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    • 专利摘要:
    Hydrometallurgical procedure for recovery of zinc in mine waters and solid metallurgical waste. Procedure for recovering zinc from metallurgical waste, which comprises the integrated treatment of mine acid water and a solid metallurgical waste, by at least the following steps: a) purifying the solid metallurgical residue of soluble elements, b) leaching the waste solid metallurgical with a leaching agent comprising at least one mineral acid and acid mine water, c) biooxidating a mixture comprising the lixiviated liquor and an additional amount of mine acid water, d) precipitating fe and al selectively, and ) cement elements nobler than zinc; and f) precipitating zinc oxide. Additionally, a method for obtaining a zinc oxide derivative comprising: g) obtaining zinc oxide by the process of the invention, and h) transforming zno into basic zinc or metallic zinc carbonate. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2565559A1
    申请号:ES201431453
    申请日:2014-10-02
    公开日:2016-04-05
    发明作者:Francisco CARRANZA MORA；Rafael ROMERO ALETA；Nieves IGLESIAS GONZÁLEZ；Alfonso MAZUELOS ROJAS
    申请人:AGENCIA DE MEDIO AMBIENTE Y AGUA DE ANDALUCIA；Siderurgica Sevillana S A；Siderurgica Sevillana Sa；
    IPC主号:
    专利说明:

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    leaching of solid metallurgical residue and mine water would remain in solution in the precipitation stage of Fe and coprecipitate with the Zn impurifying it.
    It is the first time that the integrated treatment of two different environmental management problems is proposed: steel dust and mine waters, in a synergistic and complementary way, improving the quality of management in both cases and obtaining salable products.
    In the recovery of zinc from steelmaking powders, it is the first time that Fe-Zn separation has been considered with total efficiency by bio-oxidation and sequential alkaline hydrolysis.
    In the zinc recovery process of the present invention, the treatment of mine water implies that the process takes place in an open water circuit and, with it, the final purification of this water. This supposes a clear advantage over any hydrometallurgical process known so far, since in these procedures it is necessary to work in a closed water circuit. DETAILED DESCRIPTION OF THE INVENTION
    In a first aspect, the present invention provides a process for recovering zinc from metallurgical waste, characterized in that said process comprises the integrated treatment of acid mine water and a solid metallurgical residue by at least the following steps:
    a) purify the solid metallurgical residue from soluble elements,
    b) leaching the solid metallurgical residue with a leaching agent comprising the
    minus a mineral acid and acid mine water to get leachate liquor that
    comprises dissolved zinc,
    c) biooxidating a mixture comprising the leached liquor obtained in step b) and
    an additional amount of acid mine water,
    d) precipitate Fe and Al selectively,
    e) cement the noblest elements that zinc, and
    f) precipitate zinc oxide.
    The schematic representation, without limitation, of the procedure comprising steps a) to f) is shown in Figure 1.
    7
    In this patent application, "solid metallurgical residue" means any solid residue of the mining-metallurgical sector that contains appreciable amounts of zinc, for example in the form of oxides, sulfates or basic sulfates. Among them, steelmaking powders, pyrite roasting ashes, zinc calcines, cottrell powders or gas absorption bids from the electric sedimentation furnace from copper smelters. Preferably, the solid metallurgical residue is steel powder, waste produced in steelmaking plants from iron scrap in electric arc furnaces (in English terminology, EAF dust). It is a very fine granulometry material, generally between 0.5 and 5 µm, whose main characteristic is the high content of heavy metals, mostly zinc, in the form of oxides.
    The process of the present invention allows the joint environmental management of two different pollutant sources: a solid metallurgical residue as described in the previous paragraph and acid mine water, characteristic aqueous effluent from the facilities where minerals are extracted and / or processed. sulfurized Both foci are characterized by their acid character and contain heavy metals, zinc among others; and are therefore dangerous.
    Thus, the present invention allows the purification of acid mine waters and the declassification of solid metallurgical waste, in particular steel powder, as a hazardous waste, achieving a more correct environmental management by transforming said metallurgical residue into zinc oxide, raw material for obtaining various commercial products, in particular zinc carbonate or metallic zinc.
    Additionally, the process of the present invention is also suitable for purifying other industrial effluents that comprise zinc and have an acidic character.
    From the perspective of environmental management, the presence of zinc justifies the treatment by the process of the present invention with the aim of eliminating the hazardous nature of the residue; From the economic point of view, it is unquestionable that the higher the content of metals to be recovered, the more advantageous the application of the process will be.
    In a preferred embodiment, the solid metallurgical residue used in the process of the present invention comprises at least 0.1% w / w zinc, while the acid mine water comprises a minimum of 100 ppm of zinc and a maximum pH of 4. In a
    8
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    The solid metallurgical residues used in the process of the present invention, preferably steel mill powders, may have significant contents of one or more soluble constituents in aqueous medium such as, for example, chlorides, and lime. These constituents can significantly alter the equilibrium conditions and the effectiveness of the different stages of the zinc recovery process described in this patent application. Additionally, the reduction or elimination of the chlorides and lime present in the solid metallurgical residue improves the final quality of the purified mine water, obtained after the precipitation of the zinc oxide in step f) of the process of the present invention.
    In a preferred embodiment, the purification treatment of step a) comprises:
    a-i) wash the solid metallurgical residue, preferably steel powder as it is
    described in this patent application, in aqueous medium at a pH between 8 and 11,
    preferably 10, and
    a-ii) separating the solid metallurgical residue from the aqueous wash solution.
    To reach the target pH in step a-i), given the free lime content of the solid residue, an inorganic acid must be added. The amphoteric character of elements such as lead guarantees the appearance of traces of these species in solution, at a pH greater than 11, an unfavorable circumstance for the procedure.
    In step a-i) any inorganic acid can be used, for example, sulfuric, nitric or hydrochloric acid. Preferably, in step i) sulfuric acid is added, in particular a 1: 1 aqueous solution of sulfuric acid (v: v).
    The use of sulfuric acid in step a-i) of the purification treatment, together with the presence of lime in the residue, results in calcium sulfate as a byproduct. This compound is insoluble under the conditions of stage b) leaching.
    In a particularly preferred embodiment, the residue purification treatment
    Solid metallurgical as described in this patent application comprises:
    a-i) wash steel powder in an aqueous medium at pH 10 for a period of residence
    15 to 30 min, more preferably 20 min, and
    a-ii) separating the solid metallurgical residue from the aqueous wash solution by
    sedimentation or filtration.
    10
    The tests carried out by the inventors show that the extraction of chlorides, in particular sodium and potassium chloride, is independent of pH. However, it is especially preferred that step a-i) takes place at pH 10 with a residence time of 20 min since this results in less mobilization of other metals, in particular zinc (see table IV in example 1). The purification treatment to reduce or eliminate chlorides as described in this patent application may also comprise a step of washing the filter cake obtained in step a-ii) to remove the retained stock solution in said cake and thus avoid the contamination of the leaching liquor subsequently obtained in step b). However, this washing step is not necessary when the content of chlorides in the solid metallurgical residue is maximum 4% w / w, thus reducing the filtration area needs of the process.
    ACID LIXIVIATION OF THE SOLID METALLURGICAL WASTE Step b) of the zinc recovery process of the present invention comprises leaching the solid metallurgical residue, preferably steel powder as described in this patent application, using at least one mineral acid as a leaching agent and acid mine water.
    In another preferred embodiment, step b) of leaching the zinc recovery process from metallurgical residues of the present invention comprises the use of sulfuric acid as a mineral acid.
    As the mineral acid, any inorganic acid known to the person skilled in the art can be used for metal leaching processes, for example, sulfuric acid, hydrochloric acid or nitric acid. The use of sulfuric acid is preferred for reasons of cost and quality of the purified final waters.
    This stage of the INAMPA process differs from conventional methods of acid leaching by incorporating contaminated water into the leaching reagent. Mine water has an acidic pH and a significant concentration of Zn. The INAMPA procedure, a procedure to which the present invention refers, allows to take advantage of both qualities of the mine waters contributing additionally to its purification.
    In another preferred embodiment, the present invention relates to the process of recovering zinc from a solid metallurgical residue, preferably powder
    eleven
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    solid-liquid can comprise a sedimentation process, preferably in the presence of a flocculating agent preferably a non-ionic polyacrylamide, since this increases the sedimentation rate, being able to become 4 times higher, and a practically total clarification of the liquid is obtained in considerably less time.
    In another preferred embodiment, the separation of the precipitate obtained in step d) of the process of the invention may comprise filtration of the precipitate obtained. Preferably, the filtration takes place after a sedimentation process with the addition of flocculant.
    In an even more preferred embodiment, step d) of selective precipitation of Fe and Al comprises:
    di) adjust the pH of the liquor obtained after stage b) of biooxidation between 2 and 6 and keep between 10 and 30 min, preferably, preferably the pH adjustment is performed with micronized lime slurry and the pH is maintained between 2 and 6 for 15 min,
    d-ii) sediment the precipitate, preferably in the presence of a non-ionic polyacrylamide, and
    d-iii) filter the sediment obtained, and
    d-iv) wash the filtered cake with water.
    CEMENTATION The zinc recovery process by integrated treatment of acid mine waters and a solid metallurgical residue, preferably steel powder, comprises a step e) of cementing elements more noble than zinc. These elements are mainly copper and cadmium, which would precipitate together with the zinc oxide in step f) of the process of the invention, if this stage was not included in the process.
    In another preferred embodiment, step e) of cementing metals more noble than zinc, preferably copper, cadmium, nickel, cobalt or a mixture of any of these, takes place in the presence of zinc, preferably powder, as a reducing agent. Although it is possible to use other reducing agents known to those skilled in the art, these would impurify the fertile zinc solution. On the other hand, the use of metallic zinc does not contaminate the solution, enriches it and allows its subsequent recovery in the form of a salable product.
    17
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    image18 Example 2. Leaching of steel powder.
    The present example demonstrates the dual purpose of the action of acid mine waters properly mixed with mineral acid as a leaching agent. On the one hand, due to its acidic nature, it acts by solubilizing the solid metallurgical residue, in this example steel powder, the zinc necessary for later stages of the process. On the other hand, it acts by reducing the danger of solid metallurgical waste.
    In order to optimize this leaching stage, three variables have been tested: acid concentration, pulp density and temperature. The leaching time in these trials was set at 1 hour. For these tests, purified steel powder was used by the washing treatment described in example 1, in particular, by washing at pH 10, between 23-25 ° C and with a residence time of 20 min. On the other hand, the mine water used has the composition indicated previously in Table II.
    2.1 Effect of the acidity of the medium For the study of the influence of the acidity of the leaching medium, an automatic pH control device has been used that has allowed testing at a constant pH. To do this, a 1: 1 sulfuric acid solution (v: v) is dosed to maintain the target pH over time.
    Regarding the solubilization of zinc, table V shows the results of tests performed at 20% pulp density (200 g solid / L liquor).
    Table V. - Leaching at 20% pulp density
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    Table XXIII.- Analysis of electrolytic zinc deposits
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    As can be seen, the compositions of the three deposits are very similar, and it can be concluded that the nature of the deposit, the applied voltage and the type of precipitate of the starting ZnO do not influence the quality of the electrolytic zinc.
    44
    权利要求:
    Claims (1)
    [1]
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