• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the treatment of raw materials which contain arsenic and metal to produce a metal-free arsenic product and an arsenic-free metal sulfate is disclosed, in which the raw material is leached by using an aqueous solution of sulfuric acid and then the metals are crystallized as sulfates from the separated aqueous solution, which is separated from the metal sulfate crystals. The leach is performed at elevated temperature under oxidizing conditions, in order to bring the arsenic to a 5-valent form, the metal sulfates are crystallized out from the selectively separated, arsenate-bearing aqueous solution by cooling, and arsenic is removed from at least part of this aqueous solution before the aqueous solution is returned to the leach.
    公开号:SU867319A3
    申请号:SU782690955
    申请日:1978-11-28
    公开日:1981-09-23
    发明作者:Педер Фуглеберг Сигмунд；Хальтхольм Стиг-Эрик；Геран Нюман Брор；Калеви Растас Юсси
    申请人:Оутокумпу Ой (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR PROCESSING MATERIALS CONTAINING NO.1 FIAC AND METAL The invention relates to hydrometallurgy of non-ferrous metals, in particular, to methods of processing materials containing mouse and metal, to obtain metal-free sulfates from mouse and mouse products that do not contain metals and metals. . Closest to the present invention is a method for processing materials containing arsenic and metal, including leaching the starting material with an aqueous solution of sulfuric acid, separating the solution from the precipitate, and crystallizing the sulphate metasters from the solution. According to this method, the raw materials are treated with a solution of sulfuric acid, and then the metal sulfates are precipitated by evaporation and the mouse is reduced to form it as a HjAs04 solution containing sulfuric acid l. However, this method makes it difficult to efficiently separate the arsenic and metal sulfates, since it is necessary to use strong sulfuric acid and mouse acid to completely precipitate the metal sulfates, resulting in a very viscous solution, which complicates the separation and washing of the mass. crystals. The purpose of the invention is to increase the efficiency of the process of separating the mouse from metal. This goal is achieved by the fact that in the method of processing materials containing arsenic and metal, including leaching the starting material with an aqueous solution of sulfuric acid, separating the solution from the precipitate and cryo-. the sulphates of metals are metalized from solution, leaching is carried out at bb-CU, when dispersed in an air or oxygen solution, before crystallization, sulfuric acid is added to the solution in an amount sufficient to obtain a sulfuric acid concentration at the leaching stage 100-300 g / l, - The crystallization of sulphates from the separated solution is carried out by cooling and, before returning a part of this solution to leaching, the mouse is removed from it to limestone and methods, the leaching is carried out at 90-100 seconds, if the metal is copper and / or nickel, and and 65-70 ° C, if the metal is cobalt j, the mouse is removed from the solution by reducing
    arsenate to arsenite with sulfuric anhydride at.
    In the proposed method, it is not necessary to crystallize the metal sulphates completely from the separated aqueous solution containing arsenate first, because a closed solution cycle is used, and secondly, because the mouse can be released very selectively from the mother liquor after crystallization. Removing the mouse from this mother liquor does not necessarily have to be complete, because after removing the mouse, the solution returns to the leaching stage of the starting material.
    The essence of the invention is as follows.
    The starting material — an arsenide precipitate — is fed to the step of targeting, at which an appropriate concentration of sulfuric acid is maintained, and the oxidizing agent is dispersed either as gaseous oxygen or as air in an aqueous solution. The concentration of sulfuric acid is maintained at 100 g / l. When leaching the source material, which contains copper and nickel, the temperature is preferably maintained by EO-SE with if the metal is cobalt, then the temperature is maintained at 65-70 €, at selected temperatures the solubility of the sulfates of the corresponding metals is maximum. When treating a zinc arsenide precipitate, it contains all three of the mentioned metals and the temperature is an average value between the said temperature ranges depending on the prevailing metal.
    At the end of the acceleration stage, the solution is subjected to cooling. It can be cooled to approximately 30 ° C, which is fully achievable with ordinary water for cooling. When this occurs, the sulfates of metals crystallize. At this stage of the cycle: fresh sulfuric acid is preferably added. The sulfate crystals are removed by filtration and the next washing.
    The next step is to remove the mouse, which can be done in various ways.
    Mouse k can be removed by reducing arsenate to arsenite, which results in the release of AsaOj.
    Reduction can be carried out using sulfur dioxide. Thereafter, it can be returned to the stage of solution cleaning either in this form or in the form of a solution of NaAsOa, which is less hazardous to the environment, which is obtained by dissolving the precipitated soda in caustic soda after removing the mother liquor from the precipitated by transfusion.
    Mouse k can be removed from solution by extraction. selectively removed by tributyl phosphate or dibutyl butyl phosphate from the solution obtained from crystallization. The extraction is carried out without the addition of any neutralizers or other reagents. The concentration of sulfuric acid is high. lots in solution contributes to the extraction, and therefore the addition of fresh sulfuric acid at the crystallization stage is an advantage at this stage as well. Some higher alcohols can be added to a solution of tributyl phosphate or dibutyl butyl phosphate in the corresponding hydrocarbon in order to improve the separation or separation of the phases. Reextraction is carried out with water. The solution at the exit contains 100 g / l of the mouse and can then be returned to the solution purification stage. The mouse can thus be kept in the aqueous solution throughout the whole process, which is gigantic.
    The metal sulphates obtained in the process can be used as raw materials for the production of pure metals or pure metal salts, and the resulting mouse is a marketable product.
    Example. The precipitate obtained from the purification of the solution in the process of obtaining zinc was leached under the following conditions:
    Solid content: 200 g / l
    Temperature EZ C
    Initial concentration of sulfuric acid 300 g / l. Final concentration of sulfuric acid 120 g / l. Air was introduced into the solution, which was well dispersed.
    After 6 hours, the color of the leach residue became white and the leaching was stopped. The results of the experiment are given in table. G. Table
    Precipitate to leach 45, 2 3.6 vani I Precipitate after distillation 0, 14 0.025 1 min 4,2 6.0 0.28 16.5 5.3 0.025 0.13 0.2 30 Exit from leach 99 99 9.9 vani Solution before vytselachi28 17 vani Solution after vyschelail8 24 siwani
    The solution fed to the leach is obtained by passing the solution;
    HaAsOi. AsaO Sulfuric acid was added to the solution, after leaching to a concentration of 200 g / L, the solution was cooled to and kept at this temperature b. The obtained crystals were removed by, 40 118
    24 35 48 2.6 153
    e 26
    17 26 37 2.1 152 102
    110 113 92 83
    1.4 1.7 2.4 0.1 0.1 18
    Continuation of ta6l.1
    300 120
    pa several times through the process as shown in the figure.
    NqAsOg
    120
    320
    1.5 99.9 99.6 99.7 27 36 2 120 35 48 2.6 153 filtration and then washed with a small amount of water (0.2 ml of water per gram of sediment). The results of the study are shown in Table 2. l and c a 2
    Half of the solution was purified from the mouse using tributyl phosphate.
    To remove the mouse from the solution obtained from the crystallization of metal sulphates, an extractant was prepared containing 85% (volume) tributyl phosphate and 15% (volume) Shellisoc K (aliphatic hydrocarbon with a sampling temperature of 194-251 with a specific gravity of 0.79 g /cm)..
    One part (volume) of the solution obtained from crystallization and
    The presence of elements in solutions, g / l
    26 17 26 37 2.1 152
    27 17 25 38 2.1 76 a
    0.20 0.30 0.25 0.15 0.01 128
    0,014 0,013 0,011 0,010 0,001 86
    From the table it can be seen that the mouse can be selectively removed. The residual amount of co-recovered metals is simply removed by washing the extracting agent with a small amount of water. The separation factor for both the extraction step and the washing step with water is 2.5, and thus the extraction is carried out to obtain the sulfate-free arsenic acid.
    The other half of the solution was served
    The presence of elements in solutions, g / l
    28
    17 27
    17 27
    28
    1.4 parts (a bulk solution of tributyl phosphate (already used to remove the mouse and regenerated) were stirred for 5 minutes at. The separated organic phase was stirred for 5 minutes at 0.1 volume of water, after which the separated organic phase was stirred the same way and a half of its volume of water.
    The compositions of aqueous solutions are given in table 3, IT table
    320
    228
    292
    66
    in the reactor, where sulfur dioxide was introduced through the solution, while the temperature was maintained in the order.
    After 10 hours, the As concentration decreased to 26 g / l, and a precipitate was obtained. The solution was cooled to 30 ° C and removed by transfusion. A solution containing 60 g / l of caustic soda was fed to the reactor and stirred until the precipitate completely dissolved. Before leaching, the sample was taken and washed with a small amount of water. The results of the experiment are given in table.4.
    Table 4
    36
    110
    300
    36 2
    26
    405
    权利要求:
    Claims (3)
    [1]
    Yield The solution was returned to the leaching stage of the starting material. The invention of the method of processing materials containing arsenic and metal, including leaching the starting material with an aqueous solution of sulfuric acid, separating the solution from the precipitate and crystallizing the metal sulfates from the solution, characterized in that in order to improve the efficiency of the process of separating the mouse from the metal, leaching carried out at 65 ° S-oh when dispersed in a solution of air or oxygen, before crystallization, sulfuric acids are introduced into the solution in an amount sufficient to obtain a concentration of sulfuric acid s on staProdolzhenie Table 4
    88 dii leaching 100-300 g / l, crystallization of sulfates from the separated solution is carried out by cooling and before returning part of this solution for leaching, remove the mouse to known methods.
    [2]
    2 .. The method according to pl, that is, and that the leaching is carried out at 90-100 ° C, if the metal is copper and / or nickel, and at 65-70 ° C; if the metal is cobalt.
    [3]
    3. The method of claim 1, wherein the mouse is removed from the solution by reducing arsenate to arsenite with sulfur dioxide at 60 ° C. Sources of information taken into account in the examination of the South African Institute of Mining and Metallurgy. July. 1969, p.
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    同族专利:
    公开号 | 公开日
    IT7852048D0|1978-11-24|
    AU526119B2|1982-12-16|
    ES474728A1|1979-03-16|
    BR7807788A|1979-07-24|
    CA1113253A|1981-12-01|
    FI773589A|1979-05-29|
    IT1106940B|1985-11-18|
    JPS5730893B2|1982-07-01|
    AU4190378A|1979-06-07|
    DE2850707A1|1979-05-31|
    YU275178A|1982-06-30|
    FI58354C|1981-01-12|
    JPS5483621A|1979-07-03|
    US4220627A|1980-09-02|
    FI58354B|1980-09-30|
    MX152090A|1985-05-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB372189A|1930-09-09|1932-05-05|Norddeutsche Affinerie|Process for the recovery of arsenic from arseniferous metallurgical intermediate products and by-products|
    BE382584A|1930-09-09|1900-01-01|
    CA1069316A|1975-04-01|1980-01-08|Metallurgie Hoboken-Overpelt|Treatment of ores or metallurgical by-products containing arsenic and antimony|
    LU72319A1|1975-04-18|1977-02-10|FR2473556B1|1980-01-15|1984-05-18|Pechiney Ugine Kuhlmann Uran|
    FI63781B|1980-03-19|1983-04-29|Outokumpu Oy|FOERFARANDE FOER AOTERVINNING AV VAERDEMETALLER UR FINMALEN PYIT|
    FI64646C|1980-06-19|1983-12-12|Outokumpu Oy|HYDROMETALLURGICAL FOERFARANDE FOER UTVINNING AV VAERDEMETALLER UR METALLISKA LEGERINGAR|
    DE3048404C2|1980-12-22|1986-04-24|Sumitomo Metal Mining Co. Ltd., Tokio/Tokyo|Process for the production of a mixed copper-arsenic compound|
    DE3050832C2|1980-12-22|1986-09-04|Sumitomo Metal Mining Co. Ltd., Tokio/Tokyo|Process for the production of copper arsenate / copper hydroxide|
    GB2098187B|1981-03-30|1985-06-12|Sumitomo Metal Mining Co|Extracting arsenic|
    ES8504266A1|1983-10-04|1985-04-01|Diaz Nogueira Eduardo|Process for leaching sulphide concentrates of the tetrahedrite type containing high concentrations of arsenic and antimony|
    FI68422C|1983-10-21|1985-09-10|Outokumpu Oy|HYDROMETALLURGICAL FOERFARANDE FOER BEHANDLING AV CHLORIDER OCHFLUORIDER INNEHAOLLANDE RAOAEMNEN AV VAERDEFULLA METALLER|
    US5089241A|1990-12-20|1992-02-18|Allied-Signal Inc.|Process for converting hexafluoroarsenic acid or any salt thereof to arsenic acid or salt thereof which can then be rendered nonhazardous|
    US5182023A|1991-10-17|1993-01-26|Texas Romec, Inc.|Process for removing arsenic from water|
    EP0620189B1|1993-04-08|1998-01-07|AlliedSignal Inc.|Process for separating arsenic acid from an aqueous mixture comprising sulfuric and arsenic acids|
    US5788740A|1995-03-06|1998-08-04|Bay Zinc Company, Inc.|Method for the hydrometallurgical separation and recovery of biological nutrients, lead, gypsum and cadmium from raw materials|
    ES2140312B1|1997-08-07|2000-10-16|Consejo Superior Investigacion|PROCEDURE FOR THE DESARSENIFICATION OF OXIDIZED METALLURGICAL MATERIALS FROM THE COPPER INDUSTRY.|
    WO2014061037A1|2012-10-18|2014-04-24|Hindalco Industries Limited|Treatment of hazardous solid waste generated in copper manufacturing process|
    CN103074499B|2013-01-31|2014-07-30|云南驰宏锌锗股份有限公司|Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FI773589A|FI58354C|1977-11-28|1977-11-28|FOERFARANDE FOER BEHANDLING AV RAOMATERIAL INNEHAOLLANDE ARSENIK OCH METALL|
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