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US20080229882A1 - Process for Purifying Sulphuric Acids - Google Patents

Process for Purifying Sulphuric Acids Download PDF

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Publication number
US20080229882A1
US20080229882A1 US10/570,455 US57045504A US2008229882A1 US 20080229882 A1 US20080229882 A1 US 20080229882A1 US 57045504 A US57045504 A US 57045504A US 2008229882 A1 US2008229882 A1 US 2008229882A1
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US
United States
Prior art keywords
monodisperse
copper
metal
sulphuric acid
sulfuric acid
Prior art date
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Abandoned
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US10/570,455
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English (en)
Inventor
Olaf Halle
Wolfgang Podszun
Bruno Hees
Rheinhold Klipper
Jean-Marc Vesselle
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Lanxess Deutschland GmbH
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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.)
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Publication date
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Assigned to LANXESS DEUTSCHLAND GMBH reassignment LANXESS DEUTSCHLAND GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEES, BRUNO, VESSELLE, JEAN-MARC, KLIPPER, RHEINHOLD, PODSZUN, WOLFGANG, HALLE, OLAF, ROSSONI, DUILIO
Publication of US20080229882A1 publication Critical patent/US20080229882A1/en
Abandoned legal-status Critical Current

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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 purifying sulphuric acids, in particular metal-containing sulphuric acids, using monodisperse ion exchangers containing chelating functional groups.
  • U.S. Pat. No. 4,559,216 describes a process for removing antimony, bismuth or iron from copper electrolytes containing sulphuric acid using heterodisperse ion exchangers having specific chelating aminomethylenephosphonic acid groups. For example, Unicellex® UR 3300 is mentioned there.
  • U.S. Pat. No. 5,366,715 describes a process for removing antimony, bismuth or iron from copper electrolytes containing sulphuric acid by means of heterodisperse ion exchangers functionalized with aminomethylenephosphonic acid, preferably DuoliteTM C-467, with a reduction of iron(III) to iron(II) firstly being carried out.
  • the particle size of the ion exchangers used according to the invention is from 5 to 500 ⁇ m, preferably from 10 to 400 ⁇ m, particularly preferably from 20 to 300 ⁇ m.
  • monodisperse ion exchangers are ion exchangers which have a small width of the particle size distribution.
  • Customary methods such as sieve analysis or image analysis are suitable for determining the mean particle size and the particle size distribution.
  • the ratio of the 90% value ⁇ (90) and the 10% value ⁇ (10) of the volume distribution is employed as measure for the width of the particle size distribution of the ion exchangers used according to the invention.
  • the 90% value ⁇ (90) is the diameter at which 90% of the particles have a smaller diameter.
  • Monodisperse particle size distributions for the purposes of the invention are distributions such that ⁇ (90)/ ⁇ (10) ⁇ 1.50, preferably ⁇ (90)/ ⁇ (10) ⁇ 1.25, very particularly preferably ⁇ (90)/ ⁇ (10) ⁇ 1.20.
  • Monodisperse ion exchangers can be obtained by functionalization of monodisperse bead polymers.
  • One possible way of preparing monodisperse bead polymers is to generate monodisperse monomer droplets by means of specific spraying techniques and curing these by polymerization. The formation of a uniform droplet size can be effected by vibrational excitation, as described, for example, in EP-A 0 051 210. If the degree of monodispersity of the monomer droplets is to be retained in the polymerization, agglomeration and coalescence and also formation of new droplets has to be reliably prevented. A particularly effective method of preventing agglomeration and coalescence and formation of new droplets is microencapsulation according to EP-A 0 046 535.
  • the present invention achieves this object by providing a process for purifying sulphuric acids, preferably metal-containing solutions containing sulphuric acid, particularly preferably copper electrolytes containing sulphuric acid, characterized in that metals, particularly preferably metals which can be present as anions or cations, particularly preferably metals which can be present in the oxidation state +III, are treated with monodisperse ion exchangers having chelating functional groups, preferably of the aminomethylenephosphonic acid type or whose functionalization has been effected via the phthalimide stage.
  • contaminated sulphuric acids as are obtained in industrial production processes preferably metal-containing sulphuric acids, particularly preferably copper electrolytes which contain sulphuric acid and, in addition to copper, contain further metals such as iron, antimony or bismuth, can be worked up in this way and returned to the industrial production processes.
  • metal-containing sulphuric acids particularly preferably copper electrolytes which contain sulphuric acid and, in addition to copper, contain further metals such as iron, antimony or bismuth
  • a metal-containing sulphuric acid in the case of copper winning, there are various ways in which a metal-containing sulphuric acid can be produced.
  • copper-containing milled ore is extracted with sulphuric acid and the pH is subsequently increased by addition of alkalis. Copper and other metals are extracted from this ore/sulphuric acid slurry by means of one or more extractants.
  • the extractant phase is separated off and the metals are reextracted into the sulphuric acid phase by addition of sulphuric acid.
  • This sulphuric acid is then used as metal-containing sulphuric acid in the process of the invention.
  • extractants or mixtures of sulphuric acid with a plurality of extractants.
  • Suitable extractants are substances which form one or more phases in the presence of sulphuric acid and preferentially dissolve a metal, in the case of copper winning copper, in ionic or complexed form.
  • Preferred extractants are aliphatic or aromatic or mixed aliphatic and aromatic organic compounds having functional groups.
  • Preferred functional groups are, for example, phosphate (e.g. in trialkyl phosphate), aldoxime, ketoxime, alcohol, ketone, ⁇ -diketone, ester and sulphonamide.
  • elemental copper contaminated with metals which can occur in the oxidation state +III is brought into solution in the presence of sulphuric acid by anodic oxidation in an electric field.
  • sulphuric acid can also be used as appropriate metal-containing sulphuric acid in the process of the invention.
  • the concentration of these sulphuric acids can vary within a wide range.
  • the preferred sulphuric acid concentration for the process of the invention is 50-500 g/l, particularly preferably 75-400 g/l, very particularly preferably 125-275 g/l.
  • the amounts of metals in the sulphuric acid to be used according to the invention can fluctuate within a wide range and are dependent on the quality of the ore and the extraction process.
  • the preferred concentration of copper in the sulphuric acid is 5-100 g/l, particularly preferably 20-50 g/l, very particularly preferably 25-35 g/l.
  • metals which can occur in the oxidation state +III from the sulphuric acids.
  • Preferred metals are one or more metals of the group consisting of antimony, bismuth, arsenic, cobalt, nickel, molybdenum and iron.
  • Particularly preferred metals are one or more metals from the group consisting of antimony, bismuth and molybdenum, very particularly preferably antimony or bismuth.
  • the preferred antimony concentration is 0-5 g/l, particularly preferably 0-2 g/l, very particularly preferably 0.1-1 g/l.
  • the preferred bismuth concentration is 0-5 g/l, particularly preferably 0-2 g/l, very particularly preferably 0.1-1 g/l.
  • the process of the invention can be carried out continuously or batchwise. Preference is given to continuous processes.
  • the resin is employed in a column provided with perforated plates.
  • the speed at which the sulphuric acid to be purified travels through the column should be chosen so that a high volume flow passes through the column but elevated concentrations of the metals to be removed do not remain in the stream leaving the column.
  • the preferred flow rate through the column is 5-30 times the ion exchanger bed volume per hour (this unit is hereinafter referred to as bed volume per hour (BV/h)), particularly preferably 10-20 BV/h.
  • the metals to be removed accumulate in the ion-exchange resin. These can be eluted by setting conditions under which the chemical affinity of the metals to the ion-exchange resin is reduced.
  • An effective method of eluting ion exchangers is treatment with mineral acids or organic acids, preferably in a concentration of 0.1-10 eq/1. Elution is usually carried out using 1-10 bed volumes (BV), preferably 2-5 BV.
  • Preferred mineral acids are hydrochloric acid or sulphuric acid, while preferred organic acids are acetic acid, formic acid or tartaric acid.
  • Organic salts (e.g. tartrates) or inorganic salts (e.g. sodium chloride) can also be present during elution.
  • the sulphuric acid purified by means of the monodisperse chelating exchanger can finally be used directly in electrolytic processes for the production of elemental copper by reduction of the cathode.
  • Functional groups in the monodisperse chelating exchangers used according to the invention can be all chelate-forming functional groups. Preference is given to functional groups of the type
  • R 1 is hydrogen or a CH 2 —COOH or CH 2 —P(O)(OH) 2 radical and R 2 is a CH 2 —COOH or CH 2 —P(O)(OH) 2 radical and n is an integer from 1 to 4.
  • R 1 is hydrogen or the radical CH 2 P(O)(OH) 2 ,
  • R 2 is CH 2 P(O)(OH) 2 and
  • n 1, 2, 3 or 4.
  • ion exchangers based on crosslinked vinylaromatic polymers As polymer base of the monodisperse chelating exchangers to be used according to the invention, various basic structures are known. It is customary to employ ion exchangers based on crosslinked vinylaromatic polymers and ion exchangers based on condensation products of hydroxyaromatics and formaldehyde. However, ion exchangers based on aliphatic polyamines, polyesters or natural products, e.g. cellulose or wood, are also known. According to the invention, preference is given to monodisperse chelating exchangers based on crosslinked vinylaromatic polymers.
  • the monodisperse, crosslinked, vinylaromatic base polymer can be prepared by methods known from the literature. For example, such methods are described in U.S. Pat. No. 4,444,961, EP-A 0 046 535, U.S. Pat. No. 4,419,245, WO 93/12167.
  • a possible copolymer for the purposes of the present invention is, for example, a copolymer composed of a monovinylaromatic compound and a polyvinylaromatic compound.
  • monovinylaromatic compounds preference is given, for the purposes of the present invention, to monoethylenically unsaturated compounds such as styrene, vinyltoluene, ethylstyrene, ⁇ -methylstyrene, chlorostyrene, chloromethylstyrene, alkyl acrylates and alkyl methacrylates.
  • Polyvinylaromatic compounds which are preferred for the purposes of the present invention are multifunctional ethylenically unsaturated compounds such as divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, 1,7-octadiene, 1,5-hexadiene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate.
  • multifunctional ethylenically unsaturated compounds such as divinylbenzene, divinyltoluene, trivinylbenzene, divinylnaphthalene, trivinylnaphthalene, 1,7-octadiene, 1,5-hexadiene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate.
  • the polyvinylaromatic 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 polyvinylaromatic compounds (crosslinkers) is selected with a view to the later use of the spherical polymers.
  • Divinylbenzene is suitable in many cases. Commercial divinylbenzene grades which contain ethylvinylbenzene in addition to the isomers of divinylbenzene are satisfactory for most applications.
  • microencapsulated monomer droplets are used as bead polymers.
  • the microencapsulation of the monomer droplets can be by means of the materials known for use as complex coacervates, in particular polyesters, natural and synthetic polyamides, polyurethanes, polyureas.
  • a particularly useful natural polyamide is, for example, gelatin. This is employed, in particular, as coacervate and complex coacervate.
  • gelatin-containing complex coacervates are, in particular, combinations of gelatin with synthetic polyelectrolytes.
  • Suitable synthetic polyelectrolytes are copolymers containing built-in units of, for example, maleic acid, acrylic acid, methacrylic acid, acrylamide and methacrylamide. Particular preference is given to using acrylic acid and acrylamide.
  • Gelatin-containing capsules can be cured by means of customary curing agents such as formaldehyde or glutaraldehyde.
  • the optionally microencapsulated monomer droplets may, if appropriate, contain an initiator or mixtures of initiators to trigger the polymerization.
  • initiators preferred in the preparation of bead polymers, for example peroxy compounds such as dibenzoyl peroxide, dilauryl 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-amyl-peroxy-2-ethylhexane, and also azo compounds such as 2,2′-azobis(isobutyronitrile) or 2,2′-azobis(2-methylisobutyronitrile).
  • the initiators are generally employed in amounts of from 0.05 to 2.5% by weight, preferably from 0.1 to 1.5% by weight, based on the monomer mixture.
  • porogens in order to produce spherical bead polymers (starting material for the preparation of the monodisperse chelating exchanger) having a macroporous structure.
  • suitable porogens are organic solvents which do not readily dissolve or swell the bead polymer formed. Examples which may be mentioned are hexane, octane, isooctane, isododecane, methyl ethyl ketone, butanol or octanol and their isomers.
  • microporous or gel-like or macroporous are described in detail in the specialist literature.
  • the optionally microencapsulated monomer droplet can, if desired, also contain up to 30% by weight (based on the monomer) of crosslinked or uncrosslinked polymer.
  • Preferred polymers are derived from the abovementioned monomers, particularly preferably from styrene.
  • the mean particle size of the optionally encapsulated monomer droplets necessary for preparing the bead polymer is 10-1000 ⁇ m, preferably 100-1000 ⁇ m.
  • the functionalization of the bead polymers to produce the desired monodisperse chelating exchanger used according to the invention can be carried out via haloalkylation of the crosslinked polymer and subsequent conversion into the desired functional group.
  • Methods of haloalkylating polymers are known from U.S. Pat. No. 4,444,961.
  • a preferred haloalkylating agent is chloromethyl methyl ether.
  • the chloromethyl methyl ether can be used in unpurified form, in which case it can contain, for example, methylal or methanol as secondary components.
  • the chloromethylation reaction is catalysed by addition of Lewis acids. Suitable catalysts are, for example, iron(III) chloride, zinc chloride, tin(IV) chloride and aluminium chloride.
  • heterodisperse ion-exchange resins containing chelating groups is described, for example, in U.S. Pat. No. 2,888,441, but can be applied to monodisperse ion exchangers.
  • the haloalkylated bead polymer is aminated and the aminated bead polymer is reacted with a suitable carboxyl-containing compound, e.g. chloroacetic acid.
  • a suitable carboxyl-containing compound e.g. chloroacetic acid.
  • suitable amino acids such as aminodiacetic acid, glycine, 2-picolylamine or N-methyl-2-picolylamine.
  • the functionalization of the bead polymer to the desired monodisperse chelating exchanger is carried out by direct amination.
  • the amidomethylation reagent is prepared first.
  • phthalimide or a phthalimide derivative for example, is dissolved in a solvent and admixed with formaldehyde or paraformaldehyde.
  • a bis(phthalimido) ether is subsequently formed from this by elimination of water.
  • the bead polymer is subsequently condensed with phthalimide derivatives.
  • catalyst use is made here of oleum, sulphuric acid or sulphur trioxide.
  • the phthalic ester is split off to set the aminomethyl group free by treatment of the phthalimidomethylated crosslinked bead polymer with aqueous or alcoholic solutions of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at temperatures of from 100 to 250° C., preferably 120-190° C.
  • concentration of the sodium hydroxide solution is in the range from 10 to 50% by weight, preferably from 20 to 40% by weight.
  • the ion exchangers to be used according to the invention are subsequently prepared by reacting the aminated monodisperse, crosslinked, vinylaromatic base polymer in suspension with compounds which finally develop, as functional amine, chelating properties.
  • Preferred reagents are chloroacetic acid and its derivatives, formaldehyde in combination with P—H-acidic (after modified Mannich reaction) compounds such as phosphorous acid, monoalkylphosphorous esters or dialkylphosphorous esters.
  • chloroacetic acid or formaldehyde in combination with P—H-acidic compounds such as phosphorous acid.
  • the monodisperse chelating exchangers to be used according to the invention preferably have a macroporous structure.
  • 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 hydrogenphosphate dodecahydrate and 0.73 g of resorcinol in 320 g of deionized water is introduced and the mixture is mixed. The mixture is brought to 25° C.
  • a mixture of 3200 g of microencapsulated monomer droplets having a narrow particle size distribution and comprising 3.6% by weight of divinylbenzene and 0.9% by weight of ethylstyrene (used as commercial isomer mixture of divinylbenzene and ethylstyrene containing 80% of divinylbenzene), 0.5% by weight of dibenzoyl peroxide, 56.2% by weight of styrene and 38.8% by weight of isododecane (industrial isomer mixture having a high proportion of penta-methylheptane), with the microcapsule comprising a formaldehyde-cured complex coacervate of gelatin and a copolymer of acrylamide and acrylic acid, is subsequently introduced and 3200 g of aqueous phase having a pH of 12 are added.
  • the mean particle size of the monomer droplets is 460 ⁇ m.
  • the mixture is polymerized while stirring by increasing the temperature according to a temperature programme commencing at 25° C. and ending at 95° C.
  • the mixture is cooled, washed on a 32 ⁇ m sieve and subsequently dried at 80° C. under reduced pressure. This gives 1893 g of a spherical polymer having a mean particle size of 440 ⁇ m, a narrow particle size distribution and a smooth surface.
  • the polymer is chalky white in appearance and has a bulk density of about 370 g/l.
  • the bead polymer obtained is washed with deionized water.
  • the total yield is 1399 ml.
  • the reaction mixture is cooled, poured onto a sieve and washed with deionized water until the washings remain neutral.
  • the resin is subsequently transferred to a glass column having a glass frit bottom and is converted into the sodium form by means of 3 bed volumes of 4% strength by weight sodium hydroxide solution which is introduced into the ion exchanger bed from the top.
  • the ion exchanger is then washed with 5 bed volumes of deionized water. This gives 1060 ml of a moist ion exchanger.
  • the ion exchanger Before use for the intended purpose, the ion exchanger is again transferred to the glass column and converted into the hydrogen form by means of 2 bed volumes of 10% strength by weight sulphuric acid which is introduced into the ion exchanger bed from the top. The ion exchanger is then washed with 5 bed volumes of deionized water and removed from the glass column again.
  • 3 l of deionized water are placed in a 5 l glass beaker, 1000 g of 98% strength sulphuric acid are added and, while stirring, 3.28 g of antimony(III) chloride and 517.5 g of copper(II) sulphate pentahydrate are dissolved in the mixture.
  • the mixture is subsequently made up to 5000 g with deionized water and cooled to room temperature.
  • the sulphuric acid from 1e) is passed through this glass column at a volume flow of 500 ml/h in such a way that a constant small volume of sulphuric acid is always present over the ion exchanger bed.
  • the sulphuric acid exiting the glass column is analysed and compared with the inflowing sulphuric acid from 1e).
  • the reduction in the antimony content of the sulphuric acid to be purified by means of a monodisperse chelating exchanger is significantly better than when using the abovementioned heterodisperse ion exchangers known from the prior art.

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  • 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)
US10/570,455 2003-09-04 2004-08-23 Process for Purifying Sulphuric Acids Abandoned US20080229882A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITRM2003A000416 2003-09-04
IT000416A ITRM20030416A1 (it) 2003-09-04 2003-09-04 Procedimento per la purificazione di acidi solforici.
PCT/EP2004/009398 WO2005028362A2 (de) 2003-09-04 2004-08-23 Verfahren zur reinigung von schwefelsäuren

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090158896A1 (en) * 2006-02-01 2009-06-25 Duilio Rossoni Monodisperse, Macroporous Chelating Resins in Metal Winning
EP2835384A1 (de) * 2013-08-09 2015-02-11 LANXESS Deutschland GmbH Verfahren zur Herstellung von monodispersen, amidomethylierten vinylaromatischen Perlpolymerisaten

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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
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

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US2888441A (en) * 1956-10-12 1959-05-26 Dow Chemical Co Chelating resins having alpha-aminocarboxylic acid groups on a polymerized vinylbenzylamine resin structure
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
US4427794A (en) * 1980-08-22 1984-01-24 Bayer Aktiengesellschaft Process for the preparation of bead polymers of uniform particle size by polymerization of microencapsulated monomer
US4444961A (en) * 1980-10-30 1984-04-24 The Dow Chemical Company Process and apparatus for preparing uniform size polymer beads
US4559216A (en) * 1983-03-03 1985-12-17 Unitika Limited Method for purification of sulfuric acid solution
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
US20020042450A1 (en) * 2000-10-09 2002-04-11 Lailach G?Uuml;Nter Use of monodisperse ion exchangers for arsenic and/or antimony removal
US6649663B1 (en) * 1999-08-27 2003-11-18 Bayer Aktiengesellschaft Process for preparing monodisperse ion exchangers having chelating functional groups and the use thereof

Patent Citations (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
US4427794A (en) * 1980-08-22 1984-01-24 Bayer Aktiengesellschaft Process for the preparation of bead polymers of uniform particle size by polymerization of microencapsulated monomer
US4444961A (en) * 1980-10-30 1984-04-24 The Dow Chemical Company Process and apparatus for preparing uniform size polymer beads
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
US4559216A (en) * 1983-03-03 1985-12-17 Unitika Limited Method for purification of sulfuric acid solution
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
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US6649663B1 (en) * 1999-08-27 2003-11-18 Bayer Aktiengesellschaft Process for preparing monodisperse ion exchangers having chelating functional groups and the use thereof
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Cited By (4)

* Cited by examiner, † Cited by third party
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US20090158896A1 (en) * 2006-02-01 2009-06-25 Duilio Rossoni Monodisperse, Macroporous Chelating Resins in Metal Winning
EP2835384A1 (de) * 2013-08-09 2015-02-11 LANXESS Deutschland GmbH Verfahren zur Herstellung von monodispersen, amidomethylierten vinylaromatischen Perlpolymerisaten
WO2015018931A1 (de) * 2013-08-09 2015-02-12 Lanxess Deutschland Gmbh Verfahren zur herstellung von monodispersen, amidomethylierten vinylaromatischen perlpolymerisaten
US9834653B2 (en) 2013-08-09 2017-12-05 Lanxess Deutschland Gmbh Method for producing monodisperse, amido-methylated vinyl-aromatic bead polymers

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WO2005028362A2 (de) 2005-03-31
ITRM20030416A1 (it) 2005-03-05
KR20060079206A (ko) 2006-07-05
CN1878726A (zh) 2006-12-13
RU2006109814A (ru) 2007-10-10
JP2007533578A (ja) 2007-11-22
AU2004274134B2 (en) 2009-10-15
ITRM20030416A0 (it) 2003-09-04
WO2005028362A3 (de) 2006-01-26
EP1663860A2 (de) 2006-06-07
AU2004274134A1 (en) 2005-03-31

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