• 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:
    An integrated hydrometallurgical process for working up metal-containing starting materials comprising the steps of: a) dissolving metal-containing starting materials in aqueous hydrochloric acid; b) separating the insoluble components; c) introducing dry gaseous HCl; d) filtering off the solid; d1) cooling the filtrate from step d) to about room temperature; d2) introducing dry gaseous HCl; d3) filtering the solution from step d2); d4) dissolving the solid from step d3) in water and spray roasting at temperatures of 400 to 900 ° C; d5) introducing S03 into the filtrate from step d3); d6) filtering the solution of step d5); d7) heating the filter residue from d6) to 500-1100 ° C; d8) adding aqueous hydrochloric acid to the product of d7); d9) filtering off CaSO 4; d10) hydrolysis of the FeCl3 contained in the filtrate from step d9); d11) filtering off Fe 2 O 3 and washing with water; e) heating the solid from step d) to 200-300 ° C; f) cooling the solid mixture to about room temperature; optionally g) separating LiCl by washing with ethanol and recovering LiCl; h) separating NaCl and KCl and, if step g) was not performed, LiCl by washing with water and then recovering NaCl, KCl and LiCl; j) heating the amorphous Al 2 O 3 and / or the solid from step i) to 1200-1400 ° C to form a-Al 2 O 3.
    公开号:AT516089A1
    申请号:T640/2014
    申请日:2014-08-14
    公开日:2016-02-15
    发明作者:Roman Schiesser
    申请人:Mme Engineering E U；
    IPC主号:
    专利说明:

    The invention relates to an integrated hydrometallurgical process for the treatment of metal-containing starting materials.
    State of the art
    The reprocessing of metal-containing starting materials is an important process, as there are many waste materials that contain valuable substances (called recyclables) that can be reused. For this purpose, these recyclables must be obtained from the starting materials. This can be done by acidic or basic leaching.
    The extraction of alumina is now carried out industrially by the Bayer process. This is a basic process in which the aluminum-containing starting material bauxite is reacted with sodium hydroxide solution. In this case, aluminum dissolves as Na [Al (OH) 4], iron precipitates as Fe203. The insoluble residue is disposed of as so-called red mud. In the process, important raw materials are lost and disposal is an environmental problem.
    An acidic leaching of metal-containing starting materials often leads to incomplete separation, since the concentration of the acid or temperature is chosen incorrectly. Not all valuable materials can be recovered from the metal-containing starting material, since they either do not separate from other substances or are not dissolved.
    The aim of the invention is to provide a process in which valuable substances can be obtained from the starting material.
    According to the invention, this is achieved by providing an integrated hydrometallurgical process for working up metal-containing starting materials comprising the steps of: a) dissolving metal-containing starting materials in aqueous hydrochloric acid, the concentration of hydrochloric acid being 2-10% by weight; b) separating the insoluble components; c) introducing dry gaseous HCl until an HCl concentration of 20-28% by weight is reached.
    Reaction mixture at 40-60 ° C, wherein LiCl, NaCl and KCl and AlCl3'6H20 precipitate; d) filtering off the solid; d1) cooling the filtrate from step d) to about room temperature; d2) introducing dry gaseous HCl until an HCl concentration of 28-35 wt.% is reached whereby MgCl2 precipitates leaving Ca 2+ and Fe 3+ in solution; d3) filtering the solution from step d2); d4) dissolving the solid from step d3) in water and spray roasting at temperatures of 400 to 900 ° C to form MgO + HCl (gaseous) + H 2 O (gaseous); d5) introducing SO3 into the filtrate of step d3) to form H2SO4, precipitating Fe2 (SC> 4) 3 and CaSC> 4 and driving off HCl; d6) filtering the solution of step d5); d7) heating the filter residue from d6) to 500-1100 ° C, whereby Fe2 (8 () 4) 3 decomposes to Fe2Ü3 + 3 SO3, with 2SO3 again decomposing to 2SO 2 + O 2, and CaSC> 4 remaining unchanged ; d8) adding aqueous hydrochloric acid to the product of d7), whereby Fe 2 O 3 dissolves selectively and CaSO 4 remains unchanged as insoluble sulfate as a solid; d9) filtering off CaSO 4; dlO) hydrolysis of the FeCl3 contained in the filtrate from step d9) according to the reaction equation 2 FeCl3 + 3 H20 · Fe203 + 6 HCl at 160-200 ° C, wherein the equilibrium is shifted to the right by addition of H 2 O and removal of HCl; dll) filtering off Fe 2 O 3 and washing with water to obtain purified Fe 2 O 3; e) heating the solid from step d) to 200-300 ° C, wherein amorphous Al203 is formed and the chlorides of the elements sodium, potassium and lithium remain unchanged; f) cooling the solid mixture to about room temperature; optionally g) separating LiCl by washing with ethanol and recovering LiCl; h) separating NaCl and KCl and, if step g) was not performed, LiCl by washing with water and then recovering NaCl, KCl and LiCl; if appropriate i) dissolving the amorphous Al 2 O 3 with aqueous hydrochloric acid at a concentration of 2-10% by weight, separating off the insoluble constituents, introducing dry gaseous HCl until an HCl concentration of 20-28% by weight has been reached the reaction mixture at 20-30 ° C, preferably about 25 ° C, filtering off the solid and washing with water; j) heating the amorphous Al 2 O 3 and / or the solid from step i) to 1200-1400 ° C to form a-Al 2 O 3.
    With this method, the valuable substances CaSO 4, Fe 2 O 3, LiCl, NaCl, KCl and Al 2 O 3 can be obtained from the metal-containing starting material. In addition, HCl, S03 and H2SO4 are formed in this reaction, which can also be reused. The advantage of this process lies in the compact, integrated process management and the extraction of high-purity metals in their salt or oxide form. The alumina has a purity of > 99.999%.
    In one embodiment of the invention, the process after step h) can comprise a step h1), in which SO3 is introduced into the aqueous solution obtained in step h), Na2SO4 and K2SO4 and optionally Li2SO4 being obtained and HCl being formed.
    The Na2S04 and K2S04 as well as the hydrogen chloride HCl are also valuable substances that can be reused.
    In another embodiment of the invention, the S03 produced in step d7) can be reused in step d5) and / or h1). This reuse reduces the required amount of externally produced SO3.
    In yet another embodiment of the invention, the HCl obtained in step d4), step d5), step d10) and / or step h1) can be used in aqueous solution in step a) and / or i) and / or after drying in step c) and / or d2) are used. This achieves a closed loop of HCl; An additional supply of HCl is necessary only to the extent that process-related losses of HCl gas occur.
    In one embodiment of the present invention, Na 2 SO 4 may be used to dry HCl. Dry Na 2 SO 4 can take up 10 mol H 2 O. Before using Na2S04 to dry HCl, it must be cleared of water of crystallization at just above 100 ° C. The water of crystallization is released from the crystal structure at Na2S04 from 32 ° C. Then Na2SO4 can be used to dry HCl.
    In another embodiment of the invention, the filtrate from step d6) comprising H2SO4 may be used to dry HCl, optionally after prior concentration of H2SO4. Sulfuric acid is known to be hygroscopic and can therefore be used for drying chemicals. HCl can be easily dried with H2S04 by passing it through H2S04. If the resulting H2SO4 is too low concentrated to act as a desiccant, it must first be concentrated, e.g. to 80 to 100%, for which the H2S04 must be heated to approx. 250 to 350 ° C.
    In one embodiment of the invention, the introduction of HCl into the aqueous phase in step c) and / or d2) may be effected by dripping the aqueous solution through an atmosphere enriched with dry, gaseous HCl. As a result, the aqueous phase is enriched with HCl in a countercurrent process. This allows a large interface between gaseous HCl and the aqueous phase, thereby enriching it to the desired concentration.
    In another embodiment of the invention, the SO3 may be generated by burning sulfur and / or sulfur-containing fuels to SO2 and passing over an oxidation catalyst, and using the resulting heat in the process. By burning sulfur and / or sulfur-containing fuels, on the one hand, the necessary SO 2 is produced, which is converted to SO 3 via an oxidation catalyst and can be used in the process, and on the other hand generates heat which can be used in the process, e.g. directly for adjusting the required temperatures in the individual steps, or for obtaining electrical energy by power generation, e.g. in a steam turbine.
    In yet another embodiment of the invention, the amount of sulfur may be adjusted stoichiometrically to the amount of Na, K, Li Fe and Ca present in the metal-containing starting materials. As a result, these metals are completely converted to the sulfates and removed from the process. An excess of SO3 in the process does not occur. With "sulfur quantity" is meant both the amount of elemental sulfur that is burned and the amount of sulfur in the sulfur-containing fuel.
    In one embodiment of the invention, in step c) heating to about 50 ° C take place. This results in a sharper separation of LiCl, NaCl and KCl and AlCl3-6H20 from the remaining recyclables. The solubilities of the chlorides of Li, Na, K and Al are almost temperature-independent, while the solubility of the other elements is increased by a temperature increase in the liquor.
    In another embodiment of the invention, in step e), the heating may be carried out at about 300 ° C. This achieves a better conversion of AlCl3'6H20 to amorphous Al203.
    In another embodiment of the invention, in step j), the heating may be carried out at about 1200 ° C. This temperature is sufficient to produce a-Al 2 O 3.
    In another embodiment of the invention, in step d4) the heating to 500-800 ° C, preferably 600-700 ° C, take place. At these temperature ranges, more efficient formation of MgO + HCl (gaseous) + H 2 O (gaseous) can be observed.
    In another embodiment of the invention, in step d7) the heating to 700-1000 ° C, in particular 900-1000 ° C, take place. At this temperature range, more efficient conversion of Fe 2 (SO 4) 3 to Fe 2 O 3 + 3 SO 3 > where 2 S03 in turn decomposes to 2 S02 + 02. The S02 must be converted back to S03 by passing it through an oxidation catalyst.
    In another embodiment of the invention, in step d10) heating to about 180 ° C can take place. The hydrolysis takes place more completely.
    In another embodiment of the invention, in step a), the concentration of hydrochloric acid may be 4-8% by weight. This concentration leads to an efficient dissolution of the metal-containing ingredients of the starting materials.
    In another embodiment of the invention, in step c), the concentration of hydrochloric acid may be 22-26% by weight. At this concentration range, selective precipitation of LiCl, NaCl and KCl and A1C13'6H20 occurs.
    In another embodiment of the invention, in step i), the concentration of hydrochloric acid 4-8 wt .-% amount. This concentration range allows complete dissolution of amorphous Al 2 O 3.
    In another embodiment of the invention, in step d2), the concentration of hydrochloric acid may be 30-33% by weight. At this concentration range, complete precipitation of MgCl2 is observed.
    EXAMPLE
    In one example of this invention, metal-containing starting materials are dissolved in aqueous hydrochloric acid wherein the concentration of hydrochloric acid is 2-10% by weight. Preferably, the concentration of hydrochloric acid is 4-8 wt .-%. Thereafter, the insoluble components are separated, e.g. filtered off. Dry gaseous hydrogen chloride HCl is introduced until an HCl concentration of 20-28 wt .-% is reached, wherein the temperature of the reaction mixture is at 40-60 ° C, wherein LiCl, NaCl and KCl and AlCl3'6H20 precipitate. The HCl obtained later in the course of the reaction can be reused in this step. HCl can be introduced into the aqueous phase by dropping (spraying) the aqueous solution (liquor) through a dry, gaseous HCl-enriched atmosphere. In this way, the aqueous phase (lye) is enriched with HCl in countercurrent. Preferably, the temperature at the introduction of HCl is about 50 ° C and the concentration of the free hydrochloric acid in the liquor 22-26 wt .-%. Due to the extremely good solubility of HCl gas in the aqueous phase (caustic), the solubility limits of the individual chloride salts are forced, causing the chlorides to precipitate. The resulting solid is filtered off and the filtrate is cooled to about room temperature. Thereafter, dry gaseous HCl is further introduced until an HCl concentration of 28-35% by weight is reached, whereby MgCl2 precipitates and Ca2 + and Fe3 + remain in solution. The hydrogen chloride obtained later in the course of the reaction can be reused in this step. The introduction of HCl into the aqueous phase can be carried out by dripping the aqueous solution through a dry, gaseous HCl-enriched atmosphere. In this way, the aqueous phase is enriched with HCl in countercurrent. Preferably, the concentration of free hydrochloric acid in the liquor in this step is 30-33% by weight. This solution is filtered, and the solid is dissolved in water and spray roasted at temperatures of 400 to 900 ° C to form MgO + HCl (gaseous) + H 2 O (gaseous). The resulting HCl may be introduced further up and further down the reaction process as described. The heating is preferably carried out at 500-800 ° C, in particular 600-700 ° C. Thereafter, SO 3 is introduced into the above filtrate to form H 2 SO 4, whereby Fe 2 (SO 4) 3 and CaSO 4 precipitate and HCl is driven off. This step is called outcrossing of HCl.
    The SO3 is produced by burning sulfur or sulfur-containing fuels. Sulfur reacts to SO 2, which is then passed over an oxidation catalyst to produce SO 3, which can be used in the process. The resulting HCl may be introduced further up and further down the reaction process as described. The S03 produced later in the process can be reused here. The solution can now be filtered. The filtrate comprises H2SO4 and can be used to dry HCl, optionally after prior concentration of H2SO4. As a result, the desiccant needed for the drying of HCl is produced even in the process.
    The filter residue is heated to 500-1100 ° C, whereby Fe2 (SO4) 3 decomposes to Fe203 + 3 SO3, whereby 2 SO3 decomposes again to 2 SO2 + 02, and CaSO4 remains unchanged. Preference is given to 700-1000 ° C, in particular 900-1000 ° C, heated. The phase diagram indicates a maximum value for Fe203 and a minimum value of Fe2 (SO 4) 3 and FeSO 4 especially at 900-1000 ° C; thus, there is an optimal conversion of Fe2 (SO 4) 3 to Fe 2 O 3 with minimal by-products. The resulting S02-containing flue gas is passed through an oxidation catalyst for the oxidation of S02 to S03. S03 may be used at the points where S03 is supplied, as described. Aqueous hydrochloric acid is added to the product, whereby Fe 2 O 3 dissolves selectively and CaSO 4 remains unchanged as an insoluble sulfate as a solid. CaSO 4 is filtered off. The purity of CaSO 4 is about 95% by weight. The hydrolysis of the FeCl3 contained in the filtrate according to the reaction equation
    takes place at 160-200 ° C, with the balance being shifted to the right by addition of H 2 O and removal of HCl. The resulting HCl may be introduced further up and further down the reaction process as described. Preferably, the hydrolysis is carried out at about 180 ° C. Fe 2 O 3 is filtered off and washed with water to give purified Fe 2 O 3. The purity of Fe 2 C > 3 is about 99% by weight. The solid from the first crystallization stage by introduction of HCl gas is heated to 200-300 ° C, whereby amorphous Al203 is formed and the chlorides of the elements sodium, potassium and lithium remain unchanged. Preferably, the heating is carried out at about 300 ° C. Thereafter, the solid mixture is cooled to about room temperature. Optionally, LiCl is separated by washing with ethanol and recovered. The purity of LiCl is about 99.5% by weight. Due to the high covalent amount of binding in LiCl, LiCl dissolves in ethanol. NaCl and KCl and, if the step of separating LiCl with ethanol was not carried out, LiCl are separated by washing with water and then recovered. NaCl, KCl and LiCl are present as a mixture in this case. It can be introduced into the resulting aqueous solution SO3, wherein Na2S04 and K2SO4 and optionally Li2S04 is obtained and HCl is formed. The SO3 previously produced in the process, as described, can be reused in this step. Na2SO4 can be used to dry HCl. Dry Na2SC> 4 can take up 10 moles of H 2 O. Before using Na2S04 to dry HCl, it must be cleared of water of crystallization at just above 100 ° C. The water of crystallization is released from the crystal structure at Na2SC> 4 from 32 ° C. Then Na2SO4 can be used to dry HCl. The resulting HCl may be introduced further up and further down the reaction process as described. Optionally, the amorphous Al 2 O 3 is dissolved with aqueous hydrochloric acid at a concentration of 2-10% by weight, preferably 4-8% by weight and again separated from the insoluble constituents, then dry gaseous HCl is introduced until an HCl concentration of 20-28% by weight, preferably 22-26% by weight, at 20-30 ° C, preferably about 25 ° C, and the solid is filtered off and washed with water. The amorphous Al 2 O 3 and / or the filtered solid from the previous step is heated to 1200-1400 ° C, preferably about 1200 ° C, to produce a-Al 2 O 3. The a-Al2C > 3 has a purity of 99.999%.
    As an integral part of this hydrometallurgical process, the provision of energy for the entire process is an essential component. A classic method of obtaining electrical energy is the operation of steam turbine plants. For the generation of the necessary thermal energy, sulfur and natural gas can be used as fuels. The main energy supplier is mostly natural gas. The amount of natural gas that is to be burned depends on the required thermal and electrical energy necessary for operating the proposed method and can therefore be used variably. As a fuel additive is liquid sulfur to consider, which is fired as an additional energy supplier together with natural gas. However, sulfur is not only an additional source of energy but is also used as a precursor for SO2 / SO3 recovery. The sulfur oxides are essential as described for the overall HCl cross-out process for precipitating Fe 2 (SO 4) 3 and CaSC> 4 and for recovering Na 2 SO 4, which in turn is used as a wet HCl desiccant. The amount of sulfur that is incinerated depends on the mass flows of sodium, potassium, lithium, iron and calcium. These substances must be quantitatively converted to sulfate. Considering that the selective roasting of ferrous sulfate serves as the second S02 / S03 source, the
    Mass balance of the amount of sulfur to be co-incinerated for each case.
    Most of the thermal energy is to be used for electricity generation via a steam turbine, which means that all electrical consumers can be supplied with energy. Part of the thermal energy can be used for the regeneration of the desiccants Na2S04, H2S04, FeCl3 hydrolysis and evaporation steps.
    As an alternative to generating energy from the combustion of natural gas and sulfur, the condensation enthalpy of sulfuric acid can also be recovered from the SC> 3 containing gas streams after the oxidation catalyst stage. The condensation enthalpy can be decoupled by means of a gas / gas heat exchanger. This recovered energy can be reused for low energy consumers, such as the dehydration of Na 2 SO 4 (-100 ° C).
    权利要求:
    Claims (19)
    [1]
    Claims 1. An integrated hydrometallurgical process for the treatment of metal-containing starting materials, characterized in that it comprises the following steps: a) dissolving metal-containing starting materials in aqueous hydrochloric acid, the concentration of hydrochloric acid being 2-10% by weight; b) separating the insoluble components; c) introducing dry gaseous HCl until an HCl concentration of 20-28% by weight is reached, into the reaction mixture at 40-60 ° C, whereby LiCl, NaCl and KCl and A1C13'6H20 precipitate; d) filtering off the solid; d1) cooling the filtrate from step d) to about room temperature; d2) introducing dry gaseous HCl until an HCl concentration of 28-35 wt.% is reached whereby MgCl2 precipitates leaving Ca 2+ and Fe 3+ in solution; d3) filtering the solution from step d2); d4) dissolving the solid from step d3) in water and spray roasting at temperatures of 400 to 900 ° C to form MgO + HCl (gaseous) + H 2 O (gaseous); d5) introducing S03 into the filtrate from step d3), forming H2SO4, precipitating Fe2 (SO4) 3 and CaSO4 and expelling HCl; d6) filtering the solution of step d5); d7) heating the filter residue from d6) to 500-1100 ° C, whereby Fe2 (SO4) 3 decomposes to Fe203 + 3 SO3, whereby 2 SO3 decomposes again to 2 SO2 + 02, and CaSO4 remains unchanged; d8) adding aqueous hydrochloric acid to the product of d7), whereby Fe 2 O 3 dissolves selectively and CaSO 4 remains unchanged as insoluble sulfate as a solid; d9) filtering off CaSO 4, " dlO) hydrolysis of FeCl3 contained in the filtrate from step d9) according to the reaction equation

    at 160-200 ° C, shifting the equilibrium to the right by addition of H 2 O and removal of HCl; dll) filtering off Fe 2 O 3 and washing with water to obtain purified Fe 2 O 3; e) heating the solid from step d) to 200-300 ° C, wherein amorphous A1203 is formed and the chlorides of the elements sodium, potassium and lithium remain unchanged; f) cooling the solids mixture to about room temperature; optionally g) separating LiCl by washing with ethanol and recovering LiCl; h) separating NaCl and KCl and, if step g) was not performed, LiCl by washing with water and then recovering NaCl, KCl and LiCl; if appropriate i) dissolving the amorphous Al 2 O 3 with aqueous hydrochloric acid at a concentration of 2-10% by weight, separating off the insoluble constituents, introducing dry gaseous HCl until an HCl concentration of 20-28% by weight has been reached the reaction mixture at 20-30 ° C, preferably about 25 ° C, filtering off the solid and washing with water; j) heating the amorphous Al 2 O 3 and / or the solid from step i) to 1200-1400 ° C to form α-Α1203.
    [2]
    2. The method according to claim 1, characterized in that it comprises after step h) a step hl), is introduced in the SO 3 in the aqueous solution obtained in step h), wherein Na 2 SO 4 and K 2 SO 4 and optionally obtained Li 2 SO 4 and HCl is formed.
    [3]
    3. The method according to claim 1 or 2, characterized in that in step d7) resulting S03 in step d5) and / or hl) is reused.
    [4]
    4. The method according to any one of the preceding claims, characterized in that the HCl obtained in step d4), step d5), step d10) and / or step hl) is used in aqueous solution in step a) and / or i) and / / or after drying in step c) and / or d2) is used.
    [5]
    5. The method according to any one of claims 2 to 4, characterized in that Na 2 SO 4 is used for drying HCl.
    [6]
    6. The method according to any one of the preceding claims, characterized in that the filtrate from step d6), which comprises H2SO4, for the drying of HCl, optionally after prior concentration of the H2SO4, is used.
    [7]
    7. The method according to any one of the preceding claims, characterized in that the introduction of HCl into the aqueous phase in step c) and / or d2) by dropping the aqueous solution through an atmosphere enriched with dry, gaseous HCl atmosphere.
    [8]
    8. The method according to any one of the preceding claims, characterized in that the SO3 is generated by burning sulfur and / or sulfur-containing fuels to SO2 and conducting via an oxidation catalyst and the resulting heat is used in the process.
    [9]
    9. The method according to claim 8, characterized in that the amount of sulfur is adjusted stoichiometrically to the amount contained in the metal-containing starting materials of Na, K, Li Fe and Ca.
    [10]
    10. The method according to any one of the preceding claims, characterized in that the heating takes place in step c) to about 50 ° C.
    [11]
    11. The method according to any one of the preceding claims, characterized in that in step e) the heating takes place at about 300 ° C.
    [12]
    12. The method according to any one of the preceding claims, characterized in that in step j), the heating takes place at about 1200 ° C.
    [13]
    13. The method according to any one of the preceding claims, characterized in that in step d4) the heating to 500-800 ° C, preferably 600-700 ° C, takes place.
    [14]
    14. The method according to any one of the preceding claims, characterized in that in step d7) the heating to 700-1000 ° C, in particular 900-1000 ° C, takes place.
    [15]
    15. The method according to any one of the preceding claims, characterized in that in step d10) the heating takes place at about 180 ° C.
    [16]
    16. The method according to any one of the preceding claims, characterized in that in step a), the concentration of hydrochloric acid is 4-8 wt .-%.
    [17]
    17. The method according to any one of the preceding claims, characterized in that in step c), the concentration of hydrochloric acid is 22-26 wt .-%.
    [18]
    18. The method according to any one of the preceding claims, characterized in that in step i), the concentration of hydrochloric acid is 4-8 wt .-%.
    [19]
    19. The method according to any one of the preceding claims, characterized in that in step d2), the concentration of hydrochloric acid is 30-33 wt .-%. Vienna, am

    MME Engineering e.U. represented by \ i ίξ. ... Häupl & Ellmeyer
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    引用文献:
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    DE2700718A1|1976-01-09|1977-07-14|Asturienne Mines Comp Royale|PROCESS FOR THE EVALUATION OF AN Aqueous IRON CHLORIDE SOLUTION FOR THE PRODUCTION OF IRON OXIDE PIGMENT AND HYDRO CHLORIC ACID|
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    法律状态:
    2020-04-15| MM01| Lapse because of not paying annual fees|Effective date: 20190814 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA640/2014A|AT516089B1|2014-08-14|2014-08-14|Hydrometallurgical process|ATA640/2014A| AT516089B1|2014-08-14|2014-08-14|Hydrometallurgical process|
    AU2015303810A| AU2015303810A1|2014-08-14|2015-07-30|Integrated hydrometallurgical method|
    PCT/AT2015/050188| WO2016023054A1|2014-08-14|2015-07-30|Integrated hydrometallurgical method|
    CA2957733A| CA2957733A1|2014-08-14|2015-07-30|Integrated hydrometallurgical process|
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