201033374 六、發明說明： 【發明所屬之技術領域】 本發明是有關含有白金族金屬之組成物的製造方法。 【先前技術】 在日本公開專利2005-194546號公報令，係揭示藉由 將單獨吡啶或與雜多酸溶液一起添加到酸性溶液中，可使 白金族金屬離子沉澱之方法。 【發明内容】 ® 本發明提供有效得到白金族金屬之方法。 本發明是有關以下之發明。 [1] 一種含有白金族金屬之組成物之製造方法，係包含： 將含有白金族金屬離子及雜多酸之溶液與腈 (nitile)化合物混合的第i步驟，與，回收由前述 第1步驟所得之含有白金族金屬之組成物的第2步 =如[1]之製造方法，其中，白金族金屬離子是纪離子 [3] 如[1]或[2]之土 , 」Μ」^乂方法，其中，腈化合物是乙腈。 [4] 如[3]之製造方法，1中 /、中乙腈係以相對於白金族^ 屬離子1莫耳為4莫 1〇〇重量份幻舌Γ 以相對於和 「51 & Μ 1 5「/Π、量份以上之量添加到前述溶液中。 []至[4]中任1項之贺 ^ 喟炙裝以方法，其中，溶液是含; 相對於白金族金屬離201033374 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a composition containing a platinum group metal. [Prior Art] Japanese Laid-Open Patent Publication No. 2005-194546 discloses a method of precipitating a platinum group metal ion by adding pyridine alone or together with a heteropoly acid solution to an acidic solution. SUMMARY OF THE INVENTION The present invention provides a method for efficiently obtaining a platinum group metal. The present invention relates to the following invention. [1] A method for producing a composition containing a platinum group metal, comprising: an i-th step of mixing a solution containing a platinum group metal ion and a heteropoly acid with a nitrile compound, and recovering by the first step Step 2 of the obtained composition containing a platinum group metal = the manufacturing method of [1], wherein the platinum metal ion is a seed of the [3] such as [1] or [2], and "Μ" The method wherein the nitrile compound is acetonitrile. [4] As in the manufacturing method of [3], 1 medium/medium acetonitrile is 4 moles per gram of weight relative to the platinum ion of the platinum group, relative to the sum "51 & Μ 1 5" / Π, the amount of the above amount is added to the above solution. [] to [4] in the 1 item of the ^ ^ 喟炙 以 method, wherein the solution is contained; relative to the platinum group metal
的雜多酸。 莫耳而有〇·5莫耳以上WHeteropoly acid. Moore and 〇·5 Moules or more W
[6]如[1]至[5]中任} : 項之製k方法，其中，雜多酸是i 321702 3 201033374 自由磷鉬酸、矽鉬酸、磷鎢酸、矽鎢酸、磷鉬鎢酸、 矽鉬鎢酸、磷鉬釩酸、矽鉬釩酸、磷鎢釩酸、及矽鎢 釩酸所成群組中至少一種。 ’’ [7] 如[1]至[6]中任1項之製造方法，其中，溶液是含有 水溶性有機化合物。 [8] 如[7]之製造方法，其中，水溶性有機化合物是選自由 乙醯胺、己二酸及環己酮所成群組中至少一種的化入 物。 〇 [9]如[1]至[8]中任丨項之製造方法，其中，溶液是經由 混合含有白金族金屬離子之液與雜多酸而得。 旧]一種用途，係藉由⑴至[9]中任i項之方法而得的含 有白金族金屬之組成物之氧化化合物製造中作 媒的使用。 [11] -種得到氧化化合物之方法，在藉由⑴至[9]中任i 項之方法而得之含有自金族金屬之組成物的存在下 由烯烴與氧氣而得。 【實施方式】 實施發明之形態： 阡鈿說明本發明。 本發明之含有白金族金屬之組成物的製造方法，包括 白金族金屬離子及雜多酸之溶液與腈化合物混合的 與，回收經由上述第1步驟所得之含有白金族 金屬之組成物的第2步驟。 在本發明中，含有白金族金屬之組成物是指至少含有 321702 4 201033374 1種之白金族金屬粉末或淤泥之意思。上述白金族金屬是 指屬於元素周期表第1〇族之元素，例如列舉··鈀、铑、釕、 鉑、銥、锇。 上述含有白金族金屬之組成物，並無特別限制，但通 常含有0· 01至15重量％之白金族金屬。 上述含有白金族金屬之組成物，可以含有後述之「其 他之成分」。 ❹ 在上述含有白金族金屬之組成物中，雖然上述其他之 成分的量並無特別限定，但其合計量以在1〇重量％以下 佳。 ’、、、 本發明中之溶液，一般為白金族金屬離子及雜多酸溶 解在溶劑中。 本發明中之白金族金屬離子係指屬於元素周期表第 族之元素的金屬離子。作為上述白金族金屬離子者，可以 列舉如：鈀離子、铑離子、釕離子、鉑離子、銥離子、餓 參離子，而以鈀離子為特佳。 上述白金族金屬離子之含量，雖無特別限制，但相對 於上述溶液，一般為1〇質量％以下，而以〇.〇1 為佳。 員^ 本發明之雜多酸一般以式（1)所示。 (A)e(XkMnOy) (1) (式中，A表示陽離子。X表示選自由屬於丨至“族元素所 成群組的1個元素，k表示i至5之整數，M表示選自由屬 於5、6族元素所成群組的至少丨個過渡元素，M在丨至 321702 5 201033374 種類之範圍内，亦可以為相異β n表示…〇之整數， 表示15至80之整數，e表示3至12之整數。） 5 特別=ί(1)中，A只要是―m雜子即可而無 特別的限疋’而以氫離子為佳。 上述雜多酸，以選自磷飽酸、石夕錮酸、碟鶴酸、 酸、鱗闕酸1賴酸、璘軸酸、独織、韻叙 酸、及料_所成群財至少—種為佳，較佳是仙酸、 磷翻叙酸，更佳是碟鉬釩酸。 〃上述雜多酸之含量雖無特別限制，因應其種類、白金 族金屬離子之種類及量，其理想範圍雖為相異，但每 耳白金族金屬離子，通常是在〇 5莫耳以上，而以耳 m更佳是3莫耳以上之量。上述雜多酸，因為藉 由添加，鎚、燒基銨、㈣等而可回收不溶之雜多酸鹽， 故其含^:之上限無特別限制，較佳是相對於每1莫耳 族金屬離子，為1〇莫耳以下之量。 、、’ 上述溶液中之溶劑，—般係水性溶劑，無特別限定， 但以水為佳。上述溶劑，口 _ 釗，、要在不使含有白金族金屬之組 =之生成效率降低之範圍，亦可以進 有機溶劑。 e 雜夕上述溶液只要不與白金族金屬離子反應並與 金:離鹽者，亦可以含有白金族金屬以外之 銅、鈥、飢 分」)。作為上述金屬離子者，例如列舉鐵，、他之成 鎢等之離子。 321702 6 201033374 作為上述水溶性有機化合物者，可列舉如選自由乙酿 胺、己二酸及環已鲷所成群組中至少〗種之化合物。 作為上述之其他之成分者，進一步可列舉:金族金屬 離子及雜多酸以外的水溶性無機化合物。作為如此之水汾 性無機化合物者，可列舉如選自由硫酸鐵及硫酸録鐵所^ 群組中至少1種之化合物。 其蚊化合㈣含量，只衫錢含有白金族金 馨屬之組成物之生成效率降低之範圍，就無特別限定。 作為含有白金族金屬離子與雜多酸之溶液者，可列舉 例如，使用白金族金屬及雜多酸作為觸媒而由烯烴製造氧 化化合物時的反應溶液等之含有白金族金屬離子與雜多酸 之反應溶液；使用白金族金屬離子與雜多酸之氧化化合物 之製造時生成的廢液。作為在製造上述氧化化合物中之反 應溶液者，可列舉如在國際公開第2009/116512號小冊、 日本國公開專利2008-231043號公報（特願2007-074374號） #等揭示的製法中之反應溶液。 ) 上述溶液，可為藉由混合含有白金族金屬離子之液與 雜多酸而得之液。作為如此之液者，可列舉如，在含有白 金族金屬離子之液中加入雜多酸而成之液。作為上述含有 白金族金屬離子之液者’例如可列舉如：使用白金族金屬 作為觸媒而由烯烴製造氧化化合物之時的反應溶液等，含 有白金族金屬離子之反應溶液；在使用上述白金族金屬之 氣化化合物之製造時生成的廢液；酸洗（pickling)浴液等 之廢液；地質學試料等，含有白金族金屬試料之分析中生 321702 7 201033374 成的廢液；使用過之裝飾品用洗淨液。 本發明中之溶液，亦可以含有如上述之其他的化合 物，但以預先除去環己烯等的烯烴後，才供予第1步驟者 為佳。經由自上述溶液除去烯烴即可更提高含有白金族金 屬之組成物之生成效率。 本發明中，作為腈化合物者，無特別限定，但可以用 下式表示。[6] The method according to any one of [1] to [5]: wherein the heteropoly acid is i 321702 3 201033374 free phosphomolybdic acid, lanthanum molybdate, phosphotungstic acid, lanthanum tungstic acid, phosphorus molybdenum At least one of the group consisting of tungstic acid, lanthanum molybdenum tungstic acid, phosphomolybdic vanadate, lanthanum molybdenum vanadate, phosphotungstic acid, and lanthanum tungstovanic acid. [7] The production method according to any one of [1] to [6] wherein the solution contains a water-soluble organic compound. [8] The production method according to [7], wherein the water-soluble organic compound is an chemical selected from at least one selected from the group consisting of acetamide, adipic acid, and cyclohexanone. [9] The method according to any one of [1] to [8] wherein the solution is obtained by mixing a liquid containing a platinum group metal ion with a heteropoly acid. The use of the oxidized compound in the composition of the platinum group-containing metal obtained by the method of any one of (1) to [9] is used as a medium. [11] A method for obtaining an oxidized compound derived from an olefin and oxygen in the presence of a composition derived from a metal group obtained by the method of any one of (1) to [9]. [Embodiment] Mode for carrying out the invention: The present invention will be described. The method for producing a composition containing a platinum group metal according to the present invention comprises mixing a solution of a platinum group metal ion and a heteropoly acid with a nitrile compound, and recovering the second composition containing the platinum group metal obtained by the first step. step. In the present invention, the composition containing a platinum group metal means at least 321702 4 201033374 of a platinum group metal powder or sludge. The above-mentioned platinum group metal refers to an element belonging to the first group of the periodic table, and examples thereof include palladium, rhodium, iridium, platinum, rhodium, iridium. The composition containing the platinum group metal is not particularly limited, but usually contains 0.1 to 15% by weight of a platinum group metal. The composition containing the platinum group metal may contain "other components" which will be described later. ❹ In the composition containing the platinum group metal, the amount of the other components is not particularly limited, but the total amount thereof is preferably 1% by weight or less. The solution in the present invention is generally a platinum metal ion and a heteropoly acid dissolved in a solvent. The platinum group metal ion in the present invention means a metal ion belonging to an element of the group of the periodic table. Examples of the platinum group metal ion include palladium ions, cerium ions, cerium ions, platinum ions, cerium ions, and cerium ions, and palladium ions are particularly preferred. The content of the platinum group metal ion is not particularly limited, but is generally 1% by mass or less based on the above solution, and preferably 〇.〇1. The heteropoly acid of the present invention is generally represented by the formula (1). (A) e(XkMnOy) (1) (wherein A represents a cation. X represents an element selected from the group consisting of 丨 to "group elements, k represents an integer from i to 5, and M represents a selected from 5, 6 elements of the group of at least one transition element, M in the range of 321702 5 201033374, can also be different β n represents ... 〇 integer, representing an integer from 15 to 80, e represents An integer from 3 to 12.) 5 In particular = ί (1), A is only a "m hetero group without special limitation" and hydrogen ions are preferred. The above heteropoly acid is selected from phosphorus saturated acid. , Shixi citrate, tarantic acid, acid, squaric acid 1 lysine, porphyric acid, solo, rhyme, and materials _ at least a group of good fortune, preferably is sorrow, phosphorus It is better to use a molybdenum vanadic acid. The content of the above heteropoly acid is not particularly limited. The ideal range of the type and amount of the platinum metal ion is different, but the white gold family is different. The metal ion is usually above 5 mA, and the ear m is more preferably 3 mA or more. The above heteropoly acid is added by hammer, amide, (4), etc. The upper limit of the inclusion of the heteropoly acid salt is not particularly limited, and is preferably an amount of less than 1 mole per 1 mole of the metal ion. The water-based solvent is not particularly limited, but water is preferred. The above solvent, the mouth _ 钊, may be added to the organic solvent in a range in which the production efficiency of the group containing the platinum group metal is not lowered. As long as the above solution does not react with the platinum metal ions and with gold: from the salt, it can also contain copper, bismuth, and hunger other than the platinum group metal. Examples of the metal ion include iron, and other ions such as tungsten. 321702 6 201033374 The above-mentioned water-soluble organic compound may, for example, be a compound selected from at least the group consisting of ethyleneamine, adipic acid and cyclohexanone. Further, as the other components described above, a water-soluble inorganic compound other than a gold metal ion and a heteropoly acid may be mentioned. As such a water-based inorganic compound, for example, a compound selected from at least one selected from the group consisting of iron sulfate and iron sulfate can be mentioned. The content of the mosquito (4) is not particularly limited as long as the production efficiency of the composition of the genus Platinum is reduced. Examples of the solution containing a platinum group metal ion and a heteropoly acid include a platinum group metal ion and a heteropoly acid, such as a reaction solution when an oxidized compound is produced from an olefin using a platinum group metal or a heteropoly acid as a catalyst. The reaction solution; the waste liquid generated when the oxidized compound of the platinum group metal ion and the heteropoly acid is used. The method of producing a reaction solution in the above-mentioned oxidized compound is exemplified in the method disclosed in International Publication No. 2009/116512, Japanese Laid-Open Patent Publication No. 2008-231043 (Japanese Patent Application No. 2007-074374). Reaction solution. The above solution may be a solution obtained by mixing a liquid containing a platinum group metal ion with a heteropoly acid. As such a liquid, for example, a liquid obtained by adding a heteropoly acid to a liquid containing a platinum group metal ion can be mentioned. For example, a reaction solution in which an oxidized compound is produced from an olefin using a platinum group metal as a catalyst, a reaction solution containing a platinum group metal ion, and the use of the above-mentioned platinum group are used. Waste liquid generated during the manufacture of metal gasification compounds; waste liquid such as pickling bath; geological samples, etc., containing the analysis of the platinum metal sample, the raw liquid of 321702 7 201033374; used Washing liquid for decorations. The solution of the present invention may contain other compounds as described above, but it is preferred to supply the olefin such as cyclohexene before the first step. The production efficiency of the composition containing the platinum group metal can be further improved by removing the olefin from the above solution. In the present invention, the nitrile compound is not particularly limited, but may be represented by the following formula.
R-CN (上述式中，R表示可經取代之碳數1至10的烷基、或是 可經取代之碳數6至10之芳香族基）。 作為上述腈化合物者，以碳數1至10的烷基腈為佳， 較佳是碳數1至5的炫基腈，更佳是乙腈。 上述第1步驟中之腈化合物之量，並無特別限定，可 對應腈化合物、雜多酸及白金族金屬離子之各種類以及濃 度而適當地選擇。 如上述腈化合物為乙腈時，每1莫耳白金族金屬離 子，通常，腈化合物是在1莫耳以上，而以15莫耳以上為 佳，更佳是50莫耳以上之量。上述腈化合物，因為可以藉 由蒸餾或萃取等來回收，故其量並無特別上限，但每1莫 耳白金族金屬離子，通常是在800莫耳以下，而以400莫 耳以下之量為佳。 如上述腈化合物為乙腈時，相對於溶液100重量份， 通常，腈化合物是在1重量份以上，而以5重量份以上為 佳，較佳是10重量份以上之量。上述腈化合物，因為可以 8 321702 201033374 藉由蒸鶴或萃取等來回收，故在其添加量上並無特別上 限，但相對於溶液100重量份，以100重量份以下為佳。 如上述腈化合物為乙腈時，以相對於白金族金屬離子1莫 耳為4莫耳以上且相對於溶液100重量份為1重量份以上 之量，與上述溶液混合為佳。 在上述第1步驟中，上述腈化合物，亦可以一次全量 混合，亦可分批混合。上述含有白金族金屬之組成物，通 常在腈化合物與溶液混合之同時，生成沉澱物。 ® 上述第1步驟，一般係以設定在0至100°C之溫度中 使溶劑等不蒸發下進行者為佳。上述第1步驟，因為通常 是在常溫、常壓下迅速進行，故不需要特別之反應裝置。 為了提高含有白金族金屬之組成物之收率，上述溶液 宜在混合腈化合物後靜置。該靜置時間通常為5分鐘至12 小時，但以製造效率之觀點而言，以5分鐘至30分鐘為佳。 本發明中之第2步驟，係回收上述第1步驟所得之含 φ 有白金族金屬之組成物之步驟。 上述含有白金族金屬之組成物，係如上述，經由第1 步驟而得到沉殿物。該沉殿物係藉也藤拆、你抽痛;r離心分 離等習用之固液分離操作可作為漿液或粉末而回收。 該含有白金族金屬之組成物，可以藉由以往習知方法 而調製成適當的形態。例如，藉由在烯烴（例如，環己烯） 溶劑中添加含有該白金族金屬之組成物之粉末，即可調製 含有白金族金屬之組成物之溶液〜 由本發明而得之含有白金族金屬之組成物，可以利用 9 321702 201033374 在各個領域中。 上述含有白金族金屬之組成物，例如，在由稀烴與氧 氣而得之氧化化合物之反應中，可以作為觸媒來使用。 具體上，由在國際公開第2009/1 16512號小冊、日本 國公開專利2008-231043號公報等揭示的由環己烯製造環 己酮之反應中產生的廢液，由本發明之方法製造含有白金 族金屬之組成物，即可將該含有白金族金屬之組成物作為 製造上述環己酮之觸媒使用。 實施例 以下，藉由實施例說明本發明，但本發明並不侷限該 等實施例。 參考例1至4 本參考例中，作為腈化物者，係直接使用乙腈（Naca 1 a i Tesque公司製）。作為雜多酸者，係直接使用H7PM08V4O40 或是H6PM09V3O4。（以上，曰本無機化學公司製）。 1. 在100 ml試樣瓶中，置入離子交換水（50g)、Fe2(S〇4)3 · nMKl. 2g，關東化學公司製）、Pd(OAc)2(0. 23g，Sigma-Aldrich公司）、雜多酸（7. 0g，日本無機化學公司； H7PM〇8V4〇4D)，進行6小時之超音波處理。 之後，將溶液以桐山漏斗抽濾（薄膜過濾器， No. 5B、SB-40)，除去微量之不溶物而得溶液A。 2. 在溶液A(12g)中，藉由溶解乙醯胺（0. 52g，關東化學 公司製）、己二酸（0. 16g，Nacalai Tesque 公司製）， 得到溶液B。 10 321702 201033374 3. 在100 ml試樣瓶中置入離子交換水（50g)、Fe2(S〇4)3, ηίί2〇(1. 2g)、Pd(OAcM0. 23g)、雜多酸（7. 0g， HtPMosVAd)，進行6小時之超音波處理。之後，將溶液 抽濾（四氟乙烯[PTFE]薄膜過濾器，細孔0.2//m、47mm φ)，除去微量之不溶物。藉由在所得之溶液（29g)中， 溶解乙醯胺（1. 2g)、環己酮（0. 31g，關東化學公司製） 得到溶液C。 4. 在200ml三角燒瓶中，置入離子交換水（101g)、Fe2 ft (S〇4)3 · nH2〇(2. 36g)、己二酸（1. 6g)、Pd(0Ac)2 (0. 46g)、雜多酸（14g，H3PM09V3O4。），進行6小時之超 音波處理。之後，將溶液抽濾（PTFE薄膜過濾器，細孔 0. 2 /i m、47mm φ )，除去微量之不溶物，得到溶液D。 溶液Α至D之各化學組成在表1中顯示。 11 321702 201033374 表1 成分元素 濃度（ppm) 溶液A Pd 1800 Fe 4200 S 3400 溶液B Pd 1700 Fe 3400 S 3200 己二酸 14000 乙醯胺 41000 溶液C Pd 1900 Fe 3500 S 3500 乙醯胺 38000 環己酮 10000 溶液D Pd 1500 Fe 3300 S 3300 己二酸 12000 實施例1至4 分別針對溶液A至D，在常溫常壓下，混入所預定之 乙腈。在任何溶液中，都可以用肉眼確認在混合乙腈之同 時有沉澱生成。 在混入乙腈後靜置5分鐘至12小時之後，所得之液， 分別在常溫下進行抽遽（PTFE薄膜過遽器，細孔0. 1 // m、 12 321702 201033374 2 5 mm φ ) 0 將回收之各沉澱物，分別以乙腈（4ml)洗淨之後，在 80°C藉由減壓乾燥3小時可得含有白金族金屬之組成物。 對於所得含有白金族金屬之各組成物，藉由微波分解 —ICP發光分析法進行元素分析之結果，Pd : P : N之平均 莫耳比約為2 : 1 : 8。 - 在上述抽濾時回收之液及溶液A至D，分別將各個化 學組成及回收率在表2中顯示。同時，化學組成及回收率， 係由下述方法進行。 •對於以溶液A至C作為材料製造時所得之各個濾液，Pd 及Fe之各別定量是藉由微波分解一ICP發光分析法進 行，S之定量是藉由氧氣燃燒一離子層析分析法進行。 •對於在以溶液D作為材料製造之時所得之濾液，Pd、Fe 及S之各別定量，係藉由螢光X線分析法來進行。 •對於全部溶液，己二酸之定量是藉由離子層析分析法來 φ 進行。 •對於全部溶液，乙醯胺及環己酮係藉由FID—氣體層析 分析法來進行。 •回收率是以下述之式計算出。 回收率={(溶液中之元素含量）一（濾液中之含量）}/ (溶液中之含量）χ100 13 321702 201033374 表2 添加量 渡液中之成分元素 濃度（ppm) 回收率（％) 溶液A 8 Pd <10 >99 Fe 4000 8 s 3600 <1 溶液B 7 Pd 45 97 Fe 2600 6 s 2500 4 己二酸 15000 <1 溶液C 5 Pd 160 91 Fe 3300 2 S 3200 5 乙醯胺 41000 1 環己酮 5400 47 溶液D 1 Pd 520 66 Fe 3200 <20 s 3500 <20 己二酸 12000 5 溶液D 5 Pd 100 91 Fe 3200 <20 S 3500 <20 己二酸 13000 <1 溶液D 10 Pd <10 >99 Fe 2900 <20 s 3100 <20 己二酸 13000 <1 溶液D 21 Pd <10 >99 Fe 2700 <20 S 3100 <20 己二酸 10000 10 14 321702 201033374 溶液D 30 Pd <10 >99 Fe 2600 <20 S 2800 <20 己二酸 12000 <1 溶液D 39 Pd <10 >99 Fe 2600 <20 S 2900 <20 己二酸 11000 <1 溶液D 56 Pd <10 >99 Fe 2000 <20 S 2400 <20 | 註：混合量係表示相對於溶液100重量份之乙腈的添加量（重量份）。 實施例5 具體上，將環己烯（1.6g，關東化學公司製）、乙腈（3 ml)、離子交換水（2ml)、由上述溶液A所得之含有白金族 金屬之組成物（Is含量 8 重量％)(24mg)、H7PM〇8V4〇4d(0. lg)、 及Fe2(S〇4)3 · nH2〇(27mg)置入120 ml容量之高壓锅内，導 入氮氣3 MPa及加壓空氣2MPa，在323 K反應2小時，可 得環己酮。環己烯之轉化率為32%，環己酮之選擇率為 93%，轉化（turnover)數（每1莫耳Ιε生成之環已酮的莫耳 數）是354。 產業上之可利用性 本發明之含有白金族金屬之組成物的製造方法，可以 使用為在由各種之廢棄觸媒的浸出液、各植金展的酸洗淨 液或各種礦/工業排水中含有微量之白金族金屬離子得到 15 321702 201033374 白金族金屬的方法。 依上述之製造方法，因為可以回收/再利用貴重金屬 之白金族金屬，故可以解除源自白金族金屬而引起之環境 問題。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 16 321702R-CN (In the above formula, R represents an alkyl group having 1 to 10 carbon atoms which may be substituted, or an aromatic group having 6 to 10 carbon atoms which may be substituted). As the nitrile compound, an alkyl nitrile having 1 to 10 carbon atoms is preferred, and a fluorenyl nitrile having 1 to 5 carbon atoms is preferred, and acetonitrile is more preferred. The amount of the nitrile compound in the first step is not particularly limited, and may be appropriately selected depending on various types and concentrations of the nitrile compound, the heteropoly acid, and the platinum group metal ion. When the nitrile compound is acetonitrile, the amount of the metal ion per 1 mol of the platinum group is usually 1 mol or more, more preferably 15 mol or more, and still more preferably 50 mol or more. The above nitrile compound is not particularly limited because it can be recovered by distillation or extraction, but is usually at least 800 m per 1 mol of the platinum metal ion, and is less than 400 m. good. When the nitrile compound is acetonitrile, the nitrile compound is usually 1 part by weight or more, more preferably 5 parts by weight or more, and more preferably 10 parts by weight or more based on 100 parts by weight of the solution. The nitrile compound is recovered by steaming or extraction, etc., and is not particularly limited in its amount, but it is preferably 100 parts by weight or less based on 100 parts by weight of the solution. When the nitrile compound is acetonitrile, it is preferably mixed with the above solution in an amount of 4 mol or more per mol of the platinum group metal ion and 1 part by weight or more based on 100 parts by weight of the solution. In the above first step, the nitrile compound may be mixed in a single amount or may be mixed in portions. The above composition containing a platinum group metal usually forms a precipitate while the nitrile compound is mixed with the solution. ® The above first step is generally carried out at a temperature of 0 to 100 ° C so that the solvent or the like does not evaporate. Since the first step described above is usually carried out rapidly at normal temperature and normal pressure, a special reaction apparatus is not required. In order to increase the yield of the composition containing the platinum group metal, the above solution is preferably allowed to stand after mixing the nitrile compound. The standing time is usually from 5 minutes to 12 hours, but from the viewpoint of production efficiency, it is preferably from 5 minutes to 30 minutes. In the second step of the present invention, the step of recovering the composition containing the platinum group metal obtained in the first step is recovered. The composition containing the platinum group metal is obtained as described above through the first step. The system of the sacred temple is removed by the vine, and you are painful; the solid-liquid separation operation such as centrifugation separation can be recovered as a slurry or a powder. The composition containing the platinum group metal can be prepared into an appropriate form by a conventional method. For example, by adding a powder containing a composition of the platinum group metal to an olefin (for example, cyclohexene) solvent, a solution containing a composition of a platinum group metal can be prepared~ a white gold group-containing metal obtained by the present invention The composition can be utilized in various fields in 9 321702 201033374. The composition containing the platinum group metal, for example, can be used as a catalyst in the reaction of an oxidizing compound derived from a rare hydrocarbon and oxygen. Specifically, the waste liquid generated in the reaction of producing cyclohexanone from cyclohexene disclosed in the pamphlet of International Publication No. 2009/1 16512, Japanese Laid-Open Patent Publication No. 2008-231043, etc., is produced by the method of the present invention. The composition of the platinum group metal can be used as a catalyst for producing the above cyclohexanone. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples. Reference Examples 1 to 4 In the present Reference Example, as the nitrile compound, acetonitrile (manufactured by Naca 1 a Te Tesque Co., Ltd.) was used as it is. As a heteropoly acid, H7PM08V4O40 or H6PM09V3O4 is used directly. (The above, manufactured by Sakamoto Inorganic Chemical Co., Ltd.). 1. In a 100 ml sample vial, place ion-exchanged water (50g), Fe2(S〇4)3 · nMKl. 2g, manufactured by Kanto Chemical Co., Ltd., Pd(OAc)2 (0. 23g, Sigma-Aldrich) Company), heteropoly acid (7. 0g, Nippon Inorganic Chemical Co., Ltd.; H7PM 〇 8V4 〇 4D), for 6 hours of ultrasonic processing. Thereafter, the solution was filtered with a Kiriyama funnel (membrane filter, No. 5B, SB-40) to remove a trace amount of insoluble matter to obtain a solution A. 2. In solution A (12 g), solution B was obtained by dissolving acetamide (0.52 g, manufactured by Kanto Chemical Co., Ltd.) and adipic acid (0.16 g, manufactured by Nacalai Tesque Co., Ltd.). 10 321702 201033374 3. Place ion-exchanged water (50g), Fe2(S〇4)3, ηίί2〇 (1.2g), Pd(OAcM0.23g), heteropolyacid in a 100 ml sample vial (7. 0g, HtPMosVAd), 6 hours of ultrasonic processing. Thereafter, the solution was suction filtered (tetrafluoroethylene [PTFE] membrane filter, pores 0.2//m, 47 mm φ) to remove traces of insoluble matter. Solution C was obtained by dissolving acetamidine (1.2 g) and cyclohexanone (0.11 g, manufactured by Kanto Chemical Co., Ltd.) in the obtained solution (29 g). 4. In a 200 ml Erlenmeyer flask, ion-exchanged water (101 g), Fe2 ft (S〇4) 3 · nH2 〇 (2.36 g), adipic acid (1.6 g), Pd(0Ac) 2 (0) 46g), heteropoly acid (14g, H3PM09V3O4.), 6 hours of ultrasonic processing. Thereafter, the solution was suction filtered (PTFE membrane filter, pores 0. 2 /i m, 47 mm φ ), and a trace amount of insoluble matter was removed to obtain a solution D. The chemical compositions of the solutions Α to D are shown in Table 1. 11 321702 201033374 Table 1 Concentration of constituent elements (ppm) Solution A Pd 1800 Fe 4200 S 3400 Solution B Pd 1700 Fe 3400 S 3200 Adipic acid 14000 Acetamide 41000 Solution C Pd 1900 Fe 3500 S 3500 Acetamide 38000 Cyclohexanone 10000 solution D Pd 1500 Fe 3300 S 3300 Adipic acid 12000 Examples 1 to 4 For the solutions A to D, respectively, the predetermined acetonitrile was mixed under normal temperature and normal pressure. In any solution, it was confirmed with the naked eye that a precipitate was formed while mixing acetonitrile. After standing for 5 minutes to 12 hours after mixing with acetonitrile, the resulting liquid is subjected to suction at room temperature (PTFE film filter, pores 0.11 m, 12 321702 201033374 2 5 mm φ ) 0 Each of the recovered precipitates was washed with acetonitrile (4 ml), and then dried under reduced pressure at 80 ° C for 3 hours to obtain a composition containing a platinum group metal. As a result of elemental analysis of each of the obtained compositions containing a platinum group metal by microwave decomposition-ICP luminescence analysis, the average molar ratio of Pd : P : N was about 2:1:8. - The respective chemical compositions and recovery rates are shown in Table 2 for the liquids recovered in the above-mentioned filtration and the solutions A to D. At the same time, the chemical composition and recovery rate were carried out by the following methods. • For each filtrate obtained by using the solutions A to C as a material, the respective quantifications of Pd and Fe are carried out by microwave decomposition-ICP luminescence analysis, and the quantification of S is performed by oxygen combustion-ion chromatography. . • For the filtrate obtained when the solution D is used as a material, the respective quantitative amounts of Pd, Fe and S are determined by fluorescent X-ray analysis. • For all solutions, the adipic acid is quantified by ion chromatography to φ. • For all solutions, acetamide and cyclohexanone were carried out by FID-gas chromatography. • The recovery rate is calculated as follows. Recovery rate = {(the content of the element in the solution) - (the content in the filtrate)} / (the content in the solution) χ 100 13 321702 201033374 Table 2 The concentration of the element in the added amount of the liquid (ppm) Recovery (%) Solution A 8 Pd <10 >99 Fe 4000 8 s 3600 <1 Solution B 7 Pd 45 97 Fe 2600 6 s 2500 4 Adipic acid 15000 <1 Solution C 5 Pd 160 91 Fe 3300 2 S 3200 5 Acetyl Amine 41000 1 cyclohexanone 5400 47 solution D 1 Pd 520 66 Fe 3200 <20 s 3500 <20 adipic acid 12000 5 solution D 5 Pd 100 91 Fe 3200 <20 S 3500 <20 adipic acid 13000 <;1 solution D 10 Pd <10 >99 Fe 2900 <20 s 3100 <20 adipic acid 13000 <1 solution D 21 Pd <10 >99 Fe 2700 <20 S 3100 <20 Diacid 10000 10 14 321702 201033374 Solution D 30 Pd <10 >99 Fe 2600 <20 S 2800 <20 Adipic acid 12000 <1 Solution D 39 Pd <10 >99 Fe 2600 <20 S 2900 <20 adipic acid 11000 <1 solution D 56 Pd <10 >99 Fe 2000 <20 S 2400 <20 | Note: The mixed amount means 100 parts by weight relative to the solution. Addition amount (parts by weight). Example 5 Specifically, cyclohexene (1.6 g, manufactured by Kanto Chemical Co., Ltd.), acetonitrile (3 ml), ion-exchanged water (2 ml), and a composition containing a platinum group metal obtained from the above solution A (Is content 8) (% by weight) (24mg), H7PM 〇 8V4 〇 4d (0. lg), and Fe2 (S〇4) 3 · nH2 〇 (27mg) placed in a 120 ml capacity pressure cooker, introducing nitrogen 3 MPa and pressurized air 2 MPa, reacted at 323 K for 2 hours to obtain cyclohexanone. The conversion of cyclohexene was 32%, the selectivity of cyclohexanone was 93%, and the number of turnovers (the number of moles of cyclohexanone per 1 mole of ε) was 354. INDUSTRIAL APPLICABILITY The method for producing a composition containing a platinum group metal of the present invention can be used in a leachate containing various waste catalysts, an acid cleaning solution for each planting gold, or various mineral/industrial drainages. A trace of the platinum group metal ion is obtained by the method of 15 321702 201033374 Platinum metal. According to the above manufacturing method, since the platinum metal of the precious metal can be recovered/recycled, environmental problems caused by the platinum group metal can be removed. [Simple description of the diagram] None. [Main component symbol description] None 0 16 321702