JP2009028653A - Method of recovering catalytic metal - Google Patents
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- JP2009028653A JP2009028653A JP2007195673A JP2007195673A JP2009028653A JP 2009028653 A JP2009028653 A JP 2009028653A JP 2007195673 A JP2007195673 A JP 2007195673A JP 2007195673 A JP2007195673 A JP 2007195673A JP 2009028653 A JP2009028653 A JP 2009028653A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 61
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 61
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000000446 fuel Substances 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011669 selenium Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- 229910052697 platinum Inorganic materials 0.000 description 14
- 150000003624 transition metals Chemical class 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000005518 polymer electrolyte Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004770 chalcogenides Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019887 RuMo Inorganic materials 0.000 description 1
- 229910019851 Ru—Se Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
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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
- 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
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—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
- 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
- C22B3/065—Nitric acids or salts thereof
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/008—Disposal or recycling of fuel cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
Description
本発明は、燃料電池用電極触媒などのカルコゲン元素含有触媒からの触媒金属回収方法に関する。特に、白金触媒の代替となる、少なくとも１種の遷移金属元素と少なくとも１種のカルコゲン元素からなる燃料電池用電極触媒からＳＯｘなどの有毒ガスを発生させることの無い触媒金属回収方法に関する。 The present invention relates to a method for recovering catalytic metal from a chalcogen element-containing catalyst such as a fuel cell electrode catalyst. In particular, the present invention relates to a catalytic metal recovery method that does not generate a toxic gas such as SOx from an electrode catalyst for a fuel cell, which is an alternative to a platinum catalyst and includes at least one transition metal element and at least one chalcogen element.
固体高分子型燃料電池には電極触媒として、一般に白金等の高価な貴金属類が用いられている。そこで、貴金属等の触媒金属をリサイクルすることが考えられている。例えば、下記特許文献１には、含フッ素ポリマーを溶解する溶媒中で、燃料電池用イオン交換膜／電極接合体の溶解処理を行い、該含フッ素ポリマー溶液と触媒金属を含む不溶物部分とに分離し、回収された含フッ素ポリマーを、イオン交換膜および／または電極触媒被覆剤として再利用する方法が開示されている。又、触媒金属の回収方法として、触媒金属を担持した導電性担体を含む不溶物部分に、燃焼または王水処理を施すことが開示されている。 In the polymer electrolyte fuel cell, an expensive noble metal such as platinum is generally used as an electrode catalyst. Therefore, it is considered to recycle catalyst metals such as noble metals. For example, in Patent Document 1 below, the ion-exchange membrane / electrode assembly for a fuel cell is dissolved in a solvent that dissolves the fluorine-containing polymer, and the fluorine-containing polymer solution and the insoluble part containing the catalyst metal are separated. A method of recycling the separated and recovered fluorine-containing polymer as an ion exchange membrane and / or an electrocatalyst coating agent is disclosed. In addition, as a method for recovering a catalyst metal, it is disclosed that an insoluble part including a conductive carrier carrying a catalyst metal is subjected to combustion or aqua regia treatment.
本出願人は、下記特許文献２〜４に、使用済み燃料電池から触媒金属と、同じく高価で有用な材料であるスルホン酸基を有する含フッ素ポリマーを回収する方法を発明したが、いずれも触媒金属の具体的回収方法は、触媒金属を担持した導電性担体を含む不溶物部分を燃焼させてカーボンなどの担体を除去するか、又は該不溶物部分に王水処理を施すことによりカーボンなどの担体を酸化・除去して、触媒金属を回収するものである。 The present applicants invented a method for recovering a catalyst metal and a fluorine-containing polymer having a sulfonic acid group, which is also an expensive and useful material, from spent fuel cells in Patent Documents 2 to 4 below. A specific method for recovering a metal is to remove a carrier such as carbon by burning an insoluble part including a conductive carrier carrying a catalyst metal, or by applying aqua regia treatment to the insoluble part. The catalyst is recovered by oxidizing and removing the support.
下記特許文献１〜４に開示された触媒金属は、いずれも白金や白金合金を対象とするものであり、カルコゲン元素含有触媒（カルコゲナイド系触媒）からの触媒金属回収方法に関するものではない。仮に、カルコゲン元素含有触媒（カルコゲナイド系触媒）からの触媒金属回収に、上記のような、触媒金属を担持した導電性担体を含む不溶物部分を燃焼させるか、又は該不溶物部分に王水処理を施したとすると、回収時にＣＯ２と同時に有毒ガスであるＳＯｘなどのカルコゲン元素の酸化物が発生するという問題がある。 The catalyst metals disclosed in the following Patent Documents 1 to 4 are all directed to platinum and platinum alloys, and are not related to a method for recovering a catalyst metal from a chalcogen element-containing catalyst (chalcogenide catalyst). Temporarily, in the recovery of the catalytic metal from the chalcogen element-containing catalyst (chalcogenide-based catalyst), the insoluble matter portion containing the conductive carrier supporting the catalytic metal as described above is burned, or the insoluble matter portion is treated with aqua regia. When subjected to, oxides of chalcogen elements such as SOx is CO 2 at the same time toxic gases is a problem that occurs during recovery.
ところで、高分子電解質型燃料電池のアノード用触媒としては主として白金や白金合金系触媒が用いられることは上述の通りである。具体的には、白金を含む貴金属をカーボンブラックに担持した触媒が用いられてきた。高分子電解質型燃料電池を実用化する上での課題の一つは、材料コストである。これを解決する手段の一つが白金量の低減である。 By the way, as described above, platinum or a platinum alloy-based catalyst is mainly used as the anode catalyst of the polymer electrolyte fuel cell. Specifically, a catalyst in which a noble metal including platinum is supported on carbon black has been used. One of the problems in putting a polymer electrolyte fuel cell into practical use is material cost. One means for solving this is to reduce the amount of platinum.
一方、酸素（Ｏ２）を電解還元すると、１電子還元ではスーパーオキシドが生成し、２電子還元では過酸化水素が生成し、４電子還元では水が生成することが知られている。電極として白金や白金系触媒を用いた燃料電池セルスタックでは、何らかの原因で電圧低下が生じると、４電子還元性が低下し、２電子還元性となってしまう。このため、過酸化水素を発生し、ＭＥＡの劣化の原因となっていた。 On the other hand, it is known that when oxygen (O 2 ) is electrolytically reduced, superoxide is generated by one-electron reduction, hydrogen peroxide is generated by two-electron reduction, and water is generated by four-electron reduction. In a fuel cell stack using platinum or a platinum-based catalyst as an electrode, if a voltage drop occurs for some reason, the 4-electron reducibility is reduced and the 2-electron reducibility is obtained. For this reason, hydrogen peroxide is generated, which causes deterioration of MEA.
最近、酸素を４電子還元して水を生成させる反応により、高価な白金触媒を必要としない低コスト型の燃料電池触媒の開発が行われている。下記非特許文献１には、カルコゲン元素を有する触媒が４電子還元性に優れていることが開示され、燃料電池への適用も示唆されている。 Recently, a low-cost fuel cell catalyst that does not require an expensive platinum catalyst has been developed by a reaction in which oxygen is reduced by four electrons to generate water. Non-Patent Document 1 below discloses that a catalyst having a chalcogen element is excellent in 4-electron reducibility and suggests application to a fuel cell.
同様に、下記特許文献５には、白金代替触媒として、少なくとも１種の遷移金属及びカルコゲンからなる電極触媒であって、該遷移金属としてＲｕ、カルコゲンとしてＳ又はＳｅからなる電極触媒が開示されている。ここで、Ｒｕ：Ｓｅのモル比が０．５〜２の範囲であり、且つ（Ｒｕ）ｎＳｅの化学量論数ｎが１．５〜２である旨が開示されている。 Similarly, Patent Document 5 below discloses an electrode catalyst composed of at least one transition metal and a chalcogen as a platinum substitute catalyst, wherein Ru is used as the transition metal, and S or Se is used as the chalcogen. Yes. Here, it is disclosed that the Ru: Se molar ratio is in the range of 0.5 to 2 and the stoichiometric number n of (Ru) nSe is 1.5 to 2.
また、下記特許文献６には、Ｐｔ代替触媒として、Ｆｅ又はＲｕから選択される遷移金属と、窒素含有有機金属遷移錯体、及びＳ等のカルコゲン成分を有する燃料電池用触媒材料が開示されている。 Patent Document 6 below discloses a fuel cell catalyst material having a transition metal selected from Fe or Ru, a nitrogen-containing organometallic transition complex, and a chalcogen component such as S as a Pt substitute catalyst. .
また、下記非特許文献１には、Ｍｏ−Ｒｕ−Ｓｅ三元系電極触媒、及びその合成方法が開示されている。 Non-Patent Document 1 below discloses a Mo—Ru—Se ternary electrode catalyst and a synthesis method thereof.
更に、下記非特許文献２には、Ｒｕ−Ｓ、Ｍｏ−Ｓ、Ｍｏ−Ｒｕ−Ｓの二元系及び三元系電極触媒、及びその合成方法が開示されている。 Furthermore, Non-Patent Document 2 below discloses Ru-S, Mo-S, Mo-Ru-S binary and ternary electrode catalysts, and a synthesis method thereof.
更に、下記非特許文献３には、Ｒｕ−Ｍｏ−Ｓ、Ｒｕ−Ｍｏ−Ｓｅの三元系カルコゲナイド電極触媒が開示されている。 Further, Non-Patent Document 3 below discloses Ru—Mo—S and Ru—Mo—Se ternary chalcogenide electrode catalysts.
本発明は、使用済みのカルコゲン元素含有触媒から、カルコゲン元素含有触媒の構成成分である触媒金属を無公害的に回収することで、稀少且つ高価な触媒金属を効率的に再利用することを目的とする。 An object of the present invention is to efficiently recycle rare and expensive catalyst metals by recovering the catalyst metals, which are constituent components of the chalcogen element-containing catalyst, from the used chalcogen element-containing catalyst in a pollution-free manner. And
本発明者は、従来の熱い王水を用いて使用済み触媒から直接炭素成分を除去する方法に代わる新たな方法で、使用済み触媒から先ずカルコゲン元素成分を除去する方法によって上記課題が解決されることを見出し、本発明に到達した。 The present inventor solves the above-mentioned problems by a method of first removing a chalcogen element component from a used catalyst, which is a new method instead of a conventional method of directly removing a carbon component from a used catalyst using hot aqua regia. The present invention has been found.
即ち、第１に、本発明は、カルコゲン元素含有触媒からの触媒金属回収方法の発明であって、該電極触媒を水素含有不活性ガス中で加熱して該電極触媒中のカルコゲン元素を除去するカルコゲン元素成分除去工程を含むことを特徴とする。 That is, first, the present invention is an invention of a method for recovering a catalytic metal from a chalcogen element-containing catalyst, wherein the electrode catalyst is heated in a hydrogen-containing inert gas to remove the chalcogen element in the electrode catalyst. It includes a chalcogen element component removing step.
本発明の触媒金属回収方法を採用することにより、ＳＯｘなどのカルコゲン元素酸化物が発生しないで、カルコゲン元素含有触媒に含まれるカルコゲン元素を容易に且つ安全に除去することができる。 By employing the catalytic metal recovery method of the present invention, chalcogen elements contained in the chalcogen element-containing catalyst can be easily and safely removed without generating chalcogen element oxides such as SOx.
本発明では、前記カルコゲン元素成分除去工程の後に、該電極触媒を熱い王水に浸漬して炭素成分を除去する炭素成分除去工程を含むことが好ましい。カルコゲン元素成分除去工程と炭素成分除去工程を連続させることで、カルコゲン元素含有触媒に含まれるカルコゲン元素と、同様にカルコゲン元素含有触媒に含まれる炭素成分を除去することができ、後工程で有用な金属成分の回収が容易になる。 In the present invention, it is preferable to include a carbon component removal step of removing the carbon component by immersing the electrode catalyst in hot aqua regia after the chalcogen element component removal step. By continuing the chalcogen element component removal step and the carbon component removal step, the chalcogen element contained in the chalcogen element-containing catalyst and the carbon component contained in the chalcogen element-containing catalyst can be removed, which is useful in subsequent steps. Recovery of metal components is facilitated.
金属成分の回収は、前記炭素成分除去工程の後に、該王水に溶解した金属成分を回収するとともに、該王水に溶解しない沈殿物から他の金属成分を回収する工程を行うことが好ましい。なお、王水（おうすい）とは、濃塩酸と濃硝酸とを３：１の体積比で混合した液体であり、特に熱した王水は、酸化力が強く、通常の酸には溶けない遷移金属も溶解できる。 The metal component is preferably recovered after the carbon component removing step by recovering the metal component dissolved in the aqua regia and recovering another metal component from the precipitate not dissolved in the aqua regia. In addition, aqua regia is a liquid in which concentrated hydrochloric acid and concentrated nitric acid are mixed at a volume ratio of 3: 1. Particularly, heated aqua regia has strong oxidizing power and does not dissolve in ordinary acids. Transition metals can also be dissolved.
具体的な、前記王水に溶解した金属成分を回収する工程としては、ゼオライトなどの吸着剤に金属成分を吸着させる方法が好ましく例示される。 A specific example of the step of recovering the metal component dissolved in the aqua regia is preferably a method of adsorbing the metal component on an adsorbent such as zeolite.
本発明の触媒金属回収方法は、使用済みのカルコゲン元素含有触媒を広く対象とすることができる。この中で、カルコゲン元素含有触媒として、固体高分子型燃料電池用に白金代替触媒として注目されている、カルコゲン元素含有燃料電池用電極触媒が好適である。 The catalytic metal recovery method of the present invention can be used widely for used chalcogen element-containing catalysts. Among these, as the chalcogen element-containing catalyst, an electrode catalyst for a chalcogen element-containing fuel cell that is attracting attention as a platinum substitute catalyst for a polymer electrolyte fuel cell is suitable.
前記カルコゲン元素含有燃料電池用電極触媒としては、カーボンブラックなどの導電性担体に、少なくとも１種の遷移金属元素（Ｍ）と少なくとも１種のカルコゲン元素（Ｘ）とが担持された燃料電池用電極触媒が挙げられる。 As the electrode catalyst for a chalcogen element-containing fuel cell, an electrode for a fuel cell in which at least one transition metal element (M) and at least one chalcogen element (X) are supported on a conductive carrier such as carbon black. A catalyst is mentioned.
遷移金属元素（Ｍ）としては、ルテニウム（Ｒｕ）、モリブデン（Ｍｏ）、オスニウム（Ｏｓ）、コバルト（Ｃｏ）、ロジウム（Ｒｈ）、イリジウム（Ｉｒ）、鉄（Ｆｅ）、ニッケル（Ｎｉ）、チタン（Ｔｉ）、及びタングステン（Ｗ）から選択される１種以上が好ましく例示され、カルコゲン元素（Ｘ）としては、イオウ（Ｓ）、セレン（Ｓｅ）、及びテルル（Ｔｅ）から選択される１種以上が好ましく例示される。 Examples of transition metal elements (M) include ruthenium (Ru), molybdenum (Mo), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), iron (Fe), nickel (Ni), and titanium. One or more selected from (Ti) and tungsten (W) are preferably exemplified, and the chalcogen element (X) is selected from sulfur (S), selenium (Se), and tellurium (Te). The above is preferably exemplified.
これらの中で、遷移金属元素（Ｍ）がルテニウム（Ｒｕ）及びモリブデン（Ｍｏ）であり、カルコゲン元素（Ｘ）がイオウ（Ｓ）である触媒金属がカーボン材料に担持されたＲｕ−Ｍｏ−Ｓ／Ｃが好ましく例示される。 Among these, the transition metal element (M) is ruthenium (Ru) and molybdenum (Mo), and the catalytic metal whose chalcogen element (X) is sulfur (S) is supported on a carbon material. / C is preferably exemplified.
使用済みのカルコゲン元素含有触媒から、カルコゲン元素含有触媒の構成成分である触媒金属を無公害的に回収することで、稀少且つ高価な触媒金属を効率的に再利用することが可能となる。特に、白金触媒の代替となりうるカルコゲン元素含有燃料電池用電極触媒に適用することで、貴重な遷移金属等のリサイクルが促進される。 By recovering the catalytic metal, which is a component of the chalcogen element-containing catalyst, from the used chalcogen element-containing catalyst in a non-polluting manner, it is possible to efficiently reuse a rare and expensive catalytic metal. In particular, when applied to an electrode catalyst for a chalcogen element-containing fuel cell that can be used as a substitute for a platinum catalyst, recycling of a valuable transition metal or the like is promoted.
以下、実施例によって本発明をさらに詳細に説明する。
図１に、本実施例の金属回収のフロー図を示す。
カルコゲン元素含有触媒として、白金代替触媒として注目されるＲｕＭｏＳ／Ｃ触媒を用いた。カーボン担体としてＫｅｔｊｅｎ Ｂｌａｃｋ（商標名）を用い、ルテニウムカルボニル、モリブデンカルボニル、イオウをアルゴン中で１４０℃で加熱し、冷却の後、アセトンで洗浄し、ろ過をする。ろ過物であるＲｕＭｏＳ／Ｃを３５０℃で２時間焼成してＲｕＭｏＳ／Ｃ触媒を調整した。
Hereinafter, the present invention will be described in more detail with reference to examples.
FIG. 1 shows a flow chart of metal recovery of this example.
As the chalcogen element-containing catalyst, a RuMoS / C catalyst which is attracting attention as a platinum substitute catalyst was used. Using Ketjen Black (trade name) as a carbon support, ruthenium carbonyl, molybdenum carbonyl, and sulfur are heated in argon at 140 ° C., cooled, washed with acetone, and filtered. RuMoS / C as a filtrate was calcined at 350 ° C. for 2 hours to prepare a RuMoS / C catalyst.
なお、使用済みのＲｕＭｏＳ／Ｃ触媒をＭＥＡから分離するには、例えば、加熱メタノールを用いて溶解し、遠心分離などで分離する。この際、高分子電解質や補強材料として用いられていた含フッ素ポリマーは分離する。 In order to separate the used RuMoS / C catalyst from the MEA, for example, it is dissolved using heated methanol and separated by centrifugation or the like. At this time, the fluorine-containing polymer used as a polymer electrolyte or a reinforcing material is separated.
従来技術のように、ＲｕＭｏＳ／Ｃに対して直接熱い王水によって炭素成分の除去を図るとＣＯ２とともに有害なＳＯｘが発生して好ましくない。又、ＲｕＭｏＳ／Ｃに対して燃料電池処理を行うと揮発性のＲｕ酸化物が飛散するという問題もある。 If the carbon component is removed by aqua regia directly hot against RuMoS / C as in the prior art, harmful SOx is generated together with CO 2 , which is not preferable. Further, when a fuel cell process is performed on RuMoS / C, there is a problem that volatile Ru oxides are scattered.
そこで、本実施例では、ＲｕＭｏＳ／ＣをＨ２ガスとＮ２などの不活性ガスの混合ガス中で例えば４００℃に加熱してＳ成分を除去してＲｕＭｏ／Ｃとする（カルコゲン元素成分除去工程）。これにより、ＳＯｘなどのカルコゲン元素酸化物が発生しないで、カルコゲン元素含有触媒に含まれるカルコゲン元素を容易に且つ安全に除去することができる。なお、除去されたＳ成分はフィルターなどで捕捉出来る。 Therefore, in this embodiment, RuMoS / C is heated to, for example, 400 ° C. in a mixed gas of H 2 gas and inert gas such as N 2 to remove S component to RuMo / C (removal of chalcogen element component) Process). Thereby, the chalcogen element contained in the chalcogen element-containing catalyst can be easily and safely removed without generating a chalcogen element oxide such as SOx. The removed S component can be captured by a filter or the like.
次に、カルコゲン元素成分除去工程の後に、ＲｕＭｏＳ／Ｃを熱い王水に浸漬して炭素成分を除去する（炭素成分除去工程）。カルコゲン元素成分除去工程と炭素成分除去工程を連続させることで、カルコゲン元素含有触媒に含まれるカルコゲン元素と、同様にカルコゲン元素含有触媒に含まれる炭素成分を除去することができる。なお、発生したＳ分は、光触媒などで分解・回収する。 Next, after the chalcogen element component removal step, RuMoS / C is immersed in hot aqua regia to remove the carbon component (carbon component removal step). By continuing the chalcogen element component removal step and the carbon component removal step, the chalcogen element contained in the chalcogen element-containing catalyst and the carbon component contained in the chalcogen element-containing catalyst similarly can be removed. The generated S component is decomposed and collected by a photocatalyst or the like.
金属成分の回収は、前記炭素成分除去工程の後に、王水に溶解しない沈殿物から他の金属成分であるＲｕＣｌ３を回収する工程を行う。又、王水に溶解した金属成分であるＭｏ塩化物を回収する（金属成分回収工程）。なお、これらの金属回収方法としては、対象とする触媒に含まれる金属種によって適宜好ましい回収が用いられる。 In the recovery of the metal component, after the carbon component removal step, a step of recovering RuCl 3 which is another metal component from a precipitate that does not dissolve in aqua regia is performed. Further, Mo chloride which is a metal component dissolved in aqua regia is recovered (metal component recovery step). In addition, as these metal collection | recovery methods, preferable collection | recovery is suitably used according to the metal seed | species contained in the target catalyst.
本実施例では、不溶性塩として沈殿したＲｕＣｌ３を、ＮａＨＳＯ４等によりアルカリ溶融し、Ｈ２Ｏ浸出させて、Ｒｕ水溶液とする。次に、Ｒｕ水溶液に過剰のＮａＯＨを加え、Ｃｌ２ガスを吹き込んで（ＮＨ４）２ＲｕＣｌ６を揮発・分離する。揮発成分から（ＮＨ４）２ＲｕＣｌ６を含む塩を沈殿させ、回収する。最後に、揮発成分から（ＮＨ４）２ＲｕＣｌ６をＨ２ガスで還元してＲｕ単体として回収する。回収率はほぼ１００％であった。 In this example, RuCl 3 precipitated as an insoluble salt is alkali-melted with NaHSO 4 or the like and leached with H 2 O to obtain a Ru aqueous solution. Then, an excess of NaOH was added to Ru solution is blown with Cl 2 gas (NH 4) a 2 RuCl 6 volatilized and separated. A salt containing (NH 4 ) 2 RuCl 6 is precipitated from the volatile components and recovered. Finally, (NH 4 ) 2 RuCl 6 is reduced from the volatile components with H 2 gas and recovered as Ru alone. The recovery rate was almost 100%.
又、王水に溶解したＭｏＣｌ５はゼオライト等の吸着剤に吸着させ、ＭｏＣｌ５として分離して回収する。 Further, MoCl 5 dissolved in aqua regia is adsorbed by an adsorbent such as zeolite and separated and recovered as MoCl 5 .
本実施例により、ＲｕＭｏＳ／Ｃ触媒から有害なＳＯｘを発生させること無く貴重な遷移金属であるＲｕとＭｏを分離・回収できた。 According to this example, it was possible to separate and recover the valuable transition metals Ru and Mo without generating harmful SOx from the RuMoS / C catalyst.
使用済みのカルコゲン元素含有触媒から、カルコゲン元素含有触媒の構成成分である触媒金属を無公害的に回収すること環境保全に貢献するとともに、稀少且つ高価な触媒金属を効率的に再利用する。特に、白金触媒の代替となりうるカルコゲン元素含有燃料電池用電極触媒に適用することで、貴重な遷移金属等のリサイクルが促進され、燃料電池のコスト低減により、その実用化と普及に貢献する。 The catalyst metal, which is a constituent component of the chalcogen element-containing catalyst, is recovered from the used chalcogen element-containing catalyst in a pollution-free manner, contributing to environmental conservation and efficiently reusing the rare and expensive catalyst metal. In particular, when applied to a chalcogen element-containing fuel cell electrode catalyst that can be used as a substitute for a platinum catalyst, recycling of precious transition metals and the like is promoted, and the cost reduction of the fuel cell contributes to its practical use and spread.
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| KR101143566B1 (en) * | 2009-09-22 | 2012-05-09 | 리컴 주식회사 | Recovery of tungsten and cobalt from hardmetal alloy sludge by the hydrometallurgical process using aqua regia |
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| JPS5339283A (en) * | 1976-09-22 | 1978-04-11 | Mitsui Toatsu Chem Inc | Reactivating method for catalyst |
| JPS63161129A (en) * | 1986-12-23 | 1988-07-04 | Tanaka Kikinzoku Kogyo Kk | Method for recovering platinum from fuel cell electrode |
| JPS63210246A (en) * | 1987-02-25 | 1988-08-31 | Tokuriki Honten Co Ltd | Method for recovering noble metal from fuel cell electrode waste material and the like |
| JP2005087989A (en) * | 2003-08-08 | 2005-04-07 | Hitachi Ltd | Catalyst material, method for manufacturing the same, and fuel cell using the method |
| JP2005235504A (en) * | 2004-02-18 | 2005-09-02 | Toyota Motor Corp | Method for reutilizing fluorine-containing polymers |
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| JPS5339283A (en) * | 1976-09-22 | 1978-04-11 | Mitsui Toatsu Chem Inc | Reactivating method for catalyst |
| JPS63161129A (en) * | 1986-12-23 | 1988-07-04 | Tanaka Kikinzoku Kogyo Kk | Method for recovering platinum from fuel cell electrode |
| JPS63210246A (en) * | 1987-02-25 | 1988-08-31 | Tokuriki Honten Co Ltd | Method for recovering noble metal from fuel cell electrode waste material and the like |
| JP2005087989A (en) * | 2003-08-08 | 2005-04-07 | Hitachi Ltd | Catalyst material, method for manufacturing the same, and fuel cell using the method |
| JP2005235504A (en) * | 2004-02-18 | 2005-09-02 | Toyota Motor Corp | Method for reutilizing fluorine-containing polymers |
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| KR101143566B1 (en) * | 2009-09-22 | 2012-05-09 | 리컴 주식회사 | Recovery of tungsten and cobalt from hardmetal alloy sludge by the hydrometallurgical process using aqua regia |
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