• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    A process for eluting indium from a chelate resin having a phosphorus atom-containing, chelate-forming group which contains adsorbed indium, which comprises contacting said resin firstly with a primary eluent containing an acid containing no halogen atom in the molecule at a concentration of 0.1 N or higher and then with an eluent for indium which is selected from the group consisting of (1) a solution of an acid containing a halogen atom in the molecule, (2) a mixed solution of (a) a metal halide, an ammonium halide or a mixture thereof and (b) an acid and (3) a mixed solution of a sulfide and a base compound.
    公开号:SU1471934A3
    申请号:SU853833355
    申请日:1985-01-04
    公开日:1989-04-07
    发明作者:Катаока Юсин；Матсуда Масааки；Аои Масахиро；Тино Кунитаке
    申请人:Сумитомо Кемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    one
    This invention relates to hydrometallurgy of rare and non-ferrous metals and can be used for the selective extraction of indium from metallurgical wastes using phosphorus-containing chelate sorbents.
    The aim of the invention is to reduce foreign metal impurities in the eluate.
    Example 1. The solution, obtained-. the extrusion of iron dust with sulfuric acid, results in
    contact with a chelating resin having an aminomethylene phosphonic acid group (Duolite ES-467, manufactured by Diamond Shamrock Corp.) (hereinafter, this resin will be called chelate resin A) to obtain a chelate resin containing 2.2 g of indium, 1.444 g of zinc, 43 g of iron and 105 g of cadmium adsorbed in 1 kg of resin. The resin is placed in a column and an aqueous solution of 2 N sulfuric acid is passed through it from top to bottom as the primary solvent at room temperature.
    and

    :about
    00 4
     CM
    volume rate 2 and a total volume that exceeds the resin volume by 20 times, resulting in the elution of 0.01 g indium, 1.494 g zinc, 23 g iron and 105 g cadmium. Then, a 4 N aqueous solution of hydrochloric acid is passed through the column with a volume velocity of 1, the total volume of the solution exceeds five times the volume of pitch, as a result of which 2.1 g of indium is eluted.
    Examples 2-11. Indium impurities of Example 1 are eluted except that the types and concentrations of the primary eluent and eluent are indistinguishable. The results are shown in table 1.
    Examples 12-19 and example 20 (comparative). The solution containing indium and other metals, which is obtained by leaching of lead sclac, which is a by-product of cadmium refining, sulfuric acid, is contacted with chelate resins with the symbol BS and chelate resin having iminodiacetic acid group (duolit ES-466, produced Diamond Shamrock Corp.). The metals adsorbed by the corresponding resins are shown in Table 2.
    These resins, containing adsorbed metals, are then subjected to a two-stage elution using different types of primary eluents and eluents as in Example 1. The specific types of eluents and the results obtained are presented in Table 2. The sorbents used in these examples are as follows.
    Chelate resin; a commercial resin with a phosphonate group (ES-63 duolite manufactured by Diamond Shamrock Corp).
    Chelate resin C: A resin with an aminoalkylene phosphonate group which is obtained by reacting on 60 May. h. polyacrylonitrile with 103 ma.h. diethylenetriamine in aqueous medium to obtain the aminated polyacrylonitrile, then as a result of the interaction of the aminated polyacrylonitrile with 281 wt.h. formalin and 498 wt.h. triethyl phosphite in the presence of 36% hydrochloric acid.
    ..




    five
    0
    Chelate resin D: A resin having a base of quaternary phosphonium, which is obtained as a result of a mutual 20 wt.h. chloromethylated polystyrene e 200 mac. tributylphosphine in dimethylformamide.
    Chelate resin B: A resin having a phosphine group, which is obtained by the interaction of 150 wt.h. Brominated polystyrene with 64 ma.ch. Hekane plant containing 1.6 mol of 9 p-butyl lithium in tetrahydrofuran as a solvent in order to obtain lithium polystyrene, by reacting the lithium polystyrene with 300 wt. chlorophenylphosphine in tetrahydrofuran and oxidation of the reaction product With 371 wt.h. 40% nadukeuenoy cue, lots in methylene chloride as a solvent.
    Chelate emole F: a resin having a sodium phoenerphate group, which is obtained by hydrolysis of a chelate emole D e with a 20% sodium hydroxide aqueous solution.
    Chelate resin G: emola, having a group of foefin bilelots, which is obtained by reacting 100 wt.h. polyetherol 150 ma.ch. trichloride phosphorus in chloroform as a solvent and then hydrolysis of the reaction product.
    Chelate emola H: emol having a group of pheofin bileta ester group, which is obtained by the interaction of 100 wt.h. aminated polystyrene e 120 mac. Chloromethylphosphinate cresyl in 1 2-dichloroethane as a solvent.
    Chelate emol I: a resin having a group of diethylenetriaminomethylenephosphonic kielta that was prepared by hydrolysis of the chelate emole C e with a 20% aqueous solution of sodium hydroxide.
    Chelate emola S: resin, which has an aminoalkylene-phonon bilelot group, which is also obtained as in the case of chelate resin C, except that 498 parts by weight. triethylphophyte used in the preparation of chelate resin C is replaced by 246 wt.h. phosphorous acid.
    Example 21. A solution obtained by treating a pulp obtained by purifying zinc by leaching with sulfuric acid is contacted with a chelating resin containing an aminomethylene phosphonic acid group (DUOZITE ES-476,
    5147
    prepared by Dimond Shamrock Corp.) to obtain a chelate resin containing 5.3 g of indium, 1894 g of zinc, 13 g of iron and 37 g of cadmium adsorbed per kg of resin. The resin is then placed in a column, and the elution of the impurities is 10 n. an aqueous solution of sulfuric acid at room temperature with a bulk velocity of 1 hour in volume, five times the volume of the resin, resulting in elute 0.08 g of indium, 1894 g of zinc, 13 g of iron and 37 g of cadmium. Then miss 2 n. an aqueous solution of hydrofluoric acid with a bulk velocity I in full, 10 times the volume of the resin, resulting in a gain of 5.2 g of indium,
    Example 22. According to example i, indium was eluted from a sorbent (chelate resin A) containing 3.21 g of indium, 0.08 g of a mouse, 1.25 g of copper on | kg of resin. In the first stage, the sorbent is in contact with a 0.1 N solution of sulfuric acid, resulting in elute 0.02 g of indium, 0.07 g of baby, and 1.4 g of copper. In the second stage, the sorbent is contacted with a solution containing 0.3 mol / l sodium sulfide and 2 N sodium hydroxide. In 20 volumes of the solution, 3.1 g of indium are eluted from the volume of the resin.
    Examples 23-32. In Example 22, indium and impurities are eluted except that the composition and concentration of the eluent solutions are changed in the first and second stages. The results are presented
    in table 3.
    EXAMPLE 33 A solution obtained by leaching a cast iron powder of sulfuric acid is contacted with a chelating resin containing an aminomethylene phosphonic acid radical (Sumiciate R MS-45, manufactured by Suito Chemical Company Ltd.), to obtain a chelag resin, containing 2.6 g of indium, 1350 g of zinc, 39 g of iron and 85 g of cadmium adsorbed in
    1kg resin. The resin is loaded into the column. In the upper part of the column is entered
    2N aqueous solution of nitric acid as the main eluent and pass it at room temperature, with a bulk velocity of 2 hours in a volume exceeding 20 times the volume of the resin, resulting in eluted .1.1 g of indium, 1350 g of zinc, 39 g of iron and 85 g cadmium.

    Subsequently, an aqueous solution containing 2 N nitric acid and 2 mol / l calcium chloride as eluent with respect to indium is passed at room temperature with a volume rate of 1 h in a volume exceeding five times the volume of the resin, resulting in with an aqueous solution containing 2 N nitric acid and 2 MOL / L calcium chloride, 2.5 g of indium are eluted.
    As can be seen from the above examples, the elution of indie by the proposed method allows to obtain an indium eluate which is almost pure by impurity of foreign metals.
    权利要求:
    Claims (3)
    [1]
    1. An elution procedure for indie from a chelate phosphorus-containing sorbent having a functional group represented by a phosphonium base,
    5 with phosphonic acid, aminoalkylenephosphonic acid or phosphinic acid, phosphonic acid ester or aminoalkylphosphonic acid, bound to the adsorbent matrix through an aminoalkyl group and containing impurities of other metals, including its contact with chemical reagents, which is reducing impurities of foreign metals in the eluate; contacting is carried out in two stages: in the first stage with a 0.1-15 N acid solution that does not contain halide and nitrate ions, or a 0.1-2.2 N solution
    Q nitric acid and in the second stage with a compound selected from the group consisting of a halogen-containing acid, a mixture of an alkali metal or alkaline earth metal halogen, or ammonium or an acid, or a mixture of sulfide and an alkaline base.
    [2]
    2. Method 1, which differs from the fact that as an acid that does not contain halogen ions, a solution of sulfuric acid, phosphoric acid, boric acid, acetic acid or formic acid or their mixture is used.
    [3]
    3. The method according to claim 1, which is consistent with the fact that hydrochloric acid, hydrobromic acid, hydroiodic acid or their mixture at a concentration of 0.5-12 N is used as the halogen-containing acid,
    0
    five
    or hydrofluoric acid in an alkaline or alkaline earth center equilibrium of 0.5-2 N. N. The metal or ammonium in a mixture with an acid is 0.3-2 mol / l and is con4. The method according to claim 1, distinguishes between acid and acid, not x: obsessed with u and with the fact that caderatradium is hafluoro- and nitrate-ions or containing
    containing
    holding content
    containing
    4 N aqueous solution of 0.0 phosphoric acid
    1N aqueous solution of 0.1
    nitric acid
    2N aqueous solution. 0.0
    acetic acid
    3N aqueous solution 0.0
    sulfuric acid
    2 N aqueous solution of 0.0 sulfuric acid
    2 N aqueous solution of 0.0 sulfuric acid
    2 N aqueous solution of W, 00 sulfuric acid
    2 N aqueous solution of 0.0 oxalic acid
    2 N aqueous solution of 0.0 boric acid
    2 N aqueous solution of 0.0 formic acid
    1492105
    1493104
    1492105
    1494105
    1494105
    1494105
    1493103
    1492103
    1492103
    9 .. 1471934 °
    these ions are 0.5–15 N and 0.5–2 N, respectively, or ammonium, and as alkaline. bases - hydroxal alkali 5. The method according to claim 1, characterized by a metal or ammonium with them and with the fact that as a sul - concentration in a mixture of 0.03-5 mol / l and sodium sulfide is 0.3-5-5 N
     use
    respectively. Table I
    o metal or amm centration in a mixture of 0, -5 N
    respectively. Table I
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    Example
    Type and contact amount
    2i 0.3 N aqueous solution of phosphoric acid
    2D 0.1 N aqueous solution of nitric acid
    2S 15 O aqueous solution of sulfuric acid
    260.1 I am water solution
    sulfuric acid
    270.5 K water solution
    sulfuric acid
    28 0.5 N aqueous solution
    acetic acid
    29 0.3 N aqueous solution of sulfuric acid
    0,010,07
    0.340.08 1.25
    0.02 0.04
    0.03
    30 12 N aqueous solution 0.22
    phosphoric acid
    31 0.3 N aqueous solution 0.09
    nitric acid
    32
    I H aqueous solution of sulfuric acid
    0.06
    0.07 0.08
    0.04 0.08
    1,09 1,20
    0.07 1.1
    0.08
    0.07 1.21 0.08 1.20
    obsessed - 3.17 0.00 0.0 ent 5 mol / l sodium chloride) and 0.3 N guanidiv
    1.10 Aqueous solution, with a content of 3.18 V, 01 0.11 and 0.03 mol / l hydrochloride 4 "and sodium sodium hydroxide
    An aqueous solution containing 2.81 0.00. 0.00 ml 0.3 mol / l sodium chloride and 15 N sulfuric acid
    2 N aqueous solution of salt - 3.16 0.01 0.13 hydrochloric acid
    An aqueous solution containing 3.03 0.00-0.05% of 0.3 mol / l ammonium chloride and 5 N sodium hydroxide
    An aqueous solution containing - 3.01 0.01 0.11 nessing 5 mol / l of ammonium fluoride and 0.3 N of hydroxide
    1.23 Aqueous solution containing - 3.07 0.00 0.01 Å 2 mol / l ammonium sulfide to 2 N sodium hydroxide
    1.23 Aqueous solution, containing - 2,9t 0,00. 0,00% 0.05 mol / l hydroscopic ammonium feed n 2 K potassium hydroxide
    The aqueous solution contains Ea-3.11 0.01 0.01 di 5 mol / L potassium sulfide and 1 N ammonium
    An aqueous solution containing 3.14 0.00 0.00% 4 nol / l sulfide.
    sodium and 2 and trimethyl-,
    amine
    T "d" J
    Elping Ind
    Amount of metal, g
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP59000391A|JPH0463015B2|1984-01-05|1984-01-05|
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