JP6076925B2 - Noble metal recovery method and recovery system - Google Patents

Noble metal recovery method and recovery system Download PDF

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JP6076925B2
JP6076925B2 JP2014033857A JP2014033857A JP6076925B2 JP 6076925 B2 JP6076925 B2 JP 6076925B2 JP 2014033857 A JP2014033857 A JP 2014033857A JP 2014033857 A JP2014033857 A JP 2014033857A JP 6076925 B2 JP6076925 B2 JP 6076925B2
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noble metal
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孝次 根岸
孝次 根岸
雅人 岡村
雅人 岡村
基茂 柳生
基茂 柳生
祥平 金村
祥平 金村
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本発明の実施形態は、貴金属の回収方法および回収システムに関する。   Embodiments described herein relate generally to a precious metal recovery method and a recovery system.

燃料電池は、従来の燃焼機関等と比較してエネルギー変換効率が高く、また二酸化炭素（ＣＯ２）排出量が大幅に少なく、天然ガスや灯油、メタノール、バイオ燃料といった石油以外の燃料が使用可能であることから、次世代の発電システムでの利用が期待されている。燃料電池の主要部品である膜電極接合体（Membrane Electrode Assembly：ＭＥＡ）には、白金（Ｐｔ）、ルテニウム（Ｒｕ）、コバルト（Ｃｏ）等の貴金属が使用されている。これらの貴金属は埋蔵量に限りがあるため、燃料電池を廃棄する際にＭＥＡからの回収・再利用が求められている。 Fuel cells have higher energy conversion efficiency compared to conventional combustion engines, etc., and carbon dioxide (CO 2 ) emissions are significantly less, and non-oil fuels such as natural gas, kerosene, methanol, and biofuel can be used. Therefore, it is expected to be used in the next generation power generation system. Noble metals such as platinum (Pt), ruthenium (Ru), and cobalt (Co) are used for membrane electrode assemblies (MEA), which are main components of fuel cells. Since these precious metals have limited reserves, recovery and reuse from the MEA is required when the fuel cell is discarded.

ＭＥＡからの貴金属の回収・再利用方法として、ＭＥＡの膜部分を溶解し、フッ素ポリマーを含む溶解液から不溶物成分を遠心分離やフィルターで分離して、不溶物成分に含まれる触媒又は触媒担持担体を回収する技術が知られている（例えば、特許文献１参照。）。しかし、この方法では、遠心分離等により溶解液から貴金属を含む不溶物成分を分離する工程において、分離精度を上げると費用が増大する。   As a method for recovering and reusing precious metals from MEA, the MEA membrane part is dissolved, the insoluble component is separated from the solution containing the fluoropolymer by centrifugation or a filter, and the catalyst or catalyst support contained in the insoluble component A technique for recovering a carrier is known (for example, see Patent Document 1). However, in this method, the cost increases when the separation accuracy is increased in the step of separating the insoluble component containing the noble metal from the solution by centrifugation or the like.

また、拡散層を剥離した電解質膜を所定濃度のエタノール水溶液中で撹拌・超音波洗浄することにより、貴金属を電極剤粒子として回収する方法が提案されている（例えば、特許文献２参照。）。しかし、この方法では、電解質膜と電極粒子を分離するものの、貴金属と炭素を分離することや、貴金属を元素ごとに分離することができない。   In addition, a method has been proposed in which the electrolyte membrane from which the diffusion layer has been peeled is stirred and ultrasonically washed in an aqueous ethanol solution having a predetermined concentration to recover the noble metal as electrode agent particles (see, for example, Patent Document 2). However, although this method separates the electrolyte membrane and the electrode particles, it cannot separate the noble metal and carbon, or the noble metal for each element.

また、湿式浸出処理により、貴金属を抽出して回収する方法（例えば、特許文献３参照。）が提案されているが、この方法でも、物性が類似するため、貴金属の種類ごとの分離は困難である。また、貴金属を含む固形部材を王水で溶解後、薬品を投入して回収する方法（例えば、特許文献４参照。）が知られているが、この方法では、多量の薬品と複雑な工程を要するためシステムが複雑化する。   In addition, a method for extracting and recovering noble metals by wet leaching treatment (see, for example, Patent Document 3) has been proposed, but even with this method, since the physical properties are similar, it is difficult to separate the types of noble metals. is there. In addition, a method is known in which a solid member containing a noble metal is dissolved in aqua regia and then charged and recovered (see, for example, Patent Document 4). However, in this method, a large amount of chemicals and complicated steps are required. This complicates the system.

ここで、特許文献５には、二酸化チタンの薄膜からなる光触媒による光触媒反応を利用した光触媒装置に関する発明が提案されている。そして、この光触媒装置を用い、紫外線と光触媒の作用を利用して、例えば、海上に流出した原油を分解することや、臭気化合物あるいは煙草のヤニ等の有機物を分解することが開示されている。しかしながらこの装置は、主に、脱臭、殺菌、防汚、飲料水等の、空気及び水の浄化を対象としている。   Here, Patent Document 5 proposes an invention relating to a photocatalyst device using a photocatalytic reaction by a photocatalyst formed of a thin film of titanium dioxide. And using this photocatalyst apparatus, utilizing the effect | action of an ultraviolet-ray and a photocatalyst, for example, decomposing | disassembling the crude oil which flowed out on the sea, or decomposing | disassembling organic substances, such as an odor compound or cigarette dust. However, this device is mainly intended for the purification of air and water, such as deodorization, sterilization, antifouling and drinking water.

特開２００４−１７１９２１号公報JP 2004-171921 A 特開２０１０−１１４０３１号公報JP 2010-114031 A 特開２０１０−１００９０８号公報JP 2010-100908 A 特開２００９−１９７３２１号公報JP 2009-197321 A 特開平９−３８５０３号公報Japanese Patent Laid-Open No. 9-38503

本発明は上記した課題を解決するためになされたものであって、簡単な装置構成で、ＭＥＡから貴金属を回収することのできる貴金属の回収方法および回収システムを提供することを目的とする。   The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a noble metal recovery method and recovery system capable of recovering noble metal from an MEA with a simple apparatus configuration.

本発明の貴金属の回収方法の一態様は、燃料電池の膜電極接合体からの貴金属の回収方法であって、塩化物イオンを含む処理液中に前記膜電極接合体を浸漬して、前記貴金属を錯体として前記処理液に溶解させる溶解工程と、前記処理液に溶解した前記貴金属を、犠牲剤及び光触媒を用い、金属粉体として析出させる析出工程と、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離して、前記金属粉体を回収する回収工程とを備えることを特徴とする。   One aspect of the noble metal recovery method of the present invention is a method for recovering a noble metal from a membrane electrode assembly of a fuel cell, wherein the membrane electrode assembly is immersed in a treatment liquid containing chloride ions, and the noble metal is recovered. A dissolution step of dissolving the noble metal in the treatment liquid as a complex, a precipitation step of depositing the noble metal dissolved in the treatment liquid as a metal powder using a sacrificial agent and a photocatalyst, and the metal powder and the sacrificial agent. And a recovery step of recovering the metal powder by solid-liquid separation of the treatment liquid into the liquid phase from which the metal powder and the metal powder have been removed.

本発明の貴金属の回収システムの一態様は、燃料電池の膜電極接合体からの貴金属の回収システムであって、内部に処理液を収容し、前記膜電極接合体を前記処理液に浸漬して、前記貴金属を金属錯体として前記処理液に溶解させる溶解装置と、光触媒装置を備え、内部に犠牲剤及び前記貴金属の溶解した処理液を収容し、前記光触媒装置を用いて前記貴金属を金属粉体として析出させる反応槽と、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記反応槽から送り出し、再度前記反応槽に供給させる循環配管と、前記循環配管に介挿され、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に分離する固液分離装置とを備えることを特徴とする。   One aspect of the noble metal recovery system of the present invention is a system for recovering a noble metal from a membrane electrode assembly of a fuel cell, containing a treatment liquid therein, and immersing the membrane electrode assembly in the treatment liquid. A dissolving device for dissolving the noble metal in the treatment liquid as a metal complex, and a photocatalyst device, containing a treatment solution in which a sacrificial agent and the noble metal are dissolved, and using the photocatalyst device to convert the noble metal into a metal powder A reaction tank to be deposited as the above, the processing liquid containing the metal powder and the sacrificial agent is sent out from the reaction tank and supplied again to the reaction tank, and the metal powder is inserted into the circulation pipe. A solid-liquid separation device that separates the treatment liquid containing the body and the sacrificial agent into the metal powder and the liquid phase from which the metal powder has been removed.

本発明によれば、簡単な装置構成で、ＭＥＡから貴金属を回収することのできる貴金属の回収方法および回収システムを提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the collection | recovery method and collection | recovery system of a noble metal which can collect | recover a noble metal from MEA with a simple apparatus structure can be provided.

第１の実施形態に係る貴金属の回収システムを概略的に表す図。1 is a diagram schematically illustrating a noble metal recovery system according to a first embodiment. FIG. 実施形態における光触媒の種類とＰｔの析出率の関係を示すグラフ。The graph which shows the relationship between the kind of photocatalyst in embodiment, and the precipitation rate of Pt. 実施形態における処理液中の金属粉体のＸ線回折スペクトル。The X-ray diffraction spectrum of the metal powder in the process liquid in embodiment. 実施形態におけるＰｔを除去した後の処理液中の金属粉体のＸ線回折スペクトル。The X-ray-diffraction spectrum of the metal powder in the process liquid after removing Pt in embodiment.

以下、図面を参照して、本発明の実施形態を詳細に説明する。
図１は、本実施形態の貴金属の回収方法に用いられる貴金属の回収システム１０を示す概略構成図である。回収システム１０は、例えば燃料電池の膜電極接合体（ＭＥＡ１）を構成する電解質膜中に含まれる、白金（Ｐｔ）、ルテニウム（Ｒｕ）、コバルト（Ｃｏ）等の貴金属を回収するシステムである。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing a noble metal recovery system 10 used in the noble metal recovery method of this embodiment. The recovery system 10 is a system that recovers a noble metal such as platinum (Pt), ruthenium (Ru), cobalt (Co) and the like contained in an electrolyte membrane constituting a membrane electrode assembly (MEA1) of a fuel cell, for example.

本実施形態の貴金属の回収方法は、処理液Ｌ中にＭＥＡ１を浸漬して、ＭＥＡ１に含まれる貴金属を金属錯体として処理液Ｌに溶解させる溶解工程と、処理液Ｌに溶解した貴金属を、犠牲剤２及び光触媒３を用いて金属粉体Ｍとして析出させる析出工程と、金属粉体Ｍ及び犠牲剤２を含む処理液Ｌを、金属粉体Ｍと金属粉体Ｍの除去された液相に固液分離して、金属粉体Ｍを回収する回収工程とを備えている。   The noble metal recovery method of the present embodiment includes a dissolution step of immersing MEA1 in the processing liquid L and dissolving the noble metal contained in MEA1 as a metal complex in the processing liquid L, and sacrificing the noble metal dissolved in the processing liquid L. The deposition step of depositing the metal powder M using the agent 2 and the photocatalyst 3 and the treatment liquid L containing the metal powder M and the sacrificial agent 2 into the liquid phase from which the metal powder M and the metal powder M have been removed. And a recovery step of recovering the metal powder M by solid-liquid separation.

回収システム１０は、ＭＥＡ１を処理液Ｌに浸漬して、ＭＥＡ１に含まれる貴金属を処理液Ｌに溶解させる溶解装置４と、溶解装置４で貴金属を溶解した処理液Ｌと犠牲剤２を混合する反応槽５を備えている。溶解装置４は、配管６により処理液ポンプ７を介して反応槽５に接続されている。   The recovery system 10 immerses the MEA 1 in the processing liquid L and mixes the dissolution apparatus 4 that dissolves the noble metal contained in the MEA 1 in the processing liquid L, and the processing liquid L in which the noble metal is dissolved in the dissolution apparatus 4 and the sacrificial agent 2. A reaction vessel 5 is provided. The dissolution apparatus 4 is connected to the reaction tank 5 through a treatment liquid pump 7 by a pipe 6.

処理液Ｌとしては、塩化物イオンを含む水溶液、例えば、塩酸、塩化ナトリウム水溶液等が用いられる。ＭＥＡ１に含まれる貴金属は、処理液Ｌ中の塩化物イオンと反応し、塩化物の錯体（金属錯体）として処理液Ｌに溶解する（溶解工程）。貴金属の溶解した処理液Ｌは、処理液ポンプ７によって反応槽５に送液される。   As the treatment liquid L, an aqueous solution containing chloride ions, for example, hydrochloric acid, an aqueous sodium chloride solution, or the like is used. The noble metal contained in the MEA 1 reacts with chloride ions in the treatment liquid L and dissolves in the treatment liquid L as a chloride complex (metal complex) (dissolution step). The processing liquid L in which the precious metal is dissolved is sent to the reaction tank 5 by the processing liquid pump 7.

反応槽５には、配管８により犠牲剤供給装置９が接続されている。配管８にはポンプ１１が介装されている。犠牲剤供給装置９により、犠牲剤２が反応槽５内に供給されて貴金属の溶解した処理液Ｌと混合される（混合工程）。反応槽５内の処理液Ｌと犠牲剤２は、例えば撹拌機によって撹拌されてもよい。   A sacrificial agent supply device 9 is connected to the reaction tank 5 by a pipe 8. A pump 11 is interposed in the pipe 8. The sacrificial agent supply device 9 supplies the sacrificial agent 2 into the reaction vessel 5 and mixes it with the processing liquid L in which the precious metal is dissolved (mixing step). The treatment liquid L and the sacrificial agent 2 in the reaction tank 5 may be stirred by, for example, a stirrer.

また、反応槽５には、反応槽５内の犠牲剤２の濃度を測定するセンサー１２と、センサー１２の測定値に応じて、犠牲剤供給装置９から犠牲剤２を供給する制御装置１３とを備えている。制御装置１３は、例えばポンプ１１の吐出量を制御することで、犠牲剤２の供給を制御する。   The reaction tank 5 includes a sensor 12 that measures the concentration of the sacrificial agent 2 in the reaction tank 5, and a control device 13 that supplies the sacrificial agent 2 from the sacrificial agent supply device 9 according to the measurement value of the sensor 12. It has. For example, the control device 13 controls the supply of the sacrificial agent 2 by controlling the discharge amount of the pump 11.

反応槽５には、反応槽５内の処理液Ｌを反応槽５から送り出し、再度反応槽５に供給する循環配管１４が接続されている。循環配管１４には、固液分離装置１９が介挿されている。また、循環配管１４には、反応槽５内の処理液Ｌを循環配管１４に循環させるスラリーポンプ１５が介装されている。   Connected to the reaction tank 5 is a circulation pipe 14 that feeds the processing liquid L in the reaction tank 5 from the reaction tank 5 and supplies it again to the reaction tank 5. A solid-liquid separator 19 is inserted in the circulation pipe 14. The circulation pipe 14 is provided with a slurry pump 15 that circulates the processing liquid L in the reaction tank 5 to the circulation pipe 14.

また、反応槽５には、光触媒装置１６が備えられている。光触媒装置１６は、光源１７と、光源１７を覆うケース１８と、光触媒３とを備えている。光触媒３はケース１８の外表面（処理液Ｌと接触する側）に付着されている。このとき、光触媒３は、薄膜状に付着されていることが好ましい。光源１７は、放射線、Ｘ線、紫外線、可視光の中から光触媒３のバンドギャップ値により適宜選択して用いられる。   The reaction vessel 5 is provided with a photocatalytic device 16. The photocatalyst device 16 includes a light source 17, a case 18 that covers the light source 17, and the photocatalyst 3. The photocatalyst 3 is attached to the outer surface of the case 18 (the side in contact with the processing liquid L). At this time, the photocatalyst 3 is preferably attached in a thin film. The light source 17 is appropriately selected from radiation, X-rays, ultraviolet rays, and visible light according to the band gap value of the photocatalyst 3 and used.

ケース１８は、光源１７と反応槽内の処理液Ｌの接触を防止する役割をする。そのため、ケース１８としては、光源１７から発する光の透過度が高い材料であって、処理液Ｌに対して耐食性のある材料、例えば、石英ガラス等の透明ガラス、透明樹脂等が用いられる。また、ケース１８は光源１７から発せられる光の波長を区切るフィルターの機能を有してもよい。   The case 18 serves to prevent contact between the light source 17 and the processing liquid L in the reaction vessel. For this reason, the case 18 is made of a material having high transmittance of light emitted from the light source 17 and having corrosion resistance to the processing liquid L, for example, transparent glass such as quartz glass, transparent resin, and the like. In addition, the case 18 may have a function of a filter that partitions the wavelength of light emitted from the light source 17.

光触媒３は、光源１７から照射される光により励起されて、電子を発生する（励起工程）。光触媒３としては、ｎ型半導体の性質を持つものが用いられる。光触媒３としては例えば、酸化チタン（ＴｉＯ２）、酸化ジルコニウム（ＺｒＯ２）、酸化スズ（ＳｎＯ２）が用いられる。中でも、ＭＥＡ１に含まれる貴金属の錯体（金属錯体）を効率よく還元できることから、酸化チタンが好ましい。なお、光触媒３は、光触媒作用を高めるために、その粒子径が十分に小さいことが好ましく、例えば微粒子状であることが好ましい。 The photocatalyst 3 is excited by light irradiated from the light source 17 to generate electrons (excitation process). As the photocatalyst 3, one having an n-type semiconductor property is used. As the photocatalyst 3, for example, titanium oxide (TiO 2 ), zirconium oxide (ZrO 2 ), or tin oxide (SnO 2 ) is used. Among these, titanium oxide is preferable because a noble metal complex (metal complex) contained in MEA 1 can be efficiently reduced. In addition, it is preferable that the particle diameter of the photocatalyst 3 is sufficiently small in order to enhance the photocatalytic action, for example, it is preferably in the form of fine particles.

犠牲剤２は、光触媒３が励起することで生じた正孔に電子を供給して犠牲剤２由来のラジカルを発生する。犠牲剤２は、メタノール、エタノール等のアルコール類、エチレンジアミン、トリエタノールアミン等のアミン系化合物及びギ酸、酢酸等の有機酸のうち少なくとも１種以上の化合物を含むことが好ましい。これらのなかでも、回収システム１０を構成する機器への影響が小さいことから、メタノール、エタノール等のアルコール類を用いることがより好ましい。   The sacrificial agent 2 generates electrons derived from the sacrificial agent 2 by supplying electrons to holes generated by the excitation of the photocatalyst 3. The sacrificial agent 2 preferably contains at least one compound among alcohols such as methanol and ethanol, amine compounds such as ethylenediamine and triethanolamine, and organic acids such as formic acid and acetic acid. Among these, it is more preferable to use alcohols such as methanol and ethanol because the influence on the equipment constituting the recovery system 10 is small.

処理液Ｌは、光源１７から発する光により励起された光触媒３と接触することでヒドロキシラジカル（ＯＨラジカル）及びハロゲン化物ラジカルを発生する。さらに、犠牲剤２は、反応槽５内で発生したＯＨラジカル及びハロゲン化物ラジカルと反応して、犠牲剤２由来のラジカルを発生する。また、犠牲剤２は、光触媒３が励起することで発生した正孔に電子を供給し、犠牲剤２由来のラジカルを発生する。これらのラジカル（ＯＨラジカル、ハロゲン化物ラジカル、犠牲剤２由来のラジカル）と光触媒３の励起により発生した電子によって金属錯体が還元され、金属粉体Ｍを生成する（析出工程）。   The treatment liquid L generates hydroxy radicals (OH radicals) and halide radicals by coming into contact with the photocatalyst 3 excited by light emitted from the light source 17. Further, the sacrificial agent 2 reacts with OH radicals and halide radicals generated in the reaction vessel 5 to generate radicals derived from the sacrificial agent 2. The sacrificial agent 2 supplies electrons to the holes generated by the excitation of the photocatalyst 3 to generate radicals derived from the sacrificial agent 2. The metal complex is reduced by these radicals (OH radicals, halide radicals, radicals derived from the sacrificial agent 2) and electrons generated by the excitation of the photocatalyst 3 to form a metal powder M (precipitation step).

犠牲剤２の量は、反応槽５、循環配管１４及び固液分離装置１９内を循環する、犠牲剤２、金属粉体Ｍ及び処理液Ｌの全量に対して２〜６質量％であることが好ましい。犠牲剤２の量が２質量％未満では、金属粉体Ｍが十分に析出せず、貴金属の回収率が低下する。また、犠牲剤２の量の消費量を少なくするため、６質量％以下であることが好ましい。   The amount of the sacrificial agent 2 is 2 to 6% by mass with respect to the total amount of the sacrificial agent 2, the metal powder M, and the processing liquid L circulated in the reaction tank 5, the circulation pipe 14, and the solid-liquid separator 19. Is preferred. When the amount of the sacrificial agent 2 is less than 2% by mass, the metal powder M is not sufficiently precipitated and the recovery rate of the noble metal is lowered. Moreover, in order to reduce the consumption of the quantity of the sacrificial agent 2, it is preferable that it is 6 mass% or less.

金属粉体Ｍの生成反応により犠牲剤２が消費された場合には、制御装置１３が、センサー１２の測定値に基いて、犠牲剤供給装置９及びポンプ１１を制御する。これにより、犠牲剤２が反応槽５内に再供給され、犠牲剤２の量が上記した範囲に維持される。このとき、センサー１２の測定値が３％を下回ったときに、制御装置１３は、犠牲剤２が反応槽５内に供給されるように犠牲剤供給装置９及びポンプ１１を制御することが好ましい。   When the sacrificial agent 2 is consumed due to the formation reaction of the metal powder M, the control device 13 controls the sacrificial agent supply device 9 and the pump 11 based on the measured value of the sensor 12. Thereby, the sacrificial agent 2 is re-supplied into the reaction vessel 5 and the amount of the sacrificial agent 2 is maintained in the above-described range. At this time, when the measured value of the sensor 12 falls below 3%, the control device 13 preferably controls the sacrificial agent supply device 9 and the pump 11 so that the sacrificial agent 2 is supplied into the reaction tank 5. .

処理液Ｌ及び犠牲剤２は、循環配管１４を循環する過程で、さらに十分に混合される。また、この過程で、処理液Ｌは、循環配管１４に介挿された固液分離装置１９により、固相である金属粉体Ｍと金属粉体Ｍの除去された液相に分離され、金属粉体Ｍが回収される（回収工程）。   The treatment liquid L and the sacrificial agent 2 are further sufficiently mixed in the process of circulating through the circulation pipe 14. Further, in this process, the treatment liquid L is separated into a solid phase metal powder M and a liquid phase from which the metal powder M has been removed by a solid-liquid separation device 19 inserted in the circulation pipe 14. The powder M is recovered (recovery process).

固液分離装置１９は、第１の固液分離装置２０及び第２の固液分離装置２１を備えている。循環配管１４は、固液分離装置１９の上流側で２つの分岐配管に分岐しており、第１の固液分離装置２０及び第２の固液分離装置２１は、それぞれ電磁弁２２及び電磁弁２３を介して、当該分岐配管に介挿されている。循環配管１４は、第１の固液分離装置２０又は第２の固液分離装置２１によって分離された液相を、反応槽５に循環させる。第１の固液分離装置２０及び第２の固液分離装置２１としては、特に限定されず、フィルター装置や遠心分離器等を用いることができる。   The solid-liquid separation device 19 includes a first solid-liquid separation device 20 and a second solid-liquid separation device 21. The circulation pipe 14 is branched into two branch pipes on the upstream side of the solid-liquid separator 19, and the first solid-liquid separator 20 and the second solid-liquid separator 21 are an electromagnetic valve 22 and an electromagnetic valve, respectively. 23, and is inserted into the branch pipe. The circulation pipe 14 circulates the liquid phase separated by the first solid-liquid separator 20 or the second solid-liquid separator 21 to the reaction vessel 5. It does not specifically limit as the 1st solid-liquid separator 20 and the 2nd solid-liquid separator 21, A filter apparatus, a centrifuge, etc. can be used.

循環配管１４には、固液分離装置１９に供給される処理液Ｌ中のＰｔ錯体濃度を測定するＰｔ錯体濃度測定装置２４が介装されている。Ｐｔ錯体濃度測定装置２４としては、例えば、誘導結合プラズマ質量分析計（ＩＣＰ−ＭＳ）を利用したものを使用することができる。Ｐｔ錯体濃度測定装置２４の測定値に応じて、電磁弁２２、２３の開閉が制御される。   The circulation pipe 14 is provided with a Pt complex concentration measuring device 24 that measures the Pt complex concentration in the treatment liquid L supplied to the solid-liquid separation device 19. As the Pt complex concentration measuring device 24, for example, a device using an inductively coupled plasma mass spectrometer (ICP-MS) can be used. According to the measured value of the Pt complex concentration measuring device 24, the opening and closing of the electromagnetic valves 22 and 23 are controlled.

ここで、図２に、光触媒３としてＴｉＯ２、ＺｒＯ２、ＳｎＯ２を、犠牲剤２としてエタノールを、光源１７としてＵＶランプ（浜松ホトニクス社製 LC8-L9566-02A、200W Hg-Xe）を使用し、光触媒に紫外線を１０ｍＷ／ｃｍ２で３時間照射したときのＰｔの析出率を測定した結果を示す。図２に示すように、Ｐｔの析出率は、光触媒３がＴｉＯ２、ＺｒＯ２、ＳｎＯ２の順に高くなっている。 Here, in FIG. 2, TiO 2 , ZrO 2 , SnO 2 are used as the photocatalyst 3, ethanol is used as the sacrificial agent 2, and a UV lamp (LC8-L9566-02A, 200 W Hg-Xe manufactured by Hamamatsu Photonics) is used as the light source 17. The results of measuring the deposition rate of Pt when the photocatalyst was irradiated with ultraviolet rays at 10 mW / cm 2 for 3 hours are shown. As shown in FIG. 2, the Pt deposition rate is higher for the photocatalyst 3 in the order of TiO 2 , ZrO 2 , and SnO 2 .

図３は、光触媒３としてＴｉＯ２を、犠牲剤２としてエタノールを、光源１７としてＵＶランプ（浜松ホトニクス社製 LC8-L9566-02A、200W Hg-Xe）を使用し、反応槽５において、Ｐｔ錯体とＲｕ錯体が２：１の割合（質量比）で溶解した処理液Ｌを処理したときの金属粉体ＭのＸ線回折スペクトル（ＸＲＤ）を示す。このとき、光触媒３には、紫外線を１０ｍＷ／ｃｍ２で３時間照射した。図３では、Ｐｔのピークのみ検出された。 FIG. 3 shows a case where TiO 2 is used as the photocatalyst 3, ethanol is used as the sacrificial agent 2, and a UV lamp (LC8-L9566-02A, 200 W Hg-Xe manufactured by Hamamatsu Photonics) is used as the light source 17. 2 shows an X-ray diffraction spectrum (XRD) of the metal powder M when the treatment liquid L in which the Ru complex is dissolved at a ratio (mass ratio) of 2: 1 is treated. At this time, the photocatalyst 3 was irradiated with ultraviolet rays at 10 mW / cm 2 for 3 hours. In FIG. 3, only the peak of Pt was detected.

図４は、上記で処理した処理液Ｌから、固液分離装置によってＰｔを除去した後、さらに、光触媒３に紫外線を１０ｍＷ／ｃｍ２で３時間照射したときに得られた金属粉体ＭのＸＲＤを示す。図４では、Ｒｕのピークが検出された。 FIG. 4 shows the metal powder M obtained when the photocatalyst 3 was irradiated with ultraviolet rays at 10 mW / cm 2 for 3 hours after Pt was removed from the treatment liquid L treated above by a solid-liquid separator. XRD is shown. In FIG. 4, a Ru peak was detected.

図３、４より、ＰｔとＲｕのイオン化傾向の違いによりＰｔとＲｕを分離回収できることが分かる。また、イオン化傾向の違いを利用して、例えば、励起波長の異なる光触媒３を複数付着させることにより、貴な金属（イオン化傾向の低い金属）から順に析出させていくことが可能となる。さらに、犠牲剤２の種類が異なると、犠牲剤２由来のラジカルの電位が異なるため、犠牲剤２の種類を変更することで上記と同様のことが可能である。   3 and 4, it can be seen that Pt and Ru can be separated and recovered by the difference in ionization tendency between Pt and Ru. Further, by utilizing the difference in ionization tendency, for example, by depositing a plurality of photocatalysts 3 having different excitation wavelengths, it becomes possible to deposit in order from a noble metal (a metal having a low ionization tendency). Further, since the potential of the radical derived from the sacrificial agent 2 differs when the type of the sacrificial agent 2 is different, the same as described above can be performed by changing the type of the sacrificial agent 2.

また、回収工程を次のように行うことで、ＰｔとＲｕを分離回収することが可能である。Ｐｔ錯体濃度測定装置２４が、循環配管１４を循環する処理液Ｌ中のＰｔ錯体濃度を測定する（金属錯体濃度測定工程）。Ｐｔ錯体濃度測定装置２４の測定値に基いて、制御装置１３は、電磁弁２２、２３の開閉を制御し、処理液Ｌを第１の固液分離装置２０又は第２の固液分離装置２１のいずれかに供給する。具体的には、Ｐｔ錯体濃度測定装置２４の測定値があらかじめ決定した所定の値以上である場合には、電磁弁２２を開、電磁弁２３を閉に制御し、処理液Ｌを第１の固液分離装置２０に供給する。これにより、処理液Ｌ中のＰｔを回収する（第１の固液分離工程）。また、測定値が上記所定の値未満となったときに、電磁弁２２を閉、電磁弁２３を開に制御し、処理液Ｌを第２の固液分離装置２１に供給する。これにより、処理液Ｌ中のＲｕを回収する（第２の固液分離工程）。   Further, Pt and Ru can be separated and recovered by performing the recovery process as follows. The Pt complex concentration measuring device 24 measures the Pt complex concentration in the treatment liquid L circulating through the circulation pipe 14 (metal complex concentration measuring step). Based on the measured value of the Pt complex concentration measuring device 24, the control device 13 controls the opening and closing of the electromagnetic valves 22 and 23, and the processing liquid L is supplied to the first solid-liquid separation device 20 or the second solid-liquid separation device 21. Supply to either. Specifically, when the measured value of the Pt complex concentration measuring device 24 is equal to or larger than a predetermined value determined in advance, the electromagnetic valve 22 is controlled to be opened and the electromagnetic valve 23 is controlled to be closed, so that the treatment liquid L The solid-liquid separator 20 is supplied. Thereby, Pt in the processing liquid L is recovered (first solid-liquid separation step). Further, when the measured value becomes less than the predetermined value, the electromagnetic valve 22 is closed and the electromagnetic valve 23 is controlled to be opened, and the processing liquid L is supplied to the second solid-liquid separator 21. Thereby, Ru in the processing liquid L is recovered (second solid-liquid separation step).

このとき、Ｐｔ錯体濃度測定装置２４の測定値が、初期値に対し２％以上のときに、電磁弁２２を開、電磁弁２３を閉に制御し、処理液Ｌを第１の固液分離装置２０に通液させ、Ｐｔを回収することが好ましい。また、測定値が２％未満となったときに、電磁弁２２を閉、電磁弁２３を開に制御して、処理液Ｌを第２の固液分離装置２１に通液し、Ｒｕを回収することが好ましい。   At this time, when the measured value of the Pt complex concentration measuring device 24 is 2% or more with respect to the initial value, the electromagnetic valve 22 is controlled to be opened and the electromagnetic valve 23 is controlled to be closed, and the treatment liquid L is separated into the first solid-liquid separation. It is preferable to pass the liquid through the apparatus 20 and collect Pt. Further, when the measured value becomes less than 2%, the electromagnetic valve 22 is closed and the electromagnetic valve 23 is controlled to open, and the processing liquid L is passed through the second solid-liquid separator 21 to recover Ru. It is preferable to do.

以上、本実施形態によれば、ＭＥＡに含まれる貴金属を、光触媒装置を用いた簡単な装置構成で回収することができる。また、貴金属が、少なくとも２種の異なる貴金属を含む場合に、これらを分離回収することが可能である。   As mentioned above, according to this embodiment, the noble metal contained in MEA can be collect | recovered with the simple apparatus structure using a photocatalyst apparatus. Further, when the noble metal contains at least two different kinds of noble metals, these can be separated and recovered.

本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら新規な実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれるとともに、特許請求の範囲に記載された発明とその均等の範囲に含まれる。   Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

１０…回収システム、１…ＭＥＡ、２…犠牲剤、３…光触媒、４…溶解装置、５…反応槽、６，８…配管、７…処理液ポンプ、９…犠牲剤供給装置、１１…ポンプ、１２…センサー、１３…制御装置、１４…循環配管、１５…スラリーポンプ、１６…光触媒装置、１７…光源、１８…ケース、１９…固液分離装置、２０…第１の固液分離装置、２１…第２の固液分離装置、２２，２３…電磁弁、２４…Ｐｔ錯体濃度測定装置、Ｌ…処理液、Ｍ…金属粉体。   DESCRIPTION OF SYMBOLS 10 ... Recovery system, 1 ... MEA, 2 ... Sacrificial agent, 3 ... Photocatalyst, 4 ... Dissolution apparatus, 5 ... Reaction tank, 6, 8 ... Pipe, 7 ... Treatment liquid pump, 9 ... Sacrificial agent supply apparatus, 11 ... Pump DESCRIPTION OF SYMBOLS 12 ... Sensor, 13 ... Control apparatus, 14 ... Circulation piping, 15 ... Slurry pump, 16 ... Photocatalyst device, 17 ... Light source, 18 ... Case, 19 ... Solid-liquid separator, 20 ... First solid-liquid separator, 21 ... 2nd solid-liquid separator, 22, 23 ... Solenoid valve, 24 ... Pt complex density | concentration measuring device, L ... Treatment liquid, M ... Metal powder.

Claims (10)

燃料電池の膜電極接合体からの貴金属の回収方法であって、
塩化物イオンを含む処理液中に前記膜電極接合体を浸漬して、前記貴金属を錯体として前記処理液に溶解させる溶解工程と、
前記処理液に溶解した前記貴金属を、犠牲剤及び光触媒を用い、金属粉体として析出させる析出工程と、
前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離して、前記金属粉体を回収する回収工程と
を備えることを特徴とする貴金属の回収方法。 A method for recovering a noble metal from a membrane electrode assembly of a fuel cell,
Immersing the membrane electrode assembly in a treatment liquid containing chloride ions, and dissolving the noble metal in the treatment liquid as a complex;
A deposition step of depositing the noble metal dissolved in the treatment liquid as a metal powder using a sacrificial agent and a photocatalyst;
A recovery step of recovering the metal powder by solid-liquid separation of the treatment liquid containing the metal powder and the sacrificial agent into a liquid phase from which the metal powder and the metal powder have been removed. A precious metal recovery method characterized by 前記析出工程は、
前記貴金属の溶解した処理液と前記犠牲剤を混合する混合工程と、
光源から光を発して前記光触媒を励起させ、励起した前記光触媒と前記貴金属の溶解した処理液及び前記犠牲剤を接触させて前記貴金属を金属粉体として析出させる励起工程と、
を備えることを特徴とする請求項１記載の貴金属の回収方法。 The precipitation step
A mixing step of mixing the processing solution in which the noble metal is dissolved and the sacrificial agent;
Exciting the photocatalyst by emitting light from a light source, bringing the excited photocatalyst into contact with the precious metal-dissolved treatment liquid and the sacrificial agent, and precipitating the noble metal as a metal powder;
The method for recovering a noble metal according to claim 1, comprising: さらに、前記金属粉体の除去された液相を前記析出工程に送る循環工程を備えることを特徴とする請求項１又は２記載の貴金属の回収方法。   The method for recovering a noble metal according to claim 1, further comprising a circulation step of sending the liquid phase from which the metal powder has been removed to the precipitation step. 前記貴金属は、少なくとも第１の貴金属及び第２の貴金属を含み、
前記回収工程は、前記金属粉体および前記犠牲剤を含む前記処理液中の前記第１の貴金属の錯体の濃度を測定する金属錯体濃度測定工程と、
前記金属錯体濃度測定工程における測定値が所定の値以上のときに、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離する第１の固液分離工程と、
前記金属錯体濃度測定工程における測定値が上記所定の値未満のときに、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離する第２の固液分離工程と
を備えることを特徴とする請求項１乃至３のいずれか１項記載の貴金属の回収方法。 The noble metal includes at least a first noble metal and a second noble metal,
The recovery step includes a metal complex concentration measurement step of measuring a concentration of the first noble metal complex in the treatment liquid containing the metal powder and the sacrificial agent,
When the measurement value in the metal complex concentration measurement step is a predetermined value or more, the treatment liquid containing the metal powder and the sacrificial agent is solidified in the liquid phase from which the metal powder and the metal powder have been removed. A first solid-liquid separation step for liquid separation;
When the measurement value in the metal complex concentration measurement step is less than the predetermined value, the treatment liquid containing the metal powder and the sacrificial agent is changed to a liquid phase from which the metal powder and the metal powder are removed. The method for recovering a noble metal according to any one of claims 1 to 3, further comprising a second solid-liquid separation step for solid-liquid separation. 前記第１の貴金属はＰｔであり、前記第２の貴金属はＲｕであることを特徴とする請求項４記載の貴金属の回収方法。   5. The method for recovering a noble metal according to claim 4, wherein the first noble metal is Pt, and the second noble metal is Ru. 前記犠牲剤は、アルコール類、アミン系化合物及び有機酸から選ばれる１種以上の化合物を含むことを特徴とする請求項１乃至５のいずれか１項記載の貴金属の回収方法。   The method for recovering a noble metal according to any one of claims 1 to 5, wherein the sacrificial agent includes one or more compounds selected from alcohols, amine compounds, and organic acids. 前記光触媒は、酸化チタン、酸化ジルコニウム及び酸化スズから選ばれる１種以上を含むことを特徴とする請求項１乃至６のいずれか１項記載の貴金属の回収方法。   The noble metal recovery method according to any one of claims 1 to 6, wherein the photocatalyst includes one or more selected from titanium oxide, zirconium oxide, and tin oxide. 燃料電池の膜電極接合体からの貴金属の回収システムであって、
内部に処理液を収容し、前記膜電極接合体を前記処理液に浸漬して、前記貴金属を金属錯体として前記処理液に溶解させる溶解装置と、
光触媒装置を備え、内部に犠牲剤及び前記貴金属の溶解した処理液を収容し、前記光触媒装置を用いて前記貴金属を金属粉体として析出させる反応槽と、
前記金属粉体及び前記犠牲剤を含む前記処理液を、前記反応槽から送り出し、再度前記反応槽に供給させる循環配管と、
前記循環配管に介挿され、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に分離する固液分離装置と
を備えることを特徴とする貴金属の回収システム。 A system for recovering noble metals from a membrane electrode assembly of a fuel cell,
A dissolution apparatus for containing a treatment liquid therein, immersing the membrane electrode assembly in the treatment liquid, and dissolving the noble metal in the treatment liquid as a metal complex;
A reaction tank comprising a photocatalyst device, containing therein a treatment liquid in which a sacrificial agent and the noble metal are dissolved, and depositing the noble metal as a metal powder using the photocatalyst device;
A circulation pipe for sending out the treatment liquid containing the metal powder and the sacrificial agent from the reaction tank and supplying the treatment liquid again to the reaction tank;
A solid-liquid separator that is inserted in the circulation pipe and separates the processing liquid containing the metal powder and the sacrificial agent into the liquid phase from which the metal powder and the metal powder have been removed. Characteristic precious metal recovery system. 前記光触媒装置は、
ケースと、
前記ケースの外表面に付着された光触媒と、
前記ケースに覆われるとともに、光を発して前記光により前記光触媒を励起する光源とを備え、
前記光により励起した前記光触媒と前記貴金属の溶解した処理液及び前記犠牲剤を接触させて、前記貴金属を金属粉体として析出させることを特徴とする請求項８記載の貴金属の回収システム。 The photocatalytic device comprises:
Case and
A photocatalyst attached to the outer surface of the case;
A light source that is covered with the case and emits light to excite the photocatalyst with the light;
9. The noble metal recovery system according to claim 8, wherein the photocatalyst excited by the light is brought into contact with the treatment solution in which the noble metal is dissolved and the sacrificial agent to deposit the noble metal as metal powder. 前記貴金属は、少なくとも第１の貴金属及び第２の貴金属を含み、
前記回収システムは、前記金属粉体および前記犠牲剤を含む前記処理液中の第１の貴金属の錯体の濃度を測定する金属錯体濃度測定装置を備え、
前記固液分離装置は、前記金属錯体濃度測定装置の測定値が所定の値以上のときに、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離する第１の固液分離装置と、
前記金属錯体濃度測定装置の測定値が前記所定の値未満のときに、前記金属粉体及び前記犠牲剤を含む前記処理液を、前記金属粉体と前記金属粉体の除去された液相に固液分離する第２の固液分離装置と
を備えることを特徴とする請求項８又は９記載の貴金属の回収システム。 The noble metal includes at least a first noble metal and a second noble metal,
The recovery system includes a metal complex concentration measurement device that measures the concentration of the first noble metal complex in the treatment liquid containing the metal powder and the sacrificial agent,
When the measured value of the metal complex concentration measuring device is equal to or greater than a predetermined value, the solid-liquid separator is configured to treat the processing liquid containing the metal powder and the sacrificial agent between the metal powder and the metal powder. A first solid-liquid separation device for solid-liquid separation into the removed liquid phase;
When the measurement value of the metal complex concentration measuring device is less than the predetermined value, the treatment liquid containing the metal powder and the sacrificial agent is changed to a liquid phase from which the metal powder and the metal powder are removed. A noble metal recovery system according to claim 8 or 9, further comprising: a second solid-liquid separation device for solid-liquid separation.
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