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1.
The structures of different Cu(II)-thiol, dithiocarbamate, methylthiourea and amino complexes have been investigated on the basis of their spectroscopic properties. The influence of the chemical structure, both the nature of the functional groups and the spacers, on the resin chelating behaviour towards Cu(II) ions in diluted solution has been evaluated. The resins are macroporous polystyrene–divinylbenzene polymer functionalized with two spacer groups, poly(ethylene glycol) and poly(ethylene imine) chains, supporting thiol, dithiocarbamate, methylthiourea and amino groups. Electron paramagnetic resonance (EPR) was employed to show the coordination of Cu(II) ions into the complexes. Cu(II)-dithiocarbamate complexes have a square planar coordination with two dithiocarbamate groups bound to the metal. The resins with methylthiourea as functional group form Cu(II)-complexes in tetragonal symmetry with four nitrogen atoms as equatorial ligands. Further, a partial reduction of Cu(II) to diamagnetic Cu(I) with formation of Cu(I)-methylthiourea complexes, where copper is S-bonded to the methylthiourea group, could be suggested. In Cu(II)-thiol complexes, Cu(II) ions are bound through sulfur bridges.  相似文献   

2.
Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO3. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000  相似文献   

3.
《分离科学与技术》2012,47(6):1245-1254
Abstract

In this study, Poly(N,N dimethyl‐amino ethylmethacrylate) (Poly(DMAEMA)) hydrogels with varying compositions were prepared in the form of rods by irradiating ternary mixtures of N,N‐dimethylamino ethylmethacrylate/ethyleneglycoldimethacrylate/water with gamma rays at ambient temperature. Swelling studies of poly (DMAEMA) hydrogels were performed at different pH values and maximum swelling values reached at pH 2. The adsorption characteristics of Pb(II), Cd(II), Ni(II), Zn(II), Cu(II), and Co(II) ions to poly(N,N dimethylamino ethylmethacrylate) hydrogels were investigated by a batch process. The order of affinity based on amount of metal ion uptake was found as follows: Cu(II)>Zn(II)?Co(II)>Pb(II) >> Ni(II)>Cd(II). In the adsorption studies of Cu(II), Zn(II), Co(II), Pb(II), Ni(II), and Cd(II) ions the Langmuir type adsorption isotherms were observed for all gel systems.  相似文献   

4.
Crosslinked poly(acrylic acid), PAA, and poly(2‐acrylamidoglycolic acid), PAAG, were synthesized by radical polymerization. Both resins contain carboxylic acid groups. PAA at basic pH exists basically as an acrylate anion and PAAG shows three atoms or groups, carboxylic acid, hydroxyl, and amide groups, that can act as ion exchanger or chelating groups. Both resins are studied as adsorbents to trace metal ions from saline aqueous solutions and natural sea water and their properties by Batch equilibrium procedure are compared. The metal ions studied under competitive and noncompetitive conditions were Cu(II), Pb(II), Cd(II), and Ni(II). The effects of pH, time of contact, amount of resin, temperature, and salinity were studied. Resin PAA shows a high affinity (>80%) for Cu(II) and Cd(II) and resin PAAG shows also a high affinity for Ni(II), Pb(II), and Cd(II). By treatment of the metal ion‐loaded resin with 4M HNO3 it is possible to recover completely the Cu(II) ions from resin PAA and Ni(II) and Pb(II) from resin PAAG. The metal ion retention properties were studied with natural sea water. For those natural sea waters containing Cu(II) and Cd(II), the resins showed a high affinity for Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 697–705, 2006  相似文献   

5.
The complexation behaviour of dithiocarbamate functions supported on polyacrylamides with varying extents (2-20 mol%) of N,N′-methylene-bis-acrylamide (NNMBA) crosslinks was investigated. The crosslinked polyacrylamides were prepared by the free radical solution polymerization of the monomers in water at 80°C using potassium persulphate as initiator. The dithiocarbamate ligands were introduced by polymer-analogous reaction involving transamidation with ethylenediamine and dithiocarbamylation with carbon disulphide and alkali. The complexation behaviour of these dithiocarbamate resins with the ligand functions in different macromolecular environments were investigated towards Co(II), Ni(II), Cu(II), Zn(II) and Hg(II) ions by a batch equilibration technique. The metal ion intake varied with the extent of the NNMBA-crosslinking. Thus the 8% crosslinked system has the highest complexation capacity. The values for metal ion intake followed the order Hg(II)> Cu(II)> Zn(II)> Ni(II)> Co(II). The time-course of complexation, the possibility of recycling and the swelling characteristics of the uncomplexed and complexed resins were considered, and IR characterization and thermal studies were undertaken. The swelling values of the complexed resins are lower than those of the uncomplexed resins. The thermal stability of dithiocarbamates varied with the extent of NNMBA-crosslinks and with the metal ion.  相似文献   

6.
Various adsorbent materials have been reported in the literature for heavy metal removal. We have developed a novel approach to obtain high metal sorption capacity utilising cysteine containing adsorbent. Metal complexing aminoacid-ligand cysteine was immobilised onto poly(hydroxyethylmethacrylate) (PHEMA) microbeads. PHEMA-cysteine affinity microbeads containing 0.318 mmol cysteine/g were used in the removal of heavy metal ions (i.e. copper, lead and cadmium) from aqueous media containing different amounts of these ions (50–400 mg/l for Pb(II) and Cd(II), 25–60 mg/l for Cu(II)) and at different pH values (4.0–7.0). The maximum adsorption capacity of heavy metal ions onto the cysteine-containing microbeads under non-competitive conditions were 0.259 mmol/g for Pb(II), 0.330 mmol/g for Cd(II) and 0.229 mmol/g for Cu(II). The affinity order was observed as follows: Cd(II)>Pb(II)>Cu(II). The competitive adsorption capacities of the heavy metals were 0.260 mmol/g for Cd(II) and 0.120 mmol/g for Cu(II). Pb(II) adsorption onto cysteine-immobilised microbeads was zero under competitive conditions. The affinity order was as follows: Cd(II)>Cu(II)>Pb(II). The formation constants of cysteine–metal ion complexes have been investigated applying the method of Ruzic. The calculated value of stability constants were 1.75×104 l/mol for Pb(II)–cysteine complex and 4.35×104 l/mol for Cd(II)–cysteine complex and 1.39×104 l/mol for Cu(II)–cysteine complex. PHEMA microbeads carrying cysteine can be regenerated by washing with a solution of hydrochloric acid (0.05 M). The maximum desorption ratio was greater than 99%. These PHEMA microbeads are suitable for repeated use for more than three adsorption–desorption cycles without considerable loss in adsorption capacity.  相似文献   

7.
Poly(methyl methacrylate) (PMMA) microspheres carrying poly(ethylene imine) (PEI) were prepared for the removal of heavy‐metal ions (copper, cadmium, and lead) from aqueous solutions with different amounts of these ions (50–600 mg/L) and different pH values (3.0–7.0). Ester groups in the PMMA structures were converted to imine groups in a reaction with PEI as a metal‐chelating ligand in the presence of NaH. The adsorption of heavy‐metal ions on the unmodified PMMA microspheres was very low [3.6 μmol/g for Cu(II), 4.6 μmol/g for Cd(II), and 4.2 μmol/g for Pb(II)]. PEI immobilization significantly increased the heavy‐metal adsorption [0.224 mmol/g for Cu(II), 0.276 mmol/g for Cd(II), and 0.126 mmol/g for Pb(II)]. The affinity order of adsorption (in moles) was Cd(II) > Cu(II) > Pb(II). The adsorption of heavy‐metal ions increased with increasing pH and reached a plateau value around pH 5.5. Their adsorption behavior was approximately described with the Langmuir equation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 197–205, 2001  相似文献   

8.
Three network crown ether resins with a high content of pendent functional groups were prepared and characterized by IR, elemental analysis, and thermal analysis. The slight variance of the thermal stability of the resins was related to the kind and content of the pendent functional group. The adsorption capacity of the resins for Mg(II), Cu(II), Co(II), Pb(II), and Hg(II) was determined. Toward Hg(II), the adsorption capacity of the resins was high and the adsorption process was easy and spontaneously performed. The XPS study showed that the adsorption of the NCR–SN resin toward Cu(II), Pb(II), and Hg(II) was mainly the coordinate interactions between the ligand atom (S, N) of the pendent functional groups and the metal ions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1457–1465, 2000  相似文献   

9.
《分离科学与技术》2012,47(3):579-590
Abstract

Adsorption gel was prepared from waste recycled paper by immobilizing iminodiacetic acid (IDA) functional group by chemical modification. The gel exhibited good adsorption behavior for a number of metal ions viz. Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. The order of selectivity was found to be as follows: Cu(II)>Pb(II)>Fe(III)>Ni(II)~Cd(II)~Co(II). From the adsorption isotherms, the maximum adsorption capacity of the gel for both Cu(II) and Pb(II) was found to be 0.47 mol/kg whereas that for Cd(II) was 0.24 mol/kg. A continuous flow experiment for Cd(II) showed that the gel can be useful for pre‐concentration and complete removal of Cd(II) from aqueous solution.  相似文献   

10.
《分离科学与技术》2012,47(5):729-741
Chelating PS-EDTA resins modified by metal (Fe, Al, and Zr) oxides were used as adsorbents to remove Hg(II) from aqueous solutions. The modified resins were characterized by BET, FTIR, and XPS. The amino, carboxylate, and the metal oxides on resins exhibited a synergistic effect for Hg(II) removal. It was observed that the modification of PS-EDTA resin not only increased the adsorption of Hg(II) but also accelerated the adsorption rate of Hg(II). The equilibrium data of Hg(II) were best described by the Freundlich isotherm, and the kinetics were found to follow the pseudo-second-order kinetic model. Also, thermodynamic parameters showed that Hg(II) adsorption was endothermic and spontaneous in nature. The increasing the concentration (0.1–2.0 g/L) of NaNO3 in Hg(II) solution did not affect the adsorption of Hg(II). Moreover, the competitive adsorption indicated that the modified resins had higher selectivity towards Hg(II) over Cd(II), Pb(II), Zn(II), or Cu(II) in a binary system. All of the above results indicated that the modified resin was an efficient and reusable adsorbent for Hg(II) removal due to its simple preparation, high adsorption capacity, fast adsorption rate, ionic strength independence, high selectivity, and good reusability. These properties are of potential application in the fixed-bed continuous-flow column for Hg(II) removal from wastewaters.  相似文献   

11.
In this study, a fibrous adsorbent containing amidoxime groups was prepared by graft copolymerization of acrylonitrile (AN) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (Bz2O2) as initiator in aqueous solution, and subsequent chemical modification of cyano groups by reaction with hydroxylamine hydrochloride in methanol. The grafted and modified fibers were characterized by FTIR, TGA, SEM, and XRD analysis. The crystallinity increased, but thermal stability decreased with grafting and amidoximation. The removal of Cu(II), Ni(II), Co(II), Pb(II), and Cd(II) ions from aqueous solution onto chelating fibers were studied using batch adsorption method. These properties were investigated under competitive conditions. The effects of the pH, contact time, and initial ion concentration on the removal percentage of ions were studied. The results show that the adsorption rate of metal ions followed the given order Co(II) > Pb(II) > Cd(II) > Ni(II) > Cu(II). The percentage removal of ions increased with initial ion concentration, shaking time, and pH of the medium. Total metal ion removal capacity was 49.75 mg/g fiber on amidoximated fiber. It was observed that amidoximated fibers can be regenerated by acid without losing their activity, and it is more selective for Pb(II) ions in the mixed solution of Pb‐Cu‐Ni–Co‐Cd at pH 4. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

12.
1,4,8,11‐Tetraazacyclotetradecane (cyclam) was reacted with acryloyl chloride in a 1 : 2 molar ratio in dichloromethane in the presence of pyridine at 0°C. The modified cyclam was polymerized by adding an azobisisobutyronitrile initiator and irradiated with a UV lamp under reflux for 6 h. Precipitated cyclam containing polymer in the bulk structure was removed from the suspension by filtration. After washing and drying the final polymeric materials were used for transition metal ion adsorption and desorption studies. A Fourier transform IR spectrophotometer and thermogravimetric analyzer were used to characterize the polymeric structure. The affinity of the polymeric material for transition metal ions was used to test the adsorption–desorption of selected ions [Cu(II), Ni(II), Co(II), Cd(II), Pb(II)] from aqueous media containing different amounts of these metal ions (5–800 ppm) at different pH values (2.0–8.0). It was found that the adsorption rates were high and the adsorption equilibrium was reached in about 30 min. The uptake of the transition metal ions onto the polymer from solutions containing a single metal ion was 3.17 mmol/g for Cu(II), 0.98 mmol/g for Cd(II), 0.79 mmol/g for Co(II), 0.78 mmol/g for Ni(II), and 0.32 mmol/g for Pb(II). This polymer showed high affinity for Cu(II) compared to the other metal ions in the single ion solution and in the mixture of transition metal ions. The affinity order of the transition metal ions was Cu(II) ? Ni(II) > Cd(II) > Co(II) > Pb(II) for competitive adsorption. More than 95% of the adsorbed transition metal ions were desorbed in 2 h in a desorption medium containing 1.0M HNO3. Poly(cyclam) was found to be suitable for repeated use of more than five cycles without a noticeable loss of adsorption capacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1406–1414, 2002  相似文献   

13.
A dye ligand Cibacron Blue F3GA, was covalently coupled with polyhydroxyethylmethacrylate (PHEMA) microbeads in the 150–200 μm particle size range. The sorbent carrying 22.3 μmol Cibacron Blue F3GA per gram of polymer was then used to remove Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions in a packed-bed column system. Heavy metal ion adsorption capacity of the column was investigated as a function of heavy metal ion-bearing solution flow rate and the inlet heavy metal ion concentration. The maximum metal ion uptake values found were: 80.60, 96.98, 78.36, 103.98 μmol/g polymer for Pb(II), Cd(II), Cu(II) and Zn(II), respectively. The heavy metal adsorption capacity of the microbeads decreased with an increase in the circulation rate of aqueous solution. The order of affinity based on molar uptake was Zn(II)>Cd(II)>Pb(II)>Cu(II). Removal percentages of heavy metals related to flow time were determined for different flow rates and initial metal ion concentrations. It was observed that PHEMA microbeads carrying Cibacron Blue F3GA can be regenerated by washing with a solution of nitric acid (0.05 M). The desorption ratio was as high as 98.5%.  相似文献   

14.
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  相似文献   

15.
Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.  相似文献   

16.
The removal of mercury and lead ions from aqueous solutions investigated by ethylenediamine, diethylenetriamine and tetraethylenepentamine functionalized polymeric adsorbent. The adsorbent was prepared by amination of terpolymer synthesized from glycidylmethacrylate, styrene and N,N′-methylenebisacrylamide. In the single metal species system (only mercury or lead ions are present) poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA), and poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA) were found to adsorb lead or mercury ions with a slightly higher adsorption uptake capacity for lead than mercury ions. Among the three functionalized polymers poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA) shows faster and higher adsorption capacity than poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA). The natural pH of both the metal ions was found to be most suitable for uptake. The uptake of Hg(II) and Pb(II) ions was investigated by using batch technique. The maximum adsorption capacities of Pb ions were predicted to be 4.74, 4.76 and 4.73 mmol/g and the maximum Hg(II) ion uptakes were found to be 4.76, 4.80 and 4.21 mmol/g respectively for PGMA–EDA, PGMA–DETA and PGMA–TEPA resins at their natural pH. The uptakes of Hg(II) and Pb(II) ions on the resins were found to follow Langmuir adsorption isotherm and pseudosecond order kinetics.  相似文献   

17.
The crosslinked resins poly(acrylic acid) (PAA) and poly[N‐3‐(dimethylamino)propyl acrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] are obtained by radical polymerization and characterized by FTIR spectroscopy. PAA at basic pH exists basically as an acrylate anion that may contain end carboxylate groups or form bridges acting as mono‐ or bidentate ligands. P(NDAPA‐co‐AA) presents three potential ligand groups in its structure: carboxylic acid, amide, and amine. The trace metal ion retention properties of these two resins is compared by using the batch equilibrium procedure. The metal ions are contained in saline aqueous solutions and are found in natural seawater. The retention of Cu(II), Pb(II), Cd(II), and Ni(II) metal ions is studied under competitive and noncompetitive conditions. The effects on the pH, contact time, amount of adsorbent, temperature, and salinity are investigated. The PAA resin presents a high affinity (>80%) for Cu(II) and Cd(II) ions. The P(NDAPA‐co‐AA) resin shows a high affinity for Pb(II) and Cd(II) ions. With 4M HNO3 it is possible to completely recover the PAA resin charged with Cu(II) ions and the P(NDAPA‐co‐AA) resin charged with Pb(II) ions. The two resins show a high affinity for Cd(II) ions from the seawater containing Cu(II) and Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1385–1394, 2005  相似文献   

18.
Poly(N‐vinyl‐2‐pyrrolidone) and poly(N‐vinyl‐2‐pyrrolidone/acrylic acid) hydrogels were prepared by gamma irradiation for the removal of heavy metal ions (i.e., lead, copper, zinc, and cadmium) from aqueous solutions containing different amounts of these ions (2.5–10 mg/L) and at different pH values (1–13). The observed affinity order in adsorption of these metal ions on the hydrogels was Zn(II) > Pb(II) > Cu(II) > Cd(II) under competitive conditions. The optimal pH range for the heavy metal ions was from 7 to 9. The adsorption of the heavy metal ions decreased with increasing temperature in both water and synthetic seawater conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2013–2018, 2003  相似文献   

19.
《分离科学与技术》2012,47(8):1313-1320
The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.  相似文献   

20.
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  相似文献   

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