• 专利附录
  • 专利说明
  • 权利要求
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  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention relates to the use of a monodisperse ion exchanger, in particular a monodisperse anion exchanger or a monodisperse chelate resin, for selectively removing arsenic and / or antimony in the form of AsF 6 - ions or SbF 6 - ions from an aqueous solution.
    公开号:KR20020028796A
    申请号:KR1020010061745
    申请日:2001-10-08
    公开日:2002-04-17
    发明作者:귄터 라일라흐；라인홀트 클립퍼
    申请人:빌프리더 하이더；바이엘 악티엔게젤샤프트；
    IPC主号:
    专利说明:

    Use of Monodisperse Ion Exchangers for Arsenic / Antimony Removal for the Removal of Arsenic and Antimony [
    [1] The present invention relates to the use of monodisperse anion exchangers or monodisperse chelate resins to selectively adsorb arsenic ions and / or antimony ions from an aqueous solution.
    [2] The present invention relates to the use of monodispersed amino / ammonium-functionalized ion exchangers or monodisperse chelate resins for selectively removing arsenic ions or antimony ions from an aqueous solution.
    [3] Many kinds of natural minerals are generated in significant quantities during the extraction process and are contaminated with chemical elements which are generated as undesirable side products in the purification process to obtain the actual chemical compounds. One such chemical element is, for example, arsenic which is present in the fluoro-spar and arises in the synthesis of hydrogen fluoride, and the other element is antimony. The treatment of product residues containing arsenic or antimony is highly resource-intensive and cost-intensive, especially when these residues are contacted with water and the water has to be circulated from the process circulation system into the environment.
    [4] DD 254 373 A1 discloses a process for obtaining high purity hydrofluoric acid, which is treated through a heterodisperse ion exchanger having a central thiol group in the H + form.
    [5] WO 89/11321 describes a process for preparing hydrofluoric acid, for example using an anion exchanger as well as a device operating with a cation exchanger to remove arsenic from the reaction medium. Preferably, weakly basic anion exchangers such as Dowex M-43 or Biorad AGW-W4A are used, but also Amberlite 900 and Lewatit MP-62 are also used. Is used. This resin is functionalized with a tertiary amino group, but all are heterodisperse structures.
    [6] DE-A 19 958 390 discloses the use of monodisperse adsorbent resins to remove arsenic, particularly from aqueous solutions. However, these resins were not functionalized with amino and / or ammonium groups.
    [7] Accordingly, the object of the present invention is firstly to provide a process for the selective removal of arsenic ions and / or antimony ions from the reaction solution, particularly suitable for arsenic ions and / or antimony ions, Thereby providing an ion exchanger capable of releasing water from the process circulation system back into the environment.
    [8] However, there is an environmental or health problem in which it is necessary to completely remove the arsenic compound and / or the antimony compound from the dilute aqueous solution. This type of solution may be leachate from a slag pile of a mine or metallurgical process, leachate from a landfill, wash liquor from a waste incineration site, or other process water from the electrical or chemical industries. Arsenic compounds and antimony compounds are generally problematic in their removal due to the amalgamity of metalloids. In particular, ion exchangers are preferred for removing low concentrations of ions in other cases, but are less successful in the case of arsenic and antimony compounds.
    [9] By using monodisperse amino / ammonium-functionalized ion exchangers or monodisperse chelate resins according to the invention, arsenic and antimony from the arsenic- and / or antimony-contaminated ground or surface water can be recirculated back into the environment It is generally possible to remove it to such an extent that it can be removed.
    [10] Surprisingly, as long as the arsenic compound and the antimony compound are previously converted to the hexafluoroarsenate ion and / or the hexafluoroantimonate ion, a monodisperse anion exchanger functionalized with an amino group or an ammonium group may be used, It has been found in accordance with the present invention that resins can be used to remove arsenic and / or antimony with high selectivity from aqueous solutions. Since the AsF 6 - and SbF 6 - ions are very stable, they start from dissolved arsenic compounds or dissolved antimony compounds and are exposed to other oxidizing agents that are active in the presence of fluoride, hydrogen peroxide, or fluoride ions, . It is preferable to oxidize and react the arsenic compound or the antimony compound in the aqueous solution in the presence of the fluoride ion to obtain AsF 6 - ion and SbF 6 - ion.
    [11] Accordingly, the present invention relates to a method for the selective adsorption of arsenic ions and / or antimony ions from an aqueous solution, comprising the steps of reacting a monodisperse anion exchanger or a monodisperse chelate resin, in particular a monodispersed amino / ammonium-functionalized anion exchanger or monodisperse chelate resin And a method for removing arsenic ions and / or antimony ions from an aqueous solution. If the arsenic or antimony compound is not present at +5 oxidation, they must be oxidatively converted to AsF 6 - or SbF 6 - ions in advance, which are in ionic form in aqueous solution, particularly preferably neutral or weakly alkaline Or an aqueous acid solution.
    [12] The anion exchanger or chelate resin used in accordance with the use of the present invention is in the form of a monodisperse bead polymer and is functionalized with a primary or tertiary amino group, a quaternary ammonium group, or a mixture thereof, Is a monodisperse chelate resin as disclosed in DE-A 19 940 866 to be incorporated.
    [13] The anion exchanger or chelate resin used in accordance with the present invention should be of a monodisperse type.
    [14] For the purposes of the present invention, particles in a monodisperse form are those in which the diameter of 90% or more of particles by volume or weight ranges from the most frequent diameter to within ± 10% of the most frequent diameter. For example, for a bead polymer with the most frequent bead diameter of 0.5 mm, for a bead polymer having a particle diameter of 90% or more by volume or weight of 0.45 to 0.55 mm and the most frequent bead diameter of 0.70 mm, The particle diameter of 90% or more is 0.77 to 0.63 mm. The present invention provides for the use of bead polymers whose monodisperse properties are derived from the production process, namely jet technology, feed / feed or direct spray. The most recent production processes are described, for example, in US 3 922 255, US 4 444 961 and US 4 427 794.
    [15] The anion exchanger or chelating resin used in accordance with the present invention is a crosslinked polymer of a single ethylenically unsaturated monomer wherein the monomers are composed predominantly of cyclic halogenated derivatives such as styrene, vinyl toluene, ethyl styrene, a-methyl styrene and chlorostyrene In addition to these compounds, vinyl benzyl chloride, acrylic acid, its salts or esters, in particular methyl esters, also vinyl naphthalene, vinyl xylene, and nitriles and amides of acrylic acid or methacrylic acid At least one compound.
    [16] The polymer preferably has crosslinking through copolymerization of a crosslinkable monomer having two or more, two or three copolymerizable carbon-carbon double bonds per molecule. Examples of such types of crosslinkable monomers include polyfunctional vinyl aromatic compounds such as di- or trivinyl benzene, divinyl ethyl benzene, divinyl toluene, divinyl xylene, divinyl ethyl benzene, divinyl naphthalene; Multifunctional allyl aromatic compounds such as di- or triallylbenzene; Polyfunctional vinyl- or allyl heterocycles such as trivinyl or triallyl cyanurate or trivinyl or triallyl isocyanurate; N, N'-C 1 -C 6 -alkylenediacrylamides such as N, N'-methylene diacrylamide or -dimethacrylamide, N, N'-ethylene diacrylamide or dimethacrylamide, Methane acrylamide; Polyvinyl or polyallyl of a saturated C 2 -C 20 polyol having 2 to 4 OH groups per molecule such as ethylene glycol divinyl ether or ethylene glycol diallyl ether or diethylene glycol divinyl ether or diethylene glycol diallyl ether ether; (Meth) acrylates such as allyl methacrylate, ethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, divinylethylene urea, divinyl propylene urea, divinyl adipate Esters of unsaturated C 3 -C 12 alcohols or saturated C 2 -C 20 polyols having 2 to 4 OH groups; 2 to 3 separate carbon-carbon double bonds such as 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,7-octadiene or 1,2,4-trivinylcyclohexane Lt; RTI ID = 0.0 > cycloaliphatic < / RTI > Monomers that have been shown to be particularly successful as crosslinking monomers are divinylbenzene (in the form of an isomeric mixture) and also a mixture of aliphatic C 6 -C 12 hydrocarbons and divinylbenzene having 2 to 3 carbon-carbon double bonds. Typical amounts of cross-linking monomers used are from 1 to 80% by weight, preferably from 2 to 25% by weight, based on the total amount of polymerizable monomers used.
    [17] The cross-linking monomer used need not be in pure form, but may be in the form of an industrially available low purity mixture (e.g., divinylbenzene mixed with ethyl styrene).
    [18] The copolymerization of monomers with crosslinkers is usually initiated by monomer-water-soluble free-radical generators. Preferred free-radical generating catalysts include, for example, diacyl peroxides such as diacetyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide and lauroyl peroxide; Butyl peroxybenzoate, dicyclohexyl peroxybenzoate, t-butyl peroxybenzoate, t-butyl peroxybenzoate, t-butyl peroxybenzoate, t-butyl peroxyacetate, Peroxy esters such as hexyl peroxydicarbonate; Alkyl peroxides such as bis (tert-butylperoxybutane), dicumyl peroxide and tert-butyl cumyl peroxide; Hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; Ketone peroxides such as cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide and acetylacetone peroxide; And preferably azoisobutyrodinitrile.
    [19] The free-radical generator may be used in a catalytic amount, preferably from 0.01 to 2.5% by weight, especially from 0.12 to 1.5% by weight, based on the total amount of monomer and crosslinking agent.
    [20] The water-insoluble monomer / crosslinker mixture is preferably added to the aqueous phase comprising at least one protective colloid to stabilize the monomer / crosslinking agent droplets in the dispersion phase and the resulting bead polymer. Preferred protective colloids are those prepared from natural or synthetic water soluble polymers such as gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, or (meth) acrylic acid or (meth) Lt; / RTI > Other highly suitable materials include cellulosic derivatives, especially cellulose ethers or cellulosic esters, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose or carboxymethylcellulose It is loose. The amount of the protective colloid to be used is generally 0.02 to 1% by weight, preferably 0.05 to 0.3% by weight, based on the water phase.
    [21] The weight ratio of the aqueous phase to the organic phase is preferably 0.5 to 20, especially 0.75 to 5.
    [22] In one particular embodiment, the base polymer is prepared in the presence of a buffer system during polymerization. A buffer system in which the pH of the aqueous phase is adjusted to 14 to 6, preferably 12 to 8 at the initiation of polymerization is preferable. Under these conditions, protective colloids having carboxylic acid groups are present in the form of some or all of the salts. This has a beneficial effect on the action of the protective colloid. The concentration of the buffer solution in water is expressed as mmol per liter of water, preferably 0.5 to 500, especially 2.5 to 100.
    [23] In order to produce monodisperse bead polymers with a very uniform particle size, a stream of monomers is injected into the water phase, where uniform size droplet production without agglomeration is caused by vibration-induced destruction of the jet and / And are reliably provided by microencapsulating monomer droplets (see EP 0 046 535 B1 and EP 0 051 210 B1).
    [24] The polymerization temperature varies depending on the decomposition temperature of the initiator used. The polymerization temperature is generally from 50 to 150 캜, preferably from 55 to 100 캜. The polymerization takes 0.5 to several hours. It has been found useful to use a temperature program to start the polymerization at a low temperature, e.g., 60 < 0 > C and raise the reaction temperature as the conversion during polymerization progresses.
    [25] The resulting bead polymer is sent to the functionalization process in an enlarged particle size by an intermediate step through a so-called seed / feed process that leaves it as is. This seed / seed process step involves the use of a monomer (feed) that can be copolymerized to initiate the swelling of the initially obtained polymer (seed) and polymerizing the penetrating monomer into the polymer. Examples of suitable seed / feed processes are described in EP 0 098 130 B1, EP 0 101 943 B1 or EP 0 802 936 B1.
    [26] The ion exchanger may be a microporous, gel-like or macroporous bead polymer.
    [27] Microporous, gel-like and macroporous are described, for example, in Adv. Polymer Sci., Vol. 5, pages 113-213 (1967)).
    [28] To obtain monodisperse ion exchangers for use in accordance with the present invention, see Seidl et al., Adv. Polym. Sci., Vol. 5 (1967), pp. 131-213] is added to the monomer / crosslinker mixture. Examples of porogens are aliphatic hydrocarbons, alcohols, esters, ethers, ketones, trialkylamines and nitro compounds, preferably hexane, octane, isooctane, isododecane, methylisobutylketone or methylisobutylcarbinol, In an amount of 1 to 150% by weight, preferably 40 to 100% by weight, based on the total amount of crosslinking agent.
    [29] The pore diameter of the macroporous bead polymer is greater than about 50 Angstroms.
    [30] The ion exchanger obtained without the use of a porogen is of a microporous or gel-like structure.
    [31] Practical anion exchangers or chelating resins used in accordance with the present invention for adsorbing AsF 6 - ions and / or SbF 6 - are prepared by functionalizing bead polymers.
    [32] Processes that are industrially practiced to prepare monodisperse anion exchangers or monodisperse chelate resins functionalized with amino groups and / or ammonium groups are starting from bead polymers based on styrene and divinylbenzene (DVB) (Chloromethylating) the aromatic ring system present in the molecule and subsequently reacting with an amine or respectively iminodiacetic acid or thiourea.
    [33] Preferred amines are trimethylamine, dimethylaminoethanol, triethylamine, tripropylamine, tributylamine, ammonia, europrophin and amino diacetic acid. The product to be produced is an anion exchange group and is also a quaternary ammonium group or a primary or secondary amine group such as an aminomethyl group, a dimethylaminomethyl group, a trimethylaminomethyl group, a dimethylaminomethylhydroxyethyl group, an iminodiacetic acid group, a thiourea or aminomethylphosphonic acid group, It is a chelating resin functionalized with a secondary amino group.
    [34] An ion exchanger having an iminodiacetic acid group is prepared by reacting a bead polymer functionalized with an aminomethyl group with chloroacetic acid or is reacted with a formalin / phosphorus (3) compound to prepare an ion exchanger having an aminomethylphosphonic acid group.
    [35] Another process which has been industrially carried out to produce anion exchangers or chelating resins to be used in accordance with the present invention for adsorbing AsF 6 - ions and / or SbF 6 - is to introduce styrene and divinylbenzene (DVB) (Phthalimidomethyl) ether, bis (phthalimidomethyl) ether or a SO 3 adduct of N-acetoxymethylphthalimide, the aromatic ring system present in the bead polymer can be converted into a phthalimide derivative (See, for example, US-A 3 989 650 or EP-A 0 046 535 B1), followed by another reaction step to obtain an anion exchanger or chelate resin with various basic degrees.
    [36] However, macroporous or gel-type monodisperse anion exchangers based on acrylic esters can also be used to remove the arsenic-containing and / or antimony-containing anions. A crosslinked monodisperse bead polymer based on an acrylic ester is reacted with a polyamine such as, for example, N, N-dimethyl-1,3-propylenediamine to form an amide. The resulting product is a weakly basic anion exchanger capable of reacting with chloromethane to produce a strong basic anion exchanger (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 14, p.
    [37] In the experiments carried out in connection with the present invention monodisperse ion exchangers containing quaternary ammonium groups have been found to be particularly suitable for adsorption from neutral or weakly basic aqueous solutions. For adsorption from an acid solution, both an ion exchange group having a quaternary ammonium group and a tertiary or primary amino group or an ion exchange group having these groups are suitable. Anion exchangers having a tertiary amino group are preferred for adsorption selectivity of AsF 6 - and / or SbF 6 - .
    [38] Since the AsF 6 - ion and / or SbF 6 - ion have particularly excellent adsorption power, all the arsenic ions and antimony ions to be adsorbed in the adsorption medium are preferably adsorbed on hexafluoroarsenes desirable to switch to the acid or HSbF 6 or combinations thereof, preferably a salt of an acid or HSbF 6 hexafluoropropane, most preferably Arsene acid or a sodium or potassium salt of HSbF 6 hexafluoro-fold.
    [39] <Examples>
    [40] As 20 ppm of 3.5 ppm concentration of leachate was treated with 2.8 g of 40% strength Hf and 10 ml of H 2 O 2 . This liquid was passed through an ion exchanger column packed with Lewatit VPOC 1094 (a monodisperse resin based on styrene / divinylbenzene functionalized with 25% quaternary ammonium groups and 75% tertiary amino groups). The arsenic content of the eluent was less than 0.05 ppm arsenic per liter of liquid.
    [41] The monodisperse anion exchanger and the monodisperse chelate resin according to the present invention have particularly useful hydrodynamic properties and are thus used to purify arsenic or antimony from the process water from the electrical industry, especially the semiconductor industry or the chemical industry, It is useful when purifying dilute solutions of these metalloids or salts.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] The use of monodisperse anion exchangers or monodisperse chelate resins for the selective adsorption of arsenic and / or antimony, characterized in that the arsenic and / or antimony is adsorbed from the aqueous solution in the form of SbF 6 - ions or AsF 6 - ions.
    [2" claim-type="Currently amended] The use according to claim 1, wherein the monodisperse anion exchanger or the monodisperse chelate resin is functionalized with a quaternary ammonium group, a tertiary or primary amino group, or a mixture thereof.
    [3" claim-type="Currently amended] 3. Use according to claim 1 or 2, characterized in that the monodisperse anion exchanger or the monodisperse chelate resin is macroporous, gel-like or microporous.
    [4" claim-type="Currently amended] The process of claim 1, wherein the monodisperse anion exchanger or chelate resin is selected from the group consisting of unsaturated monomers selected from the group consisting of styrene, vinyl toluene, -Methyl styrene and their ring-halogenated derivatives, or bead polymers based on acrylic materials &Lt; / RTI &gt;
    [5" claim-type="Currently amended] Arsenic compounds or antimony compounds in the presence of a fluoride ion AsF 6 -, and (or) SbF 6 -, comprising a step of ion adsorbed to the monodisperse anion exchangers or monodisperse chelate resins in a state switched to, arsenic or antimony from an aqueous solution / RTI &gt;
    [6" claim-type="Currently amended] 6. The method of claim 5, SbF 6 - ions, and (or) AsF 6 - The adsorption of the ions will take place from the neutral, acid or weakly alkaline aqueous solution method.
    [7" claim-type="Currently amended] The use according to claim 1, wherein the arsenic or arsenic compound, or the antimony or antimony compound, is removed from the water, ground water or surface water in the process circulation system.
    [8" claim-type="Currently amended] In order to remove contaminants from arsenic or antimony of the monodisperse anion exchanger or monodisperse chelate resin functionalized with amino groups and / or ammonium groups, the process water of the electrical industry or chemical industry is purified or the leachate is purified, .
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    同族专利:
    公开号 | 公开日
    CN1346805A|2002-05-01|
    EP1195199A1|2002-04-10|
    CA2358225A1|2002-04-09|
    US20020042450A1|2002-04-11|
    DE10049807A1|2002-04-18|
    JP2002177955A|2002-06-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-10-09|Priority to DE10049807A
    2000-10-09|Priority to DE10049807.8
    2001-10-08|Application filed by 빌프리더 하이더, 바이엘 악티엔게젤샤프트
    2002-04-17|Publication of KR20020028796A
    优先权:
    申请号 | 申请日 | 专利标题
    DE10049807A|DE10049807A1|2000-10-09|2000-10-09|Use of monodisperse ion exchangers for arsenic / antimony removal|
    DE10049807.8|2000-10-09|
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