WO2015030243A1 - Composition for recovering ruthenium and iridium and method for recovering ruthenium and iridium - Google Patents
Composition for recovering ruthenium and iridium and method for recovering ruthenium and iridium Download PDFInfo
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- WO2015030243A1 WO2015030243A1 PCT/JP2014/072952 JP2014072952W WO2015030243A1 WO 2015030243 A1 WO2015030243 A1 WO 2015030243A1 JP 2014072952 W JP2014072952 W JP 2014072952W WO 2015030243 A1 WO2015030243 A1 WO 2015030243A1
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- iridium
- ruthenium
- iron
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- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 113
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 107
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052742 iron Inorganic materials 0.000 claims abstract description 47
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000155 melt Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 description 13
- 238000010587 phase diagram Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000014509 gene expression Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000611 regression analysis Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- 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
-
- 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
- C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
-
- 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 composition for recovering ruthenium and iridium, and a method for recovering ruthenium and iridium.
- Iridium and ruthenium belong to platinum group metals (hereinafter abbreviated as PGM), have high melting point, high corrosion resistance, and are useful as catalysts, and thus are industrially valuable metals. Since both iridium and ruthenium have a very high melting point of 2300 ° C. or higher, a metal solvent such as copper having a high solubility of iridium and ruthenium is used for the recovery.
- PGM platinum group metals
- the recovery rate of iridium and ruthenium can be increased by recovering iridium and ruthenium from a melt obtained by uniformly melting iridium and ruthenium in a metal solvent. Therefore, in order to know the performance as a metal solvent, the phase diagram of iridium and ruthenium and the metal solvent is important.
- Non-Patent Document 1 discloses an Fe—Ir binary system and an Fe—Ru binary system phase diagram as iridium, ruthenium and iron phase diagrams.
- Non-Patent Document 2 describes a ternary phase diagram of Cu—Ir—Ru, but the solubility of iridium and ruthenium in molten copper is low, and the amount of iridium and ruthenium that can be recovered at one time is low. Further improvement is desired.
- an object of the present invention is to provide a composition and a recovery method for economically recovering iridium and ruthenium with high purity.
- the present inventors use Fe as a metal solvent, determine a Fe—Ir—Ru ternary phase diagram, and from this Fe—Ir—Ru ternary phase diagram, a composition range in which iridium and ruthenium can be uniformly melted into molten iron The present invention was completed.
- the present invention is as follows. 1.
- y ⁇ ⁇ 1.64x + 47.73 (Formula 1) [Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ] 2.
- a method for recovering ruthenium and iridium from a substance containing ruthenium and iridium comprising the following steps (1) to (3): (1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ⁇ ⁇ 1.64x + 47.
- FIG. 1 is a graph showing the relationship between the concentrations of iridium and ruthenium in the liquid phase (iron).
- 2A and 2B are EPMA structure observation photographs of the samples of Examples 1 and 3, respectively.
- FIG. 2C is a EPMA structure observation photograph of the sample of Comparative Example 3.
- FIG. 3 is a diagram showing the relationship between the concentrations of iridium and ruthenium in the liquid phase (iron) in the uniform melt range.
- FIG. 1 is a graph showing the relationship between the concentrations of iridium and ruthenium in the liquid phase (iron).
- this relationship can be expressed by the following formula 1.
- y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron
- x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron
- the range (Liquid) that satisfies Formula 1 indicates the uniform melt range. It can be seen that the ruthenium concentration in the liquid phase monotonously decreases as the iridium concentration in the liquid phase increases, and the linear function (Equation 1) can be derived by regression analysis.
- a uniform melt of iridium and ruthenium can be prepared by adjusting the amount of iridium and ruthenium in the molten iron so as to satisfy the above formula 1, and the recovery method described below can be applied to make iridium and ruthenium highly economical. Can be recovered automatically.
- the method includes the following steps (1) to (3).
- Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2)
- the recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3)
- a step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ⁇ ⁇ 1.64x + 47.
- Iridium and ruthenium belong to PGM, have a high melting point and high corrosion resistance, are useful as catalysts, and have high industrial value. Therefore, there is a strong demand for reuse in the industry.
- the material containing iridium and ruthenium to be recovered is not particularly limited.
- the metal is contained in an electronic material, polishing / cutting waste generated during manufacture of a target used for sputtering, a used target after sputtering, and a target device. And a catalyst used for exhaust gas purification, chemical synthesis, and the like.
- the material containing iridium and ruthenium is pulverized, and recovered from these materials by adjusting the amount of ruthenium, iridium and iron within the range represented by the formula 1.
- a composition can be prepared.
- the recovery composition prepared in the step (1) of the present invention is heated in the subsequent step (2) to melt ruthenium and iridium into iron.
- the heating temperature at this time is preferably 1550 ° C. or higher, more preferably 1550 to 1700 ° C., and particularly preferably 1550 to 1650 ° C. for the reason of uniformly melting iridium and ruthenium in the molten iron.
- ruthenium and / or iridium are separated in the subsequent step (3).
- Separation methods include, for example, a method in which a molten solid in a melt is dissolved in aqua regia, etc., and an iron solution and ruthenium and iridium are separated, and a molten solid in a melt is wet-dissolved in an acidic liquid such as hydrochloric acid / chlorine.
- the recovery method include wet extraction such as a method in which each of iron, ruthenium and iridium is collected and separated as a solid or liquid by solvent extraction, solid-liquid separation by reduction, electrolysis or separation by an adsorbent from the solution.
- Examples 1 to 11, Comparative Examples 1 to 4 and Reference Examples 1 to 4 Ruthenium powder, iridium powder and iron powder were weighed and blended so as to have the composition shown in Table 1. The total amount of the sample was 5 g.
- the blended sample was placed in an Al 2 O 3 crucible and held at various temperatures shown in Table 1 for 24 hours in an electric furnace, and then a melt in which ruthenium and iridium were melted into iron was obtained.
- the melt was taken out from the electric furnace, and in the atmosphere, argon gas was blown directly onto the melt at 2 to 3 (L / min), cooled to about 600 ° C. or less, and then allowed to cool to room temperature in the atmosphere. The structure was observed after cooling. The tissue observation was performed using EPMA (Electron Probe Micro Analyzer).
- FIG. 1 is a graph showing plots and Formula 1 for each data of the above Examples, Comparative Examples, and Reference Examples.
- the obtained discriminant is an equation indicating that the evaluation of the tissue observation is “good” when Y ⁇ 0 and the evaluation of the tissue observation becomes “x” when Y ⁇ 0. That is, in Y ⁇ 0 for obtaining the effect of the present invention, a functional expression of the iridium content and the ruthenium content is expressed by the following expression 3. 0 ⁇ ⁇ 0.1173X 1 + ( ⁇ 0.0715) X 2 +3.4128 (Formula 3)
- the contents of iridium and ruthenium are set to Ir 0 mass% and Ru 39 mass%.
- Point 1 Ir 10 mass% and Ru 30 mass% point 2, Ir 18 mass% and Ru 16 mass% point 3, Ir 22 mass% and Ru 10 mass% point 4, Ir 23 mass% and Ru 5 mass% point 5, Ir 26 mass It can also be said that this is achieved by setting the area surrounded by the point 6 and the origin of% and Ru 0 mass% (except for the point where Ir and / or Ru is 0 mass%).
- Example 12 The uniformly melted solid of ruthenium, iridium and iron obtained in Example 1 was dissolved in 10 times the volume of aqua regia to obtain a liquid containing iron, ruthenium and iridium. The liquefaction rate of the uniformly molten solid was 95%. Liquefied ruthenium and iridium were separated and recovered as ruthenium and iridium by conventional methods such as solvent extraction, solid-liquid separation by reduction, separation by electrolysis and adsorbent, and the like.
- Comparative Example 5 A test was conducted in the same manner as in Example 12 except that the heterogeneous molten solid of ruthenium, iridium and iron obtained in Comparative Example 3 was used. The liquefaction rate of iridium and ruthenium in the heterogeneous molten solid was 70%. It was.
- Example 13 To the composition described in Example 1, 10% by mass of aluminum oxide (hereinafter referred to as “alumina”) powder is added to the total mass of the composition, and when the melt is taken out from the electric furnace, the upper alumina solid and the lower layer The test was performed in the same manner as in Example 1 except that the melt was separated and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
- alumina aluminum oxide
- Example 14 When 5 mass% each of alumina powder and silicon dioxide (hereinafter referred to as “silica”) powder is added to the composition described in Example 1 with respect to the total mass of the composition, and the melt is taken out from the electric furnace, The test was performed in the same manner as in Example 1 except that the alumina and silica solids were separated from the lower layer melt and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
- silicon dioxide silicon dioxide
Abstract
This invention pertains to the following: a recovery composition that contains ruthenium, iridium, and iron, with the ruthenium content and the iridium content satisfying relation (1); and a method in which said composition is used to recover ruthenium and iridium from a substance that contains same.
(1) y ≤ −1.64x + 47.73
(In relation (1), y represents the ruthenium content (in mass%) relative to the total mass of ruthenium, iridium, and iron; x represents the iridium content (in mass%) relative to the total mass of ruthenium, iridium, and iron; x > 0; and y > 0.)
Description
本発明は、ルテニウムおよびイリジウム回収用組成物、並びにルテニウムおよびイリジウムの回収方法、に関する。
The present invention relates to a composition for recovering ruthenium and iridium, and a method for recovering ruthenium and iridium.
イリジウムおよびルテニウムは、白金族金属（Ｐｌａｔｉｎｕｍ Ｇｒｏｕｐ Ｍｅｔａｌｓ：以後ＰＧＭと略称する）に属し、高融点、高耐食性に優れ、触媒としても有用であるため、工業的な価値が高い金属である。イリジウムおよびルテニウムは共に融点が２３００℃以上と非常に高いため、その回収にあたってはイリジウムおよびルテニウムの溶解度が大きい、銅などの金属溶媒が使用される。
Iridium and ruthenium belong to platinum group metals (hereinafter abbreviated as PGM), have high melting point, high corrosion resistance, and are useful as catalysts, and thus are industrially valuable metals. Since both iridium and ruthenium have a very high melting point of 2300 ° C. or higher, a metal solvent such as copper having a high solubility of iridium and ruthenium is used for the recovery.
イリジウムおよびルテニウムの回収においては、イリジウムおよびルテニウムを金属溶媒に均一に熔融した熔融物からイリジウムおよびルテニウムを回収することによりイリジウムおよびルテニウムの回収率を高めることが可能となる。そのため、金属溶媒としての性能を知るうえでイリジウムおよびルテニウムと金属溶媒との状態図が重要となる。
In the recovery of iridium and ruthenium, the recovery rate of iridium and ruthenium can be increased by recovering iridium and ruthenium from a melt obtained by uniformly melting iridium and ruthenium in a metal solvent. Therefore, in order to know the performance as a metal solvent, the phase diagram of iridium and ruthenium and the metal solvent is important.
イリジウム、ルテニウムおよび鉄の状態図として、非特許文献１には、Ｆｅ－Ｉｒ二元系およびＦｅ－Ｒｕ二元系状態図が開示されている。
Non-Patent Document 1 discloses an Fe—Ir binary system and an Fe—Ru binary system phase diagram as iridium, ruthenium and iron phase diagrams.
しかしながら、非特許文献１に記載のＦｅ－Ｉｒ二元系状態図およびＦｅ－Ｒｕ二元系状態図では液相線が点線で描かれており、溶鉄に対するイリジウムの溶解度とルテニウムの溶解度の正確な値は明らかになっていない。また、これまでにＦｅ－Ｉｒ－Ｒｕ三元系状態図に関する報告例は存在していない。
However, in the Fe—Ir binary phase diagram and the Fe—Ru binary phase diagram described in Non-Patent Document 1, the liquidus is drawn with a dotted line, and the iridium solubility in molten iron and the ruthenium solubility are accurate. The value is not clear. In addition, there has been no report on a Fe—Ir—Ru ternary phase diagram so far.
また、非特許文献２には、Ｃｕ－Ｉｒ－Ｒｕの三元系状態図が記載されているが、溶銅中のイリジウムおよびルテニウムの溶解度は低く、一度に回収できるイリジウムおよびルテニウムの処理量をより向上させることが望まれている。
Non-Patent Document 2 describes a ternary phase diagram of Cu—Ir—Ru, but the solubility of iridium and ruthenium in molten copper is low, and the amount of iridium and ruthenium that can be recovered at one time is low. Further improvement is desired.
したがって、本発明は、イリジウムおよびルテニウムを高純度で経済的に回収する組成物および回収方法を提供することを目的とする。
Therefore, an object of the present invention is to provide a composition and a recovery method for economically recovering iridium and ruthenium with high purity.
本発明者らは金属溶媒としてＦｅを用い、Ｆｅ－Ｉｒ－Ｒｕ三元系状態図を決定し、該Ｆｅ－Ｉｒ－Ｒｕ三元系状態図からイリジウムおよびルテニウムを溶鉄に均一に熔融できる組成範囲を見出し、本発明を完成させた。
The present inventors use Fe as a metal solvent, determine a Fe—Ir—Ru ternary phase diagram, and from this Fe—Ir—Ru ternary phase diagram, a composition range in which iridium and ruthenium can be uniformly melted into molten iron The present invention was completed.
すなわち、本発明は以下の通りである。
１．ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物。
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］
２．以下の工程（１）～（３）を含む、ルテニウムおよびイリジウムを含有する物質から該ルテニウムおよびイリジウムを回収する方法。
（１）ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物を調製する工程
（２）前記工程（１）で調製した前記回収用組成物を加熱して、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得る工程
（３）前記工程（２）で得た熔融物からルテニウムおよび／またはイリジウムを分離する工程
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］
３．前記工程（２）において、前記回収用組成物を１５５０℃以上で加熱する前記２に記載のルテニウムおよびイリジウムを回収する方法。
４．前記工程（３）において、湿式回収法により熔融物からルテニウムおよび／またはイリジウムを分離する前記２または３に記載のルテニウムおよびイリジウムを回収する方法。 That is, the present invention is as follows.
1. A composition for recovery containing ruthenium, iridium and iron, and wherein the content of ruthenium and iridium satisfies the followingformula 1.
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
2. A method for recovering ruthenium and iridium from a substance containing ruthenium and iridium, comprising the following steps (1) to (3):
(1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ≦ −1.64x + 47. 73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
3. 3. The method for recovering ruthenium and iridium according to 2, wherein the recovery composition is heated at 1550 ° C. or higher in the step (2).
4). 4. The method for recovering ruthenium and iridium as described in 2 or 3 above, wherein in the step (3), ruthenium and / or iridium is separated from the melt by a wet recovery method.
１．ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物。
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］
２．以下の工程（１）～（３）を含む、ルテニウムおよびイリジウムを含有する物質から該ルテニウムおよびイリジウムを回収する方法。
（１）ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物を調製する工程
（２）前記工程（１）で調製した前記回収用組成物を加熱して、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得る工程
（３）前記工程（２）で得た熔融物からルテニウムおよび／またはイリジウムを分離する工程
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］
３．前記工程（２）において、前記回収用組成物を１５５０℃以上で加熱する前記２に記載のルテニウムおよびイリジウムを回収する方法。
４．前記工程（３）において、湿式回収法により熔融物からルテニウムおよび／またはイリジウムを分離する前記２または３に記載のルテニウムおよびイリジウムを回収する方法。 That is, the present invention is as follows.
1. A composition for recovery containing ruthenium, iridium and iron, and wherein the content of ruthenium and iridium satisfies the following
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
2. A method for recovering ruthenium and iridium from a substance containing ruthenium and iridium, comprising the following steps (1) to (3):
(1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ≦ −1.64x + 47. 73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
3. 3. The method for recovering ruthenium and iridium according to 2, wherein the recovery composition is heated at 1550 ° C. or higher in the step (2).
4). 4. The method for recovering ruthenium and iridium as described in 2 or 3 above, wherein in the step (3), ruthenium and / or iridium is separated from the melt by a wet recovery method.
以下、本発明を、図面を参照しながらさらに詳細に説明する。
Hereinafter, the present invention will be described in more detail with reference to the drawings.
図１は、液相（鉄）中のイリジウムとルテニウムの濃度の関係を求めたグラフである。
FIG. 1 is a graph showing the relationship between the concentrations of iridium and ruthenium in the liquid phase (iron).
下記の実施例で詳述するように、当該関係は、下記式１により表すことができる。
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ As described in detail in the following examples, this relationship can be expressed by the followingformula 1.
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ As described in detail in the following examples, this relationship can be expressed by the following
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
式１を満たす範囲（Ｌｉｑｕｉｄ）は、均一融体範囲を示している。液相中のルテニウム濃度は液相中のイリジウム濃度の増加に伴い単調に減少していることが分かり、回帰分析により前記の一次関数（式１）を導き出すことができる。
The range (Liquid) that satisfies Formula 1 indicates the uniform melt range. It can be seen that the ruthenium concentration in the liquid phase monotonously decreases as the iridium concentration in the liquid phase increases, and the linear function (Equation 1) can be derived by regression analysis.
前記式１を満たすように溶鉄中のイリジウムおよびルテニウム量を調整することにより、イリジウムおよびルテニウムの均一融体を調製でき、以下で説明する回収方法を適用して、イリジウムおよびルテニウムを高純度で経済的に回収することが可能となる。
A uniform melt of iridium and ruthenium can be prepared by adjusting the amount of iridium and ruthenium in the molten iron so as to satisfy the above formula 1, and the recovery method described below can be applied to make iridium and ruthenium highly economical. Can be recovered automatically.
次に、本発明におけるルテニウムおよびイリジウムを回収する方法について説明する。
該方法は、以下の工程（１）～（３）を含む。
（１）ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物を調製する工程
（２）前記工程（１）で調製した前記回収用組成物を加熱して、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得る工程
（３）前記工程（２）で得た熔融物からルテニウムおよび／またはイリジウムを分離する工程
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ Next, a method for recovering ruthenium and iridium in the present invention will be described.
The method includes the following steps (1) to (3).
(1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ≦ −1.64x + 47. 73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
該方法は、以下の工程（１）～（３）を含む。
（１）ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物を調製する工程
（２）前記工程（１）で調製した前記回収用組成物を加熱して、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得る工程
（３）前記工程（２）で得た熔融物からルテニウムおよび／またはイリジウムを分離する工程
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ Next, a method for recovering ruthenium and iridium in the present invention will be described.
The method includes the following steps (1) to (3).
(1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ≦ −1.64x + 47. 73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
イリジウムおよびルテニウムは、ＰＧＭに属し、高融点、高耐食性に優れ、触媒としても有用であり、工業的な価値が高い。したがって、当業界ではその再利用が強く求められている。
Iridium and ruthenium belong to PGM, have a high melting point and high corrosion resistance, are useful as catalysts, and have high industrial value. Therefore, there is a strong demand for reuse in the industry.
回収すべきイリジウムおよびルテニウムを含む材料としては、とくに制限されないが、例えば、エレクトロニクス材料、スパッタに用いられるターゲットの製造時に発生する研磨・切削屑やスパッタ後の使用済みターゲットおよびターゲット装置内に該金属が付着した冶具、排ガス浄化や化学合成等に用いられる触媒等が挙げられる。
The material containing iridium and ruthenium to be recovered is not particularly limited. For example, the metal is contained in an electronic material, polishing / cutting waste generated during manufacture of a target used for sputtering, a used target after sputtering, and a target device. And a catalyst used for exhaust gas purification, chemical synthesis, and the like.
本発明の前記工程（１）では、イリジウムおよびルテニウムを含む材料の粉砕等を行い、かつ、前記式１で表される範囲にルテニウム、イリジウムおよび鉄の量を調整することにより、これら材料から回収用組成物を調製することができる。
In the step (1) of the present invention, the material containing iridium and ruthenium is pulverized, and recovered from these materials by adjusting the amount of ruthenium, iridium and iron within the range represented by the formula 1. A composition can be prepared.
本発明の前記工程（１）で調製された回収用組成物は、続く工程（２）において加熱され、ルテニウムおよびイリジウムを鉄中へ熔融させる。このときの加熱温度は、溶鉄中へのイリジウムおよびルテニウムと均一に溶融させるという理由から、１５５０℃以上が好ましく、１５５０～１７００℃がさらに好ましく、１５５０～１６５０℃がとくに好ましい。
The recovery composition prepared in the step (1) of the present invention is heated in the subsequent step (2) to melt ruthenium and iridium into iron. The heating temperature at this time is preferably 1550 ° C. or higher, more preferably 1550 to 1700 ° C., and particularly preferably 1550 to 1650 ° C. for the reason of uniformly melting iridium and ruthenium in the molten iron.
本発明の前記工程（２）で得られた熔融物は、続く工程（３）においてルテニウムおよび／またはイリジウムが分離される。分離方法としては、例えば、熔融物の冷却固体を王水等で溶解させ、鉄溶解液とルテニウムおよびイリジウムを分離する方法、および塩酸／塩素などの酸性液に溶融物の冷却固体を湿式溶解させ、その溶解液から溶媒抽出、還元による固液分離、電解または吸着剤による分離等により鉄、ルテニウムおよびイリジウムの夫々を固体若しくは液体として捕集分離する方法等の湿式処理による回収方法が挙げられる。
In the melt obtained in the step (2) of the present invention, ruthenium and / or iridium are separated in the subsequent step (3). Separation methods include, for example, a method in which a molten solid in a melt is dissolved in aqua regia, etc., and an iron solution and ruthenium and iridium are separated, and a molten solid in a melt is wet-dissolved in an acidic liquid such as hydrochloric acid / chlorine. Examples of the recovery method include wet extraction such as a method in which each of iron, ruthenium and iridium is collected and separated as a solid or liquid by solvent extraction, solid-liquid separation by reduction, electrolysis or separation by an adsorbent from the solution.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。
Hereinafter, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.
実施例１～１１、比較例１～４および参考例１～４
ルテニウム粉、イリジウム粉および鉄粉を表１に記載の組成となるように秤量し配合した。試料の全量は５ｇとした。配合した試料をＡｌ２Ｏ３ルツボに入れ、電気炉内で表１に記載の各種温度で２４時間保持後、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得た。 Examples 1 to 11, Comparative Examples 1 to 4 and Reference Examples 1 to 4
Ruthenium powder, iridium powder and iron powder were weighed and blended so as to have the composition shown in Table 1. The total amount of the sample was 5 g. The blended sample was placed in an Al 2 O 3 crucible and held at various temperatures shown in Table 1 for 24 hours in an electric furnace, and then a melt in which ruthenium and iridium were melted into iron was obtained.
ルテニウム粉、イリジウム粉および鉄粉を表１に記載の組成となるように秤量し配合した。試料の全量は５ｇとした。配合した試料をＡｌ２Ｏ３ルツボに入れ、電気炉内で表１に記載の各種温度で２４時間保持後、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得た。 Examples 1 to 11, Comparative Examples 1 to 4 and Reference Examples 1 to 4
Ruthenium powder, iridium powder and iron powder were weighed and blended so as to have the composition shown in Table 1. The total amount of the sample was 5 g. The blended sample was placed in an Al 2 O 3 crucible and held at various temperatures shown in Table 1 for 24 hours in an electric furnace, and then a melt in which ruthenium and iridium were melted into iron was obtained.
次に電気炉から熔融物を取り出し、大気中において、アルゴンガスを２～３（Ｌ／ｍｉｎ）で熔融物に直接吹きかけ、６００℃以下程度まで冷却し、その後大気中で室温まで放冷した。この冷却後の組織観察を行った。該組織観察は、ＥＰＭＡ（Ｅｌｅｃｔｒｏｎ Ｐｒｏｂｅ Ｍｉｃｒｏ Ａｎａｌｙｚｅｒ）を用いて行なった。
Next, the melt was taken out from the electric furnace, and in the atmosphere, argon gas was blown directly onto the melt at 2 to 3 (L / min), cooled to about 600 ° C. or less, and then allowed to cool to room temperature in the atmosphere. The structure was observed after cooling. The tissue observation was performed using EPMA (Electron Probe Micro Analyzer).
組織観察の評価は、ルテニウム、イリジウムおよび鉄が回収に適した均一に熔融している状態が確認できるものを○、ルテニウムおよびイリジウムの固体が一部析出し、回収に適さない不均一に熔融しているものを×とした。結果を表１に示す。また、実施例１および３の試料のＥＰＭＡによる組織観察写真を図２（ａ）および図２（ｂ）に、比較例３の試料のＥＰＭＡによる組織観察写真を図２（ｃ）に示す。
In the evaluation of the structure observation, the ruthenium, iridium and iron were confirmed to be in a homogeneously melted state suitable for recovery, and some solids of ruthenium and iridium were precipitated and melted unevenly unsuitable for recovery. What is being marked as x. The results are shown in Table 1. Moreover, the structure observation photograph by EPMA of the sample of Example 1 and 3 is shown to Fig.2 (a) and FIG.2 (b), and the structure observation photograph by EPMA of the sample of the comparative example 3 is shown in FIG.2 (c).
表１および図１の結果から、本発明で規定する式１を満たす回収用組成物を用いた各実施例は、ルテニウム、イリジウムおよび鉄が回収に適した均一に熔融している状態が確認できたのに対し、式１を満たさない各比較例では、ルテニウムおよびイリジウムの固体が一部析出し、回収に適さない不均一に熔融していることが確認された。
From the results of Table 1 and FIG. 1, in each Example using the recovery composition satisfying Formula 1 defined in the present invention, it can be confirmed that ruthenium, iridium and iron are uniformly melted suitable for recovery. On the other hand, in each comparative example not satisfying the formula 1, it was confirmed that a part of the ruthenium and iridium solids were precipitated and melted non-uniformly suitable for recovery.
図１は、前記各実施例、比較例および参考例の各データをプロットおよび式１を示したグラフである。
FIG. 1 is a graph showing plots and Formula 1 for each data of the above Examples, Comparative Examples, and Reference Examples.
イリジウムの含有率をＸ１、ルテニウムの含有率をＸ２、組織観察結果をＹ、組織観察結果の○評価をＹ＝１、×評価をＹ＝－１とし重回帰分析を行うと下記の判別式（式２）が得られる。
Ｙ＝－０．１１７３Ｘ１＋（－０．０７１５）Ｘ２＋３．４１２８（式２） When multiple regression analysis is performed with an iridium content of X 1 , a ruthenium content of X 2 , a structure observation result of Y, a structure observation result of ◯ evaluation of Y = 1, and an x evaluation of Y = −1, the following discrimination is made: Equation (Equation 2) is obtained.
Y = −0.1173X 1 + (− 0.0715) X 2 +3.4128 (Formula 2)
Ｙ＝－０．１１７３Ｘ１＋（－０．０７１５）Ｘ２＋３．４１２８（式２） When multiple regression analysis is performed with an iridium content of X 1 , a ruthenium content of X 2 , a structure observation result of Y, a structure observation result of ◯ evaluation of Y = 1, and an x evaluation of Y = −1, the following discrimination is made: Equation (Equation 2) is obtained.
Y = −0.1173X 1 + (− 0.0715) X 2 +3.4128 (Formula 2)
得られた判別式は、Ｙ≧０であるとき組織観察の評価が○、Ｙ＜０であるとき組織観察評価が×になることを示す式である。すなわち、本発明の効果を得るためのＹ≧０においては、イリジウム含有率とルテニウム含有率との関数式は下記の式３となる。
０≦－０．１１７３Ｘ１＋（－０．０７１５）Ｘ２＋３．４１２８（式３） The obtained discriminant is an equation indicating that the evaluation of the tissue observation is “good” when Y ≧ 0 and the evaluation of the tissue observation becomes “x” when Y <0. That is, in Y ≧ 0 for obtaining the effect of the present invention, a functional expression of the iridium content and the ruthenium content is expressed by the following expression 3.
0 ≦ −0.1173X 1 + (− 0.0715) X 2 +3.4128 (Formula 3)
０≦－０．１１７３Ｘ１＋（－０．０７１５）Ｘ２＋３．４１２８（式３） The obtained discriminant is an equation indicating that the evaluation of the tissue observation is “good” when Y ≧ 0 and the evaluation of the tissue observation becomes “x” when Y <0. That is, in Y ≧ 0 for obtaining the effect of the present invention, a functional expression of the iridium content and the ruthenium content is expressed by the following expression 3.
0 ≦ −0.1173X 1 + (− 0.0715) X 2 +3.4128 (Formula 3)
よって、イリジウム含有率（ｘ）とルテニウム含有率（ｙ）との関数式は、式３中のＸ１＝ｘ、Ｘ２＝ｙであるから下記の式１となる。
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ Therefore, since the functional expressions of the iridium content (x) and the ruthenium content (y) are X 1 = x and X 2 = y in Expression 3, the followingExpression 1 is obtained.
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ Therefore, since the functional expressions of the iridium content (x) and the ruthenium content (y) are X 1 = x and X 2 = y in Expression 3, the following
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ]
これとは別に、図１の結果から、溶鉄中にイリジウムおよびルテニウムの均一融体を得るためには、図３に示したように、イリジウムおよびルテニウムの含有率を、Ｉｒ０質量％およびＲｕ３９質量％の点１、Ｉｒ１０質量％およびＲｕ３０質量％の点２、Ｉｒ１８質量％およびＲｕ１６質量％の点３、Ｉｒ２２質量％およびＲｕ１０質量％の点４、Ｉｒ２３質量％およびＲｕ５質量％の点５、Ｉｒ２６質量％およびＲｕ０質量％の点６および原点によって囲まれる領域（ただし、Ｉｒおよび／またはＲｕが０質量％である点を除く）に設定することにより達成されるとも言える。
Apart from this, in order to obtain a uniform melt of iridium and ruthenium in the molten iron from the results of FIG. 1, as shown in FIG. 3, the contents of iridium and ruthenium are set to Ir 0 mass% and Ru 39 mass%. Point 1, Ir 10 mass% and Ru 30 mass% point 2, Ir 18 mass% and Ru 16 mass% point 3, Ir 22 mass% and Ru 10 mass% point 4, Ir 23 mass% and Ru 5 mass% point 5, Ir 26 mass It can also be said that this is achieved by setting the area surrounded by the point 6 and the origin of% and Ru 0 mass% (except for the point where Ir and / or Ru is 0 mass%).
実施例１２
実施例１で得られたルテニウム、イリジウムおよび鉄の均一熔融固体をその体積の１０倍量の王水により溶解させ、鉄とルテニウムおよびイリジウム含有液体とした。均一溶融固体の液化率は９５％であった。液化されたルテニウムおよびイリジウムは、溶媒抽出、還元による固液分離、電解や吸着剤による分離等の常法によりルテニウム、イリジウムにそれぞれ分離し回収された。 Example 12
The uniformly melted solid of ruthenium, iridium and iron obtained in Example 1 was dissolved in 10 times the volume of aqua regia to obtain a liquid containing iron, ruthenium and iridium. The liquefaction rate of the uniformly molten solid was 95%. Liquefied ruthenium and iridium were separated and recovered as ruthenium and iridium by conventional methods such as solvent extraction, solid-liquid separation by reduction, separation by electrolysis and adsorbent, and the like.
実施例１で得られたルテニウム、イリジウムおよび鉄の均一熔融固体をその体積の１０倍量の王水により溶解させ、鉄とルテニウムおよびイリジウム含有液体とした。均一溶融固体の液化率は９５％であった。液化されたルテニウムおよびイリジウムは、溶媒抽出、還元による固液分離、電解や吸着剤による分離等の常法によりルテニウム、イリジウムにそれぞれ分離し回収された。 Example 12
The uniformly melted solid of ruthenium, iridium and iron obtained in Example 1 was dissolved in 10 times the volume of aqua regia to obtain a liquid containing iron, ruthenium and iridium. The liquefaction rate of the uniformly molten solid was 95%. Liquefied ruthenium and iridium were separated and recovered as ruthenium and iridium by conventional methods such as solvent extraction, solid-liquid separation by reduction, separation by electrolysis and adsorbent, and the like.
比較例５
比較例３で得られたルテニウム、イリジウムおよび鉄の不均一溶融固体を用いたこと以外は実施例１２と同様に試験したところ、不均一熔融固体中のイリジウム、ルテニウムの液化率は７０％であった。 Comparative Example 5
A test was conducted in the same manner as in Example 12 except that the heterogeneous molten solid of ruthenium, iridium and iron obtained in Comparative Example 3 was used. The liquefaction rate of iridium and ruthenium in the heterogeneous molten solid was 70%. It was.
比較例３で得られたルテニウム、イリジウムおよび鉄の不均一溶融固体を用いたこと以外は実施例１２と同様に試験したところ、不均一熔融固体中のイリジウム、ルテニウムの液化率は７０％であった。 Comparative Example 5
A test was conducted in the same manner as in Example 12 except that the heterogeneous molten solid of ruthenium, iridium and iron obtained in Comparative Example 3 was used. The liquefaction rate of iridium and ruthenium in the heterogeneous molten solid was 70%. It was.
実施例１３
実施例１に記載の組成物に、その組成物総質量に対し酸化アルミニウム（以下、「アルミナ」という）粉を１０質量％加え、電気炉から熔融物を取り出す際に上層のアルミナ固体と下層の溶融物とを分離し溶融物を取り出したこと以外は実施例１と同様に試験を行った。その結果、ＥＰＭＡによる組織観察でルテニウム、イリジウムおよび鉄の均一熔融固体が得られたことを確認した。 Example 13
To the composition described in Example 1, 10% by mass of aluminum oxide (hereinafter referred to as “alumina”) powder is added to the total mass of the composition, and when the melt is taken out from the electric furnace, the upper alumina solid and the lower layer The test was performed in the same manner as in Example 1 except that the melt was separated and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
実施例１に記載の組成物に、その組成物総質量に対し酸化アルミニウム（以下、「アルミナ」という）粉を１０質量％加え、電気炉から熔融物を取り出す際に上層のアルミナ固体と下層の溶融物とを分離し溶融物を取り出したこと以外は実施例１と同様に試験を行った。その結果、ＥＰＭＡによる組織観察でルテニウム、イリジウムおよび鉄の均一熔融固体が得られたことを確認した。 Example 13
To the composition described in Example 1, 10% by mass of aluminum oxide (hereinafter referred to as “alumina”) powder is added to the total mass of the composition, and when the melt is taken out from the electric furnace, the upper alumina solid and the lower layer The test was performed in the same manner as in Example 1 except that the melt was separated and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
実施例１４
実施例１に記載の組成物に、その組成物総質量に対しアルミナ粉および二酸化ケイ素（以下、「シリカ」という）粉を各々５質量％ずつ加え、電気炉から熔融物を取り出す際に上層のアルミナおよびシリカ固体と下層の溶融物とを分離し溶融物を取り出したこと以外は実施例１と同様に試験を行った。その結果、ＥＰＭＡによる組織観察でルテニウム、イリジウムおよび鉄の均一熔融固体が得られたことを確認した。 Example 14
When 5 mass% each of alumina powder and silicon dioxide (hereinafter referred to as “silica”) powder is added to the composition described in Example 1 with respect to the total mass of the composition, and the melt is taken out from the electric furnace, The test was performed in the same manner as in Example 1 except that the alumina and silica solids were separated from the lower layer melt and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
実施例１に記載の組成物に、その組成物総質量に対しアルミナ粉および二酸化ケイ素（以下、「シリカ」という）粉を各々５質量％ずつ加え、電気炉から熔融物を取り出す際に上層のアルミナおよびシリカ固体と下層の溶融物とを分離し溶融物を取り出したこと以外は実施例１と同様に試験を行った。その結果、ＥＰＭＡによる組織観察でルテニウム、イリジウムおよび鉄の均一熔融固体が得られたことを確認した。 Example 14
When 5 mass% each of alumina powder and silicon dioxide (hereinafter referred to as “silica”) powder is added to the composition described in Example 1 with respect to the total mass of the composition, and the melt is taken out from the electric furnace, The test was performed in the same manner as in Example 1 except that the alumina and silica solids were separated from the lower layer melt and the melt was taken out. As a result, it was confirmed by observation of the structure with EPMA that a homogeneous molten solid of ruthenium, iridium and iron was obtained.
本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。
なお、本出願は、２０１３年９月２日付けで出願された日本特許出願（特願２０１３－１８１３２７）に基づいており、その全体が引用により援用される。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Note that this application is based on a Japanese patent application filed on September 2, 2013 (Japanese Patent Application No. 2013-181327), which is incorporated by reference in its entirety.
なお、本出願は、２０１３年９月２日付けで出願された日本特許出願（特願２０１３－１８１３２７）に基づいており、その全体が引用により援用される。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Note that this application is based on a Japanese patent application filed on September 2, 2013 (Japanese Patent Application No. 2013-181327), which is incorporated by reference in its entirety.
Claims (4)
- ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物。
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ A composition for recovery containing ruthenium, iridium and iron, and wherein the content of ruthenium and iridium satisfies the following formula 1.
y ≦ −1.64x + 47.73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ] - 以下の工程（１）～（３）を含む、ルテニウムおよびイリジウムを含有する物質から該ルテニウムおよびイリジウムを回収する方法。
（１）ルテニウム、イリジウムおよび鉄を含み、且つ前記ルテニウムおよびイリジウムの含有率が、下記式１を満たす回収用組成物を調製する工程
（２）前記工程（１）で調製した前記回収用組成物を加熱して、ルテニウムおよびイリジウムを鉄中へ熔融させた熔融物を得る工程
（３）前記工程（２）で得た熔融物からルテニウムおよび／またはイリジウムを分離する工程
ｙ≦－１．６４ｘ＋４７．７３ （式１）
［ただし、ｙはルテニウム、イリジウムおよび鉄の総量に対するルテニウム含有率（質量％）であり、ｘはルテニウム、イリジウムおよび鉄の総量に対するイリジウム含有率（質量％）であり、ｘ＞０かつｙ＞０である。］ A method for recovering ruthenium and iridium from a substance containing ruthenium and iridium, comprising the following steps (1) to (3):
(1) Step of preparing a recovery composition containing ruthenium, iridium and iron, and a content of the ruthenium and iridium satisfying the following formula 1 (2) The recovery composition prepared in the step (1) To obtain a melt obtained by melting ruthenium and iridium into iron (3) A step of separating ruthenium and / or iridium from the melt obtained in the step (2) y ≦ −1.64x + 47. 73 (Formula 1)
[Wherein y is the ruthenium content (mass%) with respect to the total amount of ruthenium, iridium and iron, x is the iridium content (mass%) with respect to the total amount of ruthenium, iridium and iron, and x> 0 and y> 0 It is. ] - 前記工程（２）において、前記回収用組成物を１５５０℃以上で加熱する請求項２に記載のルテニウムおよびイリジウムを回収する方法。 The method for recovering ruthenium and iridium according to claim 2, wherein, in the step (2), the recovery composition is heated at 1550 ° C or higher.
- 前記工程（３）において、湿式回収法により熔融物からルテニウムおよび／またはイリジウムを分離する請求項２または３に記載のルテニウムおよびイリジウムを回収する方法。 The method for recovering ruthenium and iridium according to claim 2 or 3, wherein in the step (3), ruthenium and / or iridium is separated from the melt by a wet recovery method.
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| JP2001064734A (en) * | 1999-08-27 | 2001-03-13 | Nikko Materials Co Ltd | Recovery of iridium |
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| JP5277652B2 (en) * | 2008-02-08 | 2013-08-28 | 新日鐵住金株式会社 | Method for recovering metals from scrap copper |
| AU2012213020A1 (en) * | 2011-02-03 | 2013-08-22 | Western Platinum Ltd | Refining of Platinum Group Metals concentrates |
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| Title |
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| RYO TAGAWA ET AL.: "Fe-Ir-Ru-kei Sangenkei Jotaizu ni Motozuita Iridium to Ruthenium no Yoyu Shori", SHIGEN . SOZAI 2013 (SAPPORO) KOEN SHIRYO, IPPAN SHADAN HOJIN SHIRYO . SOZAI GAKKAI, 3 September 2013 (2013-09-03), pages 353, 354 * |
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