WO2010074294A1 - Method for manufacturing composition containing platinum group metal - Google Patents

Method for manufacturing composition containing platinum group metal Download PDF

Info

Publication number
WO2010074294A1
WO2010074294A1 PCT/JP2009/071828 JP2009071828W WO2010074294A1 WO 2010074294 A1 WO2010074294 A1 WO 2010074294A1 JP 2009071828 W JP2009071828 W JP 2009071828W WO 2010074294 A1 WO2010074294 A1 WO 2010074294A1
Authority
WO
WIPO (PCT)
Prior art keywords
platinum group
group metal
acid
solution
containing composition
Prior art date
Application number
PCT/JP2009/071828
Other languages
French (fr)
Japanese (ja)
Inventor
村上昌義
西本純一
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2010074294A1 publication Critical patent/WO2010074294A1/en

Links

Classifications

    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/33—Cyanic acids, derivatives thereof
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for producing a platinum group metal-containing composition.
  • Japanese Patent Publication No. 2005-194546 describes a method of precipitating platinum group metal ions by adding pyridine alone or together with a heteropolyacid solution to an acidic solution.
  • the present invention provides a method for efficiently obtaining a platinum group metal.
  • the present application relates to the following inventions.
  • a platinum group comprising a first step of mixing a solution containing a platinum group metal ion and a heteropoly acid and a nitrile compound, and a second step of recovering the platinum group metal-containing composition obtained in the first step.
  • a method for producing a metal-containing composition [2] The production method according to [1], wherein the platinum group metal ion is palladium ion. [3] The production method according to [1] or [2], wherein the nitrile compound is acetonitrile.
  • Heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, cinnamolybdovanadic acid, and lintongue tovanadine
  • the method for producing a platinum group metal-containing composition of the present invention includes a first step of mixing a solution containing a platinum group metal ion and a heteropolyacid and a nitrile compound, and a platinum group metal-containing composition obtained by the first step. A second step of recovering.
  • the platinum group metal-containing composition means a powder or slurry containing at least one platinum group metal.
  • the platinum group metal is an element belonging to Group 10 of the periodic table of elements, and examples thereof include palladium, rhodium, ruthenium, platinum, iridium, and osmium.
  • the platinum group metal-containing composition is not particularly limited, but usually contains 0.01 to 15% by weight of a platinum group metal.
  • the platinum group metal-containing composition may contain “other components” described later.
  • the amount of the other components is not particularly limited, but the total amount is preferably 10% by weight or less.
  • a platinum group metal ion and a heteropolyacid are dissolved in a solvent.
  • the platinum group metal ion in the present invention is a metal ion of an element belonging to Group 10 of the periodic table of elements.
  • platinum group metal ion examples include palladium ion, rhodium ion, ruthenium ion, platinum ion, iridium ion, and osmium ion, and palladium ion is particularly preferable.
  • the platinum group metal ion content is not particularly limited, but is generally ⁇ 10% by mass, preferably 0.01-1% by mass, based on the above solution.
  • the heteropolyacid in the present invention is generally represented by the formula (1). (A) e (X k M n O y ) (1) (In the formula, A represents a cation.
  • X represents one element selected from the group consisting of elements belonging to groups 1 to 16, k represents an integer of 1 to 5, M represents 5, 6 Represents at least one transition element selected from the group consisting of elements belonging to the group, M may be different within a range of 1 to 3 types, n represents an integer of 5 to 20, and y represents 15 Represents an integer of ⁇ 80, and e represents an integer of 3 to 12.
  • A is not particularly limited as long as it is a monovalent or divalent cation, but is preferably a hydrogen ion.
  • the heteropolyacid is phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, xymolybdovanadic acid, lintongue It is at least one selected from the group consisting of vanadic acid and catanthost vanadic acid, more preferably phosphomolybdic acid and phosphomolybdovanadic acid, and still more preferably phosphomolybdovanadic acid.
  • the content of the heteropolyacid is not particularly limited, and the preferred range varies depending on the type and the type and amount of the platinum group metal ion, but usually 0.5 mol or more per mol of the platinum group metal ion, preferably Is an amount of 1 mol or more, more preferably 3 mol or more.
  • the heteropolyacid can be recovered as an insoluble heteropolyacid salt by adding cesium carbonate, alkylammonium, pyridine, etc., so the upper limit of the content is not particularly limited, but preferably 10 mol per mole of platinum group metal ion The amount is less than the mole.
  • the solvent in the solution is generally an aqueous solvent and is not particularly limited, but water is preferable.
  • the solvent may further contain an organic solvent such as cyclohexanone as long as the production efficiency of the platinum group metal-containing composition does not decrease.
  • organic solvent such as cyclohexanone
  • metal ions other than the platinum group metal or water-soluble organic compounds (hereinafter referred to as “other components”). May be included).
  • other components metal ions, such as iron, copper, titanium, vanadium, molybdenum, tungsten, are mentioned, for example.
  • the water-soluble organic compound include at least one compound selected from the group consisting of acetamide, adipic acid and cyclohexanone.
  • Examples of the other components further include water-soluble inorganic compounds other than platinum group metal ions and heteropolyacids.
  • a water-soluble inorganic compound include at least one compound selected from the group consisting of iron sulfate and ammonium iron sulfate.
  • the content of the other compounds is not particularly limited as long as the production efficiency of the platinum group metal-containing composition is not lowered.
  • a solution containing a platinum group metal ion and a heteropoly acid for example, a reaction solution for producing an oxide compound from an olefin using a platinum group metal and a heteropoly acid as a catalyst, a reaction containing a platinum group metal ion and a heteropoly acid.
  • a solution a waste solution generated in the production of an oxide compound using a platinum group metal ion and a heteropolyacid.
  • the reaction solution in the production of the oxidized compound include a reaction solution in the production method described in International Publication No. 2009/116512, Japanese Patent Publication No. 2008-231043 (Japanese Patent Application No. 2007-074374), and the like.
  • the solution may be a liquid obtained by mixing a liquid containing a platinum group metal ion and a heteropolyacid. Examples of such a liquid include a liquid obtained by adding a heteropolyacid to a liquid containing a platinum group metal ion.
  • the liquid containing the platinum group metal ion examples include a reaction solution containing a platinum group metal ion such as a reaction solution for producing an oxide compound from an olefin using a platinum group metal as a catalyst; Examples include waste liquids generated during the production of oxidized compounds; waste liquids such as pickling bath liquids; waste liquids generated in the analysis of samples containing platinum group metals such as geological samples; used cleaning liquids for decorative products.
  • the solution in the present invention may contain other compounds as described above, it is preferable to use the first step after removing olefins such as cyclohexene in advance. By removing the olefin from the solution, the production efficiency of the platinum group metal-containing composition can be further improved.
  • the nitrile compound is not particularly limited, but the formula R-CN (In the above formula, R represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic group having 6 to 10 carbon atoms).
  • the nitrile compound is preferably an alkyl nitrile having 1 to 10 carbon atoms, more preferably an alkyl nitrile having 1 to 5 carbon atoms, and still more preferably acetonitrile.
  • the amount of the nitrile compound in the first step is not particularly limited, and can be appropriately selected according to each kind and concentration of the nitrile compound, the heteropolyacid, and the platinum group metal ion.
  • the amount is usually 1 mol or more, preferably 15 mol or more, more preferably 50 mol or more per 1 mol of platinum group metal ion. Since the nitrile compound can be recovered by distillation, extraction or the like, the amount thereof is not particularly limited, but is usually 800 mol or less, preferably 400 mol or less per 1 mol of platinum group metal ions.
  • the amount is usually 1 part by weight or more, preferably 5 parts by weight, more preferably 10 parts by weight or more with respect to 100 parts by weight of the solution.
  • the nitrile compound can be recovered by distillation, extraction or the like, there is no particular upper limit to the amount added, but it is preferably 100 parts by weight or less with respect to 100 parts by weight of the solution.
  • the nitrile compound is preferably mixed with the solution in an amount of 4 moles or more per 1 mole of platinum group metal ions and 1 weight part or more with respect to 100 parts by weight of the solution.
  • the nitrile compound may be mixed all at once or divided and mixed.
  • the platinum group metal-containing composition is usually formed as a precipitate simultaneously with mixing the nitrile compound and the solution.
  • the first step is preferably performed at a temperature of 0 to 100 ° C.
  • the 2nd process in this invention is a process of collect
  • the platinum group metal-containing composition is obtained as a precipitate by the first step as described above. This precipitate can be recovered as a slurry or powder by a conventional solid-liquid separation operation such as decantation, suction filtration, and centrifugation.
  • Such a platinum group metal-containing composition can be prepared in an appropriate form by a conventionally known method.
  • the platinum group metal-containing composition solution can be prepared by adding the platinum group metal-containing composition powder to an olefin (eg, cyclohexene) solvent.
  • the platinum group metal-containing composition obtained by the present invention can be used in various fields.
  • the platinum group metal-containing composition can be used, for example, as a catalyst in a reaction for obtaining an oxidized compound from olefin and oxygen.
  • the platinum group metal-containing composition is produced by the method of the present invention from the waste liquid produced in the reaction for producing cyclohexanone from cyclohexene described in International Publication No. 2009/116512 pamphlet, Japanese Patent Publication No. 2008-231043, etc.
  • This platinum group metal-containing composition can be used as a catalyst for the production of cyclohexanone.
  • a solution B was obtained by dissolving acetamide (0.52 g, Kanto Chemical Co., Inc.) and adipic acid (0.16 g, Nacalai Tesque Co., Ltd.) in the solution A (12 g). 3.
  • Table 2 shows the chemical composition and the recovery rate for each of the filtrate and solutions A to D recovered during the suction filtration.
  • the chemical composition and recovery rate were determined by the following method. -For each filtrate obtained in the production using solutions A to C, each determination of Pd and Fe is performed by microwave decomposition-ICP emission spectrometry, and the determination of S is oxygen combustion-ion chromatograph Done by law. -About the filtrate obtained at the time of manufacture which used the solution D as a material, each fixed_quantity
  • quantitative_assay of adipic acid was performed by the ion chromatography method.
  • Recovery rate (%) ⁇ (content of element in solution) ⁇ (content in filtrate) ⁇ / (content in solution) ⁇ 100
  • the mixing amount represents the amount of acetonitrile (parts by weight) added to 100 parts by weight of the solution.
  • Example 5 Specifically, cyclohexene (1.6 g, Kanto Chemical Co., Inc.), acetonitrile (3 ml), ion-exchanged water (2 ml), platinum group metal-containing composition obtained from the above solution A (palladium content 8 wt%) (24 mg), H 7 PMo 8 V 4 O 40 (0.1 g) and Fe 2 (SO 4 ) 3 ⁇ nH 2 O (27 mg) were placed in a 120 ml capacity autoclave, and nitrogen gas 3 MPa and pressurized air 2 MPa were introduced. And reacted at 323 K for 2 hours to obtain cyclohexanone. The conversion rate of cyclohexene was 32%, the selectivity of cyclohexanone was 93%, and the turnover number (number of moles of cyclohexanone produced per mole of palladium) was 354.
  • the method for producing a platinum group metal-containing composition of the present invention is useful as a method for obtaining a platinum group metal from a platinum group metal ion contained in a trace amount in various metal leaching solutions, acid washing solutions of various metals and various minerals and industrial effluents. It is. According to the above manufacturing method, the platinum group metal, which is a valuable metal, can be recovered and reused, so that environmental problems caused by the platinum group metal can be solved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a method for manufacturing a composition containing a platinum group metal, said method including a first step wherein a nitrile compound and a solution containing platinum group metal ions and a heteropoly acid are mixed together, and a second step wherein the composition containing a platinum group metal which is obtained in the first step is recovered.

Description

白金族金属含有組成物の製造方法Method for producing platinum group metal-containing composition
　本発明は、白金族金属含有組成物の製造方法に関するものである。 The present invention relates to a method for producing a platinum group metal-containing composition.
　日本国公開特許２００５−１９４５４６号公報には、ピリジンを単独またはヘテロポリ酸溶液とともに酸性溶液に添加することにより白金族金属イオンを沈殿させる方法が記載されている。 Japanese Patent Publication No. 2005-194546 describes a method of precipitating platinum group metal ions by adding pyridine alone or together with a heteropolyacid solution to an acidic solution.
　本発明は、白金族金属を効率的に得る方法を提供する。
　本願は、以下の発明に関する。
［１］　白金族金属イオンおよびヘテロポリ酸を含む溶液とニトリル化合物とを混合する第１工程と、前記第１工程により得られた白金族金属含有組成物を回収する第２工程とを含む白金族金属含有組成物の製造方法。
［２］　白金族金属イオンはパラジウムイオンである［１］に記載の製造方法。
［３］　ニトリル化合物はアセトニトリルである［１］又は［２］に記載の製造方法。
［４］　アセトニトリルは、白金族金属イオン１モルに対し４モル以上且つ溶液１００重量部に対し１重量部以上の量で前記溶液に添加される［３］に記載の製造方法。
［５］　溶液は、白金族金属イオン１モルに対し０．５モル以上の量でヘテロポリ酸を含む［１］~［４］のいずれか１項に記載の製造方法。
［６］　ヘテロポリ酸は、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、ケイタングステン酸、リンモリブドタングステン酸、ケイモリブドタングステン酸、リンモリブドバナジン酸、ケイモリブドバナジン酸、リンタングストバナジン酸およびケイタングストバナジン酸からなる群より選ばれる少なくとも１つである［１］~［５］のいずれか１項に記載の製造方法。
［７］　溶液は、水溶性有機化合物を含む［１］~［６］のいずれか１項に記載の製造方法。
［８］　水溶性有機化合物は、アセトアミド、アジピン酸およびシクロヘキサノンからなる群より選ばれる少なくとも１つの化合物である［７］記載の製造方法。
［９］　溶液は、白金族金属イオンを含む液とヘテロポリ酸とを混合することにより得られる［１］~［８］のいずれか１項に記載の製造方法。
［１０］　［１］~［９］のいずれか１項に記載の方法により得られた白金族金属含有組成物の酸化化合物製造における触媒としての使用。
［１１］　［１］~［９］のいずれか１項に記載の方法により得られた白金族金属含有組成物の存在下でオレフィンと酸素とから酸化化合物を得る方法。 The present invention provides a method for efficiently obtaining a platinum group metal.
The present application relates to the following inventions.
[1] A platinum group comprising a first step of mixing a solution containing a platinum group metal ion and a heteropoly acid and a nitrile compound, and a second step of recovering the platinum group metal-containing composition obtained in the first step. A method for producing a metal-containing composition.
[2] The production method according to [1], wherein the platinum group metal ion is palladium ion.
[3] The production method according to [1] or [2], wherein the nitrile compound is acetonitrile.
[4] The production method according to [3], wherein acetonitrile is added to the solution in an amount of 4 moles or more per 1 mole of platinum group metal ions and 1 weight part or more with respect to 100 weight parts of the solution.
[5] The production method according to any one of [1] to [4], wherein the solution contains a heteropolyacid in an amount of 0.5 mol or more per 1 mol of platinum group metal ions.
[6] Heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, cinnamolybdovanadic acid, and lintongue tovanadine [1] The production method according to any one of [1] to [5], which is at least one selected from the group consisting of an acid and a catangst vanadic 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 at least one compound selected from the group consisting of acetamide, adipic acid and cyclohexanone.
[9] The production method according to any one of [1] to [8], wherein the solution is obtained by mixing a liquid containing a platinum group metal ion and a heteropolyacid.
[10] Use of the platinum group metal-containing composition obtained by the method according to any one of [1] to [9] as a catalyst in the production of an oxidized compound.
[11] A method for obtaining an oxide compound from olefin and oxygen in the presence of the platinum group metal-containing composition obtained by the method according to any one of [1] to [9].
　以下、本発明を詳細に説明する。
　本発明の白金族金属含有組成物の製造方法は、白金族金属イオンおよびヘテロポリ酸を含む溶液とニトリル化合物とを混合する第１工程と、上記第１工程により得られた白金族金属含有組成物を回収する第２工程とを含む。
　本発明において、白金族金属含有組成物とは、少なくとも１種の白金族金属を含む粉末、またはスラリーを意味する。上記白金族金属とは、元素の周期律表第１０族に属する元素であり、例えば、パラジウム、ロジウム、ルテニウム、白金、イリジウム、オスミウムが挙げられる。
　上記白金族金属含有組成物は、特に限定されないが、通常０．０１~１５重量％の白金族金属を含む。
　上記白金族金属含有組成物は、後述の「その他の成分」を含有してよい。
　上記白金族金属含有組成物において、上記その他の成分の量は特に限定されないが、その合計量が１０重量％以下であることが好ましい。
　本発明における溶液は、一般に、白金族金属イオンおよびヘテロポリ酸が溶媒に溶解している。
　本発明における白金族金属イオンとは、元素の周期律表第１０族に属する元素の金属イオンである。上記白金族金属イオンとしては、例えば、パラジウムイオン、ロジウムイオン、ルテニウムイオン、白金イオン、イリジウムイオン、オスミウムイオンが挙げられるが、パラジウムイオンが特に好ましい。
　上記白金族金属イオンの含有量は、特に制限されないが、上記溶液に対し一般に~１０質量％、好ましくは０．０１~１質量％である。
　本発明におけるヘテロポリ酸とは、一般に式（１）で示される。
　（Ａ）ｅ（ＸｋＭｎＯｙ）　（１）
　（式中、Ａは、カチオンを表す。Ｘは、１~１６族に属する元素からなる群より選択される１つの元素を表し、ｋは１~５の整数を表し、Ｍは、５、６族に属する元素からなる群より選択される少なくとも１つの遷移元素を表す。Ｍは、１~３種類の範囲内で、異なっていてもよい。ｎは５~２０の整数を表し、ｙは１５~８０の整数を表し、ｅは３~１２の整数を表す。）
　上記式（１）において、Ａは一価又は二価のカチオンであれば特に限定されないが、水素イオンが好ましい。
　上記ヘテロポリ酸は、好ましくは、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、ケイタングステン酸、リンモリブドタングステン酸、ケイモリブドタングステン酸、リンモリブドバナジン酸、ケイモリブドバナジン酸、リンタングストバナジン酸およびケイタングストバナジン酸からなる群より選ばれる少なくとも１つであり、より好ましくはリンモリブデン酸、リンモリブドバナジン酸であり、更に好ましくはリンモリブドバナジン酸である。
　上記ヘテロポリ酸の含有量は特に制限されず、その種類や、白金族金属イオンの種類および量に応じて、好ましい範囲が異なるが、白金族金属イオン１モルあたり、通常０．５モル以上、好ましくは１モル以上、より好ましくは３モル以上の量である。上記ヘテロポリ酸は、炭酸セシウム、アルキルアンモニウム、ピリジン等を添加することにより不溶なヘテロポリ酸塩として回収可能なので、その含有量の上限は特に制限されないが、好ましくは、白金族金属イオン１モルあたり１０モル以下の量である。
　上記溶液における溶媒は、一般に水性溶媒であり、特に限定されないが、水が好ましい。上記溶媒は、白金族金属含有組成物の生成効率が低下しない範囲であれは、更にシクロヘキサノン等の有機溶媒が含まれていてもよい。
　上記溶液は、更に、白金族金属イオンと反応せずヘテロポリ酸と不溶な塩を形成しないものであれば、白金族金属以外の金属イオンや水溶性有機化合物（以下、これらを「その他の成分」と称する。）を含有してもよい。上記金属イオンとしては、例えば、鉄、銅、チタン、バナジウム、モリブデン、タングステン等のイオンが挙げられる。
　上記水溶性有機化合物としては、例えば、アセトアミド、アジピン酸及びシクロヘキサノンからなる群より選ばれる少なくとも１つの化合物が挙げられる。
　上記その他の成分としては、更に、白金族金属イオン及びヘテロポリ酸以外の水溶性無機化合物が挙げられる。このような水溶性無機化合物としては、硫酸鉄および硫酸アンモニウム鉄からなる群より選ばれる少なくとも１つの化合物が挙げられる。
　上記その他の化合物の含有量は、白金族金属含有組成物の生成効率が低下しない範囲であれは、特に限定されない。
　白金族金属イオンとヘテロポリ酸とを含む溶液としては、例えば、白金族金属およびヘテロポリ酸を触媒として用いてオレフィンから酸化化合物を製造する際の反応溶液等、白金族金属イオンおよびヘテロポリ酸を含む反応溶液；白金族金属イオンとヘテロポリ酸を用いた酸化化合物の製造の際に生じる廃液；が挙げられる。上記酸化化合物の製造における反応溶液として、国際公開第２００９／１１６５１２号パンフレット、日本国公開特許２００８−２３１０４３号公報（特願２００７−０７４３７４号）等に記載の製法における反応溶液が挙げられる。
　上記溶液は、白金族金属イオンを含む液とヘテロポリ酸とを混合することにより得られる液であってよい。このような液として、例えば、白金族金属イオンを含む液にヘテロポリ酸を加えた液が挙げられる。上記白金族金属イオンを含む液としては、例えば、触媒として白金族金属を用いてオレフィンから酸化化合物を製造する際の反応溶液等、白金族金属イオンを含む反応溶液；上記白金族金属を用いた酸化化合物の製造の際に生じる廃液；ピクリング浴液等の廃液；地質学試料等、白金族金属を含む試料の分析において生じる廃液；使用済みの装飾品用洗浄液；が挙げられる。
　本発明における溶液は、上述のようにその他の化合物を含有してもよいが、シクロヘキセン等のオレフィンを予め除去した後で、第１工程に供することが好ましい。上記溶液からオレフィンを除去することにより、白金族金属含有組成物の生成効率を更に向上することができる。
　本発明において、ニトリル化合物としては、特に限定されないが、式
Ｒ−ＣＮ
（上記式において、Ｒは、置換されてもよい炭素数１~１０のアルキル基、または置換されてもよい炭素数６~１０の芳香族基を表す。）で表される。
　上記ニトリル化合物としては、好ましくは炭素数１~１０のアルキルニトリル、より好ましくは炭素数１~５のアルキルニトリル、更に好ましくはアセトニトリルである。
　上記第１工程におけるニトリル化合物の量は、特に限定されず、ニトリル化合物、ヘテロポリ酸および白金族金属イオンの各種類並びに濃度に応じて適宜選択することができる。
　上記ニトリル化合物は、例えばアセトニトリルである場合、白金族金属イオン１モルあたり、通常１モル以上、好ましくは１５モル以上、より好ましくは５０モル以上の量である。上記ニトリル化合物は、蒸留や抽出等により回収できるので、その量に特に上限はないが、白金族金属イオン１モルあたり、通常８００モル以下、好ましくは４００モル以下の量である。
　上記ニトリル化合物は、アセトニトリルである場合、溶液１００重量部に対して、通常１重量部以上、好ましくは５重量部、より好ましくは１０重量部以上の量である。上記ニトリル化合物は、蒸留や抽出等により回収できるので、その添加量に特に上限はないが、溶液１００重量部に対して、好ましくは１００重量部以下である。　上記ニトリル化合物は、アセトニトリルである場合、白金族金属イオン１モルに対し４モル以上且つ溶液１００重量部に対し１重量部以上の量で、上記溶液と混合することが好ましい。
　上記第１工程において、上記ニトリル化合物は、一度に全量混合してもよいし、分割して混合してもよい。上記白金族金属含有組成物は、通常はニトリル化合物と溶液とを混合すると同時に、沈殿物として生成する。
　上記第１工程は、一般に０~１００℃の温度下で、溶媒などが蒸散しないように設定し行うことが好ましい。上記第１工程は、通常、常温、常圧下で迅速に進行するので、特別な反応装置は不要である。
　白金族金属含有組成物の収率が向上するので、上記溶液は、ニトリル化合物を混合した後に静置することが好ましい。該静置時間は、通常５分~１２時間でよいが、製造効率の点で５分~３０分間であることが好ましい。
　本発明における第２工程は、上記第１工程により得られた白金族金属含有組成物を回収する工程である。
　上記白金族金属含有組成物は、上述のように、第１工程により沈殿物として得られる。この沈殿物は、デカンテーション、吸引ろ過、遠心分離等の慣用の固液分離操作によりスラリーや粉体として回収することができる。
　かかる白金族金属含有組成物は、従来公知の方法により適当な形態に調製することができる。例えば、オレフィン（例えば、シクロヘキセン）溶媒に該白金族金属含有組成物の粉体を添加することにより、白金族金属含有組成物の溶液を調製することができる。
　本発明により得られた白金族金属含有組成物は、種々の分野に利用することができる。
　上記白金族金属含有組成物は、例えば、オレフィンと酸素とから酸化化合物を得る反応において触媒として用いることができる。
　具体的には、国際公開第２００９／１１６５１２号パンフレット、日本国公開特許２００８−２３１０４３号公報等に記載のシクロヘキセンからシクロヘキサノンを製造する反応において生じる廃液から本発明の方法により白金族金属含有組成物を製造し、この白金族金属含有組成物を上記シクロヘキサノンの製造用触媒として使用することができる。 Hereinafter, the present invention will be described in detail.
The method for producing a platinum group metal-containing composition of the present invention includes a first step of mixing a solution containing a platinum group metal ion and a heteropolyacid and a nitrile compound, and a platinum group metal-containing composition obtained by the first step. A second step of recovering.
In the present invention, the platinum group metal-containing composition means a powder or slurry containing at least one platinum group metal. The platinum group metal is an element belonging to Group 10 of the periodic table of elements, and examples thereof include palladium, rhodium, ruthenium, platinum, iridium, and osmium.
The platinum group metal-containing composition is not particularly limited, but usually contains 0.01 to 15% by weight of a platinum group metal.
The platinum group metal-containing composition may contain “other components” described later.
In the platinum group metal-containing composition, the amount of the other components is not particularly limited, but the total amount is preferably 10% by weight or less.
In the solution of the present invention, generally, a platinum group metal ion and a heteropolyacid are dissolved in a solvent.
The platinum group metal ion in the present invention is a metal ion of an element belonging to Group 10 of the periodic table of elements. Examples of the platinum group metal ion include palladium ion, rhodium ion, ruthenium ion, platinum ion, iridium ion, and osmium ion, and palladium ion is particularly preferable.
The platinum group metal ion content is not particularly limited, but is generally ~ 10% by mass, preferably 0.01-1% by mass, based on the above solution.
The heteropolyacid in the present invention is generally represented by the formula (1).
(A) e (X k M n O y ) (1)
(In the formula, A represents a cation. X represents one element selected from the group consisting of elements belonging to groups 1 to 16, k represents an integer of 1 to 5, M represents 5, 6 Represents at least one transition element selected from the group consisting of elements belonging to the group, M may be different within a range of 1 to 3 types, n represents an integer of 5 to 20, and y represents 15 Represents an integer of ~ 80, and e represents an integer of 3 to 12.)
In the above formula (1), A is not particularly limited as long as it is a monovalent or divalent cation, but is preferably a hydrogen ion.
Preferably, the heteropolyacid is phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdotungstic acid, phosphomolybdotungstic acid, phosphomolybdovanadic acid, xymolybdovanadic acid, lintongue It is at least one selected from the group consisting of vanadic acid and catanthost vanadic acid, more preferably phosphomolybdic acid and phosphomolybdovanadic acid, and still more preferably phosphomolybdovanadic acid.
The content of the heteropolyacid is not particularly limited, and the preferred range varies depending on the type and the type and amount of the platinum group metal ion, but usually 0.5 mol or more per mol of the platinum group metal ion, preferably Is an amount of 1 mol or more, more preferably 3 mol or more. The heteropolyacid can be recovered as an insoluble heteropolyacid salt by adding cesium carbonate, alkylammonium, pyridine, etc., so the upper limit of the content is not particularly limited, but preferably 10 mol per mole of platinum group metal ion The amount is less than the mole.
The solvent in the solution is generally an aqueous solvent and is not particularly limited, but water is preferable. The solvent may further contain an organic solvent such as cyclohexanone as long as the production efficiency of the platinum group metal-containing composition does not decrease.
As long as the solution does not react with the platinum group metal ion and does not form an insoluble salt with the heteropolyacid, metal ions other than the platinum group metal or water-soluble organic compounds (hereinafter referred to as “other components”). May be included). As said metal ion, ions, such as iron, copper, titanium, vanadium, molybdenum, tungsten, are mentioned, for example.
Examples of the water-soluble organic compound include at least one compound selected from the group consisting of acetamide, adipic acid and cyclohexanone.
Examples of the other components further include water-soluble inorganic compounds other than platinum group metal ions and heteropolyacids. Examples of such a water-soluble inorganic compound include at least one compound selected from the group consisting of iron sulfate and ammonium iron sulfate.
The content of the other compounds is not particularly limited as long as the production efficiency of the platinum group metal-containing composition is not lowered.
As a solution containing a platinum group metal ion and a heteropoly acid, for example, a reaction solution for producing an oxide compound from an olefin using a platinum group metal and a heteropoly acid as a catalyst, a reaction containing a platinum group metal ion and a heteropoly acid. A solution; a waste solution generated in the production of an oxide compound using a platinum group metal ion and a heteropolyacid. Examples of the reaction solution in the production of the oxidized compound include a reaction solution in the production method described in International Publication No. 2009/116512, Japanese Patent Publication No. 2008-231043 (Japanese Patent Application No. 2007-074374), and the like.
The solution may be a liquid obtained by mixing a liquid containing a platinum group metal ion and a heteropolyacid. Examples of such a liquid include a liquid obtained by adding a heteropolyacid to a liquid containing a platinum group metal ion. Examples of the liquid containing the platinum group metal ion include a reaction solution containing a platinum group metal ion such as a reaction solution for producing an oxide compound from an olefin using a platinum group metal as a catalyst; Examples include waste liquids generated during the production of oxidized compounds; waste liquids such as pickling bath liquids; waste liquids generated in the analysis of samples containing platinum group metals such as geological samples; used cleaning liquids for decorative products.
Although the solution in the present invention may contain other compounds as described above, it is preferable to use the first step after removing olefins such as cyclohexene in advance. By removing the olefin from the solution, the production efficiency of the platinum group metal-containing composition can be further improved.
In the present invention, the nitrile compound is not particularly limited, but the formula R-CN
(In the above formula, R represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic group having 6 to 10 carbon atoms).
The nitrile compound is preferably an alkyl nitrile having 1 to 10 carbon atoms, more preferably an alkyl nitrile having 1 to 5 carbon atoms, and still more preferably acetonitrile.
The amount of the nitrile compound in the first step is not particularly limited, and can be appropriately selected according to each kind and concentration of the nitrile compound, the heteropolyacid, and the platinum group metal ion.
When the nitrile compound is, for example, acetonitrile, the amount is usually 1 mol or more, preferably 15 mol or more, more preferably 50 mol or more per 1 mol of platinum group metal ion. Since the nitrile compound can be recovered by distillation, extraction or the like, the amount thereof is not particularly limited, but is usually 800 mol or less, preferably 400 mol or less per 1 mol of platinum group metal ions.
When the nitrile compound is acetonitrile, the amount is usually 1 part by weight or more, preferably 5 parts by weight, more preferably 10 parts by weight or more with respect to 100 parts by weight of the solution. Since the nitrile compound can be recovered by distillation, extraction or the like, there is no particular upper limit to the amount added, but it is preferably 100 parts by weight or less with respect to 100 parts by weight of the solution. When the nitrile compound is acetonitrile, the nitrile compound is preferably mixed with the solution in an amount of 4 moles or more per 1 mole of platinum group metal ions and 1 weight part or more with respect to 100 parts by weight of the solution.
In the first step, the nitrile compound may be mixed all at once or divided and mixed. The platinum group metal-containing composition is usually formed as a precipitate simultaneously with mixing the nitrile compound and the solution.
In general, the first step is preferably performed at a temperature of 0 to 100 ° C. so that the solvent does not evaporate. Since the first step normally proceeds rapidly at normal temperature and normal pressure, no special reaction apparatus is required.
Since the yield of the platinum group metal-containing composition is improved, the solution is preferably allowed to stand after mixing the nitrile compound. The standing time may normally be 5 minutes to 12 hours, but is preferably 5 minutes to 30 minutes from the viewpoint of production efficiency.
The 2nd process in this invention is a process of collect | recovering the platinum group metal containing composition obtained by the said 1st process.
The platinum group metal-containing composition is obtained as a precipitate by the first step as described above. This precipitate can be recovered as a slurry or powder by a conventional solid-liquid separation operation such as decantation, suction filtration, and centrifugation.
Such a platinum group metal-containing composition can be prepared in an appropriate form by a conventionally known method. For example, the platinum group metal-containing composition solution can be prepared by adding the platinum group metal-containing composition powder to an olefin (eg, cyclohexene) solvent.
The platinum group metal-containing composition obtained by the present invention can be used in various fields.
The platinum group metal-containing composition can be used, for example, as a catalyst in a reaction for obtaining an oxidized compound from olefin and oxygen.
Specifically, the platinum group metal-containing composition is produced by the method of the present invention from the waste liquid produced in the reaction for producing cyclohexanone from cyclohexene described in International Publication No. 2009/116512 pamphlet, Japanese Patent Publication No. 2008-231043, etc. This platinum group metal-containing composition can be used as a catalyst for the production of cyclohexanone.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。
参考例１~４
本参考例において、ニトリル化合物として、アセトニトリル（ナカライテスク株式会社）をそのまま用いた。ヘテロポリ酸として、Ｈ７ＰＭｏ８Ｖ４Ｏ４０またはＨ６ＰＭｏ９Ｖ３Ｏ４０（以上、日本無機化学株式会社）をそのまま用いた。
１．イオン交換水（５０ｇ）、Ｆｅ２（ＳＯ４）３・ｎＨ２Ｏ（１．２ｇ、関東化学株式会社）、Ｐｄ（ＯＡｃ）２（０．２３ｇ、Ｓｉｇｍａ−Ａｌｄｒｉｃｈ社）、ヘテロポリ酸（７．０ｇ、日本無機化学株式会社：Ｈ７ＰＭｏ８Ｖ４Ｏ４０）を１００ｍｌサンプル瓶に入れ、６時間超音波にかけた。
その後、溶液を桐山ロートで吸引ろ過（メンブランフィルター、Ｎｏ．５Ｂ、ＳＢ−４０）し、微量の不溶物を取り除くことにより溶液Ａを得た。
２．溶液Ａ（１２ｇ）に、アセトアミド（０．５２ｇ、関東化学株式会社）、アジピン酸（０．１６ｇ、ナカライテスク株式会社）を溶解させることにより、溶液Ｂを得た。
３．イオン交換水（５０ｇ）、Ｆｅ２（ＳＯ４）３・ｎＨ２Ｏ（１．２ｇ）、Ｐｄ（ＯＡｃ）２（０．２３ｇ）、ヘテロポリ酸（７．０ｇ、Ｈ７ＰＭｏ８Ｖ４Ｏ４０）を１００ｍｌサンプル瓶に入れ、６時間超音波にかけた。その後、溶液を吸引ろ過（テトラフルオロエチレン［ＰＴＦＥ］メンブランフィルター、細孔０．２μｍ、４７ｍｍφ）で、微量の不溶物を取り除いた。得られた溶液（２９ｇ）に、アセトアミド（１．２ｇ）、シクロヘキサノン（０．３１ｇ、関東化学株式会社）を溶解させることにより、溶液Ｃを得た。
４．イオン交換水（１０１ｇ）、Ｆｅ２（ＳＯ４）３・ｎＨ２Ｏ（２．３６ｇ）、アジピン酸（１．６ｇ）、Ｐｄ（ＯＡｃ）２（０．４６ｇ）、ヘテロポリ酸（１４ｇ：Ｈ３ＰＭｏ９Ｖ３Ｏ４０）を２００ｍｌ三角フラスコに入れ、６時間超音波にかけた。その後、溶液を吸引ろ過（ＰＴＦＥメンブランフィルター、細孔０．２μｍ、４７ｍｍφ）して、微量の不溶物を取り除くことにより、溶液Ｄを得た。
溶液Ａ~Ｄの各化学組成を表１に示す。
Figure JPOXMLDOC01-appb-T000001
 実施例１~４
溶液Ａ~Ｄのそれぞれに対し、常温常圧下で、所定量のアセトニトリルを混合した。何れの溶液でも、アセトニトリルを混合すると同時に沈殿の生成が目視で確認できた。
アセトニトリルの混合後５分~１２時間静置した後、得られた液について、それぞれ吸引ろ過（ＰＴＦＥメンブランフィルター、細孔０．１μｍ、２５ｍｍφ）を常温下で行った。
回収した各沈殿物を、それぞれアセトニトリル（４ｍｌ）で洗浄後、８０℃で３時間減圧乾燥することにより白金族金属含有組成物を得た。
得られた各白金族金属含有組成物について、マイクロウェーブ分解−ＩＣＰ発光分析法により元素分析を行った結果、Ｐｄ：Ｐ：Ｎの平均モル比は、約２：１：８であった。
上記吸引ろ過時に回収したろ液および溶液Ａ~Ｄのそれぞれについて、化学組成及び回収率を表２に示す。なお、化学組成及び回収率は、次の方法により行った。
・溶液Ａ~Ｃを材料とした製造の際に得られた各ろ液について、ＰｄおよびＦｅの各定量はマイクロウェーブ分解−ＩＣＰ発光分析法により行い、Ｓの定量は、酸素燃焼−イオンクロマトグラフ法により行った。
・溶液Ｄを材料とした製造の際に得られたろ液について、Ｐｄ、ＦｅおよびＳの各定量は、蛍光Ｘ線分析法により行った。
・全ての溶液について、アジピン酸の定量は、イオンクロマトグラフ法により行った。
・全ての溶液について、アセトアミドおよびシクロヘキサノンは、ＦＩＤ−ガスクロマトグラフ法により行った。
・回収率は以下の式で算出した。
回収率（％）＝｛（溶液中における元素の含有量）−（ろ液中の含有量）｝／（溶液中における含有量）×１００
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-I000003
　注（１）：混合量は、溶液１００重量部に対するアセトニトリルの添加量（重量部）を表す。
実施例５
　具体的には、シクロヘキセン（１．６ｇ、関東化学株式会社）、アセトニトリル（３ｍｌ）、イオン交換水（２ｍｌ）、上記溶液Ａから得られた白金族金属含有組成物（パラジウム含有量８重量％）（２４ｍｇ）、Ｈ７ＰＭｏ８Ｖ４Ｏ４０（０．１ｇ）およびＦｅ２（ＳＯ４）３・ｎＨ２Ｏ（２７ｍｇ）を１２０ｍｌ容量のオートクレーブに入れ、窒素ガス３ＭＰａ及び加圧空気２ＭＰａを導入し、３２３Ｋで２時間反応させ、シクロヘキサノンを得た。シクロヘキセンの転化率は３２％、シクロヘキサノンの選択率は９３％で、ターンオーバー数（パラジウム１モルあたりに生成したシクロヘキサノンのモル数）は、３５４であった。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
Reference examples 1-4
In this reference example, acetonitrile (Nacalai Tesque, Inc.) was used as it was as the nitrile compound. As heteropolyacid, H 7 PMo 8 V 4 O 40 or H 6 PMo 9 V 3 O 40 ( or more, Nippon Inorganic Color & Chemical Co., Ltd.) was used as it.
1. Ion-exchanged water (50 g), Fe 2 (SO 4 ) 3 .nH 2 O (1.2 g, Kanto Chemical Co., Inc.), Pd (OAc) 2 (0.23 g, Sigma-Aldrich), heteropoly acid (7. 0 g, Nippon Inorganic Chemical Co., Ltd .: H 7 PMo 8 V 4 O 40 ) was placed in a 100 ml sample bottle and subjected to ultrasonic waves for 6 hours.
Thereafter, the solution was subjected to suction filtration with a Kiriyama funnel (membrane filter, No. 5B, SB-40), and a small amount of insoluble matter was removed to obtain a solution A.
2. A solution B was obtained by dissolving acetamide (0.52 g, Kanto Chemical Co., Inc.) and adipic acid (0.16 g, Nacalai Tesque Co., Ltd.) in the solution A (12 g).
3. Ion-exchanged water (50 g), Fe 2 (SO 4 ) 3 · nH 2 O (1.2 g), Pd (OAc) 2 (0.23 g), heteropolyacid (7.0 g, H 7 PMo 8 V 4 O 40 ) Was placed in a 100 ml sample bottle and sonicated for 6 hours. Thereafter, the solution was subjected to suction filtration (tetrafluoroethylene [PTFE] membrane filter, pores 0.2 μm, 47 mmφ) to remove a trace amount of insoluble matter. Solution C was obtained by dissolving acetamide (1.2 g) and cyclohexanone (0.31 g, Kanto Chemical Co., Inc.) in the resulting solution (29 g).
4). Ion-exchanged water (101 g), Fe 2 (SO 4 ) 3 .nH 2 O (2.36 g), adipic acid (1.6 g), Pd (OAc) 2 (0.46 g), heteropolyacid (14 g: H 3 PMo 9 V 3 O 40 ) was placed in a 200 ml Erlenmeyer flask and sonicated for 6 hours. Then, the solution D was obtained by carrying out suction filtration (PTFE membrane filter, 0.2 micrometer of pores, 47 mm diameter), and removing a trace amount insoluble matter.
Table 1 shows the chemical compositions of the solutions A to D.
Figure JPOXMLDOC01-appb-T000001
 Examples 1-4
A predetermined amount of acetonitrile was mixed with each of the solutions A to D under normal temperature and normal pressure. In any of the solutions, the formation of a precipitate was visually confirmed simultaneously with mixing of acetonitrile.
The mixture was allowed to stand for 5 minutes to 12 hours after mixing with acetonitrile, and the obtained liquid was subjected to suction filtration (PTFE membrane filter, 0.1 μm pore, 25 mmφ) at room temperature.
Each collected precipitate was washed with acetonitrile (4 ml) and then dried under reduced pressure at 80 ° C. for 3 hours to obtain a platinum group metal-containing composition.
The obtained platinum group metal-containing composition was subjected to elemental analysis by microwave decomposition-ICP emission analysis. As a result, the average molar ratio of Pd: P: N was about 2: 1: 8.
Table 2 shows the chemical composition and the recovery rate for each of the filtrate and solutions A to D recovered during the suction filtration. The chemical composition and recovery rate were determined by the following method.
-For each filtrate obtained in the production using solutions A to C, each determination of Pd and Fe is performed by microwave decomposition-ICP emission spectrometry, and the determination of S is oxygen combustion-ion chromatograph Done by law.
-About the filtrate obtained at the time of manufacture which used the solution D as a material, each fixed_quantity | quantitative_assay of Pd, Fe, and S was performed by the fluorescent X ray analysis method.
-About all the solutions, fixed_quantity | quantitative_assay of adipic acid was performed by the ion chromatography method.
-About all the solutions, acetamide and cyclohexanone were performed by the FID-gas chromatograph method.
・ The recovery rate was calculated using the following formula.
Recovery rate (%) = {(content of element in solution) − (content in filtrate)} / (content in solution) × 100
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-I000003
Note (1): The mixing amount represents the amount of acetonitrile (parts by weight) added to 100 parts by weight of the solution.
Example 5
Specifically, cyclohexene (1.6 g, Kanto Chemical Co., Inc.), acetonitrile (3 ml), ion-exchanged water (2 ml), platinum group metal-containing composition obtained from the above solution A (palladium content 8 wt%) (24 mg), H 7 PMo 8 V 4 O 40 (0.1 g) and Fe 2 (SO 4 ) 3 · nH 2 O (27 mg) were placed in a 120 ml capacity autoclave, and nitrogen gas 3 MPa and pressurized air 2 MPa were introduced. And reacted at 323 K for 2 hours to obtain cyclohexanone. The conversion rate of cyclohexene was 32%, the selectivity of cyclohexanone was 93%, and the turnover number (number of moles of cyclohexanone produced per mole of palladium) was 354.
　本発明の白金族金属含有組成物の製造方法は、種々の廃触媒の浸出液、各種金属の酸洗浄液や各種鉱・工業排水中に微量含まれる白金族金属イオンから白金族金属を得る方法として有用である。
　上記製造方法によれは、貴重な金属である白金族金属の回収・再利用が可能なので、白金族金属に起因する環境問題を解消することができる。 The method for producing a platinum group metal-containing composition of the present invention is useful as a method for obtaining a platinum group metal from a platinum group metal ion contained in a trace amount in various metal leaching solutions, acid washing solutions of various metals and various minerals and industrial effluents. It is.
According to the above manufacturing method, the platinum group metal, which is a valuable metal, can be recovered and reused, so that environmental problems caused by the platinum group metal can be solved.

Claims (11)

  1. 白金族金属イオンおよびヘテロポリ酸を含む溶液とニトリル化合物とを混合する第１工程と、前記第１工程により得られた白金族金属含有組成物を回収する第２工程とを含む白金族金属含有組成物の製造方法。 A platinum group metal-containing composition comprising a first step of mixing a solution containing a platinum group metal ion and a heteropolyacid and a nitrile compound, and a second step of recovering the platinum group metal-containing composition obtained in the first step. Manufacturing method.
  2. 白金族金属イオンはパラジウムイオンである請求項１に記載の製造方法。 The production method according to claim 1, wherein the platinum group metal ion is palladium ion.
  3. ニトリル化合物はアセトニトリルである請求項１又は２に記載の製造方法。 The method according to claim 1 or 2, wherein the nitrile compound is acetonitrile.
  4. アセトニトリルは、白金族金属イオン１モルに対し４モル以上且つ溶液１００重量部に対し１重量部以上の量で前記溶液に添加される請求項３に記載の製造方法。 The method according to claim 3, wherein acetonitrile is added to the solution in an amount of 4 moles or more per 1 mole of platinum group metal ions and 1 part by weight or more per 100 parts by weight of the solution.
  5. 溶液は、白金族金属イオン１モルに対し０．５モル以上の量でヘテロポリ酸を含む請求項１~４のいずれか１項に記載の製造方法。 The method according to any one of claims 1 to 4, wherein the solution contains a heteropolyacid in an amount of 0.5 mol or more per 1 mol of platinum group metal ions.
  6. ヘテロポリ酸は、リンモリブデン酸、ケイモリブデン酸、リンタングステン酸、ケイタングステン酸、リンモリブドタングステン酸、ケイモリブドタングステン酸、リンモリブドバナジン酸、ケイモリブドバナジン酸、リンタングストバナジン酸およびケイタングストバナジン酸からなる群より選ばれる少なくとも１つである請求項１~５のいずれか１項に記載の製造方法。 Heteropolyacids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdotungstic acid, cinnamolybdotungstic acid, phosphomolybdovanadic acid, cinnamolybdovanadic acid, lintangost vanadic acid, and kaitan 6. The production method according to claim 1, wherein the production method is at least one selected from the group consisting of gustovanadic acid.
  7. 溶液は、水溶性有機化合物からなる群より選ばれる少なくとも１つの化合物を含む請求項１~６のいずれか１項に記載の製造方法。 The production method according to any one of claims 1 to 6, wherein the solution contains at least one compound selected from the group consisting of water-soluble organic compounds.
  8. 水溶性有機化合物は、アセトアミド、アジピン酸およびシクロヘキサノンからなる群より選ばれる少なくとも１つの化合物である請求項７記載の製造方法。 The method according to claim 7, wherein the water-soluble organic compound is at least one compound selected from the group consisting of acetamide, adipic acid and cyclohexanone.
  9. 溶液は、白金族金属イオンを含む液とヘテロポリ酸とを混合することにより得られる請求項１~８のいずれか１項に記載の製造方法。 The method according to any one of claims 1 to 8, wherein the solution is obtained by mixing a liquid containing a platinum group metal ion and a heteropolyacid.
  10. 請求項１~９のいずれか１項に記載の方法により得られた白金族金属含有組成物の酸化化合物製造における触媒としての使用。 Use of the platinum group metal-containing composition obtained by the method according to any one of claims 1 to 9 as a catalyst in producing an oxide compound.
  11. 請求項１~９のいずれか１項に記載の方法により得られた白金族金属含有組成物の存在下でオレフィンと酸素とから酸化化合物を得る方法。 A method for obtaining an oxide compound from olefin and oxygen in the presence of a platinum group metal-containing composition obtained by the method according to any one of claims 1 to 9.
PCT/JP2009/071828 2008-12-22 2009-12-21 Method for manufacturing composition containing platinum group metal WO2010074294A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-325296 2008-12-22
JP2008325296A JP2010144240A (en) 2008-12-22 2008-12-22 Method for recovering platinum group metal ion

Publications (1)

Publication Number Publication Date
WO2010074294A1 true WO2010074294A1 (en) 2010-07-01

Family

ID=42287896

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/071828 WO2010074294A1 (en) 2008-12-22 2009-12-21 Method for manufacturing composition containing platinum group metal

Country Status (3)

Country Link
JP (1) JP2010144240A (en)
TW (1) TW201033374A (en)
WO (1) WO2010074294A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7307460B2 (en) * 2019-05-23 2023-07-12 国立研究開発法人量子科学技術研究開発機構 Recovery device, recovery system, and recovery method
JP6766942B1 (en) * 2019-11-26 2020-10-14 宇部興産株式会社 Palladium recovery method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585973A (en) * 1990-12-26 1993-04-06 Mitsui Toatsu Chem Inc Coproduction of aromatic hydroxyl compound and carbonyl compound
JPH0672920A (en) * 1992-08-26 1994-03-15 Mitsui Toatsu Chem Inc Simultaneous production of aromatic hydroxy compound and carbonyl compound
JP2005194546A (en) * 2003-12-26 2005-07-21 National Institute Of Advanced Industrial & Technology Selective recovery agent and selective recovery method for platinum group metal ion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0585973A (en) * 1990-12-26 1993-04-06 Mitsui Toatsu Chem Inc Coproduction of aromatic hydroxyl compound and carbonyl compound
JPH0672920A (en) * 1992-08-26 1994-03-15 Mitsui Toatsu Chem Inc Simultaneous production of aromatic hydroxy compound and carbonyl compound
JP2005194546A (en) * 2003-12-26 2005-07-21 National Institute Of Advanced Industrial & Technology Selective recovery agent and selective recovery method for platinum group metal ion

Also Published As

Publication number Publication date
JP2010144240A (en) 2010-07-01
TW201033374A (en) 2010-09-16

Similar Documents

Publication Publication Date Title
Mallat et al. Selectivity enhancement in heterogeneous catalysis induced by reaction modifiers
Wong et al. Recovery and reuse of ionic liquids and palladium catalyst for Suzuki reactions using organic solvent nanofiltration
JP4909526B2 (en) Acrolein production method
RU2338802C2 (en) Extraction of metallic compounds
CN106348420B (en) Method for treating glyphosate wastewater by wet catalytic oxidation
CN1260788A (en) Epoxidation process using supported silver catalyst pretreated with organic chloride
DE2225732A1 (en) Removal of cations from a solution in nitriles
CN104039441A (en) A catalyst for direct synthesis of hydrogen peroxide
EP2677047B1 (en) Method for collection of ruthenium or ruthenium compound
WO2010074294A1 (en) Method for manufacturing composition containing platinum group metal
CN1950294A (en) Process for the direct synthesis of hydrogen peroxide
CN107029764A (en) A kind of preparation method and application of support type P Modification palladium catalyst
JP4182217B2 (en) Selective recovery agent and selective recovery method for platinum group metal ions
CN1126587C (en) Method for separating a catalyst by membrane electrodialysis
CN105126871A (en) Waste water catalyst for disposing small organic molecules and preparing method of waste water catalyst
JP2010163412A (en) Method for producing carbonyl compound
WO2001024924A1 (en) Catalyst for acetic acid production, process for producing the same, and process for producing acetic acid with the same
CN114160132A (en) V-Ag-O/TiO2Catalyst and application thereof
PL228752B1 (en) Method for oxidation of limonene on active carbons
WO2015124533A1 (en) Process to obtain hydrogen peroxide, and catalyst and catalysts supports for said process
CN109647450A (en) Hydrogenation catalyst for synthesizing cyclohexane 1 amine
JP2020529969A (en) Method for Separation and Purification of Dicarboxylic Acid-Containing Mixture
CN115397799B (en) Method for producing glycolate and glycolic acid
CN111013646B (en) Method for producing nonanal and nonanoic acid or methyl nonanal and nonanoic acid
EP1659197A1 (en) Process for the recovery of acids

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09835087

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09835087

Country of ref document: EP

Kind code of ref document: A1