EP4222182A1 - Nouvelles résines chélatantes - Google Patents

Nouvelles résines chélatantes

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Publication number
EP4222182A1
EP4222182A1 EP21782987.8A EP21782987A EP4222182A1 EP 4222182 A1 EP4222182 A1 EP 4222182A1 EP 21782987 A EP21782987 A EP 21782987A EP 4222182 A1 EP4222182 A1 EP 4222182A1
Authority
EP
European Patent Office
Prior art keywords
functional groups
structural element
alkyl
containing functional
polymer
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.)
Pending
Application number
EP21782987.8A
Other languages
German (de)
English (en)
Inventor
Bernd Koop
Dirk Steinhilber
Joachim Kralik
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP4222182A1 publication Critical patent/EP4222182A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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

Definitions

  • the present invention relates to chelating resins containing aminoalkylphosphinic acid derivatives, a process for their preparation and their use for the recovery and purification of metals, preferably heavy metals, noble metals and rare earths.
  • Chelating resins containing aminoalkylphosphonic acid groups are known from DE-A 102009047848 and EP-A 1078690.
  • DE-A 102009047848 describes in particular the use of these resins for the adsorption of calcium.
  • DE-A 2848289 describes the preparation of chelating resins containing aminomethylhydroxymethylphosphinic acid groups by reacting a chloromethylated polystyrene copolymer with a polyamine and its subsequent reaction with formalin and a hypophosphite. These resins are used to remove tungsten ions.
  • a disadvantage of the prior art is that the zinc capacity of the chelate resins that can be used is not sufficient. There has therefore been a further need for a chelate resin with which zinc is adsorbed in large amounts. Surprisingly, it has now been found that specific chelating resins containing aminomethylphosphinic acid derivatives are particularly suitable for removing zinc.
  • R 1 and R 2 -CH 2 -PO(OR 3 )R 4 .
  • R 3 is preferably hydrogen and Ci-Cs-alkyl.
  • Ci-Cis-alkyl represents a straight-chain, cyclic or branched alkyl radical having 1 to 15 (C1-C15), preferably 1 to 12 (C1-C12), particularly preferably 1 to 8 (Ci-Cs) carbon atoms, even more preferably having 1 to 6 (Ci-Cs) carbon atoms.
  • Ci-Cis-alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, n-hexyl, cyclohexyl, n-pentyl, 1-methylbutyl , 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, cyclohexyl, 2,4,4-trimethylpentyl and 2-methylpentyl.
  • Ci-Cis-alkyl is particularly preferably methyl, ethyl, n-propyl, isopropyl, n-, i-, s- or t-butyl, n-pentyl, n-hexyl, 2,4,4-trimethylpentyl and 2- methylpentyl.
  • Ci-Ci 5 -alkyl or Ci-Cis-alkyl or Ci-Cs-alkyl or Ci-Cs-alkyl is very particularly preferably ethyl, 2,4,4-trimethylpentyl and 2-methylpentyl.
  • Ce-C24-aryl represents an aromatic radical having 6 to 24 skeletal carbon atoms in which none, one, two or three skeletal carbon atoms per cycle, but at least one skeletal carbon atom in the entire molecule, are replaced by heteroatoms selected from the group consisting of nitrogen, sulfur or oxygen, but preferably for a carbocyclic aromatic radical having 6 to 24 backbone carbon atoms.
  • the carbocyclic aromatic or heteroaromatic radicals can be substituted with up to five identical or different substituents per cycle, selected from the group: Ci-Cs-alkyl, Cs-C-alkenyl and C 7 -Ci 5 -arylalkyl.
  • Ce-C24-Aryl are phenyl, o-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl or fluorenyl.
  • Preferred heteroaromatic Ce-C24-aryl in which one, two or three skeletal carbon atoms per cycle, but at least one skeletal carbon atom in the entire molecule, can be substituted by heteroatoms selected from the group consisting of nitrogen, sulfur or oxygen are pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl or isoxazolyl, indolizinyl, indolyl, benzo[b]thienyl, benzo[b]furyl, indazolyl, quinolyl, isoquinolyl, naphthyridiny
  • C 7 -C 15 -Arylalkyl independently of one another, means a straight-chain, cyclic or branched C 7 -C 15 -alkyl radical as defined above, which can be monosubstituted, polysubstituted or completely substituted by aryl radicals as defined above.
  • C2-C6-alkenyl is a straight-chain, cyclic or branched alkenyl radical having 2 to 10 (C2-C10), preferably having 2 to 6 (C2-C6) carbon atoms.
  • alkenyl is vinyl, allyl, isopropenyl and n-but-2-en-1-yl.
  • polystyrene copolymers in the chelate resin containing functional groups of the structural element (I) are preferably copolymers of monovinyl aromatic monomers selected from the group styrene, vinyl toluene, ethyl styrene, ⁇ -methyl styrene, chlorostyrene or chloromethyl styrene and mixtures of these monomers with polyvinyl aromatic compounds (crosslinkers). from the group of divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene and/or trivinylnaphthalene.
  • a styrene/divinylbenzene copolymer is particularly preferably used as the polystyrene copolymer structure.
  • a styrene/divinylbenzene copolymer is a copolymer crosslinked through the use of divinylbenzene.
  • the polymerizate of the chelate resin preferably has a spherical shape.
  • the -CH2-NR 1 R 2 group is attached to a phenyl radical.
  • the chelating resins containing functional groups of structural element (I) used according to the invention preferably have a macroporous structure.
  • microporous or gel-like or macroporous have already been described in detail in the specialist literature, for example in Seidl, Malinsky, Dusek, Heitz, Adv. Polymer Sci., 1967, Vol. 5, pp. 113 to 213.
  • the possible measuring methods for macroporosity e.g. mercury porosimetry and BET determination, are also described there.
  • the pores of the macroporous polymers of the chelating resins used according to the invention containing functional groups of the structural element (I) have a diameter of 20 nm to 100 nm.
  • the chelating resins containing functional groups of structural element (I) used according to the invention preferably have a monodisperse distribution.
  • substances are referred to as monodisperse if at least 90% by volume or mass of the particles have a diameter that lies in the interval with a width of +/-10% of the most common diameter around the most common diameter.
  • a substance with a most common diameter of 0.5 mm at least 90% by volume or mass lies in a size interval between 0.45 mm and 0.55 mm
  • a substance with a most common diameter of 0.7 mm at least 90% by volume or mass in a size interval between 0.77 mm and 0.63 mm.
  • the chelate resin containing functional groups of the structural element (I) preferably has a diameter of 200 to 1500 ⁇ m.
  • At least one monovinylaromatic compound and at least one polyvinylaromatic compound are used in process step a). However, it is also possible to use mixtures of two or more monovinylaromatic compounds and mixtures of two or more polyvinylaromatic compounds.
  • Styrene, vinyl toluene, ethyl styrene, ⁇ -methyl styrene, chlorostyrene or chloromethyl styrene are preferably used as monovinylaromatic compounds for the purposes of the present invention in process step a).
  • the monovinylaromatic compounds are preferably used in amounts >50% by weight, based on the monomer or its mixture with other monomers, particularly preferably between 55% by weight and 70% by weight, based on the monomer or its mixture with other monomers.
  • styrene or mixtures of styrene with the aforementioned monomers preferably with ethyl styrene.
  • Preferred polyvinylaromatic compounds for the purposes of the present invention for process step a) are divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene or trivinylnaphthalene, particularly preferably divinylbenzene.
  • the polyvinylaromatic compounds are preferably used in amounts of 1-20% by weight, particularly preferably 2-12% by weight, particularly preferably 4-10% by weight, based on the monomer or its mixture with other monomers.
  • the kind of polyvinylaromatic compounds (crosslinkers) is selected with regard to the subsequent use of the polymer. If divinylbenzene is used, commercial grades of divinylbenzene which also contain ethylvinylbenzene in addition to the isomers of divinylbenzene are sufficient.
  • Macroporous polymers are preferably formed by adding inert materials, preferably at least one porogen, to the monomer mixture during the polymerization in order to produce a macroporous structure in the polymer.
  • porogens are hexane, octane, isooctane, isododecane, pentamethylheptane, methyl ethyl ketone, butanol or octanol and their isomers.
  • organic substances are suitable which dissolve in the monomer but dissolve or swell the polymer poorly (precipitating agent for polymers), for example aliphatic hydrocarbons (Bayer paint factory DBP 1045102, 1957; DBP 11 13570, 1957).
  • Porogens are preferably used in an amount of 25% by weight to 45% by weight, based on the amount of the organic phase.
  • At least one porogen is preferably added in process step a).
  • the polymers prepared according to process step a) can be prepared in heterodisperse or monodisperse form.
  • Heterodisperse polymers are prepared by general processes known to those skilled in the art, e.g. with the aid of suspension polymerization.
  • Monodisperse polymers are preferably prepared in process step a).
  • microencapsulated monomer droplets are used in process step a) in the production of monodisperse polymers.
  • the materials known for use as complex coacervates are suitable for the microencapsulation of the monomer droplets, in particular polyesters, natural and synthetic polyamides, polyurethanes or polyureas.
  • Gelatine is preferably used as the natural polyamide. This is used in particular as a coacervate and complex coacervate.
  • gelatin-containing complex coacervates are understood to mean, in particular, combinations of gelatin with synthetic polyelectrolytes.
  • Suitable synthetic polyelectrolytes are copolymers with built-in units of, for example, maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide. Acrylic acid and acrylamide are particularly preferably used.
  • Capsules containing gelatine can be hardened with conventional hardening agents such as formaldehyde or glutaric dialdehyde.
  • conventional hardening agents such as formaldehyde or glutaric dialdehyde.
  • the encapsulation of monomer droplets with gelatin, gelatin-containing coacervates and gelatin-containing complex coacervates is described in detail in EP-A 0 046 535.
  • the methods of encapsulation with synthetic polymers are known.
  • Phase interface condensation is preferred, in which a reactive component (in particular an isocyanate or an acid chloride) dissolved in the monomer droplet is reacted with a second reactive component (in particular an amine) dissolved in the aqueous phase.
  • the heterodisperse or optionally microencapsulated, monodisperse monomer droplets contain at least one initiator or mixtures of initiators (initiator combination) to initiate the polymerization.
  • Initiators preferred for the process according to the invention are peroxy compounds, particularly preferably dibenzoyl peroxide, dilauroyl peroxide, bis(p-chlorobenzoyl) peroxide, dicyclohexyl peroxydicarbonate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, 2,5-bis(2-ethylhexanoylperoxy )-2,5-dimethylhexane or tert-amylperoxy-2-ethylhexane, and azo compounds such as 2,2'-azobis(isobutyronitrile) or 2,2'-azobis(2-methylisobutyronitrile).
  • the initiators are preferably used in amounts of from 0.05 to 2.5% by weight, particularly preferably from 0.1 to 1.5% by weight, based on the monomer mixture.
  • the optionally monodisperse, microencapsulated monomer droplet can optionally also contain up to 30% by weight (based on the monomer) of crosslinked or uncrosslinked polymer.
  • Preferred polymers are derived from the aforementioned monomers, particularly preferably from styrene.
  • the aqueous phase can, in a further preferred embodiment, contain a dissolved polymerization inhibitor.
  • a dissolved polymerization inhibitor inorganic and organic substances can be considered as inhibitors.
  • Preferred inorganic inhibitors are nitrogen compounds, particularly preferably hydroxylamine, hydrazine, sodium nitrite and potassium nitrite, salts of phosphorous acid such as sodium hydrogen phosphite and sulfur-containing compounds such as sodium dithionite, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium thiocyanate and ammonium thiocyanate.
  • organic inhibitors examples include phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol and condensation products of phenols with aldehydes.
  • phenolic compounds such as hydroquinone, hydroquinone monomethyl ether, resorcinol, pyrocatechol, tert-butylpyrocatechol, pyrogallol and condensation products of phenols with aldehydes.
  • resorcinol pyrocatechol
  • tert-butylpyrocatechol pyrogallol
  • condensation products of phenols with aldehydes examples include butyl, pyrogallol and condensation products of phenols with aldehydes.
  • Other preferred organic inhibitors are nitrogen-containing compounds.
  • hydroxylamine derivatives such as N,N-diethylhydroxylamine, N-isopropylhydroxylamine and sulfonated or carboxylated N-alkylhydroxylamine or N,N-dialkylhydroxylamine derivatives, hydrazine derivatives such as N,N-hydrazinodiacetic acid, nitroso compounds such as N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine ammonium salt or N-nitrosophenylhydroxylamine aluminum salt.
  • concentration of the inhibitor is 5-1000 ppm (based on the aqueous phase), preferably 10-500 ppm, particularly preferably 10-250 ppm.
  • the polymerization of the optionally microencapsulated monodisperse monomer droplets to form the monodisperse polymer preferably takes place in the presence of one or more protective colloids in the aqueous phase.
  • Natural or synthetic water-soluble polymers preferably gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or copolymers of (meth)acrylic acid and (meth)acrylic acid esters are suitable as protective colloids.
  • cellulose derivatives in particular cellulose esters and cellulose ethers, such as carboxymethyl cellulose, methylhydroxyethyl cellulose, methylhydroxypropyl cellulose and hydroxyethyl cellulose.
  • Gelatin is particularly preferred.
  • the amount of protective colloid used is generally from 0.05 to 1% by weight, based on the aqueous phase, preferably from 0.05 to 0.5% by weight.
  • the polymerization to give the monodisperse polymer can be carried out in the presence of a buffer system.
  • Buffer systems which adjust the pH of the aqueous phase to a value between 14 and 6, preferably between 12 and 8, at the beginning of the polymerization are preferred.
  • protective colloids with carboxylic acid groups are wholly or partly in the form of salts. In this way, the effect of the protective colloids is favorably influenced.
  • Particularly suitable buffer systems contain phosphate or borate salts.
  • the terms phosphate and borate within the meaning of the invention also include the condensation products of the ortho forms of corresponding acids and salts.
  • the concentration of the phosphate or borate in the aqueous phase is preferably 0.5-500 mmol/l, particularly preferably 2.5-100 mmol/l.
  • the stirring speed during the polymerisation to form the monodisperse polymer is less critical and, in contrast to conventional polymerisation, has no influence on the particle size. Low agitation speeds are used, sufficient to keep the suspended monomer droplets in suspension and to aid in the removal of the heat of polymerization.
  • Various stirrer types can be used for this task. Grid stirrers with an axial effect are particularly suitable.
  • the volume ratio of encapsulated monomer droplets to aqueous phase is preferably 1:0.75 to 1:20, particularly preferably 1:1 to 1:6.
  • the polymerization temperature to give the monodisperse polymer depends on the decomposition temperature of the initiator used. It is preferably between 50 and 180.degree. C., particularly preferably between 55 and 130.degree.
  • the polymerization preferably lasts from 0.5 to about 20 hours. It has proven useful to use a temperature program in which the polymerization is started at a low temperature, preferably 60° C., and the reaction temperature is increased as the polymerization conversion progresses. In this way, for example, the requirement for a safe course of the reaction and high polymerization conversion can be met very well.
  • the monodisperse polymer is isolated using customary methods, for example by filtering or decanting, and washed if necessary.
  • the monodisperse polymers are preferably prepared using the jetting principle or the seed-feed principle.
  • a macroporous, monodisperse polymer is preferably prepared in process step a).
  • the amidomethylation reagent is preferably prepared first.
  • a phthalimide or a phthalimide derivative is preferably dissolved in a solvent, and formaldehyde or its derivatives are added.
  • a bis(phthalimido)ether is then formed therefrom with elimination of water.
  • Preferred phthalimide derivatives for the purposes of the present invention are phthalimide itself or substituted phthalimides, such as preferably methylphthalimide.
  • derivatives of formaldehyde are also, for example and preferably, aqueous solutions of formaldehyde.
  • An aqueous solution of the formaldehyde is preferably formalin.
  • Formalin is preferably a solution of formaldehyde in water.
  • Preferred derivatives of formaldehyde are formalin or paraformaldehyde.
  • Process step b) could therefore also be reacted with the polymer from step a) the phthalimide derivative or the phthalimide in the presence of paraformaldehyde.
  • the molar ratio of the phthalimide derivatives to the aromatic groups present in the polymer in process step b) is from 0.15:1 to 1.7:1, although other molar ratios can also be selected.
  • the phthalimide derivative is preferably used in a molar ratio of from 0.7:1 to 1.45:1 to the aromatic groups present in the polymer in process step b).
  • Formaldehyde or its derivatives are usually used in excess, based on the phthalimide derivative, but other amounts can also be used. Preference is given to using 1.01 to 1.2 mol of formaldehyde or its derivatives per mole of phthalimide derivative.
  • inert solvents are used which are suitable for swelling the polymer, preferably chlorinated hydrocarbons, particularly preferably dichloroethane or methylene chloride.
  • chlorinated hydrocarbons particularly preferably dichloroethane or methylene chloride.
  • the polymer is condensed with phthalimide or its derivatives and formaldehyde.
  • the catalyst used here is preferably oleum, sulfuric acid or sulfur trioxide in order to produce an SOs adduct of the phthalimide derivative in an inert solvent.
  • the catalyst is usually added in excess to the phthalimide derivative, although larger amounts can also be used.
  • the molar ratio of the catalyst to the phthalimide derivatives is preferably from 0.1:1 to 0.45:1.
  • the molar ratio of the catalyst to the phthalimide derivatives is particularly preferably 0.2:1 to 0.4:1.
  • Process step b) is carried out at temperatures of preferably from 20.degree. C. to 120.degree. C., particularly preferably from 60.degree. C. to 90.degree.
  • the elimination of the phthalic acid residue and thus the exposure of the aminomethyl group takes place in process step c) by treatment with at least one base or at least one acid.
  • the bases used in process step c) are preferably alkali metal hydroxides, alkaline earth metal hydroxides, ammonia or hydrazine.
  • the acids used in process step c) are preferably nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulphurous acid or nitrous acid.
  • the elimination of the phthalic acid radical and thus the exposure of the aminomethyl group in process step c) is particularly preferably carried out by treating the phthalimidomethylated polymer with aqueous or alcoholic solutions of an alkali metal hydroxide, such as preferably sodium hydroxide or potassium hydroxide, at temperatures of 100° C. and 250° C., preferably 120 °C to 190 °C.
  • the concentration of the sodium hydroxide solution is preferably 20% by weight to 40% by weight, based on the aqueous phase.
  • the aminomethylated polymer is generally washed alkali-free with deionized water. However, it can also be used without post-treatment.
  • the process described in steps a) to c) is known as the phthalimide process.
  • the chloromethylation process to produce an aminomethylated polymer.
  • the chloromethylation process which is described, for example, in EP-A 1 568 660, polymers - mostly based on styrene/divinylbenzene - are first produced, chloromethylated and then reacted with amines (Helfferich, ion exchanger, page 46-58, Verlag Chemie, Weinheim , 1959) and EP-A 0 481 603).
  • the ion exchanger containing chelating resin having functional groups represented by the formula (I) can be prepared by the phthalimide method or the chloromethylation method.
  • the ion exchanger according to the invention is preferably prepared by the phthalimide process, according to process steps a) to c), which is then functionalized according to step d) to give the chelate resin.
  • Formaldehyde, formalin or paraformaldehyde are preferably used as formaldehyde or its derivatives in process step d).
  • Formalin is particularly preferably used in process step d).
  • Phenylphosphinic acid, 2,4,4-trimethylpentylphosphinic acid, ethylphosphinic acid or 2-methylpentylphosphinic acid or mixtures of these compounds are preferably used as compounds of the formula (II) in process step d).
  • the compounds of the formula (II) can also be used in the salt form in process step d).
  • the sodium, potassium or lithium salts are preferably used as salts.
  • the reaction takes place in process step d) in a suspension medium.
  • Water or alcohols, or mixtures of these solvents, are used as the suspension medium.
  • the alcohols used are preferably methanol, ethanol or propanol.
  • Inorganic acids are preferably used as acids. However, organic acids can also be used. Hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid or mixtures of these acids are preferably used as inorganic acids.
  • the inorganic acids are preferably used in concentrations of from 10 to 90% by weight, particularly preferably from 40 to 80% by weight.
  • process step d preferably 1 to 4 mol of the compound of the formula (II) are used per mol of aminomethyl groups of the aminomethylated polymer from process step c).
  • process step d preferably 2 to 8 moles of formaldehyde are used per mole of aminomethyl groups in the aminomethylated polymer from process step c).
  • process step d preferably 2 to 12 moles of inorganic acid are used per mole of aminomethyl groups in the aminomethylated polymer from process step c).
  • the reaction of the aminomethyl-containing polymer to form chelate resins containing functional groups of structural element (I) in process step d) is preferably carried out at temperatures in the range from 70 to 120°C, particularly preferably at temperatures in the range from 85 to 110°C.
  • process step d) can be carried out by initially introducing the aminomethylated polymer and the compound of the formula (II) in water. Then formaldehyde or its derivatives are added, preferably with stirring. Then the inorganic acid is added. It is then heated to the reaction temperature. After the reaction has ended, the reaction mixture is cooled, the liquid phase is separated off and the resin is washed, preferably with deionized water.
  • process step d) can be carried out by initially introducing the aminomethylated polymer, the compound of the formula (II) and formaldehyde or its derivatives in water and then adding the inorganic acids at the reaction temperature. After the reaction has ended, the reaction mixture is cooled, the liquid phase is separated off and the resin is washed, preferably with deionized water.
  • the aminomethylated polymer, the inorganic acid and formaldehyde or its derivatives are initially taken in water and the compound of the formula (II) is then added at the reaction temperature. After the reaction has ended, the reaction mixture is cooled, the liquid phase is separated off and the resin is washed, preferably with deionized water.
  • the aminomethylated polymer, the compound of the formula (II), formaldehyde or its derivatives and the inorganic acid are initially taken in water and then heated to the reaction temperature. After the reaction has ended, the reaction mixture is cooled, the liquid phase is separated off and the resin is washed, preferably with deionized water.
  • the reaction mixture is stirred at the reaction temperature for about 3 to 15 hours. possibly it is also possible to convert the resin produced in process step d) into the salt form.
  • This can preferably by reaction with alkali metal hydroxides. Sodium hydroxide, potassium hydroxide or lithium hydroxide and the corresponding aqueous solutions are particularly preferably used as alkali metal hydroxides.
  • the aminomethylated polymer is suspended in water in process step d).
  • the compound of the formula (II) and the inorganic acid are added to this suspension.
  • the reaction mixture obtained in this way is heated to the reaction temperature, and formaldehyde or its derivatives are slowly added at this temperature while stirring. After the formaldehyde or its derivatives have been added, the reaction mixture is stirred at the reaction temperature for a further 3 to 15 hours. The reaction mixture is then cooled, the liquid phase is separated off and the resin is washed with deionized water.
  • the average degree of substitution of the chelating resin according to the invention can be between 0 and 2.
  • the average degree of substitution indicates the statistical molar ratio between unsubstituted, mono-substituted and disubstituted aminomethyl groups in the resin. With a degree of substitution of 0, no substitution would have taken place and the aminomethyl groups of structural element (I) would be present as primary amino groups in the resin. With a degree of substitution of 2, all of the amino groups in the resin would be disubstituted. Statistically, with a degree of substitution of 1, all the amino groups in the chelating resin according to the invention would be monosubstituted.
  • the average degree of substitution of the aminomethyl groups of the chelating resin according to the invention containing functional groups of the structural element (I) is preferably from 0.5 to 2.0.
  • the average degree of substitution of the amine groups of the chelating resin according to the invention containing functional groups of the structural element (I) is particularly preferably from 1.0 to 1.5.
  • the chelating resins according to the invention containing functional groups of the structural element (I) are outstandingly suitable for the recovery and purification of metals, preferably heavy metals, noble metals and rare earths.
  • the chelating resins according to the invention containing functional groups of the structural element (I) are suitable for the adsorption of rare earths selected from the group: scandium, lanthanum, yttrium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
  • the chelating resins according to the invention containing functional groups of the structural element (I) are suitable for the adsorption of iron, vanadium, copper, zinc, aluminum, cobalt, nickel, manganese, magnesium, calcium, lead, cadmium, uranium, mercury, elements of platinum group as well as gold or silver.
  • the chelating resins according to the invention containing functional groups of the structural element (I) are very particularly preferably suitable for the adsorption of zinc, iron, vanadium, aluminum, tungsten, manganese, magnesium, calcium, cobalt and nickel. Even more preferably, the chelating resins according to the invention containing functional groups of the structural element (I) are used for the adsorption of zinc, cobalt and nickel.
  • Adsorption from concentrated nickel and cobalt concentrate solutions for cleaning battery chemicals is particularly preferred.
  • the chelating resins according to the invention are used for the purification of inorganic acids.
  • the chelating resins according to the invention containing functional groups of structural element (I) are suitable for removing alkaline earth metals, e.g. calcium, magnesium, barium or strontium, from aqueous sols, such as are used, for example, in chloralkali electrolysis.
  • alkaline earth metals e.g. calcium, magnesium, barium or strontium
  • the chelating resins according to the invention containing functional groups of the structural element (I) are suitable for the adsorption and desorption of iron(III) cations. It has been shown that iron(III) cations can be desorbed again in large amounts by acids from the chelating resins according to the invention containing functional groups of the structural element (I).
  • the chelating resins according to the invention containing functional groups of the structural element (I) are suitable in a process for the production and purification of silicon, preferably silicon with a purity of greater than 99.99%.
  • the chelating resins according to the invention can preferably be used to remove metals from water for water purification.
  • the amount of basic groups corresponds to the molar amount of aminomethyl groups in the chelating resin.
  • the collected eluate is collected in a 500 ml volumetric flask and, if necessary, made up to the mark with deionized water.
  • the Zn concentration is determined from the 500 ml acid eluate using ICP-OES and converted to the total Zn capacity.
  • 3000 g of deionized water are placed in a 10 l glass reactor and a solution of 10 g of gelatin, 16 g of disodium hydrogen phosphate dodecahydrate and 0.73 g of resorcinol in 320 g of deionized water is added and mixed. The mixture is heated to 25°C.
  • a mixture of 3200 g of microencapsulated monomer droplets with a narrow particle size distribution of 3.1% by weight divinylbenzene and 0.6% by weight ethylstyrene (used as a commercial isomer mixture of divinylbenzene and ethylstyrene with 80% divinylbenzene), 0, 4 wt. % dibenzoyl peroxide, 58.4 wt. % styrene and 37.5 wt Acrylamide and acrylic acid, and added to 3200 g of aqueous phase with a pH of 12.
  • the mixture is polymerized with stirring by increasing the temperature according to a temperature program starting at 25°C and ending at 95°C.
  • the batch is cooled, washed through a 32 ⁇ m sieve and then dried at 80° C. in vacuo.
  • Examples 1 to 3 show that the claimed compounds surprisingly have a significantly higher total Zn capacity (TK) than the resin that is known from DE-A 2848289 and was produced with phosphinic acid.
  • TK total Zn capacity

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  • 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des résines chélatantes contenant des dérivés d'acide aminoalkylphosphinique, un procédé pour leur préparation, ainsi que leur utilisation dans la récupération et la purification de métaux, de préférence de métaux lourds, de métaux nobles et de terres rares.
EP21782987.8A 2020-09-30 2021-09-27 Nouvelles résines chélatantes Pending EP4222182A1 (fr)

Applications Claiming Priority (2)

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EP20199195 2020-09-30
PCT/EP2021/076453 WO2022069389A1 (fr) 2020-09-30 2021-09-27 Nouvelles résines chélatantes

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EP4222182A1 true EP4222182A1 (fr) 2023-08-09

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EP (1) EP4222182A1 (fr)
JP (1) JP2023543516A (fr)
KR (1) KR20230078679A (fr)
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WO (1) WO2022069389A1 (fr)

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CN117305533B (zh) * 2023-11-30 2024-05-14 上海稀固科技有限公司 从含铁铝铜料液中去除铝铜的方法
CN117986513B (zh) * 2024-04-07 2024-07-16 江西沐坤科技有限公司 一种树脂材料及其制备方法和应用、对稀土浸矿母液进行富集净化的方法

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Publication number Priority date Publication date Assignee Title
US4382124B1 (en) 1958-07-18 1994-10-04 Rohm & Haas Process for preparing macroreticular resins, copolymers and products of said process
DE2848289A1 (de) 1978-11-07 1980-06-12 Lobatschev Verfahren zur herstellung von polyampholyten
DE3031737A1 (de) 1980-08-22 1982-04-01 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von perlpolymerisaten einheitlicher teilchengroesse
CA1166413A (fr) 1980-10-30 1984-05-01 Edward E. Timm Methode et dispositif pour la preparation de perles de polymere dimensionnellement uniformes
US4419245A (en) 1982-06-30 1983-12-06 Rohm And Haas Company Copolymer process and product therefrom consisting of crosslinked seed bead swollen by styrene monomer
EP0481603A1 (fr) 1990-10-15 1992-04-22 The Dow Chemical Company Séparation d'acides organiques faibles de mélanges de liquides
US5231115A (en) 1991-12-19 1993-07-27 The Dow Chemical Company Seeded porous copolymers and ion-exchange resins prepared therefrom
EP1078690B1 (fr) 1999-08-27 2011-10-12 LANXESS Deutschland GmbH Méthode pour la préparation d'échangeurs d'ions monodisperses contenant des groupes chélatants
DE602005025268D1 (de) 2004-02-24 2011-01-27 Rohm & Haas Verfahren zur Entfernung von Arsen aus Wasser
DE102008012223A1 (de) * 2008-03-03 2009-09-10 Lanxess Deutschland Gmbh Picolylaminharze
DE102009047848A1 (de) 2009-09-30 2011-03-31 Lanxess Deutschland Gmbh Verfahren zur verbesserten Entfernung von Kationen mittels Chelatharzen

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CN116323693A (zh) 2023-06-23
WO2022069389A1 (fr) 2022-04-07
JP2023543516A (ja) 2023-10-16
US20230374180A1 (en) 2023-11-23

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