MECHANISM OF POLYMER-BASED SEPARATIONS. I. COMPARISON OF PHOSPHINIC ACID WITH SULFONIC ACID ION EXCHANGE RESINS

The metal ion complexing ability of the phosphinic acid polymeric extractant has been compared with that for the sulfonic acid ion exchange resin. Based on the performance of the extractants with Fe(III), Hg(II), and Mn(II) under dilute solution/ high acid conditions, both with and without the presence of a large excess of sodium ions, it is concluded that the phosphinic resin operates through an entropy-driven coordination for hard trivalent ions such as Fe(III), an enthalpy -driven coordination for soft ions such as Hg(II) and only ion exchange for hard divalent ions such as Mn(II). The sulfonic resin operates non-selectively through the ion exchange mechanism.     

POLYMER-SUPPORTED REAGENTS FOR MOLECULAR SEPARATIONS

A Hammett study of the complexing abilities of various polymer-supported reagents for phenols, anilines, and benzoic acids is described. For each polymeric reagent, the percent absorbed of each family of compounds is correlated with the Hammett substituent constants. A carboxylic acid resin shows no interaction with phenols and benzoic acids; only a weak interaction with anilines is found since 25% of each is absorbed regardless of the substituent present on the aromatic ring. This contrasts with the strong interaction displayed by the sulfonic resin and the moderate interaction of the phosphinic resin. Phosphonic and phosphonate monoester resins absorb increasing amounts of anilines as their basicity increases. The purely coordinating- phosphonate diester resin absorbs uniformly low levels of the three families of compounds with no substituent effect on the percent absorbed. The sulfonic resin quantitatively absorbs the anilines within the temperature range 6 to 40 C while the phosphinic resin absorbs decreasing levels within the same range. The phosphinic resin is more selective than the sulfonic resin under competitive conditions     

Introduction of bifunctionality into the phosphinic acid ion-exchange resin for enhancing metal ion complexation

In nuclear industry the role of conventional strong cation exchange resins is limited as they function less in high acid media. The phosphorous group that has got more affinity towards actinide elements is chosen as a chelating group and the phosphinic acid ion exchange resin was synthesized. The extraction ability of the phosphinic acid resin for plutonium (Pu) from HNO₃ medium as well as from H₂SO₄ medium was studied. Though the resin shows better extraction for Pu than the strong cation exchanger resins at higher acidities, its kinetics is slow. In order to enhance the kinetics as well as to improve upon selectivity, a sulphonic group is introduced into the phosphinic acid resin. To verify the effect of bifunctionality extraction studies have been carried out with Pu from different acid media of varying concentrations. Sulphonated phosphinic acid resin shows a 2-fold increase in distribution coefficient (k_d) as well as it reached equilibrium very fast compared to the phosphinic acid resin. It is postulated that the sulphonic acid ligand provides an access mechanism for the metal ions into the polymer matrix while it is the phosphinic acid group that is responsible for selective coordination of metal ions. Thus bifunctionality is coupling of an access mechanism to a recognition mechanism. The experiments carried out demonstrated the applicability of sulphonated phosphinic acid resin in the nuclear industry.     

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT

A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.     

Synthesis and Surface Modification of Mesoporous Silicate SBA‐15 for the Adsorption of Metal Ions

Abstract

In this study surface modified SBA‐15, coated with octadecyltrichlorosilane (C18), is considered as an alternative adsorbent for metal ions in water. The SBA‐C18 was loaded with Bis(2,4,4-trimethylpentyl) phosphinic acid (cyanex 272) as the metal ion extractant. The adsorption characteristics of phosphinic acid loaded SBA‐C18 were evaluated for Cu(II) and Zn(II) ions in aqueous solution. Adsorption tests indicated that a contact time of 1 hour was sufficient for adsorption equilibrium to occur. The pH_1/2 values of Zn(II) and Cu(II) onto SBA‐C18, were found to be similar to published data for levextrel ion exchange resins and around 1 pH unit lower than published solvent extraction data for cyanex 272 in xylene.     

Novel Bifunctional Resins in Metal Ion Separations: Ion Exchange/Coordination Resins and Ion Exchange/Precipitation Resins

Abstract

Dual mechanism bifunctional polymers (DMBP's) as metal ion extractants are described within the context of two new examples. The carboxylic acid/pseudocrown resin is a new example of the DMBP class of resins described as ion exchange/ coordination resins. The polyethylene glycol ligand within the resin functions as a coordinating site for metal ions which are brought into the resin via ion exchange with the acid ligand. Initial studies with alkali metal ions are presented. The third general class of DMBP's is also presented. In this case, precipitation is the reaction occurring along with ion exchange thus yielding the ion exchange/precipitation resins. Barium recovery from aqueous solution via barium sulfate precipitation is described.     

Conversion of soybean oil into ion exchange resins: Removal of copper (II), nickel (II), and cobalt (II) ions from dilute aqueous solution using carboxylate‐containing resin

An ion‐exchange resin containing carboxylic acid groups was prepared by reaction of epoxidized soybean oil with triethylene tetramine, followed by hydrolysis of glycerides by using sodium hydroxide solution. The cation exchange capacity of the resins was determined to be 3.50 mequiv/g. The adsorption capacity for Cu²⁺, Ni²⁺, and Co²⁺ on the obtained resin at pH 5.0 was found to be 192, 96, and 78 mg/g, respectively. Effect of pH on the adsorption capacity for copper (II), nickel (II), and cobalt (II) ions were also studied. Cu²⁺, Ni²⁺, and Co²⁺ were adsorbed at a pH above 3. These metal ions adsorbed on the resin are easily eluted by using 1N HCl solution. The selectivity of the resin for Cu²⁺ from mixtures containing Cu²⁺/Co²⁺/Ni²⁺ ions in the presence of sodium chloride was also investigated © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2386–2396, 2002     

Effect of gamma irradiation on the metal sorption and separation of some divalent metals by some new polymeric bifunctional resins

The metal sorption and separation of some divalent metals from solutions of varying acidity by a new series of gamma-irradiated ionic polymer resins have been investigated. Three polymeric resins, viz., phosphonic acid, phosphonate monoethyl ester, and phosphonate diethyl/monoethyl ester, were used in this study. The results of metal sorption and separation were compared with those of the well-known cation exchange resin Dowex X8. The results were correlated in the usual manner of distribution coefficients (D) of three divalent metals Sr(II), Co(II), and Ni(II). The results of metal sorption by the ionic resins under investigation compared with that of sulfonic acid resin, showed that Ni showed the highest affinity for the unirradiated monoethyl ester/phosphonic acid resin, while Sr showed the highest affinity for phosphonic acid resin and Co showed the highest affinity for mono/diethyl ester phosphonic acid resin. Moreover, the three metals (Sr, Co, Ni) showed the lowest affinity toward sulfonic acid resin. The calculated separation factors for the different resins indicate that the unirradiated phosphonic acid resin has the highest capacity to separate Sr from Ni, whereas mono/diethyl ester/phosphonic acid resins have the highest capacity to separate Co from Sr and Ni. Furthermore, the affinity of the ionic polymers for the metal ions was not greatly changed after gamma irradiation. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:1091–1101, 1997     

KINETICS OF CADMIUM ION SORPTION ON ION EXCHANGE AND CHELATING RESINS

ABSTRACT

Cadmium sorption from aqueous solutions on sulfonic (C-150) and iminodiacetic (S-930) Purolite macroporous resins was investigated. The influence of operating variables such as initial pH, Cd(H) concentration, time and temperature on the equilibrium parameters was measured. The ion preference and sorption ability of resins, i.e. binding constant (b) and saturation capacity {x_m), derived from sorption isotherm, depend on the functional group structure. The Cd(II) uptake is only particle diffusion controlled. The kinetic parameters, i.e. t_1/2 values for 50 % attainment of equilibrium sorption, rate constant (K¯ ) and diffusion coefficient (D¯) are higher on the sulfonic resin. The “moving boundary” particle diffusion model fits the entire ion sorption process on chelating resin, but only the initial sorption on the sulfonic resin, confirming the difference in chemistry between chelation and ion exchange.     

REACTION KINETICS OF POLYSTYRENE-BASED PHOSPHINIC ACID ION EXCHANGE/REDOX RESINS WITH METAL IONS

ABSTRACT

The ion exchange/redox kinetics displayed by the phosphinic acid polymer with aqueous solutions of silver and mercury is presented as a function of reaction temperature (6° to 45° C) and solution pH (0 to 5). The network variables studied include the crosslink level and macroporosity. At each pH, increasing the temperature leads to a more rapid approach to equilibrium. The amount complexed at equilibrium is lowest at pH Q relative to the higher pH solutions due to increased H⁺ competition for ligating sites. Metal ion reduction, rather than ion exchange, is the dominant component at equilibrium. Matrix rigidity and macroporosity do not affect Ag(I) kinetics. The rate of Hg(II) sorption is much faster than for Ag(I). Macroporosity is an important variable with mercury: macroporous resins complex more than twice the amount found with gels at 15 minutes contact. It is proposed that Ag kinetics are limited by a slow redox reaction while the Hg kinetics are diffusion-limited due to a fast redox reaction. Differences in reactivity arise from the reaction stoichiometry     

A cation exchange resin from poly(N-vinyl carbazole)

Poly(N-vinyl carbazole) was sulfonated with different sulfonating agents and ion exchange capacities of the resins produced were evaluated. A maximum capacity of 4.5 meq · g^?1 of dry resin was realized when sulfonation was done with 98.8% H₂SO⁴ at 30°C for 10 h. The pH titration curves reveal the nature of a strong monofunctional cation exchanger with a pK value of 2.2. The resin exhibits a moderate rate of exchange with NaCl and is thermally stable up to ca. 250°C.     

Sulfonated poly(ether ether ketone)/epoxy/phenol novolac blend proton‐exchange membranes with low methanol permeability

A crosslinked epoxy [4,4′‐diglycidyl‐(3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP)], cured by phenol novolac (PN), was introduced into a sulfonated poly(ether ether ketone) (SPEEK) membrane (ion‐exchange capacity = 2.0 mequiv/g) with a casting‐solution, evaporation, and heating crosslinking method to improve the mechanical properties, dimensional stability, water retention, and methanol resistance. By Fourier transform infrared analysis, the interactions between the sulfonic acid groups and hydroxyl groups in the blend membranes were confirmed. The microstructure and morphology of the blend membranes were investigated with atomic force microscopy. As expected, the blend membranes showed excellent mechanical properties, good thermal properties (thermal stability above 200°C), lower swelling ratios (1.4% at 25°C and 7.0% at 80°C), higher water retention (water diffusion coefficient = 9.8 × 10^?6 cm²/s), and a lower methanol permeability coefficient (3.6 × 10^?8 cm²/s) than the pristine SPEEK membrane. Although the proton conductivity of the blend membranes decreased, a higher selectivity (ratio of the proton conductivity to the methanol permeability) was obtained than that of the pristine SPEEK membrane. The results showed that the SPEEK/TMBP/PN blend membranes could have potential use as proton‐exchange membranes in direct methanol fuel cells. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

EXTRACTION AND SEPARATION OF HEAVY RARE EARTH(III) WITH EXTRACTION RESIN CONTAINING DI(2,4,4-TRIMETHYL PENTYL) PHOSPHINIC ACID (CYANEX 272)

ABSTRACT

Extraction resins, of the type of Levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(II1)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50°C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm₂O3 >99.97%, >80%; Er₂O₃ >99.9%, >94% and Yb₂O₃ >99.8%, >80% respectively, have been obtained from a feed having the composition Tm₂O₃ 60%, Er₂O₃ 10%, and Yb₂O₃ 3%, the others 27%.

The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.     

Synthesis and characterization of a bifunctional ion exchange resin with polystyrene-immobilized diphosphonic acid ligands

A new ion exchange resin for the selective complexation of metal ions has been synthesized by functionalizing vinylbenzyl chloride-styrene-divinylbenzene copolymer beads with the sodium salt of tetra(isopropyl) methylene diphosphonate. The effects of bifunctionality, matrix rigidity, degree of functionalization, and macroporosity on final resin properties have been quantified. A sulfonic acid-diphosphonic acid bifunctional resin is highly selective with rapid complexation kinetics. A macroporous polymer matrix crosslinked with 10% divinylbenzene provides optimum results; for example, 99.7% Eu(III) is complexed from a 1M nitric acid solution with a 30-min contact time. The importance of physical crosslinking as well as chemical crosslinking in limiting access of substrates into polymer-supported reagents is discussed. © 1996 John Wiley & Sons, Inc.     

Functionalization in copolymers based on 4VP:DVB for the removal of Cr(VI) ions from aqueous solution

Adsorption capacity for Cr(VI) ions has been evaluated on two ion‐exchange resins. A gel‐type precursor resin was obtained by suspension polymerization of 4‐vinylpyridine and divinylbenzene monomers with 40% crosslinking degree. It was quaternized with different functional groups to give two ion‐exchange resins. The R2 resin contained sulfobetaine groups, and R3 methyl groups. The resins were characterized by Fourier transform infrared and solid‐state ¹³C CP/MAS NMR spectroscopy and by elemental analysis. An adsorption experiment was carried out by a batch equilibrium procedure. Langmuir and Freundlich isotherm models were used to determine the adsorption capacity. R2 and R3 resins exhibited maximum adsorption capacity q_max = 75.8 and 56.2 mg/g, respectively. The resins achieve equilibrium in 60 min. The R3 and R2 resins showed a retention capacity of 95% and 80% for the Cr(VI) ions, respectively. The behaviors of both resins were explained well by a pseudo‐second‐order kinetics model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45548.     

Studies of selective adsorption resin. XXIV. Preparation and properties of macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups

The macroreticular chelating resins containing both polyethylenepolyamine side chains and mercapto groups were prepared by the reaction of 2,3-epithiopropyl methacrylate-divinylbenzene macroreticular copolymer beads with polyethylene-polyamine. The adsorption behavior of metal ions on the obtained resins was then investigated. The amination of the macroreticular copolymer beads could effectively be carried out by treatment of the polymer beads with polyethylenepolyamine in organic solvent (benzene, terahydrofuran) or in the absence of organic solvent at 80°C or 100°C for 60 min. It was found that the adsorption capacity of the resins for metal ions is not only affected by the ion exchange capacity of the resins but also by the porosity of the resins. Hg²⁺, Ag⁺, and Cu²⁺ were effectively adsorbed on the resins even at a pH below 3, whereas Co²⁺, Ni²⁺, and Cd²⁺ were adsorbed at a pH above 3, Mn²⁺ at a pH above 7, and Ca²⁺ at a pH above 8. These metal ions adsorbed on the resins could easily be eluted with dilute mineral acid solution or dilute mineral acid solution containing thiourea.     

Evaluation of Elution Parameters for Cesium Ion Exchange Resins

Abstract

Cesium ion exchange is one of the planned processes for treating and disposing of waste at the U.S. Department of Energy Hanford Site. Radioactive supernatant liquids from the waste tanks will undergo ultrafiltration, followed by cesium ion exchange using a regenerable organic ion exchange resin. Two resins, SuperLig^®644 and a resorcinol‐formaldehyde resin, are being evaluated for cesium removal and cesium elution characteristics. The main purpose of this study is to optimize the cesium elution to provide a resin that, after undergoing elution, would meet the U.S. Department of Energy/Office of River Protection Project‐Waste Treatment Plant processing and resin disposal criteria. Columns of each resin type were loaded to greater or equal to 90% breakthrough with a Hanford waste stimulant and eluted with nitric acid. The temperature, flow rate, and nitric acid concentration were varied to determine the optimal elution conditions. Temperature and eluant flow rate were the most important elution parameters. As would be predicted based upon kinetic consideration alone, decreasing the eluant flow rate and increasing the temperature provided the optimal elution conditions. Varying the nitric acid concentration did not have a significant effect on the elution completion; however, elutions performed using both high acid concentration (1 M) and elevated temperature (45°C) resulted in resin degradation, causing gas generation and resin bed disruption.     

PROTON / NICKEL(II) INTERD1FFUSION COEFFICIENTS ON STRONG ACID RESINS

ABSTRACT

Ion exchange kinetics between proton and nickel(II) ions on sulfonic acid cation resins, with polystyrene-divinylbenzene matrix, type gel and macroporous, in high concentration of the external solution was studied at 298 K using a potentiometric method. The ratio between the amount of ions in the resin and in the solution phase was kept smaller than 0.1. The integral interdiffusion coefficients were determined using the quasi-homogeneous resin phase kinetic models at infinite and finite solution volume. The results were compared and discussed in terms of their range of validity. The influence of the ionic composition of the ion exchanger and matrix nature (gel or macroporous) on the integral interdiffusion coefficients was investigated and discussed. The simpler infinite solution volume kinetic model gives higher values for the integral interdiffusion coefficients than the Paterson's finite solution volume model. The numerical values of the integral interdiffusion coefficients are greater for gel than for macroporous type resin up to     

Cation exchange resins from chemically modified poly(vinyl chloride)

Summary Poly(vinyl chloride) has been modified chemically to a cation exchange resin by halogen displacement reactions with phenol sulfonic acid, bisphenol-A sulfonic acid and phenolpthalein sulfonic acid. Ion-exchange capacity, salt-splitting capacity and pH-titration characteristics of these resins have been evaluated. pH-titration behaviour of these resins is consistent with that of a polyfunctional cation-exchanger having pK₁=2 and pK₂=9–10 corresponding to -SO₃H and phenolic-OH groups respectively. The ion-exchange capacity values are comparable in magnitude to those of polystyrene based commercial cation-exchangers such as Amberlite IR-120 and Dowex-50.     

Water‐insoluble polymers containing amine,sulfonic acid,and carboxylic acid groups: Synthesis,characterization, and metal‐ion‐retention properties

Crosslinked poly(acryloylmorpholine) and its copolymers poly(acryloyl morpholine‐co‐acrylic acid) and poly(acryloylmorpholine‐co‐2‐acrylamide‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The resins were completely insoluble in water and were characterized with Fourier transform infrared spectroscopy and thermal analysis. The metal ions Ag(I), Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Al(III), and Cr(III) were investigated under competitive and noncompetitive conditions by a batch equilibrium procedure. The resin‐metal‐ion equilibrium was achieved before 5 min. The recovery of the resin was investigated at 20°C with different concentrations of HNO₃ and HClO₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3266–3274, 2006