• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    PURPOSE:To effectively recover Ga contained in a soln. by adsorption by bringing a chelating resin having specified functional groups into contact with the soln. contg. Ga. CONSTITUTION:A column or the like is packed with a chelating resin having NOH groups (A) and functional groups (B) forming chelate bonds together with said functional groups A through Ga in the molecule. A chelating resin having amidoxime groups is not included in said resin. A soln. contg. Ga such as a strongly basic aqueous soln. of sodium aluminate from a stage for manufacturing alumina by the Bayer process is passed through the column to allow Ga in the soln. to be adsorbed on the chelating resin. The resin used in this recovering method adsorbs and removes metallic Ga ions with high selectivity from said strongly basic aqueous soln. or a soln. contg. coexisting ions in large quantities, and the chelating function of the resin is not deteriorated even after repeated use.
    公开号:SU1170959A3
    申请号:SU823492354
    申请日:1982-09-16
    公开日:1985-07-30
    发明作者:Катаока Юсин；Матсуда Масааки；Еситаке Хироси；Хиросе Есикадзу
    申请人:Сумитомо Кемикал Компани,Лимитед (Фирма)；
    IPC主号:
    专利说明:

    1 The invention relates to chemical technology, specifically to the extraction of gallium from alkaline solutions using chelated ion exchangers, and can be used to extract gallium from aluminate solutions formed during the production of alumina. A known method for producing gallium from a Bayer solution, which is formed during the production of alumina and cakes about 10-500 mg / l gallium, by extraction with organic mixtures consisting of a diluent and extractant selected from the group of substituted hydroxy hydroxyquinolines J. The disadvantage of this method is The fact that the used compositional mixtures do not have selectivity towards gallium in aluminate solutions and dissolves to a significant degree in this solution, which does not allow organizing industrial extraction of galaxies. whether. The closest to the invention to the technical essence and the achieved result is a method of extracting gallium from aluminate solutions, including their contacting with nitrogen-containing complexing sorbent G2. In this method, the extraction of galli is carried out using monofunctional chelating aminocarboxylic ion exchanger having iminodiacetic acid functional groups. The disadvantage of this method is that the resins used in its implementation have relatively low selectivity towards gallium in alkaline aluminate solutions. The aim of the invention is to increase the recovery rate of gallium in alkaline media. This goal is achieved by the method of extracting gallium from alkaline aluminate solutions, including their contact with a nitrogen-containing complexing sorbent, which uses a polyfunctional sorbent containing an oxime group and a functional group capable of forming a chelary bond with the oxime group through gallium. At the same time, a fully functional sorbent containing an oxime group and function is used as the nitrogen-containing complexing sorbent: the primary rpytiny capable of forming a chelate bond with the oxime group through gallium. In addition, in a multifunctional sorbent, oxime and chelating ;; the groups are fixed on the same Ж1 volume to the carbon atom in its elementary unit, and as a functional group capable of forming a chelating bond with the oxime group, the polyfunctional sorbent contains –B groups; NT F: de R and R2 - hydrogen or organic radicals / N - OH - SH ,, NOH, С 0, -NHOH, -NH-NH2, -СООH, -50зН, 7С 5, -СНО, -0, -5-, Р | ОЯ |, РО (ОКг) 2, РНСОЙ) з, where R is hydrogen, phenyl, alkyl or amino group. The process technology is as follows. Aluminate solutions containing gallium are preferably in dynamic contact with multifunctional sorbents having chelating groups capable of forming a chelate bond with the oxime group through halium. These sorbents can be in hydrogen or salt (sodium, potassium, calcium, magnesium, etc.) forms. Examples of such chelating resins are amidoxyl-containing resins obtained by reacting polymers of cyanide monomers such as acrylonitrile, ot-chloroacrylonitrile, vinyl cyanide cyanide, methacrylonitrile, etc., or co-polymers of methylenohydrin, etc., or co-polymers of methylenohydrin, etc., or in the co-polymers of vane cyanide, vinyl cyanide cyanide, etc. copolymer with oxylamine or oxylamine resin derivatives, which are formed as a result of homopolymerization of vinyl cyanide derivatives, obtained by reacting vinyl cyanide monomers As acrylonitrile, a-chloroacrylonitrile, vinilidentsianid, methacryl nitrile, etc. with oxylamine or oxy.
    amine derivatives, or polymerization of said vinyl cyanide derivatives with other ethylenically non-nascent monomers; gums which result from the reaction of polymers such as styrene-divinylbenzene copolymer,. phenolic resins, polyethylene polypropylene, polyvinyl chloride, etc. containing chemically active amine groups such as chloromethyl group, sulfonyl chloride group, carbonyl chloride group, epoxy isocyanate group, aldehyde group, and so on. with nitrile compounds containing an amino or imino group, such as amino acetonitrile, amino neomeonitrile, diamino maleonitrile, dicyanodiamide, iminodiacetonitrile, 1-amino-2 cyanoethane, 4-aminobenzonitpsh1, 1 amino-3-cyanopropane, etc., and subsequent with the subsequent procedure that follows. oxylamine or an oxylamine derivative, a resin, which is obtained by reacting a reaction product of said nitrile compounds containing an amino or imino group, and an oxylamine or an oxylamine derivative with said resins, containing amine chemically active group, resins, which are obtained by reacting halogenated resins, such as halogenated copolymer of styrene and divinylbenzene, phenol resin, etc., which contain (mono) sulfonic acid groups, a carboxylic acid group, a phosphoric acid group, a dithiocarboxylic group acids of the apylamino group, etc. with the reaction product of the said nitrile compounds containing an amino or imino group and an oxylamine group or an oxylamine derivative of a resin, which are obtained by a condensation reaction of a compound containing at least one amidoxime group in a molecule, such as benzamidoxime, benzylamino-N-methanediaminodioxodime; benzylamino-N-etandiamidodioksim (2-benzimidazoliltio) atset- amidoxime (2-benzimidazoliltio) etilaminodoksim (2-benzimidazoliltio) propilamidoksim, 1,2-benzisoksazol atsetamidoksi-3-5-fluoro-1,2-benzioksazol 3 - acetamidoxime, phenylsulfinyl-acetamidoxime, (3-chlorophenylsulfinyl) acetamidoxime, etc., mixtures of these compounds or mixtures
    these compounds with aniline, resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenecarboxylic acid with formaldehyde, epichlorohydri, nom, epibromohydrin, etc., which are obtained by reacting a polymer, such as a styrene-divinylbenzene copolymer, phenyl resin, polyethylene, polypropylene, etc., containing an aldehyde group or a ketone group, with oxlamine or oxyl-amine derivatives} resin, which are obtained as a result of the interaction of the said resin containing amine reactive group y, with a compound containing an amino or imino group and at least one -NOH group (A) in the molecule, such as aminoatsetaldoksim, iminodyatsetaldpksim, aminobenzilidendoksim, aminoalkilbenzildendoksim, aminobenzgidroksamova acid aminoalkilbenzgidroksamova acid, etc. or a mixture of these compounds; resin, which is obtained as a result of the condensation reaction of formaldehyde, epichlorohydrin, epibromohydrin, etc. with a compound containing at least one —NOH group (A) in a molecule, such as apkylaminobenzylidendoxime, formylbenzylidendoxime, benzyldendoxime, benzhydroxamic acid, alkylaminobenzylodendoxime, alkyl-; aminobenzgidroksamova acid alkilaminometanbenzilidendoksim, alkilaminometanbenzgidroksamova acid alkilaminoetanbenzilidendoksim, alkilaminoetanbenzgidroksamava acid formilbenzilidendoksim, formilbenzatsetaldoksim, benzizoksazolatsetaldoksim, benzizoksazolatsetogidroksadoksim, benzizoksazolatsetrgidroksamova acid fenilsulfinilatsetaldoksim, alkilaminofenilsulfinipatsetapdoksim, alkilaminofenklmetilsulfinilatsetaldoksim, alkilaminofenilztilsulfinilatsetaldoksim, alkilaminofe .nilkarbonila etaldoksim, alkilaminometilfenilkarbonilatsetaldoksim, benzildioksim, benziloksin, benz imidazoliltioatsetaldoksim etc. a mixture of the said compounds or a mixture of the said compound with aniline, resorcin, 3-aminopyridine, 4-aminopyridine, 4-affflHo6eH: 5CMi (MO) sulfonic acid, A-aminobenzenecarboxylic acid, etc., or hundreds of alkali metal resins mentioned or alkaline earth metals such as sodium, potassium, calcium, magnesium, etc.
    Until now, these sorbents have not been used to extract gallium from highly alkaline aluminate facTBopoB, such as an aqueous solution of sodium aluminate in the alumina production process by the Bayer method. Therefore, chelate resins of this type are not effective for the extraction of gallium from highly aqueous, aqueous solutions containing aluminum and having the following composition, g / l: Ga 0.01-0.5; AlaOj 50-120 and 100-200.
    The amount of chelate resin that is used to contact the solution varies depending on the concentration of gallium in the solution being treated and the type of chelate resin used, and can be determined by conducting preliminary experiments.
    The temperature of contact of the chelate salt with the gallium-containing solution does not have any special limitations, and in general it is 10-100 ° C. The contact time is also not specifically limited and contact is sufficient for a few seconds. The desorption of gallium from chelate gums can be carried out with hydrochloric, sulfuric, nitric, phosphoric acids, sodium sulfide, iminodiacetic acid, ethylenediaminetetraacetic acid, etc. or by heating the resin. The gallium separated in this way can be reduced to metallic gallium by known methods, for example, by obtaining sodium gallium from it and electrolyzing it.
    Example 1, 10 cm of vinylamidoxime polymer (hereinafter, chelate resin 1) °, obtained by reacting polyacrylonitrile fiber, hydroxylamine hydrochloride and an aqueous solution of sodium hydroxide, is placed in a column with a diameter of 12 mm 100 cm of an aqueous solution of sodium aluminate from an alumina process using a Bayer method containing 189 ppm (parts per million) Ga, 42000 ppm Al and 123,800 ppm Na, is passed from top to bottom through the column for 2 hours, after which the content of Ga and A1 is determined in fluorine and the degree of their recovery from the solution is calculated . The results of this example are shown in table 1.
    Table 1
    Metal concentration
    in filtrate, ppm 8 41,960
    The degree of extraction,% 96 O, 1
    Example 2. In Example 1, gallium is extracted from solution by the following chelating resins:
    Resin 2: Vinyl sulfonamide methane diamidione resin obtained by chlorinating a copolymer resin with vinyl (mono) sulfonic acid and divinylbenzene in the presence of a solvent, carbon tetrachloride and sulfur, the product of chlorination with aminomalononitrile and the subsequent reaction of the reaction product With oxylamine.
    Resin 3: a resin of a copolymer of vinylcarboxylic acid and amide acetamidoxime obtained by the halogenation of the resin of a copolymer of acrylic acid and divinylbenzene with phosgene in the presence of a solvent, N, N-dimethylformamide, and then reacting the product with aminoacetamidoxyl.
    Resin 4: A resin containing NOH-rpynny, W-group and -OH-group, obtained by the interaction of benzamidoxime, resorcinol and formalin.
    Resin 5: Vinylamidoxime-divinylbenzene copolymer resin obtained by reacting acrylonitrile copolymer and divinylbenzyl
    with oxylamine. I
    Resin 6: conojytMepa resin of vinyldiamidiodioxime, divinylbenzene and acrylic acid, obtained by the reaction of a copolymer of vinylidene cyanide, divirshbenzene and methyl acrylate.
    Resin 7: a resin of a copolymer of vinylamidoxime and acrylic acid, obtained by copolymerizing the reaction product of acrylonitrile, and oxylamine with ethyl acrylate and subsequent hydrolysis of the resulting copolymer.
    Resin 8 is the result. reacting the chloromethylated styrene-divinylbenzene resin with diamomeononitrile and then reacting the resulting reaction product with oxylamine.
    Resin 9 was obtained by chlorinating a strongly basic ion exchange resin containing a trimethylamino group (Duolith A-161) in the presence of a 1,2-dichloro-1,2-difloroethane solvent, reacting this resin with iminodiacetonitrile and then reacting the reaction product with oxylamine.
    Resin 10 was obtained by chlorinating a styrene-divinylbenzene resin containing a (mono) sulfonic acid group (Duolite C-26) with phosgene in the presence of N, N-dimethyl formamide solvent and the subsequent reaction of this resin with aminoacetamyl oxime.
    Resin 11 was prepared by reacting 1,2-benzisoxazole-3 acetamidoxime, resorcinol and formalin.
    Resin 12 was prepared by reacting 5-fluoro-1,2-benzisoxazole-3-acetamidoxime, phenol and formalin.
    Resin 13 is manufactured commercially and contains an amidoxime group; it has the Duolite CS-3446 trademark.
    Resin 14: A resin containing the sodium salt of the amidoxime group obtained by reacting an acrylonitrile tetraethylene glycol dimethacrylate resin resin (1: 0.2 molar ratio) with oxylamine in the presence of a solvent, toluene, and alkali treatment of the resin thus obtained (an aqueous solution of sodium hydroxide ).
    Resin 15 was obtained by reacting acrylonitrile ethyleneglycol dimethacrylate resin (1: 0.15 molar ratio) with oxylamine in the presence of a solvent, carbon tetrachloride.
    Resin 16 was obtained by reacting acrylonityl ethylene glycol monomethacrylate resin (in a molar ratio of 1: 0.25) with oxylamine in the presence of a solvent, xyl la.
    The results of the analysis of filtrates on the content of gallium and aluminum are given in table 2.
    table 2
    Example 3. 10 cm of the chelate resin 1 are contacted according to example 1 for 4 hours, and then 50 cm of an aqueous solution of 10% aqueous acid is passed through the column for 30 minutes. Next, the resin is washed with 50 cm of water, and then the sorbent is contacted twice with the solutions in the same sequence and each time the content of gallium and aluminum in the filtrates is analyzed. The results of this experiment are shown in Table 3. TABLE 4. A 10 cm-resin containing the NOH-rpynny, NHj -OH group obtained by reacting 2-aminomethyl benzyl dendoxime, resorcinol and formalin (indicated: chelate resin 17) is contacted with sodium aluminate solution containing gallium according to example 1. The results of this experiment when deny in table.4. Table 4 1 Gallium T Aluminum Indicators Metal Concentration in the Filter 37 40850 Recovery Rate,% Example 5. In Example 1, the water should be extracted from the solution with the following chelating resins: Chelate resin 18 contains the NOH group, -NHOH-rpynny, N-group and - An OH group resulting from the reaction of 1,2-benzisoxazole-Zatsehydroxamoxime, resorcinol and formalin. Chelate resin 19 contains the NOH group, -NHOH-rpynny, N-rpynny and -OH-group, obtained by the interaction of 5-fluoro-1,2-benzisox sol-3-acetohydroxamoxime, phenol and formalin. Chelate resin 20 ,. contains NOH-rpynny and the Na-CS salt of the H-group, obtained by reacting a vinyl amide-x-divinylbenzene copolymer with carbon disulfide and then reacting the reaction product with an aqueous solution of sodium hydroxide. The chelate resin 21 contains the NOH group and the Ca salt of the COOH group, obtained by reacting the polycondensation resin of benzoyliminoethanediamidiodimimim, aniline and formalin with monochloroacetic acid and subsequent alkali treatment of the reaction product using an aqueous solution of calcium hydroxide. The chelate resin 22 contains a NOH-rpynny, -NH-group, N-group and -OH-group, resulting from the interaction of 1,2-benzisoxazole-Zatsetohydroxamic acid, 3 aminopyridine, resorcinol and formalin. The chelate resin 23 contains a NOH group and a K-group, which is obtained by reacting 8-formylquino pina, benzaldehyde (benzoic aldehyde) and formalin to gum and then react the resin with oxylamine. The chelate resin 24 contains a NOH group and an -OH group obtained by the interaction of 2-hydroxybenzylidendoxime, resorcinol and formalin. The chelate resin 25 contains the NOH group and the NH-rpynny, resulting from the interaction of 2-N (N-methylaminoethyl) benzylidendoxime, N-methylaniline and formalin. The chelate resin 26 contains a NOH group and a C 0 group, resulting from the interaction of 2-formylbenzylidendoxime, benzyloxime and formalin. Chelate resin 27 contains three NaOH-groups per resin block, resulting from the interaction of benzyldioxime, benzylidendoxime and formalin. Chelate resin 28 contains a NaOH group, NaH, j-rpynny and -NHNH2 group, obtained by the interaction of acrylonitrile and divinylbenzene copolymer with oxylamine sulfate and an aqueous solution of hydrazine. Chelate resin 29 contains. The NaOH-rpynny, -NH-group, and -NHCH2 .CH2.NHCHj.CH2 NH rpynny, is obtained by reacting an acrylonitrile and divinylbenzene copolymer with chlorine hydrate oxides and a water solution of diethylene triamine. The results of the analysis of the filtrates for the content of gallium and aluminum in them are given in Table 5.
    eleven
    1170959
    12 Table
    EXAMPLE 6 10 g of each of the chelating resins 1 and 17 are added to 100 cm of the same sodium aluminate aqueous solution as used in Example 1, then the contents are shaken for 1 hour. Each of the mixtures is divided into The chelate resin and the aqueous layer are applied and the concentrations of gallium and aluminum that remain in the aqueous layer are determined.
    The results are shown in table 6,.
    Example. In example 5, gallium is extracted using polyacrylonitrile fibers.
    С - dHz- О - СНг СНз Нз
    and which is manufactured by Ashland Chemical Company, 10 g of n-decanol and
    which were used to synthesize chelate resin 1 in example 1, Duolit A-161, a strongly basic ion-exchange resin, and Sumihelate 0-10, a dithiocarbamic acid chelate resin (manufactured by Sumitomo Chemical Company LTD). The results are shown in Table 6.
    Example 8 The extraction of gallium is carried out according to the method which is the basic object, for which, 100 cm of the same Kalek 100 extractant having the structural formula is added to 100 cm of the same aqueous solution of sodium aluminate as used in example l.
    -m-CJiP
    g he (n
    80 g of kerosene, then shake the mixture for 1 hour. Then mix the mixture 13 times. i
    is divided into an aqueous layer and an organic layer, and the concentrations of gallium and aluminum that remain in the aqueous layer are determined. The results are shown in table 6.
    Table 6
    Sumihelat 0-10 186 41960
    Kelex 100
    142 4G010
    95914
    As Examples 1-5 and Comparative Examples 6-8 show, chelate resins that are used in this process can selectively and reversibly
    extract gallium ions in a multi-cycle process from highly basic aqueous solutions, such as sodium aluminate aqueous solutions, which are formed during the production of alumina
    Bayer method.
    The technical and economic efficiency of the described method lies in the fact that it allows increasing the degree of gallium recovery from aluminate solutions by 50-75% in comparison with the basic object using the prototype method 1.2 J, thereby providing the possibility of organizing industrial production of gallium based on oxide production. aluminum Bayer method,
    权利要求:
    Claims (3)
    [1]
    1. METHOD FOR REMOVING GALLIUM FROM ALUMINATE SOLUTIONS, including contacting them with a nitrogen-containing complexing sorbent, characterized in that, in order to increase the degree of extraction of gallium in alkaline media, a multifunctional sorbent containing an oxime group forming a functional group is used as a nitrogen-containing complexing sorbent chelating with the oxime group through gallium.
    [2]
    2. The method according to claim 1, characterized in that in the multifunctional sorbent, the oxime and chelating groups are fixed on the same carbon atom in its elementary unit.
    [3]
    3. The method according to claim 1, with the fact that, as a functional group capable of forming a chelate bond with an oxime group, a polyfunctional sorbent contains groups = Ν-Κ, where R 1 and B 2 -, hydrogen or organic radicals, - CS a H, = NOH ,> C = 0, -NHOH, - ΝΗ- ΝΗ χ, -COOH -, - SO s H, July 5, -CH0, -O- , -E-, RfOR / j, -PO (OR 2 ) 1 ( PH (OR) j where R is hydrogen, phenyl, alkyl or amino.
    SU ", 1170959
    1 1 70959
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    同族专利:
    公开号 | 公开日
    JPS6157899B2|1986-12-09|
    JPS5852450A|1983-03-28|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP56148444A|JPS6157899B2|1981-09-19|1981-09-19|
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