EP1663860A2 - Procede de purification d'acides sulfuriques - Google Patents

Procede de purification d'acides sulfuriques

Info

Publication number
EP1663860A2
EP1663860A2 EP04764379A EP04764379A EP1663860A2 EP 1663860 A2 EP1663860 A2 EP 1663860A2 EP 04764379 A EP04764379 A EP 04764379A EP 04764379 A EP04764379 A EP 04764379A EP 1663860 A2 EP1663860 A2 EP 1663860A2
Authority
EP
European Patent Office
Prior art keywords
sulfuric acid
monodisperse
copper
metals
acid
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.)
Withdrawn
Application number
EP04764379A
Other languages
German (de)
English (en)
Inventor
Olaf Halle
Wolfgang Podszun
Bruno Hees
Rheinhold Klipper
Jean-Marc Vesselle
Duilio Rossoni
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
Bayer SpA
Original Assignee
Lanxess Deutschland GmbH
Bayer SpA
Bayer Italia SpA
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, Bayer SpA, Bayer Italia SpA filed Critical Lanxess Deutschland GmbH
Publication of EP1663860A2 publication Critical patent/EP1663860A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C01B17/901—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids
    • C01B17/904—Recovery from spent acids containing metallic ions, e.g. hydrolysis acids, pickling acids 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C01B17/907—Removal of arsenic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/90—Separation; Purification
    • C01B17/908—Removal of antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper

Definitions

  • the present invention relates to a process for the purification of sulfuric acids, in particular of metal-containing sulfuric acids, with monodisperse ion exchangers which contain chelating, functional groups.
  • Duolite TM C-467 described wherein first a reduction of iron (TU) to iron (H) is carried out.
  • TU iron
  • HJ iron
  • the aforementioned reduction of iron (HJ) to iron (H) is carried out with copper and with sodium chloride in sulfuric acid and then the ion exchanger, after being loaded with the impurities, is subjected to a special elution in order to selectively add bismuth and then antimony isolate.
  • heterodisperse chelate exchangers are used, preferably polas® MX-2 from Miyoshi Oil Co., Duolite ⁇ M Q. 467 or Unicellex® UR 3300.
  • the object of the present invention was therefore to develop a new process for cleaning sulfuric acids, preferably for cleaning metal-containing ones
  • the particle size of the ion exchanger according to the invention is 5 to 500 ⁇ m, preferably 10 to 400 ⁇ m, particularly preferably 20 to 300 ⁇ m.
  • ion exchangers which have a small width of the particle size distribution.
  • Conventional methods such as sieve analysis or image analysis are suitable for determining the average particle size and the particle size distribution.
  • the ratio between the 90% value (0 (90) and the 10% value (0 (10) of the volume distribution) is formed as a measure of the width of the particle size distribution of the ion exchangers according to the invention
  • Monodisperse particle sizes mean distributions in the sense of the invention (0 (9O) / 0 (10) ⁇ 1.50, preferably (0 (9O) / 0 (10) ⁇ 1.25, very particularly preferably (0 (9O) / 0 (10) ⁇ 1.20.
  • Monodisperse ion exchangers can be obtained by functionalizing monodisperse bead polymers.
  • One way of producing monodisperse bead polymers is to produce monodisperse monomer droplets by means of special atomization techniques and to harden them by polymerization.
  • a uniform droplet size can be formed by vibration excitation, as described for example in EP-A 0 051 210. If the degree of monodispersity of the monomer droplets is to be maintained during the polymerization, the agglomeration and coalescence as well as the new formation of droplets must be prevented.
  • Microencapsulation according to EP-A 0 046 535 is a particularly effective method for preventing agglomeration and coalescence as well as new droplet formation.
  • the present invention and thus the solution to the problem is a process for the purification of sulfuric acids, preferably sulfuric acidic metal-containing solutions, particularly preferably sulfuric acidic copper electrolytes, characterized in that metals, particularly preferably metals which may be present as anions or cations, particularly preferably metals , which may be in the oxidation state + HI, treated with monodisperse ion exchangers with chelating, functional groups, preferably of the aminomethylphosphonic acid type or their functionalization via the phthalimide stage.
  • sulfuric acids preferably sulfuric acidic metal-containing solutions, particularly preferably sulfuric acidic copper electrolytes, characterized in that metals, particularly preferably metals which may be present as anions or cations, particularly preferably metals , which may be in the oxidation state + HI, treated with monodisperse ion exchangers with chelating, functional groups, preferably of the aminomethylphosphonic acid type or their functionalization via the phthalimide stage.
  • contaminated sulfuric acids such as those obtained in industrial production processes, preferably metal-containing sulfuric acids, particularly preferably sulfuric acid copper electrolytes which, in addition to copper, contain other metals such as iron, antimony or bismuth, can be worked up and returned to the industrial production processes.
  • metal-containing sulfuric acids particularly preferably sulfuric acid copper electrolytes which, in addition to copper, contain other metals such as iron, antimony or bismuth
  • extractants or mixtures of sulfuric acid with several extractants can also be used in the production of sulfuric acid by this method for the cleaning process according to the invention.
  • Suitable extractants are substances which form one or more further phases in the presence of sulfuric acid and preferably dissolve a metal, in the case of copper extraction, the copper, in ionic or complex-bound form.
  • Preferred extraction agents are aliphatic or aromatic or mixed aliphatic and aromatic organic compounds with functional groups.
  • Preferred functional groups are e.g. Phosphate (e.g. in trialkyl phosphate), aldoxime, ketoxime, alcohol, ketone, ß-diketone, ester and sulfonamide.
  • elemental copper with impurities in metals which can occur in the oxidation state + DI, is brought into solution in the presence of sulfuric acid by anodic oxidation in an electrical field.
  • Sulfuric acid can be used as the intended metal-containing sulfuric acid in the process according to the invention.
  • the concentration of these sulfuric acids can vary within a wide range.
  • the preferred sulfuric acid concentration for the process according to the invention is 50-500 g / 1, particularly preferably 75-400 g / 1, particularly preferably 125-275 g / 1.
  • the amounts of metal in the sulfuric acid to be used according to the invention can vary within wide ranges and are dependent on the quality of the ore and the extraction process.
  • the preferred copper concentration in sulfuric acid is 5-100 g / 1, particularly preferably 20-50 g / 1, particularly preferably 25-35 g / 1.
  • metals which may be present in the + IT1 oxidation state are preferably removed from the sulfuric acids.
  • Preferred metals are one or more metals of antimony, bismuth, arsenic, cobalt, nickel, molybdenum or iron.
  • Particularly preferred metals are one or more metals from the group of antimony, bismuth or molybdenum, particularly preferably antimony or bismuth.
  • the preferred antimony concentration is 0-5 g / 1, particularly preferably 0-2 g / 1, particularly preferably 0.1-1 g / 1.
  • the preferred bismuth concentration is 0-5 g / 1, particularly preferably 0-2 g / 1, particularly preferably 0.1-1 g / 1.
  • the process according to the invention can be carried out continuously or batchwise. Continuous processes are preferred.
  • the resin is operated in a column with perforated bottoms.
  • the speed of the sulfuric acid to be purified through the column must be selected in such a way that a high volume flow passes through the column, but no increased concentrations of the metals to be removed pass through.
  • the preferred flow rate is 5-30 times the ion exchange bulk volume per hour (this size is referred to below as bed volume per hour (BV / h)), particularly preferably 10-20 BV h.
  • the metals to be removed accumulate in the ion exchange resin. This can be done by setting
  • Conditions in which the chemical affinity of the metals for the ion exchange resin is reduced are eluted.
  • An effective method for eluting ion exchangers is treatment with mineral acids or organic acids, preferably in a concentration of 0.1-10 eq / 1.
  • the elution is usually carried out with 1-10 bed volumes (BV), preferably with 2-5 BV.
  • Preferred mineral acids are hydrochloric acid or sulfuric acid, preferred organic acids are
  • Acetic acid, formic acid or tartaric acid can also be present during the elution.
  • Organic salts e.g. tartrates
  • inorganic salts e.g. sodium chloride
  • the sulfuric acid purified by means of the monodisperse chelate exchanger can finally be used directly in galvanic processes for the production of elemental copper by reduction at the cathode.
  • chelating functional groups are suitable as functional groups for the monodisperse chelate exchangers to be used according to the invention.
  • Functional groups of the type are preferred - (CH ⁇ NF ⁇ R 2
  • Ri represents hydrogen or a radical CH 2 -COOH or CH 2 -P (0) (OH) 2 and
  • R 2 stands for a radical CH 2 -COOH or CH 2 -P (0) (OH) 2 and n stands for an integer between 1 and 4.
  • Ri represents hydrogen or the radical CH P (0) (OH) 2 ,
  • R 2 is CH P (0) (OH) 2 and n is 1, 2, 3 or 4.
  • Various base bodies are known as the polymer base of the monodisperse chelate exchangers to be used according to the invention.
  • Ion exchangers based on crosslinked vinylaromatic polymers and on the basis of condensation products of hydroxyaromatics and formaldehyde are customary. However, they are also ion exchangers based on aliphatic polyamines, polyesters or natural products, such as Cellulose or wood; known.
  • Monodisperse chelate exchangers based on crosslinked vinylaromatic polymers are preferred according to the invention.
  • the monodisperse, crosslinked, vinyl aromatic base polymer can be prepared by the processes known from the literature. For example, such processes are described in US Pat. No. 4,444,961, EP-A 0 046 535, US-A 4419 245, WO 93/12 167.
  • a copolymer with a monovinylaromatic compound and a polyvinylaromatic compound is suitable as a copolymer in the sense of the present invention.
  • Mono-vinyl aromatic compounds for the purposes of the present invention are preferably monoethylenically unsaturated compounds such as, for example, styrene, vinyl toluene, ethyl styrene, ⁇ -methyl styrene, chlorostyrene, chloromethyl styrene, alkyl acrylate and alkyl methacrylate.
  • Preferred polyvinylaromatic compounds for the purposes of the present invention are multifunctional ethylenically unsaturated compounds such as, for example, divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphtalin, trivinylnaphtalin, 1,7-octadiene, 1,5-hexadiene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate.
  • the polyvinyl aromatic compounds are generally used in amounts of 1-20% by weight, preferably 2-12% by weight, particularly preferably 4-10% by weight, based on the monomer or its mixture with further monomers.
  • the type of polyvinyl aromatic compounds (crosslinkers) is selected with a view to the later use of the spherical polymer.
  • Divinylbenzene is suitable in many cases. For most applications, commercial divinylbenzene grades, which are in addition to the isomers of
  • Divinylbenzene also contain ethylvinylbenzene, sufficient.
  • microencapsulated monomer droplets are used as bead polymers.
  • the materials known for use as complex coacervates come into question, in particular polyesters, natural and synthetic polyamides, polyurethanes, polyureas.
  • Gelatin for example, is particularly suitable as a natural polyamide. This is used in particular as a coacervate and complex coacervate.
  • gelatin-containing complex coacervates are understood to mean, above all, combinations of gelatin with synthetic polyelectrolytes. Suitable synthetic polyelectrolytes are
  • Acrylic acid and acrylamide are particularly preferably used.
  • Capsules containing gelatin can be hardened with conventional hardening agents such as, for example, formaldehyde or glutardialdehyde.
  • 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 for example, is particularly suitable, in which a reactive component (for example an isocyanate or an acid chloride) dissolved in the monomer droplet is reacted with a second reactive component (for example an amine) dissolved in the aqueous phase.
  • a reactive component for example an isocyanate or an acid chloride
  • a second reactive component for example an amine
  • the optionally microencapsulated monomer droplets optionally contain an initiator or mixtures of initiators to initiate the polymerization.
  • initiators for example peroxy compounds such as dibenzoyl peroxide, are preferably used for the preparation of the bead polymers.
  • Dilauryl peroxide bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxydicarbonate, tert-butyl peroctoate, tert-butyl peroxy-2-ethyl-hexanoate, 2,5-bis (2-ethylhexanoyl peroxy) -2,5-dimethylhexane or tert-amylperoxy-2- ethylhexane, and azo compounds such as 2 5 2'-azo-bis (isobutyronitrile) or 2,2'-azobis (2-methylisobutyronitrile) are used.
  • the initiators are generally used in amounts of 0.05 to 2.5% by weight, preferably 0.1 to
  • Porogens can optionally be used as further additives in the optionally microencapsulated monomer droplets in order to produce spherical bead polymers (starting material for the production of the monodisperse chelate exchanger) with a macroporous structure.
  • Organic solvents that dissolve or swell the resulting bead polymer are poorly suited for this. Examples include hexane, octane, isooctane, isododecane, methyl ethyl ketone, bufanol or octanol and their isomers.
  • microporous or gel-like or macroporous have already been described in detail in the specialist literature.
  • the optionally microencapsulated monomer droplet can optionally be up to
  • Preferred polymers are derived from the aforementioned monomers, particularly preferably from styrene.
  • the average particle size of the capsules necessary for the preparation of the bead polymer (starting material for the production of the monodisperse chelate exchangers), if appropriate, encapsulated
  • Monomer droplet is 10-1000 ⁇ m, preferably 100-1000 ⁇ m.
  • the bead polymers can be functionalized to the desired monodisperse chelate exchanger to be used according to the invention by haloalkylation of the crosslinked polymer and subsequent conversion into the desired functional group.
  • the methods for haloalkylating the polymers are known from US Pat. No. 4,444,961. A favorite
  • Haloalkylating agent is chloromethyl methyl ether.
  • the chloromethyl methyl ether can be used in unpurified form, it may contain, for example, mefhylal or methanol as secondary components.
  • the chloromethylation reaction is catalyzed by the addition of Lewis acids. Suitable catalysts are e.g. Iron (HI) chloride, zinc chloride, tin (rV) chloride or aluminum chloride.
  • heterodisperse ion exchange resins with chelating groups is described, for example, in US Pat. No. 2,888,441, but is based on monodisperse ion exchangers transferable.
  • the haloalkylated bead polymer is initiated and the aminated bead polymer is reacted with suitable carboxyl-containing compounds, for example chloroacetic acid.
  • suitable carboxyl-containing compounds for example chloroacetic acid.
  • suitable amino acids such as, for example, aminodiacetic acid, glycine, 2-picolylamine or N-methyl-2-picolylamine.
  • the bead polymer is functionalized to the desired monodisperse chelate exchanger via direct amination.
  • the amidomethylation reagent is first prepared for this.
  • phthalimide or a phthahmid derivative is dissolved in a solvent and mixed with formaldehyde or paraformaldehyde.
  • a bis (phthalimido) ether is then formed from this with elimination of water.
  • the bead polymer is then condensed with phthalimide derivatives. Oleum, sulfuric acid or sulfur trioxide is used as the catalyst.
  • the phthalic acid ester is split off and the aminomethyl group is thus exposed by treating the phthalimidomethylated crosslinked bead polymer with aqueous or alcoholic solutions of an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide
  • the concentration of the sodium hydroxide solution is in the range from 10 to 50% by weight ; preferably 20 to 40% by weight. This process enables the production of crosslinked bead polymers containing aminoall units, with a substitution of the aromatic nuclei greater than 1.
  • the ion exchangers to be used according to the invention are subsequently produced by
  • the preferred reagents used are chloroacetic acid and its derivatives, formaldehyde in combination with P-H acidic (after modified Marmich reaction) compounds such as phosphorous acid, monoalkylphosphoric acid ester or dialkylphosphoric acid ester.
  • Chloroacetic acid or formaldehyde are particularly preferably used in combination with P-H acidic compounds such as phosphorous acid.
  • the monodisperse chelate exchangers to be used according to the invention preferably have a macroporous structure.
  • Gelatin 16 g of di-sodium hydrogen phosphate dodecahydrate and 0.73 g of resorcinol in 320 g of deionized water are added and mixed. The mixture is heated to 25 ° C.
  • Ethylstyi-ol roit 80%. Divinylbenzene), 0.5 wt .-% of dibenzoyl peroxide, 56.2 wt .-% styrene and 38.8 wt .-% isododecane (technical isomeric mixture given with a high proportion of pentamethylheptane), the microcapsule of a formaldehyde-cured complex ' consists of gelatin and a copolymer of acrylamide and acrylic acid, and 3200 g of aqueous phase with a pH of 12 are added. The average particle size of the monomer droplets is 460 ⁇ m.
  • the batch is polymerized with stirring by increasing the temperature according to a temperature program at 25 ° C. and ending at 95 ° C.
  • the mixture is cooled, washed over a 32 ⁇ m sieve and then dried in vacuo at 80 ° C. 1893 g of a spherical polymer having an average particle size of 440 ⁇ m, narrower, are obtained
  • the polymer is chalky white when viewed from above and has a bulk density of approx. 370 g / l.
  • the bead polymer obtained is washed with deionized water.
  • the reaction mixture is cooled, placed on a sieve and washed with deionized water until the process remains neutral.
  • the resin is then transferred to a glass column with a glass frit base and, with 3 bed volumes, 4% by weight sodium hydroxide solution, which is introduced from above into the ion exchange bed, into the sodium form.
  • the ion exchanger is then washed with 5 bed volumes of deionized water. 1060 ml of a water-moist ion exchanger are obtained
  • Phosphorus 10.0% by weight
  • the ion exchanger is transferred again into the glass column and converted into the hydrogen form with 2 bed volumes of 10% strength by weight sulfuric acid, which is introduced into the ion exchange bed from above. Then the
  • Ion exchanger washed with 5 bed volumes of demineralized water and discharged again from the glass column.
  • the sulfuric acid emerging from the glass column is analyzed and with the incoming
  • Antimony concentration 0.4 g / 1
  • Antimony concentration 0.02 g / 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de purification d'acides sulfuriques, en particulier d'acides sulfuriques métallifères, lequel procédé se caractérise en ce qu'il consiste à utiliser des échangeurs d'ions monodispersés à groupes fonctionnels de chélation.
EP04764379A 2003-09-04 2004-08-23 Procede de purification d'acides sulfuriques Withdrawn EP1663860A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000416A ITRM20030416A1 (it) 2003-09-04 2003-09-04 Procedimento per la purificazione di acidi solforici.
PCT/EP2004/009398 WO2005028362A2 (fr) 2003-09-04 2004-08-23 Procede de purification d'acides sulfuriques

Publications (1)

Publication Number Publication Date
EP1663860A2 true EP1663860A2 (fr) 2006-06-07

Family

ID=30131563

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04764379A Withdrawn EP1663860A2 (fr) 2003-09-04 2004-08-23 Procede de purification d'acides sulfuriques

Country Status (10)

Country Link
US (1) US20080229882A1 (fr)
EP (1) EP1663860A2 (fr)
JP (1) JP2007533578A (fr)
KR (1) KR20060079206A (fr)
CN (1) CN1878726A (fr)
AU (1) AU2004274134B2 (fr)
CA (1) CA2537709A1 (fr)
IT (1) ITRM20030416A1 (fr)
RU (1) RU2006109814A (fr)
WO (1) WO2005028362A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006004953A1 (de) * 2006-02-01 2007-08-02 Lanxess Deutschland Gmbh Chelatharze in der Metallgewinnung
DE102007020688A1 (de) * 2007-05-03 2008-11-06 Lanxess Deutschland Gmbh Konditionierung von Ionenaustauschern zur Adsorption von Oxoanionen
CN102010082B (zh) * 2010-09-29 2013-09-18 南京梅山冶金发展有限公司 废稀硫酸回收利用处理方法
EP2835384A1 (fr) * 2013-08-09 2015-02-11 LANXESS Deutschland GmbH Procédé de fabrication de polymères en perles vinylaromatiques amidométhylés monodispersés
CN109336067A (zh) * 2018-12-12 2019-02-15 湘潭大学 一种废硫酸溶液回收净化的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888441A (en) * 1956-10-12 1959-05-26 Dow Chemical Co Chelating resins having alpha-aminocarboxylic acid groups on a polymerized vinylbenzylamine resin structure
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
JPS59162108A (ja) * 1983-03-03 1984-09-13 Tadao Nagai 硫酸溶液の浄液法
US5231115A (en) * 1991-12-19 1993-07-27 The Dow Chemical Company Seeded porous copolymers and ion-exchange resins prepared therefrom
US5366715A (en) * 1993-10-19 1994-11-22 The University Of British Columbia Method for selectively removing antimony and bismuth from sulphuric acid solutions
US6153081A (en) * 1995-01-12 2000-11-28 Fukui; Atsushi Method of recovering antimony and bismuth from copper electrolyte
EP1078690B1 (fr) * 1999-08-27 2011-10-12 LANXESS Deutschland GmbH Méthode pour la préparation d'échangeurs d'ions monodisperses contenant des groupes chélatants
DE10049807A1 (de) * 2000-10-09 2002-04-18 Bayer Ag Verwendung monodisperser Ionenaustauscher zur Arsen-/Antimonentfernung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005028362A2 *

Also Published As

Publication number Publication date
AU2004274134A1 (en) 2005-03-31
KR20060079206A (ko) 2006-07-05
CN1878726A (zh) 2006-12-13
WO2005028362A2 (fr) 2005-03-31
US20080229882A1 (en) 2008-09-25
ITRM20030416A1 (it) 2005-03-05
ITRM20030416A0 (it) 2003-09-04
AU2004274134B2 (en) 2009-10-15
RU2006109814A (ru) 2007-10-10
CA2537709A1 (fr) 2005-03-31
WO2005028362A3 (fr) 2006-01-26
JP2007533578A (ja) 2007-11-22

Similar Documents

Publication Publication Date Title
EP2259874B1 (fr) Résine picolylamine
EP1078690B1 (fr) Méthode pour la préparation d'échangeurs d'ions monodisperses contenant des groupes chélatants
EP2025387B1 (fr) Procédé de fabrication de résines de chélate monodispersées
EP1078937B1 (fr) Procédé de préparation de polymères en perles réticulés et monodispersés contenant des groupements thiourée et leur application à l'adsorption de composés métalliques
DE102007034732A1 (de) Verfahren zur Herstellung von Chelatharzen
EP2305382A1 (fr) Procédé de suppression améliorée de cations à l'aide de résines de chélate
WO2004110623A1 (fr) Echangeur d'ions adsorbeur d'arsenic
EP2259875B1 (fr) Résines à base de picolylamine
WO2005049190A2 (fr) Echangeur a chelates
EP2305381A2 (fr) Procédé pour l'élimination améliorée de cations à l'aide de résines chélatantes
DE10121163A1 (de) Verfahren zur Herstellung heterodisperser Chelatharze
EP3183275A1 (fr) Chélates aminométhylées sulfonées
EP1078689A2 (fr) Méthode pour la préparation d'échangeurs d'anions contenant des groupes fonctionels fortement basiques
WO2009013142A2 (fr) Résines chélatantes
EP1663860A2 (fr) Procede de purification d'acides sulfuriques
EP3102328B1 (fr) Nouveaux groupes d'acides iminodiacétiques dopés à l'aluminium contenant des résines de chélate
EP2330137B1 (fr) Résines de chélate d'acide méthylène-amino-éthyl-sulfonique
DE19954399A1 (de) Verfahren zur Herstellung von monodispersen Ionenaustauschern mit chelatisierenden Gruppen und ihre Verwendung
DE102006034668A1 (de) Mittel- oder starkbasische Anionenaustauscher

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL HR LT LV MK

17P Request for examination filed

Effective date: 20060726

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20071112

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100302