WO2017081802A1 - Procédé de séparation du molybdène et procédé de traitement de molybdénite contenant du cuivre - Google Patents

Procédé de séparation du molybdène et procédé de traitement de molybdénite contenant du cuivre Download PDF

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WO2017081802A1
WO2017081802A1 PCT/JP2015/081910 JP2015081910W WO2017081802A1 WO 2017081802 A1 WO2017081802 A1 WO 2017081802A1 JP 2015081910 W JP2015081910 W JP 2015081910W WO 2017081802 A1 WO2017081802 A1 WO 2017081802A1
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copper
molybdenum
leaching
iron
ions
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Japanese (ja)
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由樹 青砥
和浩 波多野
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Priority to PE2022002798A priority Critical patent/PE20230978A1/es
Priority to PCT/JP2015/081910 priority patent/WO2017081802A1/fr
Priority to JP2017503626A priority patent/JP6429990B2/ja
Publication of WO2017081802A1 publication Critical patent/WO2017081802A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for separating molybdenum from an acidic solution containing copper ions, iron ions and molybdenum ions, and a method for treating molybdenum ore containing copper, and in particular, leaching a raw material containing copper and molybdenum.
  • the present invention proposes a technique that can contribute to an improvement in the recovery rate of molybdenum in separating and recovering molybdenum from an acidic solution obtained by doing so.
  • Molybdenum is added to stainless steel, structural alloy steel, high-strength steel, alloy tool steel, cast forged steel, superalloy, etc. in the steel and special steel fields, and is used as a catalyst, chemicals and leather dyes in the chemical field. May be.
  • molybdenum may be processed into a form of molybdenum wire, machined product, or assembly part in the metal field, or may be used as a processed product for a magnetron part, a semiconductor part, an electron tube part, or the like.
  • molybdenum may be contained in the acidic solution in which the scraps of the electronic parts are leached. Therefore, it is desired to effectively separate and recover this molybdenum.
  • Molybdenite is molybdenite (MoS 2 ) (molybdenum sulfide), molybdenum lead ore (wulfenite, PbMoO 4 ) (lead molybdate), pawerite (Ca (Mo, W) O 4 ), iron-water lead ore (Fe 2 (MoO 4 ) 3 ⁇ nH 2 O) and other ores, and among these, industrial use of molybdenite is progressing.
  • the hydropyrite is often produced together with copper sulfide, and copper and molybdenum are selected from the hydropyrite by flotation, and the recovered molybdenum concentrate generally contains several percent copper sulphide. Things are mixed. When this is used as a steel additive, which is the main use of molybdenum, it is necessary to remove copper from the molybdenum concentrate in advance because copper deteriorates the properties of the steel product.
  • Patent Documents 1 and 2 As a method for separating and recovering copper from a copper-containing molybdenum concentrate, a so-called iron chloride method as described in Non-Patent Document 1, Patent Documents 1 and 2 is conventionally known.
  • the copper-containing molybdenum concentrate is leached in an autoclave heated to about 110 ° C. using a leachate containing about 120 g / L of Fe 3+ ions, so that copper is leached preferentially, and molybdenum And copper are separated to obtain decoppered molybdenum concentrate.
  • the copper-free molybdenum concentrate after leaching copper is subjected to a molybdenum smelting process.
  • the copper in the liquid after leaching obtained by copper leaching is recovered by a cementation method in which cement copper (about 90% of Cu quality) is precipitated by reacting with iron scraps and the like.
  • Patent Document 1 describes a method of removing impurities such as copper and lead by supplying an iron chloride solution and chlorine gas to molybdenum concentrate under high temperature and high pressure.
  • Patent Document 2 discloses a method in which an aqueous solution containing an alkali metal or alkaline earth metal chloride is used as a leachate in order to remove impurities such as copper and lead from molybdenum concentrate.
  • Patent Document 3 describes a method for separating and recovering copper from sulfide ore containing copper, but here, only the use of air without using a special oxidizing agent or a special device in a chlorination bath. Describes leaching and recovering 98% or more of copper in copper sulfide ore.
  • a copper mineral is added to an acidic solution (hereinafter referred to as an “acidic solution”) containing an alkali metal or alkaline earth metal chloride and bromide and copper and iron chloride or copper and iron bromide, While blowing air into the acidic solution at atmospheric pressure and below the boiling point of the aqueous solution, copper is leached from the raw material as monovalent copper and divalent copper by the oxidizing power of one or both of iron ions and copper ions in the acidic solution.
  • solid-liquid separation is performed, and air is blown into the solution after the solid-liquid separation to oxidize copper in the solution and coprecipitate iron and impurities leached from the raw material into the acidic solution.
  • Patent Document 3 is a method in which copper is leached from a copper sulfide ore using a chloride bath, and no attention is paid to the recovery of molybdenum.
  • molybdenum was slightly contained in the liquid after leaching after copper leaching. Even in this case, it is desired to effectively recover the molybdenum contained in the liquid after leaching in order to further increase the recovery rate of molybdenum.
  • An object of the present invention is to provide a method for separating molybdenum and a method for treating copper-containing molybdenum ore which can effectively recover molybdenum contained in an acidic solution containing copper ions, iron ions and molybdenum ions, such as a solution after leaching.
  • the inventors adjusted the pH of an acidic solution containing copper ions, iron ions, and molybdenum ions within a predetermined range, and precipitated at least a portion of the iron ions contained therein as an iron compound. We have found that most or nearly all of the molybdenum contained in the solution co-precipitates with the iron. Then, it was considered that molybdenum can be effectively recovered from the acidic solution.
  • the method for separating molybdenum according to the present invention is a method for separating molybdenum from an acidic solution containing copper ions, iron ions and molybdenum ions, which oxidizes iron ions in the acidic solution.
  • the pH of the acidic solution By adjusting the pH of the acidic solution to 0.5 to 3.0, at least a part of the iron ions is precipitated as an iron compound, and molybdenum ions in the acidic solution are precipitated as a solid to separate molybdenum. There is to do.
  • the separation rate of molybdenum separated as a solid by oxidation of the iron ions is 95% or more with respect to the amount of molybdenum contained in the acidic solution.
  • the copper quality in the oxidation residue obtained by oxidation of the iron ions is 0.5 mass% or less.
  • the acidic solution can be obtained by leaching a copper component in a raw material containing copper and molybdenum in an acidic halogen bath containing iron ions.
  • the raw material containing copper and molybdenum can be a copper-containing molybdenum ore.
  • the copper-containing molybdenum ore processing method of the present invention is obtained in a copper leaching step after leaching the copper component contained in the copper-containing molybdenum ore in an acidic halogen bath containing iron ions, and after the copper leaching step.
  • the pH of the solution after leaching is adjusted to 0.5 to 3.0 to oxidize the iron ions in the solution after leaching, and the molybdenum ions in the solution after leaching are removed. It is to deposit as a solid.
  • the iron oxidation step may further include a copper extraction step for extracting at least part of copper ions in the post-oxidation solution obtained in the iron oxidation step.
  • copper is extracted in the copper extraction step.
  • the post-extraction solution after extraction is preferably used for an acidic halogen bath in the copper leaching step.
  • the iron ions in the acidic solution are oxidized and the pH of the acidic solution is adjusted to 0.5 to 3.0, whereby the iron ions are precipitated as iron compounds. Since most of the molybdenum contained in the acidic solution coprecipitates with the iron, molybdenum can be effectively recovered from the acidic solution. Further, according to the copper-containing molybdenum ore processing method of the present invention, molybdenum eluted from the copper-containing molybdenum ore in the copper leaching step and recovered in the liquid after leaching is recovered as a solid in the iron oxidation step. It can be recovered effectively without leaving it in the liquid after leaching. As a result, the recovery rate of molybdenum from the copper-containing molybdenum ore can be greatly increased.
  • the method for treating molybdenum according to the present invention is a method for separating molybdenum from an acidic solution containing copper ions, iron ions and molybdenum ions, as illustrated in FIG.
  • molybdenum is used as an additive or a catalyst in various industrial fields.
  • various metals contained in raw materials such as used electronic devices or parts are used.
  • the acidic solution obtained by acid leaching by crushing an electronic device in order to separate and recover the material may contain iron ions, copper ions, and molybdenum ions that are contained and eluted in the raw material.
  • an acidic solution containing such iron ions, copper ions, and molybdenum ions can be targeted.
  • the acidic solution made into object by this invention contains iron ion, copper ion, and molybdenum ion by leaching the copper component in said raw material containing copper and molybdenum in the acidic halogen bath containing iron ion.
  • This raw material includes a copper-containing molybdenum ore described later.
  • the acidic halogen bath will be described in detail later.
  • the pH of the acidic solution is larger than 3.0, copper ions contained in the acidic solution may be precipitated, and the oxidized residue contains a large amount of copper, and the separated molybdenum is removed from the steel. It is not desirable when used as an additive.
  • the pH of the acidic solution is more preferably 0.5 to 2.0, and particularly preferably 1.0 to 2.0.
  • the oxidation of iron ions can also be performed by adding hydrogen peroxide water or the like, but the blowing of oxygen-containing gas is preferable because iron ions can be oxidized easily and inexpensively.
  • the amount of molybdenum separated as a solid by oxidation of iron ions is preferably 95% or more, expressed as a separation rate with respect to the amount of molybdenum originally contained in the acidic solution. This separation rate can be expressed by (amount of molybdenum precipitated and separated) / (amount of molybdenum contained in the acidic solution) ⁇ 100.
  • the acid residue containing iron and molybdenum precipitated by oxidation of iron ions contains copper in an amount of 0.5% by mass or less when this is used as a steel additive or the like.
  • the copper-containing molybdenum ore processing method of the present invention includes a copper leaching step of leaching a copper component contained in the copper-containing molybdenum ore in an acidic halogen bath containing iron ions, and copper. After the leaching step, an iron oxidation step of oxidizing iron ions in the liquid after leaching obtained in the copper leaching step and depositing at least a part of the iron ions as an iron compound is included.
  • molybdenite containing one or more selected from molybdenite, molybdenum ore, pawerite, and iron molybdenite
  • molybdenite Mention may be made of molybdenum concentrate after flotation of ore containing ore. Copper in the copper-containing molybdenum ore may be present in the form of sulfides, for example in the form of chalcocite and / or chalcopyrite.
  • the copper-containing molybdenum ore contains Cu in an amount of 0.5 to 10% by mass, preferably 1 to 10% by mass, more preferably 2 to 5% by mass, and the copper-containing molybdenum ore contains 20% by mass or more of Mo. It is possible to target those containing 30 to 60% by mass, more preferably 40 to 50% by mass.
  • the copper-containing molybdenum ore processing method of the present invention first performs a copper leaching step.
  • a large amount of molybdenum remains undissolved as a leaching residue, but some molybdenum is eluted together with copper from the copper-containing molybdenum ore and is contained in the liquid after leaching.
  • the molybdenum leached into the liquid after leaching is coprecipitated together with iron in the iron oxidation step in which iron ions in the liquid after leaching are oxidized. It was found that the molybdenum in the liquid after leaching can be recovered as a solid in this iron oxidation process.
  • iron ions in the post-leaching solution obtained in the copper leaching step are oxidized, and at least a part of the iron ions are removed.
  • An iron oxidation step for precipitation as an iron compound is carried out, where the molybdenum contained in the liquid after leaching is recovered as a solid.
  • the processing method of the present invention can be implemented by the embodiment shown in FIG. 2 or 3, for example. Each embodiment is described in detail below.
  • Copper leaching process In the copper leaching step, an acidic aqueous solution at 50 to 100 ° C. containing chloride ions at 100 g / L to 200 g / L, copper ions at 1 g / L to 30 g / L, and iron ions at 1 g / L to 50 g / L, respectively (
  • the copper component contained in the copper-containing molybdenum ore is leached by bringing the copper-containing molybdenum ore into contact with the copper-containing molybdenum ore under the supply of the oxygen-containing gas.
  • the concentration of chloride ions in the leaching solution used in the copper leaching step is preferably 100 g / L or more, more preferably 120 g / L or more, from the viewpoint of realizing a copper dissolution reaction with high efficiency. Further, it is particularly preferably 140 g / L or more. However, in consideration of economy, it is not necessary to make the concentration too high, and the concentration of chloride ions in the leachate is generally 200 g / L or less, preferably 180 g / L or less.
  • the concentration of copper ions in the leaching solution used in the copper leaching step is preferably 1 g / L or more, and more preferably 5 g / L or more, from the viewpoint of promoting the copper leaching reaction.
  • concentration of copper ions in the leachate is generally 30 g / L or less, preferably 20 g / L or less.
  • Iron ion is a suitable component for promoting copper leaching, and is preferably 1 g / L or more from the viewpoint of realizing a copper dissolution reaction with high efficiency, but if it exceeds 50 g / L, the leaching rate of Mo is remarkable. To increase and lose.
  • the iron ion concentration in the leachate can be 50 g / L or less, preferably 10 g / L or less.
  • the iron ion concentration is particularly preferably 8 g / L or less, and more preferably 6 g / L or less.
  • the total of copper ions and iron ions in the leaching solution is preferably 25 g / L or less, and more preferably 20 g / L or less.
  • concentration of said chloride ion, copper ion, and iron ion points out the density
  • the contact method between the leachate and the copper-containing molybdenum ore is not particularly limited, and there are methods such as spraying and dipping. From the viewpoint of reaction efficiency, a method of dipping and stirring the copper-containing molybdenum ore in the leachate is preferable.
  • the oxygen-containing gas is preferably supplied at a flow rate of 0.02 L / min or more per liter of the leachate from the viewpoint of effectively exhibiting the above-described effects, and more preferably supplied at a flow rate of 0.04 L / min or more. It is even more preferable to supply at a flow rate of 0.08 L / min or more. However, if it is supplied excessively, it consumes a lot of energy such as electric power to compensate for the heat of evaporation taken away by evaporation of the liquid into the bubbles, and a layer of bubbles with concentrate particles coated on the surface ( Floss) is generated in large quantities and overflows from the reaction tank.
  • the supply source of chloride ions is not particularly limited, and examples thereof include hydrogen chloride, hydrochloric acid, and metal chloride. However, in consideration of economy and safety, supply in the form of metal chloride is preferable.
  • the metal chloride include copper chloride (cuprous chloride, cupric chloride), chlorides of alkali metals (lithium, sodium, potassium, rubidium, cesium, francium), alkaline earth metals (beryllium, magnesium, calcium, (Strontium, barium, radium) chlorides are mentioned, and sodium chloride is preferable from the viewpoint of economy and availability. Moreover, since it can utilize also as a supply source of copper ion, it is also preferable to utilize copper chloride.
  • Copper ions and iron ions are usually supplied in the form of a salt, and can be supplied, for example, in the form of a halide salt. From the viewpoint that it can also be used as a supply source of chloride ions, copper ions are preferably supplied as copper chloride and iron ions as iron chloride. It is desirable to use cupric chloride (CuCl 2 ) and ferric chloride (FeCl 3 ) as copper chloride and iron chloride, respectively, from the viewpoint of oxidizing power, but cuprous chloride (CuCl) and ferric chloride. monoferric even when using the (FeCl 2), by supplying an oxygen-containing gas in the leaching solution, to be oxidized respectively cupric (CuCl 2) and ferric chloride (FeCl 3), There is no big difference.
  • the leaching solution should be acidic, and since it can be used as a supply source of chloride ions, it is preferably made acidic with hydrochloric acid.
  • the pH of the leaching solution is preferably about 0 to 3, more preferably about 0.2 to 2.5, as measured by the glass electrode, in order to ensure the solubility of the leached copper.
  • a mixed solution of hydrochloric acid, cupric chloride, ferric chloride, and sodium chloride can be used as the leaching solution in the copper leaching step.
  • the temperature of the leaching solution used in the copper leaching step is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher, from the viewpoint of leaching efficiency and material of the apparatus. .
  • the temperature of the leachate is too high, the leachate will evaporate and the heating cost will increase, so it is preferably 100 ° C. or less, more preferably 90 ° C. or less, and 85 ° C. or less. Even more preferred.
  • it is possible to carry out the copper leaching step under pressure for the purpose of increasing the leaching efficiency it is sufficient under atmospheric pressure. This makes it possible to use a simpler apparatus without requiring a pressure vessel for performing the leaching process at high pressure.
  • the copper leaching step is preferably carried out with an increased amount of copper-containing molybdenum ore with respect to the leaching solution used from the viewpoint of reducing the leaching cost. Therefore, for example, the leaching step can be performed at a pulp concentration of 50 g / L or higher, the leaching step can be performed at a pulp concentration of 150 g / L or higher, and the pulp concentration of 300 g / L or higher is further achieved. The leaching process can be performed.
  • the leaching step can be performed at a pulp concentration of 800 g / L or less, and 600 g
  • the leaching step can be performed at a pulp concentration of / L or less, and the leaching step can be performed at a pulp concentration of 500 g / L or less.
  • the pulp concentration is the ratio of the copper-containing molybdenum ore (dry weight (g)) to the volume (L) of the leachate used.
  • the copper leaching it is preferable to carry out the copper leaching until the copper component in the copper-containing molybdenum ore is sufficiently leached, specifically, until the copper grade in the leaching residue is 0.5% by mass or less.
  • the leaching residue from which copper is sufficiently removed can be effectively used, for example, as a steel additive.
  • the obtained leaching reaction liquid is separated into a liquid after leaching and a leaching residue by solid-liquid separation using a filter press, a thickener or the like.
  • copper leaching in the copper leaching step can be performed only once, but it is preferable to repeat the process by replacing the acidic halogen bath.
  • the molybdenum purity in the copper-free molybdenum ore which is the leaching residue is increased to increase the market value, and an advantage that more copper can be recovered is obtained.
  • copper leaching is repeated multiple times, specifically, after the first copper leaching is completed, solid-liquid separation is performed with a filter press, thickener, etc., and the leaching residue is second time, as required. It can be carried out by leaching copper after the third time.
  • copper leaching can be performed two to four times.
  • copper can be leached at a high leaching rate while suppressing leaching of molybdenum into the solution after leaching.
  • a copper leaching rate of 70% or more while suppressing the molybdenum concentration in the liquid after leaching to 0.001 g / L or less, or the molybdenum concentration in the liquid after leaching is 0.005 g / L.
  • copper leaching rate of 90% or more can be achieved, and depending on conditions, the copper leaching rate is 95% while suppressing the molybdenum concentration in the liquid after leaching to 0.005 g / L or less.
  • the embodiment of FIG. 2 is more advantageous than the embodiment of FIG.
  • the time required for the leaching depends on the copper quality in the copper-containing molybdenum ore as the raw material, but the time required for the copper quality in the leaching residue to be 0.5% by mass or less is about 4 to 10 hours, for example. Yes, typically around 5-6 hours.
  • the leached solution obtained by the copper leaching step contains iron ions in which part of iron in the copper-containing molybdenum ore is dissolved, in addition to iron ions originally contained in the leaching solution. Many of these iron ions are thought to be Fe (II).
  • Fe (II) the above iron ions are oxidized to Fe (III) and used again for leaching, and the pH is adjusted to precipitate a part of Fe (III) to produce an iron compound. By doing so, the iron concentration in the leachate can be controlled.
  • Cu (I) in the solution after leaching is also oxidized to Cu (II).
  • the leached solution contains a small amount of molybdenum eluted in the copper leaching process, and in this embodiment, iron ions are oxidized in the iron oxidation process in order to recover this molybdenum.
  • molybdenum is co-precipitated with the iron compound in which iron ions are deposited, and this is recovered as a solid. Thereby, the recovery rate of molybdenum can be increased effectively.
  • Iron oxidation in the iron oxidation step can be performed at room temperature, but may be heated a little to accelerate the reaction.
  • the temperature of the liquid after leaching here can be set to 20 to 70 ° C., for example.
  • the pH of the solution after leaching is set within the range of 0.5 to 3.0 in order to effectively oxidize iron ions and prevent precipitation of copper ions.
  • the reason for this is that if the pH of the solution after leaching is less than 0.5, iron ions may not be precipitated, and thereby molybdenum co-precipitated with iron may not be sufficiently precipitated.
  • the pH of the solution after leaching exceeds 3.0, precipitation of copper ions may occur.
  • the pH of the solution after leaching in the iron oxidation step is more preferably 0.5 to 2.0, and still more preferably 1.0 to 2.0.
  • the oxidation of iron in the iron oxidation process includes the addition of hydrogen peroxide water to the solution after leaching or the blowing of oxygen-containing gas such as oxygen, oxygen and inert gas (nitrogen, rare gas, etc.)
  • oxygen-containing gas such as oxygen, oxygen and inert gas (nitrogen, rare gas, etc.)
  • the oxygen-containing gas is blown, it is preferably supplied at a flow rate of 0.01 L / min to 1.5 L / min per liter of the leached liquid.
  • 0.01 L / min is a supply amount that does not lower the dissolved oxygen in water at 60 ° C.
  • the supply flow rate of the oxygen-containing gas is too small, it takes time to oxidize.
  • the supply flow rate of the oxygen-containing gas is too large, a large amount of energy such as electric power is consumed to compensate for the heat of evaporation taken away by the e
  • the recovery rate of molybdenum in the iron oxidation step that is, the ratio of the amount of molybdenum in the oxidation residue to the amount of molybdenum in the liquid after leaching is 95. % Or more is preferable.
  • the molybdenum concentration in the liquid after leaching and the oxidation conditions it is possible to recover almost all of the molybdenum contained in the liquid after leaching.
  • the oxidation residue obtained in the iron oxidation process contains molybdenum in the liquid after leaching as a solid, so in addition to the leaching residue obtained in the copper leaching process described above, these are the main applications of molybdenum. It can be used as a certain steel additive. However, when these residues are used as a steel additive, the properties of the steel product are lowered if a large amount of copper is contained therein, so that the copper quality in the residue is preferably small. Specifically, the copper quality in the oxidation residue is preferably 0.5% by mass or less.
  • copper extraction process copper can be recovered from the post-oxidation solution after the iron oxidation step.
  • recovery method for example, solvent extraction, ion exchange, substitution precipitation with a base metal, electrowinning, etc. can be utilized.
  • the copper in the solution after oxidation has both monovalent and divalent states.
  • the copper should be oxidized beforehand so that it becomes divalent copper ions. Is preferred.
  • the method of oxidation is not particularly limited, but a method of blowing air or oxygen into the solution after oxidation is simple.
  • This copper extraction step further includes a process of recovering copper in the solution after oxidation as electrolytic copper on the cathode by electrolytic extraction after subjecting it to solvent extraction and back extraction.
  • This process is generally called a SX-EW (Solvent® Extraction® and Electro-Winning) method and is well known to those skilled in the art.
  • an oxygen-containing gas such as air can be blown into the post-oxidation solution to oxidize copper in the solution.
  • This provides the advantage that copper can be back extracted (striped) after solvent extraction and directly electrowinned.
  • monovalent copper is present in a high concentration in the strong chloride bath, so that it is deposited as dendritic copper during electrowinning.
  • Dendritic copper precipitates in the electrolytic cell as a metal powder. It is overwhelmingly more advantageous in terms of operability such as transportation when recovered as plate-like copper on the cathode.
  • solid-liquid separation can also be performed after the oxidation treatment. Solid-liquid separation is advantageous in increasing the purity of copper in the liquid after leaching because it moves to the residue after oxidation when iron is contained in the leaching liquid.
  • the post-extraction liquid (copper post-extraction liquid) obtained after such a copper extraction process may contain copper ions and iron ions.
  • the post-extraction liquid is acidified in the copper leaching process described above. It is preferred to use repeatedly as a halogen bath leaching solution.
  • molybdenum is sufficiently removed from the liquid after leaching in the iron oxidation process, so that the liquid after extraction obtained in the copper extraction process is substantially free of molybdenum, As described above, the liquid after extraction can be effectively circulated and used.
  • the leaching residue obtained in the copper leaching step can be used as molybdenum concentrate to produce a molybdenum intermediate product through a purification process known to those skilled in the art.
  • molybdenum trioxide products can be produced by oxidation roasting
  • molybdenum trioxide briquettes can be produced through molding and drying processes
  • low carbon ferromolybdenum can be produced through thermite reduction.
  • FIG. 3 Another embodiment shown in FIG. 3 is a method commonly known in the art as the so-called iron chloride method.
  • the treatment method of the present invention can be applied to the iron chloride method as described below.
  • a copper leaching process is performed in which copper-containing molybdenum ore is leached in an autoclave heated to about 110 ° C. using a leaching solution.
  • the leaching solution here contains, for example, Fe 3+ ions at about 100 g / L to 120 g / L, halide ions at about 300 g / L to 350 g / L, and further contains copper ions. it can.
  • the halide ions include chloride ions and bromide ions. Among them, chloride ions are generally used.
  • an iron oxidation process is performed with respect to the solution obtained at the cementation process.
  • the iron ions are usually oxidized from divalent to trivalent without precipitating the iron by blowing in chlorine gas.
  • Mo dissolved in the above solution can be coprecipitated and recovered.
  • the iron oxidation step may be performed separately from the iron oxidation step using chlorine gas and the iron oxidation step using oxygen-containing gas.
  • the leached solution contains a relatively large amount of molybdenum.
  • recovered by an iron oxidation process can be used again as a leaching liquid for the leaching process of the copper in a copper-containing molybdenum ore as mentioned above.
  • the raw material containing copper and molybdenum was pulverized and processed according to the flow shown in FIG.
  • the residue in each step and the molybdenum, copper and iron contained in the solution were analyzed by ICP emission spectroscopy (ICP-OES), the results shown in FIG. 4 were obtained.
  • a leaching solution (Cu leaching solution) mixed with hydrochloric acid, ferric chloride, cupric chloride, and sodium chloride was heated to 75 ° C. with a hot stirrer, and the raw materials were added thereto. Stirring while blowing air.
  • the temperature of the liquid after leaching was set to 60 ° C., and air was blown into the liquid after leaching at 0.15 L / min for oxidation for 8 hours. The transition of pH and ORP with the lapse of oxidation time at that time is shown in a graph in FIG.
  • the concentration of iron in the liquid after leaching is effectively reduced after the pH of the liquid after leaching becomes 0.5 or more, precipitation of molybdenum co-precipitated with iron. It can be seen that the pH of the solution after leaching is preferably 0.5 or more in order to effectively promote the above.
  • molybdenum in the liquid after leaching obtained in the copper leaching step can be effectively recovered as a solid, and as a result, the recovery rate of molybdenum from the raw material containing copper and molybdenum. It was found that can be further improved.

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Abstract

La présente invention concerne un procédé de séparation du molybdène qui sépare le molybdène d'une solution acide contenant des ions cuivre, des ions ferreux et des ions molybdène. Des ions ferreux dans la solution acide sont oxydés et le pH de la solution acide est ajusté à une valeur de 0,5 à 3,0, ce qui entraîne la précipitation d'au moins une partie des ions ferreux sous la forme d'un composé ferreux et la précipitation des ions molybdène de la solution acide sous forme solide, pour séparer le molybdène.
PCT/JP2015/081910 2015-11-12 2015-11-12 Procédé de séparation du molybdène et procédé de traitement de molybdénite contenant du cuivre Ceased WO2017081802A1 (fr)

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PE2022002798A PE20230978A1 (es) 2015-11-12 2015-11-12 Metodo para separar molibdeno y metodo para tratar concentrado de molibdeno que contiene cobre
PCT/JP2015/081910 WO2017081802A1 (fr) 2015-11-12 2015-11-12 Procédé de séparation du molybdène et procédé de traitement de molybdénite contenant du cuivre
JP2017503626A JP6429990B2 (ja) 2015-11-12 2015-11-12 モリブデンの分離方法及び、含銅モリブデン鉱の処理方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662874A (zh) * 2020-12-03 2021-04-16 郑州大学 一种从铼钼混合溶液中分离提取铼并联产钼铁合金的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5224112A (en) * 1975-08-13 1977-02-23 Dowa Mining Co Ltd Recovering method of molybdenum
JP2005507457A (ja) * 2001-05-09 2005-03-17 ハー ツェー シュタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング 輝水鉛鉱を加圧酸化するためのオートクレーブ制御機構
JP2005511891A (ja) * 2001-12-03 2005-04-28 コミンコ・エンジニアリング・サービス・リミテッド モリブデン濃縮液の処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5224112A (en) * 1975-08-13 1977-02-23 Dowa Mining Co Ltd Recovering method of molybdenum
JP2005507457A (ja) * 2001-05-09 2005-03-17 ハー ツェー シュタルク ゲゼルシャフト ミット ベシュレンクテル ハフツング 輝水鉛鉱を加圧酸化するためのオートクレーブ制御機構
JP2005511891A (ja) * 2001-12-03 2005-04-28 コミンコ・エンジニアリング・サービス・リミテッド モリブデン濃縮液の処理方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662874A (zh) * 2020-12-03 2021-04-16 郑州大学 一种从铼钼混合溶液中分离提取铼并联产钼铁合金的方法
CN112662874B (zh) * 2020-12-03 2022-07-26 郑州大学 一种从铼钼混合溶液中分离提取铼并联产钼铁合金的方法

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