选择性吸附贵金属离子的螯合树脂的研究进展

树脂矿浆法(RIP)从溶液中提取与分离贵金属是目前的研究热点,其关键是制备高吸附容量和高吸附选择性的螯合树脂。讨论了选择性吸附贵金属离子的螯合树脂的分类方法、树脂结构与性能的关系、树脂与贵金属离子的配位机理,按配位原子分类综述了近10年来国内外螯合树脂的合成和吸附的研究进展,并展望了螯合树脂研究的发展方向。     

Synthesis,characterization, and properties for Hg2+ of new chelating resin containing sulfoxide and 3‐aminopyridine

A new chelating resin (PVESO‐AP) containing sulfoxide and 3‐aminopyridine (AP) was synthesized by using chloromethylated polystyrene‐co‐divinylbenzene (PS‐Cl) as material. Its structure was characterized by infrared spectra and elemental analysis. The adsorption capacities of the newly formed resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Ni²⁺ were determined at pH 2 and 5. In addition, the adsorption selective coefficients for Hg²⁺ in several binary mixture systems were investigated by batch experiment method. The results showed that this resin had high adsorption selectivity for Hg²⁺. The adsorption kinetics and isothermal of PVESO‐AP for Hg²⁺ at different temperatures were also investigated. The adsorption kinetics showed that the apparent activation energy E_a was 13.71 kJ/mol. The results also showed that the Langmuir model was better than the Frundlich model to describe the isothermal process of PVESO‐AP resin for Hg²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adsorption behavior of metal ions by amidoxime chelating resin

The adsorption properties of poly(acrylamidoxime) chelating resin for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), Cr(III), and U(VI) are investigated by the batch technique. Based on the research results of the binding capacity effect of the pH value on sorption kinetic experiments, it is shown that this resin has higher binding capacity to uranyl ions, fast kinetics, and very good selectivity from binary metal ion mixtures with Cu(II) and Pb(II). The uranyl ion sorption strongly depends on the pH value of the solution. The highest value of 99% is at pH 5, but at pH 1 there is no retention. The adsorbed UO can be eluted by sulfuric acid and sodium carbonate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1994–1999, 2000     

Synthesis and adsorption properties of magnetic resin microbeads with amine and mercaptan as chelating groups

Three magnetic chelating resins containing amino and mercapto groups were prepared by the suspended condensation polymerization of 2‐chloroethoxymethyl thiirane with diamines. The magnetic resins were microbeads whose diameter was in the range of 10 to 45 μm. The structure of the resins was characterized by XPS, IR, and elemental analysis. Their adsorption properties for Hg(II), Au(III), Pd(II), Pt(IV), Ag(I), Cu(II), Zn(II), and Pb(II) were investigated. The experimental results show the magnetic resins have high affinity for Hg(II) and noble metal ions. In the competitive adsorption, the resins predominantly adsorbed Hg(II) or Pd(II) in the coexistence of Cu(II), Zn(II), and Mg(II). Desorption of Pd(II) loaded on the resins was studied by using 2M hydrochloric acid solution containing 1% thiourea as desorbent. A high desorption ratio (up to 96.5%) was observed, and repeated adsorption/desorption operations showed the probability of repeated use of the magnetic resins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1587–1592, 2001     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

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     

Preparation,characterization, and metal binding behavior of novel chelating resins containing sulfur and polyamine

Several kinds of polyamine‐type chelating resins containing sulfide were synthesized by the reaction of polyamines, such as ethanolamine (EA), ethylenediamine (EDA), diethylenetriamine (DETA), and triethylenetetramine (TETA), with poly[4‐vinylbenzyl (2‐benzenesulfonate ethyl) sulfide] (PSMP), which was itself prepared by the reaction of poly[4‐vinylbenzyl (2‐hydroxyethyl) sulfide] (PSME) with benzenesulfonal chloride in pyridine solution. Factors affecting syntheses of PSMP, such as solvents, reaction temperature and time, and ratio of reactants, were investigated. Structures of the above resins were confirmed by FTIR and elemental analysis. Their surface morphology and pore structures were observed on a SEM and determined by the BET method, respectively. Adsorption experiments showed that these resins exhibit better adsorption selectivity for noble metal ions and Hg(II) than other heavy ones. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1558–1565, 2005     

Adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide)type chelating fiber for heavy metal ions

In this article, the adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers for Cu(II), Cd(II), Co(II), Mn(II), Pb(II), Zn(II), Ni(II), and Cr(III) are investigated by a batch technique. Based on the research results of binding capacity, adsorption isotherm, effect of pH value on sorption, and adsorption kinetics experiments, it is shown that the poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers have higher binding capacities and good adsorption kinetic properties for heavy metal ions. The sorption of the metal ions on the chelating fibers is strongly dependent on the equilibrium pH value of the solution. The adsorption isotherms of Cu(II) and Cd(II) on the chelating fiber exhibit a Langmuir-type equation. The adsorbed Cu(II), Cd(II), Zn(II), and Pb(II) could be eluted by diluted nitric acid. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 7–14, 1998     

Synthesis of polystyrene‐supported glucosamine resin and its adsorption properties for metal ions

A novel chelating resin polystyrene‐supported glucosamine was prepared by the reaction of chloromethylated polystyrene with glucosamine hydrochlorate, using anhydrous potassium carbonate as catalyst and dimethylformamide as solvent. Infrared spectra and elementary analysis were used to confirm its structure. The adsorption of the resin for Cu²⁺, Ni²⁺, Hg²⁺, Co²⁺, Cd²⁺, and Pb²⁺ was investigated, as well as various factors affecting the adsorption such as time, temperature, ion concentration, and pH. The results showed that the resin had good adsorption capacities for Cu²⁺, Ni²⁺, and Hg²⁺. The adsorption was controlled by liquid film diffusion and adsorption isothermal data could be well interpreted by the Freundlich equation. Values of adsorption activation energy and adsorption Gibbs free energy were calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 890–896, 2005     

Polymeric pseudocrown ether resins containing azacrown and azathiacrown ethers: Synthesis and adsorption for metal ions

Eight novel polymeric pseudocrown ether (PPCE) resins containing azacrown and azathiacrown ethers were prepared by chemical reactions of the precursor of 1-chloro-2,3-epoxypropane, 1-(2-chloroethoxy)-2,3-epoxypropane, 1-chloro-2,3-epithiopropane, and 1-(2-chloroethoxy)-2,3-epithiopropane with triethylolamine or diethylolamine in the presence of NaH. The maximum adsorption capacities of PPCE resins for noble metals are 4.67 mmol Au/g-resin, 2.2 mmol Pd/g-resin, 0.7 mmol Pt/g-resin, and 7.3 mmol Ag/g-resin. The structure of PPCE resins were characterized by IR spectra and element analysis. The adsorption of PPCE resins for noble metals is jointly conducted by PPCE polymer backbone and the azacrown or azathiacrown cavity. The XPS study shows that there are strong complexion interactions between PPCE and Au(III) or Pd(II). © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:931–938, 1997     

Preparation and adsorption selectivity for Hg(II) and Ag(I) of chelating resin immobilizing benzothiazolyl group on crosslinked polystyrene via hydrophilic sulfur‐containing PEG spacer

A new chelating resin incorporating 2‐mercaptobenzothiazole (MBZ) into macroporous chloromethylated polystyrene via hydrophilic spacer of polyethylene glycol containing sulfur was synthesized. The resin was characterized by elementary analysis and infrared spectra. The adsorption capacity of the resin for Ag⁺, Hg²⁺, Cu²⁺, Zn²⁺, and Pb²⁺ as a function of pH was determined. The effects of interference ions, such as Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, on percent recovery were also investigated. The results showed that the resin could effectively remove Hg²⁺ and Ag⁺ from solutions containing a large excess of Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. In column operation, it was observed that Hg²⁺ and Ag⁺ in trace quantities were effectively removed from binary metal ions. The percent recovery of the resin for Hg²⁺ and Ag⁺ was >98.6% and >97.5%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 5034–5038, 2006     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

Synthesis of sulfhydryl chitin and its adsorption properties for heavy metal ions

This article discusses the preparation of the water‐insoluble adsorbent sulfhydryl chitin (s‐chitin), by treatment of the chitin with sulfhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confirmed by elemental analysis, FTIR spectra analysis and near‐IR spectra analysis. We also investigated the adsorption properties of sulfhydryl chitin for Cu^II, Cd^II, Pb^II, Cr^III, and Ni^II. Based on the research results of adsorption capacity, the effect of pH value on adsorption, adsorption kinetics experiments, and selective adsorption experiments were observed. It has been shown that the s‐chitin has much better adsorption for Pb^II, Cu^II, and Cd^II than chitin itself. The adsorption capacities of s‐chitin for Pb^II, Cu^II, and Cd^II were 108.3, 94.7, and 57.1 mg/g, respectively. It also had good adsorption properties for heavy metal ions. The adsorption capacities were also affected by the acidity of medium. The adsorbed Cu^II, Cd^II, and Pb^II could be eluted by diluted chlorhydric acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 151–155, 2000     

High‐retention properties for Hg(II) ions of a resin containing ammonium and pyridine groups

The metal‐ion uptake behavior of the chelating resin poly([(3‐(methacryloylamino)propyl] trimethyl ammonium chloride‐co‐4‐vinyl pyridine) has been investigated. The resin is obtained by radical copolymerization in a yield of 99.6%. The hydrophilic resin shows a high retention capacity and selectivity toward Hg(II) ions in the presence of Cu(II), Pb(II), Cd(II), Zn(II), and Cr(III) ions. A retention of Hg(II) higher than 99% is observed after 5 min. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2595–2599, 2002     

Synthesis,characterization, and metal ions adsorption properties of chitosan–calixarenes (I)

Calixarene‐modified chitosans (CTS–CA‐I and CTS–CA‐II) were first synthesized by the reaction of chitosan (CTS‐NH₂) with 1,3‐bis‐chloroethoxyethoxy‐2,4‐dihydroxy‐p‐tert‐butylcalix[4]arene (CA‐I) or its benzoyl derivative (CA‐II). Their structures were characterized by infrared and X‐ray diffraction spectroscopy and scanning electron microscopy (SEM). The adsorption of Ni²⁺, Cd²⁺, Cu²⁺, Pd²⁺, Ag⁺, and Hg²⁺ by CTS–CA‐I and CTS–CA‐II was studied and the thermodynamic parameter of two calixarene‐modified chitosans toward Hg²⁺ was deduced. The adsorption properties of CTS–CA‐I and CTS–CA‐II were greatly varied compared with that CTS‐NH₂, especially with the adsorption capacity toward Ag⁺ and Hg²⁺, because of the presence of the calixarene moiety. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1139–1144, 2003     

Removal properties of crosslinked poly(2‐acrylamido glycolic acid) for trace heavy metal ions: Effect of pH,temperature, contact time,and salinity on the adsorption behavior

Crosslinked poly(2‐acrylamido glycolic acid) resin was synthesized by radical polymerization. This resin contains three potential ligand groups and was studied as an adsorbent of trace heavy metal ions from a saline aqueous solution and sea water by using the Batch equilibrium procedure. Adsorption characteristics of the resin toward Cu(II), Ni(II), Cd(II), and Pb(II) were studied spectrophotometrically, both in competitive and noncompetitive conditions. The effect of pH, contact time, amount of sorbent, temperature, and salinity were studied. The resin showed a high affinity particularly for Ni(II). It was possible to remove completely Ni(II) and Pb(II) from the resin by 4M HNO₃. The retention properties of the resin were also investigated for Cu(II) contained in natural sea waters. The retention behavior was similar to that of the synthetic metal ion aqueous solution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2614–2621, 2003     

乙二胺螯合细菌纤维素的制备及其吸附Cu~(2+)研究

以细菌纤维素为原料制备乙二胺螯合细菌纤维素.通过红外光谱仪、元素分析仪对产物进行了表征.研究了乙二胺螯合细菌纤维素对铜离子的吸附动力学、等温吸附等特征.结果表明,吸附动力学可用拟二级速度方程来描述,吸附平衡符合Freundlich等温吸附方程,并对其吸附与解吸性能进行了分析.     

Preparation of iminodiacetic acid-type composite chelating material IDAA-PGMA/SiO2 and preliminary studies on adsorption behavior of heavy metal ions and rare earth ions

A kind of iminodiacetic acid (IDAA)-type composite chelating materials was prepared by first graft polymerization and subsequent polymer reaction. Monomer glycidyl methacrylate (GMA) was grafted on micron-sized silica gel particles in the manner of “graft through” in a solution polymerization system, resulting in the grafted particles poly(glycidyl methacrylate) (PGMA)/silicon dioxide (SiO₂). Subsequently, the ring-opening reaction of the epoxy groups of the grafted PGMA was carried out with IDAA as reaction reagent, resulting in the bonding of IDAA groups onto PGMA/SiO₂ and obtaining the composite chelating material IDAA-PGMA/SiO₂ particles. The effects of the main factors on the graft polymerization of GMA and the bonding reaction of IDAA were examined emphatically, and the adsorption behavior of IDAA-PGMA/SiO₂ particles toward several kinds of heavy metal ions and rare earth ions was preliminarily explored. The experiments results show that: (a) to obtain the grafted particles PGMA/SiO₂ with high grafting degree, in the graft polymerization step, the reaction temperature and the used amount of initiator should be controlled. The suitable temperature is 70°C and the appropriate used amount of initiator is 1.4 % of the monomer mass. Under the optimal conditions, the grafted degree of PGMA can reach 17.50 g/100 g. (b) It is feasible to introducing of IDAA groups onto PGMA/SiO₂ particles via ring-opening reaction of epoxy groups of the grafted PGMA under alkaline conditions, and the bonding rate of IDAA group can get up to 70% based on epoxy groups of the grafted PGMA. (c)The composite chelating material IDAA-PGMA/SiO₂ possesses very strong chelating adsorption ability for heavy metal ions, and especially toward Pb²⁺ ion, the adsorption capacity can reach 24 g/100 g. (d) The adsorption ability of IDAA-PGMA/SiO₂ for rare earth ions is weaker than that for heavy metal ions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies of syntheses and adsorption properties of chelating resin from thiourea and formaldehyde

Chelating resins are useful substances in industry because of their extraordinary adsorption properties for specific metal ions. In this study, a new type of chelating resin is synthesized simply by reaction between thiourea and formaldehyde. The synthetic conditions and the structure of the product are approached and the adsorbing capacities for 11 metal ions, adsorbing rates, and selectivities investigated. The results of the experiments show that the resin has high adsorbing capacities for Ag(I): 13.1 mmol/g, and for Au(III): 6.95 mmol/g. Adsorbing rates are close to 100% in dilute solution. Isothermal adsorbing study reveals that the adsorption is monomolecular layer adsorption process. It is hopeful for the resin to be used for concentrating and retrieving Ag(I) and Au(III) ions from their dilute solutions in industry. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3127–3132, 2001     

Preparation of ethyleneamine functionalized crosslinked poly(acrylonitrile-ethylene glycol-dimethacrylate) chelating resins for adsorption of lead ions

Removal of lead ions was investigated by ethylenediamine, triethylenetetramine and tetraethylenepentamine functionalized polymeric adsorbent. Macroporous acrylonitrile-ethylene glycol-dimethacrylate copolymer beads were synthesized by suspension polymerization as already reported.^[17] The adsorbent was prepared by amination of copolymer synthesized from acrylonitrile-ethylene glycol-dimethacrylate. The adsorption study for removal of lead ions using functionalized poly(AN-EGDMA) copolymer as an adsorbent was carried out at room temperature at various solution concentrations of 0.483–2.4154 mmol/l at pH 4.6. Functionalized polymers were studied by Fourier transform infrared spectroscopy (FTIR). Scanning electron microscope-X-ray energy dispersive spectrometer (SEM-EDAX) was utilized to study an increase in nitrogen content of functionalized polymers.