Synthesis and Adsorption Properties of Polystyrene-supported Chelating Resins Containing Heterocyclic Functional Groups

A series of new chelating resins with incorporating heterocyclic functional groups： pyridine, thiadizole, benzothizole into macroporous chloromethylated polystyrene were synthesized via hydrophilic spacer arm of polyethylene glycol containing sulfur. These chelating resins were found to show high adsorption capacities for Ag^＋, Hg^2＋, Au^3＋ and Pd^2＋, and the presence of spacer arm can enhance adsorption ability due to increase the hydrophilicity of the chelating resins.

Synthesis and Adsorption Properties of Chelating Resins Containing Sulfoxide and Heterocyclic Functional Groups

Several of new chelating resins containing sulfoxide and heterocyclic functional groups （3-aminopyridine and 2-mercaptobenzothiazole） based on macroporous chloromethylated polystyrene were synthesized and characterized by elemental analysis and infrared spectra. Their adsorption capacities towards Zn^2＋, Cu^2＋, Pb^2＋, Hg^2＋ and Ag^＋ at pH 3.0 and 6.0 were investigated in detail. It was found that the adsorption capacities of the resins containing bis[（3-pyridylaminoethyl）sulfoxide or （2-benzothiazolylthioethyl）sulfoxide for the above ions were higher than that on ones containing single above-mentioned groups.

SYNTHESES AND ADSORPTION PROPERTIES OF PHENOL-FORMALDEHYDE-TYPE CHELATING RESINS BEARING THE FUNCTIONAL GROUP OFTAR TARIC ACID

Several kinds of novel chelating resins bearing the functional group of tartaric acid (TTA-FQ-12, TTA-FQ-23, and TTA-FQ-34) were synthesized by reacting epoxy maleic anhydride, which was prepared through the oxidization reaction of maleic anhydride by hydrogen peroxide, with phenol-formaldehyde resin containing polyamine (FQ resins series). The effects of such factors as reaction time, reaction temperature and pH value on the loading capacity of TTA in resins were investigated. The results showed that the optimum reaction conditions are as follows: time 9-12 h; temperature 90-105'C; pH value 6-10. The loading capacities of TTA can reach 0.15, 0.14, and 0.11 mmol/g-1 when the functional group of FQ resin was - OCH2CH2NHC2H4NH2, - O(CH2CH2NH)2C2H4NH2 and - O(CH2CH2NH)3C2H4NH2), respectively. The structures of resins were characterized by FTIR spectra. The primary study on the adsorption properties of the resins for metal ions showed that there are two kinds of adsorption mechanisms i.e. ion exchange and chelate in the adsorption process. TTA-FQ resins have much higher adsorption selectivity for Pb2+and Zn2+ than for Cu2+ and Ni2+. These resins can probably be used for separating Pb2+ or Zn2+ in the mixture of metal ions or for treating wastewater containing heavy metal ions.

Study on Chelating Resins XXXI Syntheses and Adsorption Properties of a New Type of Bead Resins Containing S and N

A new type of bead crosslinked chelating resins containing coordinate atoms N and S were synthesized by the reaction of polyethyleneimine with chlorometbylthiirane in suitable sovent at temperature of 2080C. These chelating resins exhibited excellent adsorption properties for precious metal ions.

Synthesis of Novel Chelating Adsorbents for Boron Uptake from Aqueous Solutions

Two kinds of novel chelating adsorbents have been synthesized to separate boron from aqueous solutions. One is the boron-specific chelating resin,synthesized by the functionalization of macroporous poly (glycidyl methacrylate-co-trimethylolpropane trimethacrylate),with N-methylglucamine. The other is the organic-inorganic hybrid mesoporous SBA-15 with polyol functional groups,prepared by a two-step post-grafting method. The resin can adsorb boron in almost all pH range,and its maximum uptake capacity reaches 1.15 mmol/g. The present study of the polyol-functionalized SBA-15 shows that the post-grafting is successful and the resulting adsorbent has the uptake capacity of 0.63 mmol/g.

Synthesis and Adsorption Studies on Magnetic Microbeads of Polythioether-arylamine Resins

By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).

STUDY ON MAGNETIC CHELATING RESIN Ⅱ.PREPARATION OF PSE2 AND ITS ADSORPTION PROPERTIES TO METAL IONS

Magnetic polythioether chelating resin (PSEZ) was pre-pared. Its average diameter was 0. 25mm and it contained magnetic parti-cles over 2,2% of the microcapsules after it had been treated with 2N hot HCl , and it ivould be destroyed in 5N hot HCl, The results showed that reaction medium had remarkable effect on physical forms of the microcap-sules. PSEZ had very high adsorption capacity to Au3+ and Hg2+, and little one towards Mg2+ , Pb2+. It was discovered that PSEZ could reduce Au3+ into elemental gold and Pti+to Pb2+.

SYNTHESES AND ADSORPTION PROPERTIES OF POLYMER RESINS CONTAINING BENZIDINE AND ITS DERIVATIVES

Three chelating resins were prepared by reacting poly (beta-chloroethyl glycidyl ether) with benzidine, o-tolidine and o-dianisidine respectively, and their structures were confirmed by IR spectra and elementary analyses. The adsorption properties of the resins for Au(III), pd(II), Pt(IV), Hg(II), Cu(II), Pb(II) and Zn(II) were also investigated. The results show that the resin incorporating o-dianisidine exhibits high affinity for Au(III) within a broad range of hydrochloric acid, and selectively sorbs Au(III) in the coexistance of Cu(II), Zn(II) and Mg(II). Desorption of Au(III), Pd(II) and Pt(IV) sorbed proceeded quantitatively using 0.1 mol/l hydrochloric acid containing 2%-10% thiourea as desorbents.

SYNTHESES AND PROPERTIES OF A CHELATING RESIN WITH MERCAPTO GROUPS

Chelating resins with thiol as functional group were synthesized from poly (β-chloroethyl gly-cidyl ether) . and adsorption of Au ( Ⅲ) , Pd (Ⅱ) , Pt (Ⅳ ), IIg ( Ⅱ ), Cu ( Ⅱ ) and Pb (Ⅱ) on the resins was also inrestigated. Both resins show high affinity for Au ( Ⅲ ),Pd( Ⅱ ) , Pt ( Ⅳ ) and Hg ( Ⅱ ) withina broad range of hydrochloric acid. Results of static and dynamic tests indicate the possibility of separation of Au ( Ⅲ ) , Pd ( Ⅱ ) , Pt ( Ⅳ ) and IIg (Ⅱ) from high concentrations of acid and neutral salt from high concentrations of acid and neutral salt solution.

ON THE SYNTHESES OF BENZIDINE CHELATE RESINS CONSISTING OF POLYETHER BACKBONE AND THEIR ADSORPTION PROPERTIES

Three new resins are synthesized by the reaction of polyepichlorohydrin with benzidine, O-tolidine and O-dianisidine, respecti v,ely. Their adsorption properties for Au(III), Pd(II), Pt(IV), Hg(II), Cu(II), Pb(II) and Zn(II) are investigated. The resin containing O-dianisidine group selectively sorbed Au(III) in the presence of transition metal ions. The results show that synergistic effect of anchor groups plays an important role in the adsorption of metal ions.

THE USE OF CHELATING RESIN FOR THE PRE-CONCENTRATION OF TRACE RARE EARTH ELEMENTS IN BIOLOGICAL SAMPLES AND THEIR DETERMINATION

Macroporous amino-carboxvlic chelating resin of acrylic acid series may concentrate trace rare earth in the presence of 0.1 mol/l α-hydroxy-isobutyric acid at pH 4.5.With 0.10 mol/l HCl as eluant rare earth may be eluted quantitatively and separated from Ca,Mg,Fe and Cu.This method is used to determine trace amount of rare earth in human hair,stone (in kidney and bladder),peanut,grape,strawberry,cucumber,pig liver and other biological samples.

Determination of Lanthanoids in Seawater by Inductively Coupled Plasma Mass Spectrometry after Pre-Concentration with a Chelating Resin Disk

A seawater sample was analyzed for its lanthanoids (Ln’s) contents by inductively coupled plasma mass spectrometry (ICP-MS). The analytical procedure included the pre-concentration and partial purification of Ln’s with a chelating resin disk and the employment of the combination of the internal standard and standard addition methods in ICP-MS, which seemed indispensable for the determination of low-level Ln’s by ICP-MS. The recoveries of the Ln’s with the disk were mostly 70% or better with the concentration factor of 200. The measured concentrations of Ln’s were on the order of ng?dm–3 or lower and reasonable except that of neodymium and samarium.

SYNTHESIS, CHARACTERIZATION, METAL-UPTAKE BEHAVIOR OF BIS(BENZIMIDAZOLE) RESIN SUPPORTED ON EPOXIDE POLYMER

The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis（2,3-epoxypropyl）benzene with the primary amine group of 1,3-bis（benzimidazol-2yl）propylamine （BBPAH）. The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2＋, Zn^2＋, Cd^2＋ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ （synthetic molar ratio = 1：1.5） under non-competitive condition were found to be 0.94 mmol/g for Cu^2＋ at pH = 2, 1.3 mmol/g for Cd^2＋ at pH = 1 and 1.75 mmol/g for Zn^2＋ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2＋ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2＋, Zn^2＋, Cd^2＋ and the contrary pH dependence.

Synthesis and Efficiency of a SphericalMacroporous Epoxy-dicyandiamide ChelateResin for Preconcentrating and SeparatingTrace Au, Hg, Pd and Ru from Samples

A novel spherical macroporous epoxy-dicyandiamide chelate resin was synthesized simply and rapidly from epoxy resin and used for the preconcentration and separation of trace amounts of Au (Ⅲ ), Hg (Ⅱ ), Pd (Ⅳ) and Ru (Ⅲ) ions from solution samples. The analyzed ions can be quantitatively concentrated by the resin at a flow rate of 2. 0 mL/min at pH 4, and can also be desorbed with 15 mL of 4 mol/L HCl + 0. 3 g thiourea from the resin column with recoveries of 96. 5%-99. 0%. After the chelate resin was reused for 7 times, the recoveries of these ions were still over 92%, and 400-1 000 times of excess of Fe(Ⅲ ), Al(Ⅲ ), Ni( II), Mn( Ⅱ ), Cr (Ⅲ ), Cu ( Ⅱ ), Cd (Ⅱ ) and Pb (Ⅱ ) caused little interference with the determination of these ions by an inductively coupled plasma optical emission spectrometer (ICP-OES ). The capacities of the resin for the analytes are in the range of 0. 35~0. 92 mmol/g. The RSDs of the proposed method are in the range of 1. 1 % ~4. 0% for each kind of the analyzed ions. The recoveries of a standard added in real solution samples are between 96. 5% and 98. 5%, and the results for the analyzed ions in a powder sample are in good agreement with their reported values.

SYNTHESIS OF SILICAS-SUPPORTED POLYETHYLENEIMINE AND ITS ADSORPTION PROPERTIES

Abstracts . In this paper, a silicas-supportedpolyethyleneimine resin is synthesized and its adsorption proper-ties are studied. Its selectivity of sorbing heavy metal ion will vary considerably as the pH value of solution varies. In hy-drochloric acid,the resin only sorbs Au(Ⅱ). This suggests that the resin is applicable to the separation of copper (Ⅱ) or gold (Ⅲ).

SYNTHESIS AND CHARACTERISTICS OF A CHELATING RESIN AS AN EXTRACTANT AND CHROMOGENIC REAGENT OF HEAVY METAL IONS IN SOLID PHASE EXTRACTION

A new chelating resin （CPS-DMA-SABA） was synthesized with the chloromethylated crossqinked polystyrene porous beads （CPS） as raw materials, which were bonded with salicylidene-o-aminobenzoic acid （SABA） on the surface via a quaternary ammonium unit as a linker. The results showed that CPS-DMA-SABA would easily change into a zwitterionic chelating resin （CPS-DMA-SABZ） when washed with distilled water. CPS-DMA-SABA was characterized by elemental analysis, infrared spectra and thermo-gravimetric analysis. The ion sorption capacities of CPS-DMA-SABA were found to be 1916 μg/g for Zn2＋ withpH at 4.5, 1620μg/g for Cu2＋ with pH at 6.2, 1291 μg/g for Ni2＋ withpH at 6.6 and 780 μg/g for Cr3＋ withpH at 5.5, respectively. The experiments showed CPS-DMA-SABA also changed its color when meeting with the metal ion in the aqueous solution. As a consequence, CPS-DMA-SABA can not only be used as a solid phase extractant but also an indicator for confirming the heavy metal ion in solutions.

Sequential separation of Cu(Ⅱ)/Ni(Ⅱ)/Fe(Ⅱ)from strong-acidic pickling wastewater with a two-stage process based on a bi-pyridine chelating resin

A self-synthesized bi-pyridine chelating resin(PAPY)could separate Cu(Ⅱ)/Ni(Ⅱ)/Fe(Ⅱ)sequentially from strong-acidic pickling wastewater by a two-stage p H-adjusted process,in which Cu(Ⅱ),Ni(Ⅱ),and Fe(Ⅱ)were successively preferred by PAPY.In the first stage(p H 1.0),the separation factor of Cu(Ⅱ)over Ni(Ⅱ)reached 61.43 in Cu(Ⅱ)-Ni(Ⅱ)-Fe(Ⅱ)systems.In the second stage(p H 2.0),the separation factor of Ni(Ⅱ)over Fe(Ⅱ)reached 92.82 in Ni(Ⅱ)-Fe(Ⅱ)systems.Emphasis was placed on the selective separation of Cu(Ⅱ)and Ni(Ⅱ)in the first-stage.The adsorption amounts of Cu(Ⅱ)onto PAPY were 1.2 mmol/g in the first stage,while those of Ni(Ⅱ)and Fe(Ⅱ)were lower than 0.3 mmol/g.Cu(Ⅱ)adsorption was hardly affected by Ni(Ⅱ)with the presence of dense Fe(Ⅱ),but Cu(Ⅱ)inhibited Ni(Ⅱ)adsorption strongly.Part of preloaded Ni(Ⅱ)could be replaced by Cu(Ⅱ)based on the replacement effect.Compared with the absence of Fe(Ⅱ),dense Fe(Ⅱ)could obviously enhance the separation of Cu(Ⅱ)-Ni(Ⅱ).More than 95.0%of Cu(Ⅱ)could be removed in the former 240 BV(BV for bed volume of the adsorbent)in the fixed-bed adsorption column process with the flow rate of 2.5 BV/h.As proved by X-ray photoelectron spectrometry(XPS)and density functional theory(DFT)analyses,Cu(Ⅱ)exerted a much stronger deprotonation and chelation ability toward PAPY than Ni(Ⅱ)and Fe(Ⅱ).Thus,the work shows a great potential in the separation and purification of heavy metal resources from strong-acidic pickling wastewaters.

Preparation and application of a novel orotic acid chelating resin for removal of Cu(Ⅱ) in aqueous solutions

A novel chelating resin OABA,capable of removing Cu（Ⅱ） from aqueous solution,was synthesized via the reaction of macroporous chloromethylated PS-DVB copolymer beads with orotic acid.The elemental analysis（EA）,Fourier transform infrared spectroscopy（FT-IR）,and scanning electron microscopy microscope-energy dispersive X-ray spectroscopy（SEM-EDS） were used in the characterization of the synthesized chelating resin.Multiple,static batch adsorption experiments were conducted at different initial concentrations and temperatures.OABA showed good adsorption capacity for Cu（Ⅱ） and the equilibrium data could be well matched with the Freundlich isotherm model.Coexisting sodium chloride and calcium chloride in solutions favored the Cu（Ⅱ） adsorption.Moreover,the desorption process of Cu（Ⅱ） was tested and over 90%regeneration efficiency for the spent OABA was achieved at ammonia concentrations ranging from 1.0%to 2.0%.The results suggested that OABA would be a potential alternative adsorbent for Cu（Ⅱ）,even with other heavy metal ion treatments of wastewater.

Effect of Fe loading quantity on reduction reactivity of nano zero-valent iron supported on chelating resin

In this study, nanoscale zero-valent iron （NZVI） were immobilized within a chelating resin （DOW 3N）. To investigate the effect of Fe loading on NZVI reactivity, three NZVI-resin composites with different Fe loading were obtained by preparing Fe（III） solution in 0, 30 and 70% （v/v） ethanol aqueous, respectively; the bromate was used as a model contami- nant. TEM reveals that increasing the Fe loading resulted in much larger size and poor dispersion of nanoscale iron particles. The results indicated that the removal efficiency of bromate and the rate constant （Kobs） were decreased with increasing the Fe loading. For the NZVI-resin composite with lower Fe loading, the removal efficiency ofbromate declined more significantly with the increase of DO concentrations. Under acidic conditions, decreasing the pH value had the most significant influence on NZVI- R3 with highest Fe loading for bromate removal; however, under alkaline conditions, the most significant influence of pH was on NZVI-R1 with lowest Fe loading. The effects of co-existing anions NO3, PO43- and HCO3- were also investigated. All of the co-existing anions showed the inhibition to bromate reduction.

Optimization of polyacrylonitrile-cysteine resin synthesis and its selective removal of Cu(Ⅱ) in aqueous solutions

Polyacrylonitrile beads（PAN） cysteine（CS） was synthesized from polyacrylonitrile beads（PAN） and cysteine（CS）.The content of the functional group and the percentage conversion of the functional group of PAN-CS prepared under the optimum condition using response surface methodology（RSM） for the first attempt were 3.22 mmol/g and 35.78%.The structure was characterized by ET-IR and elemental analysis.The adsorption properties of the resin for Cu（Ⅱ） were investigated by batch and column experiments.Batch adsorption results suggested that PAN-CS had higher adsorption capability for Cu（Ⅱ）than other metal ions and maximum saturated adsorption capacity was 184.7 mg/g.The resin and its metal complexes were studied by FT-IR.Furthermore,the resin can be eluted easily using 1 mol/L HC1.PAN-CS can provide a potential application for selective removal of copper from waste solution.