[go: up one dir, main page]

WO2010098257A1 - Résine chélatante - Google Patents

Résine chélatante Download PDF

Info

Publication number
WO2010098257A1
WO2010098257A1 PCT/JP2010/052514 JP2010052514W WO2010098257A1 WO 2010098257 A1 WO2010098257 A1 WO 2010098257A1 JP 2010052514 W JP2010052514 W JP 2010052514W WO 2010098257 A1 WO2010098257 A1 WO 2010098257A1
Authority
WO
WIPO (PCT)
Prior art keywords
chelate resin
group
capture
polymer carrier
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/052514
Other languages
English (en)
Japanese (ja)
Inventor
井上嘉則
梁井英之
齊藤満
加賀谷重浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Filcon Co Ltd
University of Toyama NUC
Original Assignee
Nippon Filcon Co Ltd
University of Toyama NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Filcon Co Ltd, University of Toyama NUC filed Critical Nippon Filcon Co Ltd
Publication of WO2010098257A1 publication Critical patent/WO2010098257A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/10—Acylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • the present invention is a chelating resin used for removal and recovery of heavy metal elements from solution to be treated such as factory effluent, irrigation water, environmental water, food, medicine, etc., and alkaline earth metals present in a large amount in the solution to be treated.
  • Aminocarboxylic acid-type chelating resin capable of highly capturing heavy metal elements including oxoacids of metals that are not disturbed and that are very difficult to capture with existing aminocarboxylic acid-type chelating resins, and a method for producing the same It is about.
  • chelating resins into which functional groups such as iminodiacetic acid (IDA), polyamine, aminophosphoric acid, isothiouronium, dithiocarbamic acid, and glucamine are introduced are commercially available.
  • IDA iminodiacetic acid
  • polyamine aminophosphoric acid
  • isothiouronium aminophosphoric acid
  • dithiocarbamic acid and glucamine
  • a kind of IDA type chelate resin of aminocarboxylic acid is often used.
  • the IDA type chelate resin has a lower stability constant of the complex than ethylenediaminetetraacetic acid (EDTA), which is a typical chelating agent. Therefore, there is a problem that the removal rate and recovery rate of heavy metals are likely to fluctuate.
  • EDTA ethylenediaminetetraacetic acid
  • the ease of forming metal complexes of chelating functional groups is generally determined by the stability constant (log K ML ). Indicated by In polyaminocarboxylic acid type chelating agents, although depending on the metal element, the greater the number of ethyleneimine repeating units or the longer the chain length of the polyethyleneimine chain, the greater the stability constant of the complex. The constant is not so large (Non-patent Document 1 and Non-Patent Document 2). This means that the longer the chain length, the higher the metal trapping property, and the relative selectivity with calcium is relatively improved. In order to solve the problem of low metal capture and selectivity in IDA type chelate resins, there are several prior art documents regarding new aminocarboxylic acid type chelate resins aimed at improving metal capture and selectivity. Are known.
  • Patent Document 1 nitrilotriacetic acid type chelate resin using ⁇ -amino- ⁇ -caprolactam as a starting material
  • Patent Document 2 diethylenetriamine-N, N, N ′, N′-tetraacetic acid type obtained by introducing diethylenetriamine and carboxymethylating Chelate resin
  • Patent Document 3 diethylenetriamine-N, N ′, N ′′, N ′′ -tetraacetic acid type chelate resin introduced with carboxymethyl by diethylenetriamine or the like
  • Patent Document 4 an anion exchange resin having a tertiary amino group
  • High-molecular-weight chelating resins having quaternary ammonium groups that have been carboxymethylated after introduction of high-molecular-weight polyethyleneimine are disclosed.
  • Patent Document 3 discloses a chelate resin in which a diethylenetriamine or triethylenetetramine skeleton functional group having a chain length longer than that of a conventional iminodiacetic acid type chelate resin is introduced.
  • Patent Document 4 is intended for metal capture in an organic solvent using a chelate resin in which a long-chain polyethyleneimine is bound to an ion exchange group of an ion exchange resin. The metal capture property is improved by utilizing the stretched state.
  • a chelate resin obtained by further carboxymethylating a polyamine type chelate resin is also described, according to the examples, the degree of carboxymethylation is very low, the carboxymethyl group is auxiliary, and is the same as the polyamine type chelate resin. .
  • a chelate resin NOBIAS Chelate-PA1 manufactured by Hitachi High-Technologies Corporation which has a function to hardly interfere with alkaline earth metals under acidic conditions has been marketed.
  • This chelate resin has diethylenetriamine-N, N ′, N ′′, N ′′ -tetraacetic acid type functional groups introduced therein and has the same functional group structure as the chelate resin disclosed in Patent Document 3.
  • This chelate resin should not trap alkaline earth metals under acidic conditions (see Non-Patent Document 3 to Non-Patent Document 5). Although it is not clear about the mechanism by which this alkaline earth metal is difficult to be trapped, it depends on the imino group remaining in the resin.
  • the aminocarboxylic acid type chelate resin is supposed to capture a wide range of metals, but has a low ability of capturing metals that form oxo acids such as arsenic, molybdenum, and vanadium.
  • Chromium Cr (III) (trivalent) forms a strong complex with aminocarboxylic acid, but the complex formation rate is slow, and it is difficult to obtain a high degree of capture in a state where the liquid to be treated is flowed.
  • Japanese Patent Laid-Open No. 5-71000 JP 2008-115439 A Japanese Patent Laying-Open No. 2005-213477 Japanese Patent Laid-Open No. 2005-21883
  • the problem to be solved by the invention is that heavy metals from the solution to be treated can be obtained without being disturbed by alkaline earth metals present in large amounts in the solution to be treated such as factory effluent, irrigation water, environmental water, food and medicine.
  • An object of the present invention is to provide a chelate resin capable of removing and highly capturing valuable heavy metals, and a method for producing the same.
  • the present invention provides a halogenated compound that is subjected to a reaction when carboxymethylating a polymer support having a polyethyleneimine skeleton having an optimal molecular weight (chain length) using an halogenated acetic acid in an alkaline solution. It has been found that by adjusting the amount of acetic acid, it is possible to produce a chelate resin having an excellent heavy metal scavenging property and a function in which alkaline earth metals are not easily captured.
  • the chelating functional group introduced into the polymer carrier is a compound having a polyethyleneimine skeleton and is carboxymethylated with halogenated acetic acid after introduction.
  • carboxymethylation is performed using halogenated acetic acid under alkaline conditions.
  • the amount of acetic acid is 1.0 to 3.0 times the amount of nitrogen in the compound having a polyethyleneimine skeleton introduced into the polymer carrier.
  • the compound having a polyethyleneimine skeleton has an average molecular weight of 200 to 600.
  • Examples of the reactive functional group possessed by the polymer carrier include a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group, which are functional groups that react with amines.
  • the polymer carrier having a reactive functional group used in the present invention includes a reactive monomer having an epoxy group that reacts with an amine such as glycidyl methacrylate or a halogenated alkylstyrene (chloromethylstyrene) or a halogenated alkyl group, and a crosslinkable monomer. And a copolymer.
  • the present invention provides a polymer carrier having a reactive functional group such as 1) a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine. 3) a chelating resin obtained by reacting a compound having a polyethyleneimine skeleton, and 3) reacting a halogenated acetic acid in an amount of 1.0 to 3.0 times the amount of nitrogen in the compound having a polyethyleneimine skeleton in an alkaline solution. And its manufacturing method.
  • a reactive functional group such as 1) a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine.
  • the chelate resin of the present invention has the property of not capturing alkaline earth metals under acidic conditions, it removes heavy metals from wastewater and water, etc., and valuable metals from environmental water and metal treatment solutions such as seawater and river water Can be efficiently recovered. Furthermore, it can be used for pretreatment applications such as removal of interfering elements in instrumental analysis of trace metals and extraction / concentration of analysis target elements.
  • FIG. 1 shows a comparison of metal (10 types) capture characteristics between the chelate resin A of Example 1 and a commercially available IDA type resin.
  • FIG. 1a shows a comparison of copper Cu capture characteristics.
  • FIG. 1b shows a comparison of nickel Ni capture characteristics.
  • FIG. 1c shows a comparison of the capture properties of cadmium Cd.
  • FIG. 1d shows a comparison of lead Pb capture characteristics.
  • FIG. 1e shows a comparison of the trapping properties of magnesium Mg.
  • FIG. 1f shows a comparison of calcium Ca capture properties.
  • FIG. 1g shows a comparison of the capture properties of chromium Cr (III) (trivalent).
  • FIG. 1h shows a comparison of the molybdenum Mo capture characteristics.
  • FIG. 1a shows a comparison of metal (10 types) capture characteristics between the chelate resin A of Example 1 and a commercially available IDA type resin.
  • FIG. 1a shows a comparison of copper Cu capture characteristics.
  • FIG. 1b shows a comparison
  • FIG. 1i shows a comparison of the trapping properties of vanadium V.
  • FIG. 1j shows a comparison of the arsenic As capture characteristics.
  • FIG. 2 shows a comparison of the trapping characteristics of 10 types of metals between the chelate resin A of Example 1 and a commercially available polyaminocarboxylic acid type chelate resin.
  • FIG. 2a shows a comparison of the capture characteristics of copper Cu.
  • FIG. 2b shows a comparison of nickel Ni capture characteristics.
  • FIG. 2c shows a comparison of the capture properties of cadmium Cd.
  • FIG. 2d shows a comparison of lead Pb capture characteristics.
  • FIG. 2e shows a comparison of the trapping properties of magnesium Mg.
  • FIG. 2f shows a comparison of calcium Ca capture properties.
  • FIG. 2g shows a comparison of the trapping properties of chromium Cr (III) (trivalent).
  • FIG. 2h shows a comparison of the molybdenum Mo capture characteristics.
  • FIG. 2 i shows a comparison of the trapping properties of vanadium V.
  • FIG. 2j shows a comparison of the arsenic As capture characteristics.
  • FIG. 3 shows a comparison of sample flow rate and relative capture recovery rate between the chelate resin A of Example 1 and a commercially available polyaminocarboxylic acid type chelate resin.
  • FIG. 4 shows a comparison of the trapping characteristics of 10 kinds of metals in the chelate resin A of Example 1, the chelate resin B of Example 2, the chelate resin f of Comparative Example 1 and a commercially available polyaminocarboxylic acid type chelate resin.
  • FIG. 4a shows the copper Cu capture characteristics comparison.
  • FIG. 4b shows a comparison of nickel Ni capture characteristics.
  • FIG. 4c shows a comparison of the cadmium Cd capture characteristics.
  • FIG. 4d shows a comparison of lead Pb capture characteristics.
  • FIG. 4e shows a comparison of the Mg Mg trapping properties.
  • FIG. 4f shows a comparison of calcium Ca capture properties.
  • FIG. 4g shows a comparison of the trapping properties of chromium Cr (III) (trivalent).
  • FIG. 4a shows the copper Cu capture characteristics comparison.
  • FIG. 4b shows a comparison of nickel Ni capture characteristics.
  • FIG. 4c shows a comparison of the cadmium Cd capture characteristics.
  • FIG. 4h shows a comparison of the trapping characteristics of molybdenum Mo.
  • FIG. 4 i shows a comparison of the capture properties of vanadium V.
  • FIG. 4j shows a comparison of the arsenic As capture characteristics.
  • FIG. 5 shows a comparison of the trapping properties of 10 kinds of metals in the chelate resin C of Example 3, the chelate resin D of Example 4, the chelate resin g of Comparative Example 2, and the commercially available polyaminocarboxylic acid type chelate resin.
  • FIG. 5a shows a comparison of the capture characteristics of copper Cu.
  • FIG. 5b shows a comparison of nickel Ni capture characteristics.
  • FIG. 5c shows a comparison of the capture properties of cadmium Cd.
  • FIG. 5d shows a comparison of lead Pb capture characteristics.
  • FIG. 5e shows a comparison of the trapping properties of magnesium Mg.
  • FIG. 5f shows a comparison of calcium Ca capture properties.
  • FIG. 5g shows a comparison of the trapping properties of chromium Cr (III) (trivalent).
  • FIG. 5h shows a comparison of molybdenum Mo capture characteristics.
  • FIG. 5 i shows a comparison of the trapping properties of vanadium V.
  • FIG. 5j shows a comparison of the arsenic As capture characteristics.
  • FIG. 6 shows a comparison of the trapping characteristics of 10 types of metals between the chelate resin E of Example 5 and a commercially available polyaminocarboxylic acid type chelate resin.
  • FIG. 6a shows the copper Cu capture characteristics comparison.
  • FIG. 6b shows a comparison of nickel Ni capture characteristics.
  • FIG. 6c shows a comparison of the capture properties of cadmium Cd.
  • FIG. 6d shows a comparison of lead Pb capture characteristics.
  • FIG. 6e shows a comparison of the trapping properties of magnesium Mg.
  • FIG. 6f shows a comparison of calcium Ca capture properties.
  • FIG. 6g shows a comparison of the capture characteristics of chromium Cr (III) (trivalent).
  • FIG. 6h shows a comparison of molybdenum Mo capture characteristics.
  • FIG. 6i shows a comparison of the capture properties of vanadium V.
  • FIG. 6 j shows a comparison of the arsenic As capture characteristics.
  • the present invention relates to a chelate resin which, as described above, performs carboxymethylation by adjusting the amount of halogenated acetic acid after introducing a compound having a polyethyleneimine skeleton having an optimal chain length into a polymer carrier.
  • Examples of the method for producing a compound having a polyethyleneimine skeleton used in the production method of the present invention include ring-opening polymerization of ethyleneimine, polycondensation of ethylene chloride and ethylenediamine, or heating reaction of 2-oxazolidone. Can also be used.
  • These compounds having a polyethyleneimine skeleton are a mixture of compounds having different chain lengths and a mixture of a plurality of compounds having different amine structures.
  • the amino group structure contained in the compound having a polyethyleneimine skeleton is a mixture of primary, secondary, and tertiary amino groups.
  • the compound having a polyethyleneimine skeleton used in the present invention may have any structure or ratio of primary to tertiary amines. In the present invention, these are collectively referred to as a compound having a polyethyleneimine skeleton.
  • the compound having a polyethyleneimine skeleton introduced into the polymer carrier is a polyethyleneimine skeleton compound having an optimum chain length, and the average molecular weight thereof is 200 to 600.
  • the relationship between the chain length of the polyethyleneimine skeleton and the stability constant of the complex is known to increase as the chain length increases.
  • the chain length of the polyethyleneimine skeleton is short (having n in Chemical Formula 1 is less than 4), the ability to capture a metal under acidic conditions is lowered and the ability to capture an oxoacid of a metal is also lowered.
  • the degree of freedom of the functional group chain is low and rapid adsorption / desorption cannot be performed, high scavenging ability cannot be exhibited for chromium Cr (III) (trivalent) soot having a slow complex formation rate.
  • a compound having a polyethyleneimine skeleton having a long chain length of the polyethyleneimine skeleton for example, an average molecular weight of 600 or more, particularly 1,000 or more, is considered to improve the metal trapping property.
  • the carrier is a porous body, there arises a problem that it is impossible to introduce a functional group to the inside of the pores of the polymer carrier. Furthermore, entanglement between polymer chains also occurs, so even if the chain length is increased unnecessarily, the degree of freedom of the functional group does not necessarily increase.
  • halogenated acetic acid As the halogenated acetic acid, chloroacetic acid, bromoacetic acid or the like is used.
  • the amount of halogenated acetic acid used for carboxymethylation is greatly related to the metal-capturing properties and the alkaline-earth metal-capturing properties and the degree of interference caused by them.
  • the amount of halogenated acetic acid used in the carboxymethylation reaction is 1.0 to 3.0 times the amount of nitrogen in the compound having a polyethyleneimine skeleton introduced into a polymer carrier having a reactive functional group, preferably 2.0 to 2.5 moles.
  • the degree of carboxymethylation is increased, and the metal-capturing ability of the resulting chelating functional group is improved, but at the same time, the trapping ability of alkaline earth metals is increased, Capture of alkaline earth metals begins when the liquid to be treated is acidic. That is, the selectivity under acidic conditions is reduced, and heavy metals cannot be stably captured to a high degree due to interference with alkaline earth metals.
  • the halogenated acetic acid is used in an amount of less than 1.0-fold mol, the degree of carboxymethylation is reduced, and the ability to capture heavy metals is reduced except for elements having high nitrogen affinity such as copper.
  • the ability to capture alkaline earth metals is extremely low, so that heavy metals and alkaline earth metals can be separated from each other under acidic conditions. It becomes difficult to apply to processing. That is, there is an optimum range of the degree of carboxymethylation in order to improve the metal capturing ability and reduce the interference of alkaline earth metals.
  • the polymer carrier having a reactive functional group a copolymer of a reactive monomer having an epoxy group or a halogenated alkyl group and a crosslinkable monomer is selected.
  • the reactive monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, vinylbenzyl glycidyl ether, and the like.
  • the reactive monomer having a halogenated alkyl group include chloromethylstyrene, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-chloroethyl methacrylate, 2-chloroethyl acrylate and the like. Is mentioned.
  • aromatic crosslinkable monomers such as divinylbenzene and divinylnaphthalene, ethylene dimethacrylate, diethylene glycol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol trimethyl.
  • Polyfunctional methacrylate monomers such as methacrylate, polyfunctional acrylate monomers such as ethylene diacrylate, diethylene glycol diacrylate, glycerin diacrylate, trimethylolpropane triacrylate, neopentyl glycol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, In addition, triallyl isocyanurate, trimethallyl isocyanurate Crosslinking monomers with cyanuric acid skeleton of the like.
  • Copolymerization of these reactive monomers and crosslinkable monomers is performed by a known suspension polymerization method, and an insoluble polymer carrier having a reactive functional group is obtained.
  • an insoluble polymer carrier having a reactive functional group may be obtained by another polymerization method, for example, a bulk polymerization method.
  • the shape of the polymer carrier is not particularly limited, and may be amorphous particles obtained by pulverization of a resin obtained by a known bulk polymerization method or spherical particles obtained by a known suspension polymerization method.
  • the physical structure of the polymer carrier may be either a non-porous type or a porous type.
  • the functional group involved in complex formation is introduced only into the surface layer of the polymer carrier.
  • the amount of functional groups introduced is low, but the element of diffusion into the pores can be ignored, so the adsorption / desorption rate increases.
  • the non-porous type or the porous type may be determined according to the purpose of use, but the porous type is more preferable in consideration of general use conditions.
  • the porous type those having a pore volume of 0.3 to 2.0 mL / g, an average pore diameter of 4 to 500 nm, and a specific surface area of 10 to 1000 m 2 / g are preferably employed.
  • the material of the polymer carrier is not particularly limited, but is insoluble having functional groups capable of reacting with amines such as halogenated alkyl groups, epoxy groups, aldehyde groups, ketone groups, acyl chloride groups, and acid anhydride groups.
  • a polymer carrier may be used as long as it is a polymer, and a polymer carrier based on crosslinked polystyrene, crosslinked polymethacrylate, crosslinked polyvinyl alcohol or the like obtained by a known method can be used.
  • transduced the functional group which reacts with these amines by secondary reaction to well-known crosslinked resin may be sufficient.
  • the chelate resin of the present invention provides (1) a polymer carrier having a reactive functional group such as a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine. Thereafter, (2) the polymer carrier is reacted with a compound having a polyethyleneimine skeleton, and then (3) a halogenated acetic acid having 1.0 to 3.0 moles of nitrogen in the compound having a polyethyleneimine skeleton is alkalinized. Produced by reacting in solution.
  • a reactive functional group such as a halogenated alkyl group, an epoxy group, an aldehyde group, a ketone group, an acyl chloride group, and an acid anhydride group that reacts with an amine.
  • a reaction between a polymer carrier having a reactive functional group and a compound having a polyethyleneimine skeleton is a reaction in which a compound having a polyethyleneimine skeleton is dissolved in water, alcohol, dimethylformamide, or a mixed solvent thereof.
  • a polymer carrier is dispersed in a solution, and polyamination is carried out by stirring at room temperature to 80 ° C. for 3 to 24 hours with stirring.
  • a polymer carrier having an aldehyde group or a ketone group since it is a Schiff base type bond, it is reduced by a known method using LiBH 3 CN, NaBH 3 CN, (CH 3 ) 2 NHBH 3 or the like. I do.
  • it may be reduced by a known method using LiAlH 4 or BH 3 -THF.
  • the amount of nitrogen in the introduced compound having a polyethyleneimine skeleton is measured with an elemental analyzer (so-called CHN meter).
  • Carboxymethylation with halogenated acetic acid is performed under alkaline conditions as is well known. At this time, the amount of halogenated acetic acid to be used is determined based on the amount of nitrogen obtained by the elemental analyzer.
  • the alkali concentration is not particularly specified, but generally 0.5 to 3 mol / L (mol / liter) sodium hydroxide or potassium hydroxide is used.
  • the chelate resin thus obtained is used after being washed in order of water, acid, and water, and subjected to counterion exchange according to the purpose.
  • Synthesis of chelate resin A (1) Production of polymer carrier The polymer carrier was synthesized according to a known suspension polymerization method. A mixture of 80 g of glycidyl methacrylate, 120 g of ethylene dimethacrylate, 200 g of butyl acetate and 2 g of azobisisobutyronitrile is added to 2,000 mL (milliliter) of 0.1% polyvinyl alcohol aqueous solution, so that the diameter of the oil droplets becomes 60 ⁇ m. Was stirred. Thereafter, a polymerization reaction was carried out at 70 ° C. for 6 hours. After the reaction product was cooled, the produced copolymer particles were collected by filtration and washed with water, methanol and water in this order. Subsequently, after air drying for one day, classification was performed to obtain 85 g of porous crosslinked polymer particles having a size of 45 to 90 ⁇ m.
  • Example 1 The chelate resin A obtained in Example 1 was filled in a solid-phase extraction cartridge in the same manner as in Example 1 (4), and the same conditioning was performed. Thereafter, mixed metal ion standard solutions adjusted to various pH (copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III) (trivalent), molybdenum Mo, vanadium V, arsenic As 10 types) were passed through to capture the metal.
  • the captured metal was eluted with 3 mL of 3M nitric acid in the same manner as in Example 1 (4), and the concentration in the solution was measured using an ICP emission analyzer (manufactured by PerkinElmer, Optima 3000 DV) to determine the capture recovery rate. Asked.
  • the same metal capture property comparison test was performed using Kilex 100 (trade name, manufactured by Bio-Rad Laboratories, exchange capacity: 0.4 meq / mL), which is an IDA-type chelate resin. The results are shown in FIG. 1 (FIGS. 1a to 1j). As shown in FIG.
  • the capture and recovery rate of heavy metals such as copper, nickel, cadmium and lead under acidic conditions was greatly improved compared to the IDA type.
  • the chelate resin A alkaline earth metals were not captured at pH 7 or lower, and heavy metals could be highly captured and recovered without being disturbed by alkaline earth metals.
  • the chelating resin A exhibited a high capture recovery rate in the entire pH range.
  • Chelate resin A obtained in Example 1 and a commercially available chelate resin cartridge NOBIAS Chelate-PA1 having a polyaminocarboxylic acid group of diethylenetriamine skeleton (manufactured by Hitachi High-Technologies Corporation, metal capture amount: 0. 0) 25 mmol-Cu / g (hereinafter simply abbreviated as PA1) was packed in a solid-phase extraction cartridge in the same manner as in Example 1 (4), and both metal capture properties (sample pH and capture recovery rate). The relationship was tested and compared. The filling amount was 250 mg for both.
  • chromium (III) which is considered to have a very slow complex formation rate in the aminocarboxylic acid type chelate resin as compared with other heavy metals
  • the chelate resin A was more highly captured from a lower pH. This is considered to be largely attributable to the improvement in the stability constant of the complex due to the increase in the functional group chain length and the increase in the degree of freedom of the functional group involved in complex formation.
  • an improvement in the trapping property on the alkali side was observed.
  • arsenic a capture recovery rate of 2 times or more was obtained in the entire pH range.
  • the chelate resin of the present invention is less susceptible to alkaline earth metals than commercially available chelate resins, and can capture and recover heavy metals at a wide range of pH, and further capture with conventional chelate resins. It has been found that it is difficult to improve the trapping properties of chromium, metal oxoacids and the like.
  • the four types of samples were each passed through a solid-phase extraction cartridge to capture the metal, and the captured metal was eluted with 3M nitric acid, and then the amount of metal captured by the ICP emission spectroscopic analyzer was measured.
  • the relative capture recovery rate was calculated as the relative capture recovery rate when the capture recovery rate (capture recovery rate of approximately 100% for both cartridges) when the sample flow rate was 10 mL was taken as 100. The result is shown in FIG. Regarding cadmium, there was almost no difference between the two, and the solution could be passed up to about 1,000 mL with 250 mg of filler.
  • Chelate resin B was synthesized in the same manner as in Example 1. That is, polyethyleneimine having an average molecular weight of 300 in 50 mL of isopropyl alcohol and 200 mL of water (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin SP-003, average molecular weight: 300, amine ratio: 45% primary, 35% secondary, 20% tertiary) 35 g were dissolved, 20 g of the porous crosslinked polymer particles obtained in Example 1 (1) were added, and the mixture was reacted at 50 ° C. for 6 hours. The reaction product was filtered and washed with water, methanol, and water in this order to obtain a polyaminated resin.
  • the amount of nitrogen of this polyaminated resin was 7.31% -N / g. 20 g of this polyaminated resin was added to a solution obtained by dissolving 29.0 g of sodium chloroacetate (corresponding to 2.4 times the amount of introduced nitrogen) in 200 mL of 1M NaOH aqueous solution, reacted at 40 ° C. for 6 hours, and the reaction product was filtered. After sufficiently washing with water, it was replaced with methanol and dried to obtain a chelate resin B. The amount of copper trapped in this chelate resin B was 0.40 mmol Cu / g.
  • the chelate resin f of Comparative Example 1 had a low capture recovery rate under acidic conditions, but chelate resin A and chelate resin B showed good capture properties.
  • chelate resin A and chelate resin B do not capture up to around pH 7, and interference of alkaline earth metals in a wider pH range than chelate resin f and PA1 obtained in Comparative Example 1 It has been found that heavy metals can be captured and recovered without being subjected to any damage. Chromium (III) could be highly captured from the low pH by the chelate resin A and the chelate resin B.
  • the chelating resin A and chelating resin B were observed to improve the capturing ability on the alkali side. Furthermore, with respect to arsenic, the chelate resin A and the chelate resin B had a capture recovery rate twice or more that of the chelate resin f of Comparative Example 1 over the entire pH range.
  • Synthesis of chelate resin C (1) Synthesis of polyaminated resin A polyaminated resin was synthesized in the same manner as in Example 1. Using 90 g of glycidyl methacrylate and 210 g of ethylene dimethacrylate, 125 g of a polymer carrier of 45 to 90 ⁇ m porous crosslinked polymer particles was obtained. Next, 250 g of polyethyleneimine 300 (manufactured by Nippon Shokubai Co., Ltd., trade name: Epomin SP-003) is dissolved in 300 mL of isopropyl alcohol and 1200 mL of water, and 125 g of the resulting polymer carrier is added thereto and reacted at 50 ° C. for 6 hours. It was. The reaction product was filtered and washed with water, methanol and water in this order to obtain a polyaminated resin. The amount of nitrogen in this polyaminated resin was 5.91% -N / g.
  • chelate resin D 20 g of the polyaminated resin obtained in Example 3 (1) and 10 g of sodium chloroacetate (corresponding to 1.0 times the mole of introduced nitrogen) were reacted in the same manner as in Example 3 to obtain polyaminocarboxylic acid. An acid-type chelate resin D was produced. The amount of copper captured by this chelate resin D was 0.31 mmol Cu / g.
  • chelate resin g 20 g of the polyaminated resin obtained in Example 3 (1) and 35 g of sodium chloroacetate (corresponding to 3.5 times mole of introduced nitrogen amount) were reacted in the same manner as in Example 3 to obtain polyaminocarboxylic acid.
  • Acid type chelate resin g was produced.
  • the amount of copper trapped by the chelate resin g was 0.32 mmol Cu / g.
  • FIG. 5 shows the results of supplemental characteristics of 10 kinds of metals, copper Cu, nickel Ni, cadmium Cd, lead Pb, magnesium Mg, calcium Ca, chromium Cr (III) (trivalent), molybdenum Mo, vanadium V, and arsenic As. 5a to 5j).
  • copper copper having a high nitrogen affinity
  • all the resins showed good capturing properties.
  • PA1 ⁇ chelate resin D ⁇ chelate resin g chelate resin C increases in this order, and for capture of molybdenum and vanadium on the alkali side, PA1 ⁇ chelate resin D The order was ⁇ chelate resin g ⁇ chelate resin C. Regarding the capture of arsenic, the order was PA1 ⁇ chelate resin g ⁇ chelate resin C ⁇ chelate resin D. From these results, it became clear that there is an optimum range of the degree of carboxymethylation in order to obtain a chelate resin having a balance between the metal trapping properties and the properties in which alkaline earth metals are not easily trapped.
  • Synthesis of chelate resin E A mixture of 30 g of chloromethylstyrene, 70 g of divinylbenzene, 150 g of toluene and 2 g of azobisisobutyronitrile is added to 2,000 mL of 0.1% polyvinyl alcohol aqueous solution, and the diameter of the oil droplets becomes 60 ⁇ m. The polymerization reaction was carried out at 70 ° C. for 6 hours. After the reaction product was cooled, the produced copolymer was collected by filtration and washed with water, methanol and water in this order. Subsequently, after air drying for one day, classification was performed to obtain 35 g of porous crosslinked polymer particles having a size of 45 to 90 ⁇ m.
  • polyethyleneimine 300 (Epomin SP-003, manufactured by Nippon Shokubai Co., Ltd.) was dissolved in 40 mL of isopropyl alcohol and 160 mL of water, and 20 g of the resulting porous crosslinked polymer particles were added thereto and reacted at 50 ° C. for 6 hours.
  • the reaction product was filtered and washed with water, methanol and water in this order to obtain a polyaminated resin.
  • the amount of nitrogen in this polyaminated resin was 6.81% -N / g.
  • the chelate resin E can capture and recover heavy metals in the wider pH range without being disturbed by alkaline earth metals.
  • the chelate resin E was more highly captured from a lower pH.
  • an improvement in the trapping property on the alkali side was observed.
  • a capture recovery rate of 2 times or more was obtained in the entire pH range.
  • the chelate resin of the present invention does not capture alkaline earth metals under acidic conditions, it removes heavy metals from wastewater and irrigation water, and recovers valuable metals from environmental water and metal treatment solutions such as seawater and river water. It can be done efficiently. Furthermore, it can be used for pretreatment applications such as removal of interfering elements in instrumental analysis of trace metals and extraction / concentration of analysis target elements.
  • ⁇ Shows the recovery rate of chelate resin A of Example 1 in FIG. 1 (FIGS. 1a to 1j).
  • ⁇ Shows the recovery rate of commercially available IDA resin in FIG. 1 (FIGS. 1a to 1j).
  • ⁇ Shows the recovery rate of chelate resin A of Example 1 in FIG. 2 (FIGS. 2a to 2j).
  • ⁇ shows the recovery rate of NOBIAS Chelate-PA1 to be compared in FIG. 2 (FIGS. 2a to 2j).
  • Element symbol -A shows the relative recovery of the chelate resin A of Example 1 in FIG.
  • Element symbol -R indicates the relative recovery rate of NOBIAS Chelate-PA1 to be compared in FIG.
  • ⁇ Shows the recovery rate of the chelate resin A of Example 1 in FIG. 4 (FIGS. 4a to 4j).
  • (Circle) The recovery rate of the type
  • delta) The recovery rate of the chelate resin f of the comparative example 1 in FIG. 4 (FIG. 4 a thru
  • ⁇ shows the recovery rate of NOBIAS Chelate-PA1 to be compared in FIG. 4 (FIGS. 4a to 4j).
  • ⁇ Shows the recovery rate of the chelate resin C of Example 3 in FIG. 5 (FIGS. 5a to 5j).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention porte sur une résine chélatante qui est obtenue par introduction d'un composé ayant un squelette de polyéthylèneimine dans un support en polymère comportant un groupe fonctionnel réactif, puis carboxyméthylation de la matière ainsi obtenue à l'aide d'acide acétique halogéné à hauteur de 1,0-3,0 fois la quantité molaire d'azote contenu dans le composé ayant un squelette de polyéthylèneimine qui a été introduit dans le support en polymère. La résine chélatante n'est pas facilement affectée par des métaux alcalinoterreux. En conséquence, la résine chélatante est apte à retirer des métaux lourds et à capter de manière très sélective des métaux lourds de valeur à partir d'une solution devant être traitée telle qu'une eau résiduaire industrielle, de l'eau de service, de l'eau environnementale, un aliment et des produits chimiques, sans être affectée par des métaux alcalinoterreux qui sont présents en grande quantité dans la solution devant être traitée.
PCT/JP2010/052514 2009-02-27 2010-02-19 Résine chélatante Ceased WO2010098257A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009045325A JP5796867B2 (ja) 2009-02-27 2009-02-27 キレート樹脂
JP2009-045325 2009-02-27

Publications (1)

Publication Number Publication Date
WO2010098257A1 true WO2010098257A1 (fr) 2010-09-02

Family

ID=42665464

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/052514 Ceased WO2010098257A1 (fr) 2009-02-27 2010-02-19 Résine chélatante

Country Status (2)

Country Link
JP (1) JP5796867B2 (fr)
WO (1) WO2010098257A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438699A (zh) * 2018-09-26 2019-03-08 上海维凯光电新材料有限公司 一种改性聚乙烯亚胺/纳米银复合材料及其制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5565377B2 (ja) * 2011-05-31 2014-08-06 コニカミノルタ株式会社 水処理剤
JP5940313B2 (ja) 2012-01-27 2016-06-29 日本フイルコン株式会社 高分子吸着体
JP5924807B2 (ja) 2012-02-14 2016-05-25 日本フイルコン株式会社 ゲル状金属吸着材およびゲル状金属吸着材担持吸着体
JP6683011B2 (ja) * 2016-05-19 2020-04-15 王子ホールディングス株式会社 質量分析方法
US10654025B2 (en) 2017-11-15 2020-05-19 Korea Advanced Institute Of Science And Technology Amine-based carbon dioxide adsorbent resistant to oxygen and sulfur dioxide and method of preparing the same
KR102071540B1 (ko) * 2017-11-15 2020-02-03 한국과학기술원 킬레이트제를 포함하는 아민계 이산화탄소 흡착제 및 이의 제조방법
US20250236861A1 (en) * 2021-11-19 2025-07-24 Liaoning Asymchem Laboratories Co., Ltd. Enzyme immobilization carrier and Preparation Method therefor, and Immobilized Enzyme and Preparation Method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54162800A (en) * 1978-06-14 1979-12-24 Unitika Ltd Preparation of spherical chelate resin having excellent selective adsorptivity
JPH07126068A (ja) * 1993-04-13 1995-05-16 Kyocera Corp 酸化物超電導体の製造方法
JP2000508706A (ja) * 1996-04-23 2000-07-11 ビーエーエスエフ アクチェンゲゼルシャフト 微細で水不溶性のアジリジン重合体の製造方法
JP2005021883A (ja) * 2003-06-12 2005-01-27 Nippon Kayaku Co Ltd キレート樹脂および微量金属イオンの除去方法
JP2005213477A (ja) * 2004-02-02 2005-08-11 Hitachi Chem Co Ltd キレート樹脂及びその製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54162800A (en) * 1978-06-14 1979-12-24 Unitika Ltd Preparation of spherical chelate resin having excellent selective adsorptivity
JPH07126068A (ja) * 1993-04-13 1995-05-16 Kyocera Corp 酸化物超電導体の製造方法
JP2000508706A (ja) * 1996-04-23 2000-07-11 ビーエーエスエフ アクチェンゲゼルシャフト 微細で水不溶性のアジリジン重合体の製造方法
JP2005021883A (ja) * 2003-06-12 2005-01-27 Nippon Kayaku Co Ltd キレート樹脂および微量金属イオンの除去方法
JP2005213477A (ja) * 2004-02-02 2005-08-11 Hitachi Chem Co Ltd キレート樹脂及びその製造法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438699A (zh) * 2018-09-26 2019-03-08 上海维凯光电新材料有限公司 一种改性聚乙烯亚胺/纳米银复合材料及其制备方法

Also Published As

Publication number Publication date
JP2010194509A (ja) 2010-09-09
JP5796867B2 (ja) 2015-10-21

Similar Documents

Publication Publication Date Title
JP5590594B2 (ja) キレート性高分子化合物含有金属吸着材
JP5796867B2 (ja) キレート樹脂
Chen et al. Removal of heavy metal ions by a chelating resin containing glycine as chelating groups
Wang et al. Simultaneous adsorption of Cu (II) and SO42− ions by a novel silica gel functionalized with a ditopic zwitterionic Schiff base ligand
Li et al. Redox Sorption and Recovery of Silver Ions as Silver Nanocrystals on Poly (aniline‐co‐5‐sulfo‐2‐anisidine) Nanosorbents
Hasanzadeh et al. Synthesis and application of modified poly (styrene‐alt‐maleic anhydride) networks as a nano chelating resin for uptake of heavy metal ions
US10889688B2 (en) Crosslinked polymer resin for contaminant adsorption from water
Muller et al. Complexation properties of water-soluble poly (vinyl alcohol)(PVA)-based acidic chelating polymers
KR101206826B1 (ko) 금속 이온 각인된 미세다공성 고분자 입자의 제조방법
US11014071B1 (en) Porous polymer material for bonding metal-containing ions or for purifying organic molecules
US6576590B2 (en) Materials for the separation of copper ions and ferric iron in liquid solutions
CN118359746A (zh) 羟肟酸功能化镓离子吸附树脂的制备方法、镓离子吸附树脂及应用
Najafi Moghadam et al. Preparation of SMA functionalized sulfanilic acid hydrogels and investigation of their metal ions adsorption behavior
Li et al. Novel pyridine-based covalent organic framework containing N, N, N-chelating sites for selective detection and effective removal of nickel
Zheng et al. Kapok fiber structure-oriented polyallylthiourea: Efficient adsorptive reduction for Au (III) for catalytic application
CN114302771B (zh) 用于螯合和/或去除有毒污染物的基于n-烷基-d-葡糖胺的大孔聚合物冷冻凝胶
JP2022517332A (ja) 金属封鎖のためのポリアミンリンデンドリマー材料
WO2020027009A1 (fr) Dérivé de cellulose, matériau d'élimination de métaux lourds contenant celui-ci, et procédé d'élimination de métaux lourds utilisant celui-ci
Zhang et al. Uniform macroporous amidoximated polyacrylonitrile monoliths for gallium recovery from Bayer liquor
JP2011240287A (ja) 固体キレート剤とその製造方法、それを用いたコバルト，マンガン，ニッケルの分離方法
JP4605432B2 (ja) キレート樹脂及びその製造法
Elsayed et al. Diels-Alder click chemistry-engineered ion-imprinted polymer for highly selective Gd3+ extraction from aqueous solutions
JP2005021883A (ja) キレート樹脂および微量金属イオンの除去方法
JP2015003295A (ja) 吸着剤、水処理タンク、吸着剤の製造方法及び水処理システム
Massoudi et al. Poly (N vinyl imidazole) Nitrogen Doped Graphene Quantum Dot Hydrogel Adsorbent with Remarkable Capability for Metal Ion Removal from Aqueous Systems

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10746138

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10746138

Country of ref document: EP

Kind code of ref document: A1