates

Abstract

A wide range of gas separations of interest in energy applications are carried out using membranes. Growing attention has been paid to the technology of making thin-film-composites(TFCs) membranes. Understanding the polymer solution and substrate property is key to successfully preparing TFCs membranes. This paper reports on some fundamental issues of coating hollow fibers with polymer from solution by dip coating. Polymeric porous hollow fibers with varying porosities and permeances were coated with polymer solutions of different viscosities in a continuous process. In addition, the fibers were coated dry and by presoaking in the coating solvent. It was found that the thickness of the coating on the low permeance/porosity/wet and dry fibers could be approximated by the Deryaguin model (h/R = 1.33 (Ca) ^0.67). For dry fibers, as the fiber porosity increased, the measured coating thickness was significantly underestimated by the Deryaguin equation. It is believed that the pores in the fiber allow rapid capillary suction of the solvent into the fiber walls and the bore, thus increasing the solution viscosity near the fiber wall, resulting in an increase in the coating thickness. Significant differences in the rate of solvent uptake were observed in these fibers by wicking experiments on a microbalance to support the above hypothesis.     

Preparation and Characterization of Poly(2,2-dimethyl-1,3-propylene oxalate) Polymer and the Study of its Metal Uptake Behavior Toward Pb(II), Cd(II), and Hg(II) Ions

Abstract

Poly(2,2-dimethyl-1,3-propylene oxalate) was synthesized from oxalyl chloride and 2,2-dimethyl-1,3-propane diol. The polymer was characterized by inherent viscosity, FT-IR, XRD, SEM, ¹H-NMR, ¹³C-NMR, DSC, and TGA. The polymer uptake behavior towards Pb(II), Cd(II), and Hg(II) ions was studied by the batch equilibrium technique as a function of pH and contact time. The adsorption isotherms of metal ions were also investigated. Column experiments were used to determine the loading capacity and study desorption of metal ions. The polymer showed high metal-ion uptake capacity towards Pb(II), but moderate capacity towards Cd(II) and Hg(II) ions. Interestingly, the polymer was found to be highly selective for Pb(II) ions at pH 5 and 25°C. The metal ion uptake properties of the polymer show fittings for both Langmuir's and Freundlich equations. The metal-bound polymer was regenerated by treatment with 1 M HNO₃. Therefore, it may be employed for the removal of heavy metal pollutants in environmental and industrial applications.     

Uptake of hazardous heavy metal ions by aqueous solution of poly(acrylamide) prepared through atom transfer radical polymerization process

Poly(acrylamide) (PACM) used in this study was prepared through an effective atom transfer radical polymerization process and characterized by NMR, FTIR, and thermo gravimetric analysis. Resulting polymer was used for the uptake of heavy metal ions from aqueous solution. Partition coefficient, retention capacity, and metal ion uptake behavior in aqueous solution of PACM at different monomer percent conversions and effect of parameters for optimization of polymerization reaction gives thermally stable PACM. Efficiency of metal ion uptake of different molecular weights of PACM were tested in batches for Ni²⁺, Pb²⁺, Cu²⁺, Zn²⁺, and Hg²⁺ ions in single metal solution. Metal ion sorption capacities increase with increase in polymer concentration. Metal ion sorption capacities in single metal system were 6.3 mg g^?1 Ni²⁺, 6.0 mg g^?1 Pb²⁺, 6.9 mg g^?1 Cu²⁺, 6.2 mg g^?1 Zn²⁺, 22.4 mg g^?1 Hg²⁺ for PACM of 88% conversion (Mn = 19,850). Uptake by the PACM indicates that they are effective in removing metal ions from single metal ion solutions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Standardization in the Production and Testing Procedures for Polyethersulfone Hollow Fiber Ultrafiltration Membranes

Abstract

Several hollow fiber ultrafiltration membranes have been produced from polyethersulfone-polyvinyl pyrrolidone-N-methyl-2-pyrrolidone solutions and tested. The effects of feed flow velocity through the fiber bore on pressure drop in the test fiber bundle, membrane separations for PEG solutes, and the obtainable mass transfer coefficients under the test conditions have been experimentally determined and discussed. Further, the effects of storage time and prefiltration of the fiber casting polymer solution on the performance characteristics of the resulting membranes have been studied. The viscosity of the fiber casting solution increased upon storage for a few weeks, and it decreased after the solution was filtered prior to use in fiber production. Storage time and filtration treatment of the fiber casting solution had significant effects on the morphology of the resulting membranes. Casting solution of longer storage time and without filtration pretreatment produced smaller size pores on the membrane bore-side skin layer, and a larger number of such pores and/or a thinner skin layer in the resulting membrane. On the basis of these results, the need for standardizing the fiber producing conditions and fiber testing procedure is pointed out, and a few suggestions are made for such standardization.     

Preparation and Characterization of Poly(bisphenol A oxalate) and Studying its Chelating Behavior Towards Some Metal Ions

Abstract

Poly(bisphenol A oxalate) was synthesized by condensation polymerization of Bisphenol A and oxalyl chloride in dichloromethane under dry nitrogen atmosphere below 5°C. The resulting linear alternating polymer was characterized by inherent viscosity, FTIR, ¹H‐NMR, and ¹³C‐NMR. The thermal behavior of the polymer was evaluated by differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The chelating behavior of the synthesized polymer towards some divalent metal ions was studied by the batch equilibrium technique as a function of pH and contact time. The isothermal behavior and kinetics of the metal ions uptake onto the polymer were also investigated. The polymer showed high rates of metal ion uptake toward Pb(II), Cu(II), and Mg(II), but low rates toward Ni(II) and Cd(II) in the measurement of metal uptake. Interestingly, the polymer was found to selectively chelate Pb(II) and Mg(II) ions in the concentration variation isotherm experiments.     

Theoretical Analysis of Copper-Ion Extraction through Hollow Fiber Supported Liquid Membranes

Abstract

An understanding of the extraction of metal ions through hollow fiber supported liquid membranes is important for the design of such systems. In this paper, copper-ion extraction through hollow fiber supported liquid membranes containing D2EHPA as a carrier agent is analyzed. Both a rigorous model and a simple model with varied permeation coefficients for the system are proposed. The once-through mode is first modeled and the parametric effects on the extraction rate are discussed. The recycling mode is then modeled. A comparison between the rigorous model and the simple model with varied/constant permeation coefficients is made. From the models it is found that the permeation coefficient is a function of copper ion concentration.     

Synthesis,spectral, thermal,and chelation potentials of polymeric hydrazone based on 2,4‐dihydroxy benzophenone

A chelating polymer, poly(2,4‐dihydroxy benzophenone hydrazone–formaldehyde) [poly(DHBPH–F)], was synthesized by the polycondensation of 2,4‐dihydroxy benzophenone hydrazone with formaldehyde in the presence of oxalic acid as a catalyst. Poly(DHBPH–F) was characterized by Fourier transform infrared and ¹H‐NMR spectral data. The molecular weight of the polymer was determined by gel permeation chromatography. Polychelates were obtained when the dimethylformamide solution of the polymer containing a few drops of ammonia was treated with an aqueous solution of metal ions. Elemental analysis of the polychelates indicated that the metal–ligand ratio was 1 : 2. The IR spectra of the polymer–metal complexes suggested that the metals were coordinated through the oxygen of the phenolic? OH group and the nitrogen of the azomethine group. The electron paramagnetic resonance and magnetic moment data indicated a square planar configuration for Cu(II) chelate and an octahedral structure for Ni(II) chelate. The thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction data indicated that the incorporation of the metal ions significantly enhanced the degree of crystallinity. The polymerization initiation, electrical conductivity, and catalytic activity of the polychelates are discussed. Heavy‐metal ions [viz., Cu(II) and Ni(II)] were removed with this formaldehyde resin, and the metal‐ion uptake efficiency at different pH's, the nature and concentration of the electrolyte, and the reusability of the resin were also studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fluorescent chemosensor for metal ions using a polymer having pendant pyridylbenzoxazole groups

Summary A polymer having fluorescent pyridylbenzoxazole groups has been prepared for the purpose of detecting of metal ions. Metal ions such as Co²⁺, Ni²⁺, Cu²⁺ and Fe²⁺ were found to coordinate with the bipyridyl-like fluorescent benzoxazole chromophores. Among the metal ions investigated, the Fe²⁺ ion was shown to be the most effective in terms of its fluorescence quenching ability. The addition of a metal scavenger 2,2'-dipyridyl to the metal ion-quenched polymer solution resulted in the recovery of the fluorescence. Received: 2 November 1999/Revised version: 19 December 1999/Accepted: 22 December 1999     

Chelating polymer bearing triazolylazophenol moiety as the functional group

The chelating polymer-bearing triazolylazophenol moiety as the functional group was synthesized, its metal adsorption properties for 6 divalent heavy metal ions; Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were investigated. The capacity of the polymer for Cu²⁺ achieved 8.7 mEq/g in pH 5.3 solution. The polymer showed remarkable color changes from orange to red violet or blue violet with its chelations to the heavy metal ions. The metal adsorption rates of the polymer were rapid in performing complete capacity saturation of heavy metal ions in about 30 min. The capacities varied little the presence of alkali or alkaline earth metal ions in solutions. The perfect elimination of metals from the polymer–M²⁺ chelates were performed with mineral acid solutions. The metal ions; Cu²⁺ and Ni²⁺ in plating-process solutions were effectively removed by the chelating polymer, and the polymer can be practically used for the removal of these ions from waste water.     

Modification of preparation method for polymer inclusion membrane (PIM) to produce hollow fiber PIM

A new preparation method for polymer inclusion membrane (PIM) was developed. The preparation method—called post‐treatment method—is very convenient to prepare a hollow fiber PIM. Using this method, a commercial cellulose triacetate (CTA) hollow fiber membrane can be easily converted into a hollow fiber PIM. Thus, a CTA hollow fiber membrane was allowed to swell in 2‐nitrophenyl‐n‐octyl ether (NPOE) in the presence of chloroform as a solvent for CTA and N,N,N′,N′‐tetraoctyl‐3‐oxapentane diamide (TODGA) as a carrier. After evaporating chloroform, a hollow fiber PIM containing NPOE and TODGA was obtained. The result of the transport experiment of cerium(III) ions using the hollow fiber PIM showed that cerium ions were effectively transported from the feed solution to the strip solution through the hollow fiber PIM, indicating that the hollow fiber PIM was successfully prepared using the post‐treatment method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4372–4377, 2006     

Selective Transport of Cu(II) across a Polymer Inclusion Membrane with 1-Alkylimidazole from Nitrate Solutions

The selective transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions from nitrate solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer, and 1-alkylimidazole (alkyl from hexyl- to decyl) as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu(II) can be separated very effectively from other transition metal cations as Zn(II), Co(II), and Ni(II) (at a concentration of 10^?3 mol/dm³ each). Alkyl substituents at position 1 of the imidazole ring have been found to affect the hydrophobic properties and initial flux of the transported metal ions. The efficiency of separation of metal ions by 1-alkylimidazole followed the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II). The highest selectivity coefficient for Cu(II) was found with 1-hexylimidazole and its 1 mol/dm³ solution in PIM. Separation of the ions was more effective for the nitrates(V) than for chlorides.     

A bipyridine-containing water-soluble conjugated polymer: Highly efficient fluorescence chemosensor for convenient transition metal ion detection in aqueous solution

A novel sulfonato-functionalized water-soluble conjugated polymer (WSCP), which containing 2′2-bipyridine units as receptors for transition metal ions in the main chain was successfully synthesized by Sonogashira-coupling reaction for the first time. This polymer could easily dissolve in water (5 mg/mL) and some polar organic solvents such as methanol. Its fluorescence in aqueous solution can be completely quenched upon addition of transition metal ions. The K_sv of different transition metal ions in aqueous solution were much higher than previous reports in organic solutions and showed highest selectivity to Ni²⁺. These results opened opportunities for developing novel chemosensors by introducing selective fluorescent chromophore into the water-soluble conjugated backbone.     

Preparation and adsorption properties of poly(N‐vinylformamide/acrylonitrile) chelating fiber for heavy metal ions

In this article we report a new chelating fiber that was prepared from a hydrolyzate of poly(N‐vinylformamide/acrylonitrile) by a wet‐spinning method. This fiber contains chelating groups, such as amidine groups, amino groups, cyano groups, and amide groups, with high densities. We examined the chelating abilities for several metal ions with this fiber, and present the morphological merit of the fibrous product compared with the globular resin. Based on the research results, it is shown that the fiber has higher binding capacities and better adsorption properties for heavy metal ions than the resin. The pH value of the metal ion solution shows strong influences on the adsorption of the metal ions. The maximum adsorption capacities of the fiber for Cu²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Mn²⁺ are 112.23, 88.11, 141.04, 108.06, and 73.51 mg/g, respectively. In mixed metal ions solution, the fiber adsorbs Cr³⁺, Cu²⁺ and Co²⁺ efficiently. The adsorbed metal ions can be quantitatively eluted by hydrochloric acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1378–1386, 2002     

Synthesis and photophysical behavior of a water‐soluble coumarin‐bearing polymer for proton and Ni2+ ion sensing

BACKGROUND: In recent years, many fluorescent chemosensors with various macromolecular structures have been prepared for the detection of protons or metal cations in the environment. Most of this research is focused on polymer sensors with fluorescent recognition sites in the main chain. In this case, the fluorescent recognition sites are covalently bonded to the polymer chain, and thus the polymer shows photophysical properties as a chemosensor for protons and metal ions. RESULTS: An acrylic monomer bearing coumarin moieties, 7‐hydroxy‐4‐methyl‐8‐(4′‐acryloylpiperazin‐1′‐yl)methylcoumarin, was synthesized. This was then copolymerized with N‐vinylpyrrolidone to obtain a blue fluorescent material. The fluorescent copolymer has good solubility in aqueous solution. Its main photophysical properties were determined in relation to its use as a sensor for protons and metal cations. It is an efficient ‘off‐on’ switcher for pH between 3.02 and 12.08. Additionally, the polymer sensor is selective to Ni²⁺ ions, with the increase in the fluorescence intensity depending on Ni²⁺ ion concentrations in the range 0.33 × 10^?5–7.67 × 10^?5 mol L^?1. CONCLUSION: The results suggest that this copolymer may offer potential as a reusable polymer sensor for protons and Ni²⁺ ions in aqueous solution. Copyright © 2009 Society of Chemical Industry     

Influence of Chelating Agents on the Recovery of Al(III), Fe(III), Ti(IV) and Na(I) from Red Mud by Cation Exchange Membranes

Abstract

The metal recovery from red mud solution containing chelating agents such as nitriloacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), citric acid, and phosphoric acid were studied by using the Neosepta CMX and CMB cation exchange membranes in Donnan dialysis process. The stripping solution was 1.0 M HCl solution and no external potential field is applied. The efficiency of chelating agents on the recovery of metal ions through membranes was correlated with the flux data. It was observed that the removal and fluxes of metals were enhanced with citrate, EDTA and NTA chelating agents in contrast were decreased with phosphate complexing agent.     

Supported Liquid Membrane Extraction Study of (MoO4)2- Ions using Tri-n-octylamine as Carrier

Abstract

The transport of (MoO₄)^2- ions across a tri-n-octylamine (TOA) xylene-based supported liquid membrane has been studied at various HCl concentrations in the feed, TOA concentrations in the membrane, and NaOH concentrations in the strip solution. The distribution coefficient and flux of the Mo(VI) ion species vary with the HCl concentration, indicating that different polymeric species of this metal ion are present in the aqueous solution. A TOA concentration increase of up to 1.308 mol/dm³ enhances flux and permeability of this metal ion, which beyond this concentration is reduced due to an increase in carrier liquid viscosity. An increase in NaOH solution concentration has been found to increase flux and permeability values. The continuous increase in pH of the feed with the transport of metal ions indicates that the (MoO₄)^2- transport does not involve a decrease or increase in concentration as a result of association of lower to higher or decomposition of higher to lower metal ions polymeric species. The optimum conditions of transport of Mo(VI) metal ions across these membranes have been found to be HCl = 0.01, [NaOH] = 1, and [TOA] = 1.308, furnishing flux and permeability values of the order of 2.49 × 10^?4 mol·m^?2·s^?1 and 2.32 × 10^?10 m²·s^?1, respectively.