WO2012124565A1 - 白金族元素の回収方法 - Google Patents
白金族元素の回収方法 Download PDFInfo
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- WO2012124565A1 WO2012124565A1 PCT/JP2012/055813 JP2012055813W WO2012124565A1 WO 2012124565 A1 WO2012124565 A1 WO 2012124565A1 JP 2012055813 W JP2012055813 W JP 2012055813W WO 2012124565 A1 WO2012124565 A1 WO 2012124565A1
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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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
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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
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
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- 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 recovering platinum group elements, and more particularly to a method for recovering platinum group elements from metallic copper containing platinum group elements.
- slag is produced by melting a copper oxide-containing material, a flux mainly for reducing the reaction temperature, and a reducing agent in a melting furnace. Then, metallic copper is produced from copper oxide using the reduction reaction that occurs in this slag. The metallic copper thus produced is heavier than the specific gravity of the slag and will sink in the slag. As described above, there is known a dry process in which metallic copper is separated and recovered from the slag by utilizing the difference in specific gravity between the metallic copper and the slag thus produced.
- the said dry process can be utilized as a method of collect
- a platinum group element PGM: Platinum Group Metals or later
- PGM Platinum Group Metals or later
- PGM means any of six elements of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt), or a combination thereof. Show. In addition to the PGM, gold (Au) and other metals may of course be recovered, but in the present specification, for convenience of explanation, the PGM will be described as an example.
- JP 2004-68071 A JP 2004-275866 A Japanese Patent Laid-Open No. 2004-277791 Unexamined-Japanese-Patent No. 2004-277792 JP, 2009-24263, A
- the above method is certainly very useful as a method of recovering PGM as a group.
- the method of recovering a predetermined element from PGM is not yet known in the case of a dry process.
- Pd, Pt and Rh are elements which are frequently used and expensive among PGMs. Therefore, when recovering Pd, Pt and Rh, it is ideal that only Pd, Pt and Rh are contained in the copper phase. Conversely, it is preferable that the content of PGM (Ru, Os and Ir) other than the above be smaller. In this case, division work can be smoothly performed, such as “a person who recovers PGM contained in the copper phase” and “a person who recovers Pd, Pt and Rh of that PGM”, and the efficiency of recovery of PGM is improved. Contributing to Moreover, for those who recover PGM, the needs of those who recover Pd, Pt and Rh can be sufficiently satisfied.
- an object of the present invention is to provide a method of causing a predetermined element of PGM present in the copper phase to be unevenly distributed in the copper phase and recovering the predetermined element from the PGM.
- the inventor examined a method that can achieve the above-mentioned purpose. At that time, the inventor reexamined the mechanism of melting PGM to the copper phase. In this review, among PGMs, Ru, Os and Ir were recognized again as being difficult to melt in the copper phase. Since it was difficult to melt in the copper phase in this way, it was recognized again that the mechanism of settling to the lower phase in the copper phase was used rather than melting these elements.
- the inventors have found that the molten copper phase (1) Further adding PGM itself, or (2) further adding copper (Cu), or (3) adding manganese (Mn), finally, a predetermined element of PGM, in particular At least a part of elements in the Pd, Pt and Rh groups and at least a part of the elements in the (Ru, Os and Ir) groups can be separately localized in the upper or lower phase of the copper phase I got the knowledge.
- the specific gravity of the metal according to the present invention Ir from high in the order (22.7g / cm 3), Os (22.6g / cm 3) Pt (21.5g / cm 3), Rh (12.5g / cm 3 ), Ru (12.4 g / cm 3 ), Pd (12.0 g / cm 3 ), Cu (8.9 g / cm 3 ), and Mn (7.5 g / cm 3 ).
- the aspect of this invention made based on this knowledge is as follows.
- the first aspect of the present invention is It is a method for recovering a platinum group element, characterized in that copper is further added to the molten copper phase containing a platinum group element containing at least rhodium to increase the distribution ratio of rhodium in the molten copper phase.
- the second aspect of the present invention is It is a method for recovering a platinum group element comprising adding iridium to a molten copper phase containing a platinum group element containing at least rhodium to increase a distribution ratio of rhodium in the molten copper phase.
- the third aspect of the present invention is It is a method for recovering a platinum group element characterized in that manganese is added to a molten copper phase containing a platinum group element containing at least rhodium to increase the distribution ratio of rhodium in the molten copper phase.
- the fourth aspect of the present invention is Recovery of a platinum group element characterized in that manganese is added to a molten copper phase containing rhodium and a platinum group element containing at least one of platinum and palladium to increase the distribution ratio of rhodium in the molten copper phase It is a method.
- a fifth aspect of the present invention is the aspect described in the first aspect, wherein Iridium may be further added to the molten copper phase to increase a distribution ratio of rhodium of the molten copper phase.
- a sixth aspect of the present invention is the aspect described in the first aspect, wherein Manganese is further added to the molten copper phase to increase the distribution ratio of rhodium in the molten copper phase.
- a seventh aspect of the present invention is the aspect described in any one of the first, second and fifth aspects, wherein The platinum group element to be recovered is rhodium.
- An eighth aspect of the present invention is the aspect according to any one of the third, fourth and sixth aspects, wherein The platinum group element to be recovered is characterized in that it is rhodium and at least one of platinum and palladium.
- a method can be provided in which a predetermined element of PGM present in the copper phase is localized in the copper phase, and the predetermined element is recovered from the PGM.
- FIG. 2 (c) the results for 12 hours
- FIG. 2 (d) shows 24 hours. Show the result of the case.
- FIG. 4 is a view showing the relationship between mass% of elements in the upper and lower phases and the melting time for the analysis sample made of metallic copper used in this example, and the result of the upper phase is shown in FIG.
- the result of the lower phase is shown in FIG. 4 (b).
- FIG. 5 (a) is a figure which shows the result of having observed with the optical microscope with respect to the sample for analysis which consists of metal copper used in the present Example.
- 5 (b) is a view showing the result of the electron beam microanalyzer performed on the analysis sample made of metal copper used in this example. It is a figure which shows the elemental-analysis result of an upper phase and a lower phase with respect to the sample which added 1 mass% of Ir in a present Example. The vertical axis indicates the depth from the outermost surface of the copper phase, and the horizontal axis indicates mass% of the element. 6 (a) shows the result in the case of 1 hour, and FIG. 6 (b) shows the result in the case of 3 hours. It is a figure which shows the elemental-analysis result of an upper phase and a lower phase with respect to the sample which added 5 mass% of Ir in a present Example.
- FIG. 7 (a) shows the result in the case of 1 hour
- FIG. 7 (b) shows the result in the case of 3 hours.
- the vertical axis indicates the depth from the outermost surface of the copper phase
- the horizontal axis indicates mass% of the element.
- FIG. 8 (a) shows the result in the case of 1 hour
- FIG. 8 (b) shows the result in the case of 3 hours.
- FIG. 9 (a) shows the result in the case of 1 hour
- FIG. 9 (b) shows the result in the case of 3 hours.
- FIG. 9 (a) shows the result in the case of 1 hour
- FIG. 9 (b) shows the result in the case of 3 hours.
- the melting furnace 1 in the present embodiment is an electric furnace 2 composed of a heating element of molybdenum disilicide (MoSi 2 ), a reaction tube 3 covered by the electric furnace 2, and magnesium oxide (MgO) covered by the reaction tube 3 And a crucible 4 consisting of The reaction tube 3 has a double structure of an outer tube 31 and an inner tube 32. Inside the inner tube 32, a crucible 4 for providing the molten copper phase 6 is provided.
- MoSi 2 molybdenum disilicide
- MgO magnesium oxide
- the tip of the reaction tube 3 is an opening, and the gas introduction part 5 for sucking in and exhausting the gas for cooling the melting furnace 1 is fitted in the outer tube 31.
- the gas introducing unit 5 is provided with an intake unit 51 for introducing a gas into the reaction tube 3 and an exhaust unit 52 for exhausting the gas.
- the intake portion 51 and the exhaust portion 52 are tubular, and have a structure in which the gas storage portion (not shown) outside the reaction tube 3 or the outside air is communicated with the inside of the inner tube 32. Then, in order to cool the molten copper phase 6 quickly, the tip of the intake portion 51 in the inner tube 32 is closer to the crucible 4 than the tip of the exhaust portion 52 in the inner tube 32.
- a PGM-containing treated member and a copper source material containing copper oxide are loaded into a sealed electric furnace together with a flux component and a reducing agent. Then, these materials loaded are reduced and smelted.
- the molten metal composed mainly of metallic copper is precipitated below the molten slag phase composed mainly of oxide.
- the mixed melt (liquid phase) of the molten oxide and the molten copper phase after the oxidation treatment in the melting furnace 1 is allowed to stand in the furnace.
- the molten oxide after the oxidation treatment has a specific gravity smaller than that of the molten copper phase, the molten oxide becomes the upper phase, and the molten copper phase becomes the lower phase, so that they are easily separated from each other.
- PGM is concentrated in the molten metal which has settled downward.
- the PGM-concentrated molten copper phase is separated from the molten slag and transferred to another furnace in the molten state. Then, in another furnace, the molten copper phase is oxidized and smelted to phase-separate into a molten copper phase in which the oxide-based slag phase and PGM are further concentrated.
- this method is repeated to recover PGM by concentrating and containing PGM in the molten copper phase.
- the above oxidation treatment is repeated twice, and the metallic copper obtained after the second oxidation treatment is used.
- the metallic copper is melted using the melting furnace 1 described above to form a molten copper phase.
- the PGM recovery device described in Patent Document 5 may be used as a device for performing the recovery method in the present embodiment.
- Ir Iridium
- the "upper phase” in this specification refers to the layer of the side in contact with the gas phase among the plurality of phases in the metallic copper formed by the melting treatment / cooling treatment (described later) on the metallic copper.
- the “plurality of phases” may be two or more phases. At least a part of elements of (Ru, Os and Ir) is relatively localized in the lower phase side by utilizing the fact that the specific gravity of Rh is lighter than that of Ir, and at least a part of (Pd, Pt and Rh) The technical idea in the present embodiment can be applied as long as the elements of (1) can be relatively localized on the upper phase side.
- the “distribution ratio” is also referred to as mass% (mass%, content) of Rh in a certain phase, for example, when a plurality of phases are formed in the copper phase, taking Rh as an example. Moreover, it is a value represented by the ratio of mass% of Rh in the other phases, also referred to as the concentration in some cases.
- a plurality of phases are the upper phase and the lower phase, they can be expressed as follows by a specific formula.
- L X u / b (mass% of element X in upper phase) / (mass% of element X in lower phase) Taking Rh as an example as described above, it can be expressed as L Rh u / b .
- the mechanism for improving the distribution ratio is currently under intense research by the inventor. Although speculation, the mechanism is considered as follows. That is, Ir has a high specific gravity among PGMs, and usually exists in the lower phase among the molten copper phase. That is, even if a large amount of Ir is present in the upper phase of the molten copper phase at the time of charging Ir, it moves to the lower phase during the melting process. At that time, Ru and Os, which have relatively similar properties of Ir and elements (such as atomic weight and specific gravity, etc.), are also moved to the lower phase in the form of being dragged by Ir. As a result, in the upper phase of the copper phase, the content of Ru, Os and Ir decreases, and the content (concentration) of Rh increases. From the above results, at least the distribution ratio of Rh is improved.
- the amount of Ir added is preferably more than 1% by mass and 10% or less by mass with respect to the molten copper phase. Furthermore, it is particularly preferable to add 5 mass% or more and 10 mass% or less to the molten copper phase. As will be described later in the Examples, in addition to increasing the distribution ratio of Rh, in the copper phase, the distribution ratios of Pt, Pd and Rh can be increased as compared to before adding Ir.
- the treatment temperature at this time may be any temperature at which PGM can be melted in the copper phase, and for example, if it is 1300 ° C. or more, treatment is possible.
- a plurality of phases are formed according to the specific gravity of the element in the copper phase.
- the Rh content in the upper phase of the plurality of phases can be increased, and the distribution ratio of Rh, which is frequently used among PGMs in the molten copper phase, can be increased as compared to that before mixing. .
- Rh can be suitably recovered as the platinum group element to be recovered.
- Au or PGM can be further separated and recovered by known methods such as various melting methods or electrolysis methods.
- the addition of Ir to the molten copper phase which should not be desirable to be contained in the molten copper phase has the special effect that the distribution ratio of Rh can be improved in the copper phase. That is, Rh among PGMs present in the molten copper phase can be localized in the copper phase.
- a predetermined element can be recovered from PGM.
- division of labor can be performed such as “a person who recovers PGM contained in the copper phase” and “a person who recovers Pd, Pt, and Rh of the PGM”, which contributes to the efficient recovery of PGM.
- the needs of those who recover Pd, Pt and Rh can be sufficiently satisfied.
- Second Embodiment (2) a method of further adding copper (Cu) will be described.
- the difference from the first embodiment is the portion of C) Ir injection. That is, in the present embodiment, the order C) is “C) additional injection of Cu”.
- the contents other than the contents described below are the same as those of the first embodiment, and thus the description thereof is omitted.
- Cu is further added to the molten copper phase.
- the mechanism for improving the distribution ratio is currently under intense research by the inventor. Although speculation, the mechanism is considered as follows. That is, Cu has a low specific gravity when compared to the entire PGM, and a large amount of Cu is present in the upper phase as viewed relatively among the molten copper phases. And, in the PGM, Cu has a relatively similar element property as compared with Pt, Pd and Rh, which are required at this time. Thus, Pt, Pd and Rh remain unevenly distributed in the upper phase together with Cu. And, in the upper phase of the copper phase, the contents of Ru, Os and Ir decrease, and the contents of Rh relatively increase.
- the amount of Cu to be added it can be selected at any time depending on which element of PGM is unevenly distributed in the upper phase or the lower phase. As an example, 50 mass% may be added to the molten copper phase. In at least this case, the distribution ratio of Au can be increased as compared to that before Cu mixing.
- Mn is added to the molten copper phase.
- the distribution ratio of Rh can be improved as compared with that before Mn mixing, as in the first embodiment.
- the distribution ratio of Pt, Pd, and Au can be improved as compared to before Mn mixing.
- the distribution ratio of Pt, Pd and Rh can be reduced in the precipitation phase consisting of precipitates generated in the copper phase as compared to before Mn mixing. That is, it is possible not to contain Pt, Pd and Rh, which are particularly required to be recovered, in the precipitation phase in which Ru, Os and Ir, which are high in specific gravity and difficult to melt in the copper phase, are accumulated among PGM. As a result, the effects described in Embodiment 1 can be further amplified.
- the “precipitated phase” is a phase generated due to precipitation because Ru, Os and Ir are hard to melt in the copper phase as described above.
- Mn has a low specific gravity when compared to the whole of PGM, and a large amount of Mn is present in the upper phase as viewed relatively among the molten copper phases.
- Pt, Pd and Rh which are required at this time among PGM, Mn has relatively similar element characteristics. Thereby, Pt, Pd and Rh remain localized in the upper phase together with Mn. Then, in the upper phase of the copper phase, the contents of Ru, Os and Ir decrease, and the contents of Pt, Pd and Rh relatively increase.
- Pt, Pd and Rh are extracted from the lower phase to the upper phase by the added Mn, and the content of Pt, Pd and Rh in the upper phase of the copper phase is increased. From the above results, the distribution ratio of Pt, Pd and Rh is improved. As a result, as PGM to be recovered, in addition to Rh, Pt or Pd, more preferably at least one of Pt and Pd can be recovered.
- the amount of Mn to be added can be selected at any time depending on which element of PGM is localized in the upper phase or the lower phase. As one example, 20 mass% may be added to the molten copper phase. In at least this case, the distribution ratio of Au can be increased as compared to that before Mn mixing.
- the melting furnace 1 is described as a simple furnace, but a converter or a rotary furnace may be used.
- the contact and mixing of the substance described in Embodiment 1 with the molten copper phase can be promoted by tilting or rotating as necessary.
- Rh in the copper phase is improved by adding Ir in the first embodiment, it is also conceivable to add Pd instead of Ir.
- Pd the distribution ratio of elements of any of Pt, Pd and Rh or their combination may be improved in the copper phase.
- PGM to be recovered in Embodiment 3 may be Pt or Pd, more specifically, at least one of Pt and Pd.
- Embodiments 1 and 3 may be further applied based on Embodiment 2 (a method of further adding copper (Cu)).
- Cu copper
- Ir may be further added to increase the distribution ratio of Rh in the molten copper phase.
- Rh can be suitably recovered as the platinum group element to be recovered.
- manganese may be further added to increase the distribution ratio of Rh, Pt or Pd in the molten copper phase.
- the platinum group element to be recovered in addition to Rh, Pt or Pd, and further, at least one of Pt and Pd can be suitably recovered.
- Example 1 In this example, as described in the first embodiment, (1) a case where PGM itself (Ir) is further added will be described.
- the vertical axis indicates the depth from the outermost surface of the copper phase, and the horizontal axis indicates mass% of the element.
- the vertical axis indicates the depth when the depth in each phase is equally divided.
- the numerical value "3" of the vertical axis of the upper phase in FIG. 2A indicates a point 3/6 deep from the outermost surface in the entire upper phase.
- an EPMA apparatus JXA-8500F manufactured by JEOL Ltd. was used for elemental analysis.
- the sample for analysis of metallic copper produced as mentioned above was divided into the upper phase and the lower phase, it was divided into both phases, and regarding the relationship between mass% of the element in both phases and the melting time, the upper phase is The lower phase is shown in FIG. 4 (b).
- FIG. 5 (a) As shown in FIG. 5 (a), before the test, the solid phase that becomes a precipitate phase when melted is homogeneously dispersed in the copper phase, and the state of segregation of the solid phase can not be seen.
- EPMA Electron Probe Micro Analyzer
- Ir Input of Ir
- the mixing amount at that time was 1 mass%, 5 mass%, and 10 mass% with respect to each of the plurality of molten copper phases.
- FIG. 6 (a) shows the results for the case where the melting time is 3 hours
- FIG. 6 (b) shows the results for the case where the melting time is 3 hours
- 7 (a) and 7 (b) in the case of 5 mass%
- FIGS. 8 (a) and 8 (b) in the case of 10 mass%.
- Example 2 In the second embodiment, as described in the second embodiment, (2) the case of further adding Cu will be described. In addition, about the part which overlaps with Example 1, description is abbreviate
- Cu was additionally mixed with the molten copper phase as described above.
- the mixing amount at that time was 50 mass% with respect to the molten copper phase, and a sample was produced.
- This sample was also divided into the upper phase and the lower phase in the same manner as the copper phase before the test, and elemental analysis was performed in both phases.
- the results are shown in FIG. 9, and FIG. 9 (a) shows the results when the melting time is 1 hour, and FIG. 9 (b) shows the results when the melting time is 3 hours.
- the vertical axis indicates the depth from the outermost surface of the copper phase, and the horizontal axis indicates mass% of the element.
- Table 5 melting time 1 hour
- Table 6 melting time 3 hours.
- Example 3 In Example 3, as described in Embodiment 3, the case where (3) Mn is further added will be described. In addition, about the part which overlaps with Example 1, description is abbreviate
- Mn was further mixed with the metallic copper melted as described above.
- the mixing amount at that time was 20 mass% with respect to the molten copper phase, and a sample was prepared with a melting time of 3 hours.
- This sample was also divided into the upper phase and the lower phase in the same manner as the copper phase before the test, and elemental analysis was performed in both phases.
- the results are shown in FIG. 11 and Table 8 showing the relationship between mass% of the ordinate and the mass% of Mn in the upper phase on the abscissa. Note that FIG. 11 and Table 8 simply show the difference in the elemental composition before and after the addition of Mn. The same applies to the subsequent figures.
- FIG. 12 shows the relationship between mass% of elements of the precipitation phase (solid phase) and mass% of Mn in the upper phase.
- FIG. 13 shows the difference in the elemental composition before and after the introduction of Mn.
- the sample for analysis of metallic copper prepared as described above was divided into upper and lower phases, and thus divided into both phases, mass% of the element in both phases and mass% of Mn in the upper phase.
- the upper phase is shown in FIG. 13 (a) and the lower phase is shown in FIG. 13 (b).
- the horizontal axis is "mass% of Mn in the upper phase” in both (a) and (b).
- the precipitation phase solid phase
- elemental analysis is performed in this state.
- the platinum group element refers to any one or a combination of six elements of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
- the upper phase refers to the outermost surface phase among the plurality of phases formed in accordance with the specific gravity of the element in the copper phase.
- the platinum group element refers to any one or a combination of six elements of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
- the upper phase refers to the outermost surface phase among the plurality of phases formed in accordance with the specific gravity of the element in the copper phase.
- the platinum group element refers to any one or a combination of six elements of ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt).
- the upper phase refers to the outermost surface phase among the plurality of phases formed in accordance with the specific gravity of the element in the copper phase.
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Abstract
Description
(1)PGMそのものを更に追加、又は
(2)銅(Cu)を更に追加、又は
(3)マンガン(Mn)を更に追加
することにより、最終的に、PGMのうち所定の元素、特に、(Pd、Pt及びRh)グループのうち少なくとも一部の元素と、(Ru、Os及びIr)のグループのうち少なくとも一部の元素とを別々に、銅相の上相又は下相に偏在させられるという知見を得た。本発明に係る各金属の比重は、高いものから順にIr(22.7g/cm3)、Os(22.6g/cm3)Pt(21.5g/cm3)、Rh(12.5g/cm3)、Ru(12.4g/cm3)、Pd(12.0g/cm3)、Cu(8.9g/cm3)、Mn(7.5g/cm3)である。
本発明の第1の形態は、
少なくともロジウムを含む白金族元素を含有する溶融銅相中に、銅を更に加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法である。
本発明の第2の形態は、
少なくともロジウムを含む白金族元素を含有する溶融銅相中に、イリジウムを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法である。
本発明の第3の形態は、
少なくともロジウムを含む白金族元素を含有する溶融銅相中に、マンガンを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法である。
本発明の第4の形態は、
ロジウムと、白金及びパラジウムのうち少なくとも一つを含む白金族元素を含有する溶融銅相中に、マンガンを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法である。
本発明の第5の形態は、第1の形態に記載の形態であって、
前記溶融銅相中にイリジウムを更に加えて前記溶融銅相のロジウムの分配比を増加させることを特徴とする。
本発明の第6の形態は、第1の形態に記載の形態であって、
前記溶融銅相中にマンガンを更に加えて前記溶融銅相のロジウムの分配比を増加させることを特徴とする。
本発明の第7の形態は、第1、2、5何れか一に記載の形態であって、
回収する前記白金族元素がロジウムであることを特徴とする。
本発明の第8の形態は、第3、4、6何れか一に記載の形態であって、
回収する前記白金族元素は、ロジウムと、白金及びパラジウムのうち少なくとも一つとであることを特徴とする。
(1)PGMそのものを更に追加、又は
(2)銅(Cu)を更に追加、又は
(3)マンガン(Mn)を更に追加
について、各々、実施の形態1~3にて説明する。
また、変形例については、実施の形態4で説明する。
本実施形態においては、(1)PGMそのものを更に追加する手法、について説明する。説明は、次の順序で行う。
A)溶融炉の準備
B)金属銅の溶融
C)イリジウム(Ir)の投入
D)溶融処理・冷却処理
E)その他の工程
F)実施の形態による効果
本実施形態においては、図1の断面概略図に示すような溶融炉を用いる場合について説明する。本実施形態における溶融炉1は、二珪化モリブデン(MoSi2)の発熱体からなる電気炉2と、電気炉2に覆われた反応チューブ3と、反応チューブ3に覆われた酸化マグネシウム(MgO)からなるるつぼ4と、を有している。また、反応チューブ3は外側チューブ31と内側チューブ32の2重構造となっており、内側チューブ32の内部には溶融銅相6を存在させるためのるつぼ4が設けられている。
本実施形態において用いる金属銅としては、特許文献5(特開2009-24263号公報)に記載のPGM回収方法の途中で発生した金属銅を用いる。なお、特許文献5に記載されたPGMの回収方法は「ROSEプロセス」と呼ばれる方法である。このROSEプロセスは掻い摘んで言うと、以下の通りである。
本実施形態においては、溶融された銅相に対してIrを加える。こうすることにより、溶融処理後に最終的に得られる金属銅の上相において、Irを加える前に比べてRhの分配比を向上させることができる。
LX u/b=(上相における元素Xのmass%)/(下相における元素Xのmass%)
上記のようにRhを例にとると、LRh u/bと表記できる。
上記の溶融炉1を用いて、溶融処理を行う。このときの処理温度としては、PGMを銅相中に溶融できる温度であれば良く、一例を挙げるとすれば1300℃以上であれば処理可能である。
本実施形態によって得られる、PGMを含有する溶融銅相からは、種々の溶融法または電解法などの公知の方法によってAuまたはPGMをさらに分別回収することができる。
本実施形態においては、以下の効果を奏する。なお、効果についての具体的な根拠については、本実施例(後述)にて説明する。
本実施形態においては、(2)銅(Cu)を更に追加する手法、について説明する。なお、上記説明内容A)~F)のうち、実施の形態1と異なるのは、C)Irの投入の部分である。つまり、本実施形態においては、順序C)が「C)更なるCuの投入」、となる。この内容及び以下に記載の内容以外については実施の形態1と同様であるため、説明を省略する。
本実施形態においては、(3)マンガン(Mn)を更に追加する手法、について説明する。なお、上記説明内容A)~F)のうち、実施の形態1と異なるのは、C)Irの投入の部分である。つまり、本実施形態においては、順序C)Irの投入が「C)Mnの投入」、となる。この内容及び以下に記載の内容以外については実施の形態1と同様であるため、説明を省略する。
その結果、実施の形態1に記載の効果を更に増幅させることができる。
本発明の技術的範囲は、上述した実施の形態に限定されるものではなく、発明の構成要件やその組み合わせによって得られる特定の効果を導き出せる範囲において、種々の変更や改良を加えた形態も含む。
以下、上記の内容以外の変形例について列挙する。
具体的に言うと、溶融銅相にCuを追加した上で、Irを更に加えて溶融銅相のRhの分配比を増加させても良い。その結果、回収する白金族元素としては、Rhを好適に回収することができる。
また、同様に、溶融銅相にCuを追加した上で、マンガンを更に加えて溶融銅相のRh、PtあるいはPdの分配比を増加させても良い。その結果、回収する白金族元素としては、Rhに加え、Pt又はPd、更に言えばPt及びPdのうち少なくとも一つを好適に回収することができる。
本実施例においては、実施の形態1に記載のように、(1)PGMそのもの(Ir)を更に追加する場合について述べる。
本実施例では、図1に示す溶融炉を用いて、以下に示す金属銅とIrとを混合して溶融した。
本実施例では、特許文献5(特開2009-24263号公報)に記載のROSEプロセスにおいて、酸化処理を2回繰り返し、2回目の酸化処理の後に得られた金属銅を用いた。この金属銅を用いて以降の実施例による試験を行う前に、この金属銅の特徴について分析した。
なお、本実施例及び以降の実施例において、元素分析にはEPMA装置(日本電子製JXA-8500F)を用いた。
本実施例においては、上記のように溶融した金属銅に対して、Irを混合した。その際の混合量は、複数の溶融銅相のうち各々に対して、1mass%、5mass%、10mass%とした。
その後、1300℃で1時間又は3時間にて溶融処理を行った。その際、各溶融時間に分けて試料を作製した。
実施例2においては、実施の形態2に記載のように、(2)Cuを更に追加する場合について述べる。なお、実施例1と重複する部分については記載を省略する。
実施例3においては、実施の形態3に記載のように、(3)Mnを更に追加する場合について述べる。なお、実施例1と重複する部分については記載を省略する。
[付記1]
白金族元素を含有する溶融銅相に対してイリジウムを溶融銅相に対して5mass%以上且つ10mass%未満加えることにより、銅相において、イリジウムを加える前に比べて、白金、パラジウム及び銅の分配比を増加させることを特徴とする白金族元素の回収方法。
[付記2]
白金族元素を含有する溶融銅相に対して銅を更に加えることにより、銅相において、銅を更に加える前に比べて、更に、金の分配比を増加させることを特徴とする白金族元素又は金の回収方法。
[付記3]
白金族元素を含有する溶融銅相に対してマンガンを加えることにより、銅相において、更に、マンガンを加える前に比べて金の分配比を増加させることを特徴とする白金族元素又は金の回収方法。
[付記4]
白金族元素を含有する溶融銅相に対してマンガンを加えることにより、銅相において発生する沈殿物からなる沈殿相において、マンガンを加える前に比べて、白金、パラジウム及びロジウムの含有率を減少させ、白金、パラジウム及びロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
[付記5]
白金族元素を含有する溶融銅相に対してマンガンを加えることにより、銅相において発生する沈殿物からなる沈殿相において、マンガンを加える前に比べて、更に、金の含有率を減少させ、白金、パラジウム及びロジウムの分配比を増加させることを特徴とする白金族元素又は金の回収方法。
[付記6]
白金族元素を含有する溶融銅相に対してイリジウムを加えることにより、銅相において、イリジウムを加える前に比べてロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
ただし、白金族元素とは、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、オスミウム(Os)、イリジウム(Ir)及び白金(Pt)の6元素のいずれか又はその組み合わせを示す。また、上相とは、銅相内の元素の比重に応じて形成される複数の相の中の最表面側の相のことを指す。
[付記7]
白金族元素を含有する溶融銅相に対して銅を更に加えることにより、銅相において、銅を更に加える前に比べてロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
ただし、白金族元素とは、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、オスミウム(Os)、イリジウム(Ir)及び白金(Pt)の6元素のいずれか又はその組み合わせを示す。また、上相とは、銅相内の元素の比重に応じて形成される複数の相の中の最表面側の相のことを指す。
[付記8]
白金族元素を含有する溶融銅相に対してマンガンを加えることにより、銅相において、マンガンを加える前に比べて、白金、パラジウム及びロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
ただし、白金族元素とは、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、オスミウム(Os)、イリジウム(Ir)及び白金(Pt)の6元素のいずれか又はその組み合わせを示す。また、上相とは、銅相内の元素の比重に応じて形成される複数の相の中の最表面側の相のことを指す。
2 電気炉
3 反応チューブ
31 外側チューブ
32 内側チューブ
4 るつぼ
5 ガス導入部
51 吸気部
52 排気部
6 溶融銅相
Claims (8)
- 少なくともロジウムを含む白金族元素を含有する溶融銅相中に、銅を更に加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
- 少なくともロジウムを含む白金族元素を含有する溶融銅相中に、イリジウムを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
- 少なくともロジウムを含む白金族元素を含有する溶融銅相中に、マンガンを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
- ロジウムと、白金及びパラジウムのうち少なくとも一つを含む白金族元素を含有する溶融銅相中に、マンガンを加えて溶融銅相のロジウムの分配比を増加させることを特徴とする白金族元素の回収方法。
- 前記溶融銅相中にイリジウムを更に加えて前記溶融銅相のロジウムの分配比を増加させることを特徴とする請求項1に記載の白金族元素の回収方法。
- 前記溶融銅相中にマンガンを更に加えて前記溶融銅相のロジウムの分配比を増加させることを特徴とする請求項1に記載の白金族元素の回収方法。
- 回収する前記白金族元素がロジウムであることを特徴とする請求項1、2、5何れか一に記載の白金族元素の回収方法。
- 回収する前記白金族元素は、ロジウムと、白金及びパラジウムのうち少なくとも一つとであることを特徴とする請求項3、4、6何れか一に記載の白金族元素の回収方法。
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US14/004,334 US9115418B2 (en) | 2011-03-11 | 2012-03-07 | Method of recovering platinum group elements |
CN201280012850.2A CN103429769B (zh) | 2011-03-11 | 2012-03-07 | 铂族元素的回收方法 |
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US20230083521A1 (en) * | 2020-01-30 | 2023-03-16 | University Of Fukui | Platinum-group metal recovery method, composition containing platinum-group metals, and ceramic material |
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JP2004277792A (ja) | 2003-03-14 | 2004-10-07 | Dowa Mining Co Ltd | 白金族元素の回収法 |
JP2004277791A (ja) | 2003-03-14 | 2004-10-07 | Dowa Mining Co Ltd | 金または白金族元素の濃縮方法 |
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DE3279625D1 (en) * | 1981-09-16 | 1989-05-24 | Matthey Rustenburg Refines | Recovery of platinum group metals from scrap and residues |
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RU2010114611A (ru) * | 2007-09-14 | 2011-10-20 | Баррик Гольд Корпорейшн (CA) | Способ восстановления металлов платиновой группы с использованием восстановителей |
AU2010246666B2 (en) * | 2009-05-14 | 2014-11-20 | Umicore | Recovery of precious metals from spent homogeneous catalysts |
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JP2004068071A (ja) | 2002-08-05 | 2004-03-04 | Dowa Mining Co Ltd | 白金族元素の乾式回収法 |
JP2004277792A (ja) | 2003-03-14 | 2004-10-07 | Dowa Mining Co Ltd | 白金族元素の回収法 |
JP2004277791A (ja) | 2003-03-14 | 2004-10-07 | Dowa Mining Co Ltd | 金または白金族元素の濃縮方法 |
JP2004275866A (ja) | 2003-03-14 | 2004-10-07 | Dowa Mining Co Ltd | 白金族元素の乾式回収法 |
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US9115418B2 (en) | 2015-08-25 |
EP2684969A1 (en) | 2014-01-15 |
CN103429769B (zh) | 2015-05-06 |
KR20140033350A (ko) | 2014-03-18 |
CN103429769A (zh) | 2013-12-04 |
JP2012188705A (ja) | 2012-10-04 |
CA2829741A1 (en) | 2012-09-20 |
EP2684969B1 (en) | 2018-05-30 |
KR101821849B1 (ko) | 2018-01-24 |
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US20140150608A1 (en) | 2014-06-05 |
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