Synthesis of novel silica-supported chelating resin containing tert-butyl 2-picolyamino-N-acetate and its properties for selective adsorption of copper from simulated nickel electrolyte

A novel silica-supported tert-butyl 2-picolyamino-N-acetate chelating resin (Si-AMPY-1) was successfully synthesized and characterized by elemental analysis, FT-IR, SEM and 13 C CP/MAS NMR. The adsorption behaviors of the Si-AMPY-1 resin for Cu(Ⅱ) and Ni(Ⅱ) were studied with batch and column methods. The batch experiments indicated that the Si-AMPY-1 resin adsorbed Ni(Ⅱ) mainly via physisorption, while adsorbed Cu(II) via chemisorption. The column dynamic breakthrough curves revealed thatthe Si-AMPY-1 resin can efficiently separate Cu(Ⅱ) from the simulated nickel electrolyte before the breakthrough point. Moreover, the concentration of Cu(Ⅱ) in the column effluent was decreased to be less than 3 mg/L within the first 43 BV (bed volumes), and the mass ratio of Cu/Ni was 21:1 in the saturated resin, which completely satisfied the industrial requirements of the nickel electrorefining process. Therefore, it was concluded that the Si-AMPY-1 resin can be a promising candidate for the deep removal of Cu(Ⅱ) from the nickel electrolyte.

Fixed-bed column study for deep removal of copper(Ⅱ) from simulated cobalt electrolyte using polystyrene-supported 2-aminomethylpyridine chelating resin

This study presents the deep removal of copper (Ⅱ) from the simulated cobalt electrolyte using fabricated polystyrene-supported 2-aminomethylpyridine chelating resin (PS-AMP) in a fixed-bed.The effects of bed height (7.0–14.0 cm),feed flow rate (4.5–9.0 mL/min),initial copper (Ⅱ) concentration of the feed (250–1000 mg/L),feed temperature (25–40 ℃) and the value of pH (2.0–4.0) on the adsorption process of the PS-AMP resin were investigated.The experimental data showed that the PS-AMP resin can deeply eliminate copper (Ⅱ) from the simulated cobalt electrolyte.The bed height,feed flow rate,initial copper (Ⅱ) concentration of the feed,feed temperature and feed pH value which corresponded to the highest removal of copper (Ⅱ) were 7.0 cm with 35 mm of the column diameter,4.5 mL/min,40℃,1000 mg/L and 4.0,respectively.The breakthrough capacity,the saturated capacity of the column and the mass ratio of Cu/Co (g/g) in the saturated resin were correspondingly 16.51 mg/g dry resin,61.72 mg/g dry resin and 37.67 under the optimal experimental conditions.The copper (Ⅱ) breakthrough curves were fitted by the empirical models of Thomas,Yoon-Nelson and Adam-Bohart,respectively.The Thomas model was found to be the most suitable one for predicting how the concentration of copper (Ⅱ) in the effluent changes with the adsorption time.

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.

Synthesis of modified D401 chelating resin and its adsorption properties for Pb^(2+)

A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating resin for Pb2+ were studied by batch adsorption, and the adsorption process was analyzed from thermodynamics and kinetics aspects. The adsorption mechanism of Pb2+ on the modified D401 chelating resin was discussed by FT-IR spectrometry. Experimental results show that in the Pb2+ concentration range of 200-400 mg/L, the adsorption capacities of the modified D401 chelating resin for Pb2+ increase by 77%-129%, and Langmuir isothermal adsorption model is more suitable for the equilibrium adsorption data. Adsorption is an endothermic process that runs spontaneously. Kinetic analysis shows that the adsorption rate is mainly governed by liquid film diffusion. The best pH value under adsorption condition is 4-5. The saturated resin can be regenerated by 3 mol/L nitric acid, and the adsorption capacity remains stable after five consecutive adsorption-desorption cycles. The maximal static saturated adsorption capacity of the resin is 206 mg/g at 333 K in the Pb2+ concentration range of 200-400 mg/L. The modified D401 chelating resin is an efficient adsorbent for the removal of Pb2+ from its single-metal ion solution.

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.

Arsenic Removal from Pinctada martensii Enzymatic Hydrolysate by Using Zr(Ⅳ)-Loaded Chelating Resin

The present study investigated the removal of inorganic arsenic from Pinctada martensii enzymatic hydrolysate through unmodified resin （D296） and Zr（IV）-loaded chelating resin （Zr-D401）. By loading Zr to macroporous chelating resin D401, the as exchange adsorption active sites are generated. This transforms D401 from a material that does not have the arsenic adsorption capacity into a material that has excellent arsenic exchange adsorption capacity. The static adsorption experiments were conducted to investigate the optimal removal condition for D296 and Zr-D401. The experimental results show that： the optimum condition for D296 is that T= 25℃, pH= 5, resin additive amount= 1 g （50 mL）-1, and contact time = 10 h, the corresponding arsenic removal rate being 65.7%, and protein loss being 2.33%; the optimum condition for Zr-D401 is that T=25 ℃, pH = 8, resin additive amount= 1 g （50 mL）-1, and contact time=10 h, the corresponding arsenic removal rate being 70.3%, and protein loss being 4.65%. These results show that both of the two resins are effective in arsenic removal for preserving useful substance. Our research provides scientific evidence and advances in the processing technology for heavy metal removal in shellfish.

Poly(styrene-co-divinylbenzene)-PAMAM-IDA chelating resin: Synthesis, characterization and application for Ni(II) removal in aqueous

PS-PAMAM-IDA chelating resins were prepared by low-generations of polyamidoamine(PAMAM) and then chloroacetic acid functionalizing commercially available ammoniated polystyrene matrix, to preconcentrate Ni2+ from synthetic aqueous samples. Different generations of PAMAM were used to obtain different chelating resins, PS-IDA, PS-1.0G PAMAM-IDA and PS-2.0G PAMAM-IDA. The synthesized resins were characterized by FTIR and elemental analysis. The effect of solution pH, kinetic studies, resin loading capacity, matrix effects etc., on metal ion adsorption to adsorbent phase, were studied by batch method. The PS-1.0G PAMAM-IDA resin was the most excellent adsorbents, with a maximum adsorption capacity of(24.09±1.79) mg/g for Ni2+ ion at pH=7. The interpretation of the equilibrium data was given by Langmuir isotherms model, and the correlation coefficient values for PS-IDA, PS-1.0G PAMAM-IDA and PS-2.0G PAMAM-IDA resins were 0.992, 0.994 and 0.987, respectively.

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.

SYNTHESIS OF A NOVEL CHELATING RESIN WITH HETEROCYCLIC RING OF S AND N

By the reaction of poly(bromoacetyl styrene) (EBPS) with thiaurea (TU), a kind of novel chelating resin with heterocyaclic ring of sulfur and nitrogen, poly[4-(2-amino)thiazoleyl-4- vinylbenzene], was synthesized. Its structure was characterized by FTIR and elemental analysis. The factors which have influence on the reaction such as reaction time, solvents, and molar ratio of reactants were investigated.

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+.

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.

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.

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.

STUDY ON DETERMINATION OF TRACE Cu（Ⅱ） BY DDCT CHELATING RESIN PRECONCENTRATION AND THIN LAYER RESIN PHASE SPECTROPHOTOMETRY

A new method for determination of Cu（Ⅱ） by DDCT chelating resin preconcentration and thin layer resin phase spectrophotometry was developed. The method has a high sensitivity （ε455= 3.6×10^5L/mol·cm）, which is 33 times higher than that of liquid phase spectrophotometry. It has a good selectivity （most coexisting ions could not influence determination） and an ideal precision [30μg Cu（Ⅱ）, n=6, RSD= l.67%]. The content of Cu（Ⅱ） in water, high purity rare earth and its oxide was determined. The detection limit of Cu（Ⅱ） is 5.3μg/L , and the linear range is 0-7.2μg/ml. The result is satisfactory.

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.

STUDY ON THE KINETICS OF POLYMERIZATION OF MMA BY COPPER（Ⅱ） CHELATING RESINS

The polymerization of MMA initiated by copper(Ⅱ） chelating resins/CCl4 system was studied.From the kinetic data,the kinetic equation of polymerization can be expressed as Rp=Ke^-56400/RT[MMA]^1.57[CCl4]^m[RESIN-Cu]^0.18 where m:3-4.5,when[CCl4] 0.1-6.93M.The free radical polymerization mechanism is proposed.The primary radicals are formed by the process of complexation-chlorine transformation among the copper(Ⅱ) chelating resin,CCl4 and methacrylate.

INVESTIGATION ON PRODUCTION OF REFINED BRINE USED IN CHLORO-ALKALI MEMBRANE BY CHELATING RESIN D412

The adsorption property, the operating life, the operating exchange capacity and regeneration of D412 macroporous phosphonomethylamina chelating resin for removing Ca2+, Mg2+ and Fe2+ from high pH brine of alkali production by ionic membrane were investigated. The resin showed good physical-chemical and kinetic property, high exchange capacity, excellent durability.

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 of new hyper cross-linked chelating resin for adsorption of Cu^(2+) and Ni^(2+) from water

The new hyper cross-linked chelating resin NDWJN2 modified with carboxyl groups was prepared for removal of Cu^（2＋） and Ni^（2＋） from water.NDWJN2 was characterized using BET,SEM and FT-IR spectroscopy.Comparing with commercial resins D113 and IRC84,NDWJN2 could remove Cu^（2＋） and Ni^（2＋） from water more effectively.Langmuir model could fit adsorption isotherms well.