US20100113258A1 - Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au - Google Patents

Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au Download PDF

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Publication number
US20100113258A1
US20100113258A1 US12/531,795 US53179508A US2010113258A1 US 20100113258 A1 US20100113258 A1 US 20100113258A1 US 53179508 A US53179508 A US 53179508A US 2010113258 A1 US2010113258 A1 US 2010113258A1
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US
United States
Prior art keywords
noble metal
substance
oxalic acid
acid
salt
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US12/531,795
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English (en)
Inventor
Richard Walter
Horst Meyer
Steffen Voss
Jan Schapp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
Original Assignee
WC Heraus GmbH and Co KG
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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39535720&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20100113258(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by WC Heraus GmbH and Co KG filed Critical WC Heraus GmbH and Co KG
Assigned to W.C. HERAEUS GMBH reassignment W.C. HERAEUS GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SCHAPP, JAN, VOSS, STEFFEN, MEYER, HORST, WALTER, RICHARD
Publication of US20100113258A1 publication Critical patent/US20100113258A1/en
Assigned to HERAEUS PRECIOUS METALS GMBH & CO. KG reassignment HERAEUS PRECIOUS METALS GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: W.C. HERAEUS GMBH & CO. KG
Priority to US14/294,672 priority Critical patent/US20140274670A1/en
Priority to US15/879,681 priority patent/US11045795B2/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium

Definitions

  • the invention relates to catalytically highly effective noble metal carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au and to processes for their production.
  • iridium, ruthenium and their compounds are that as catalyst and catalyst precursor.
  • iridium catalysts are used in carbonylation reactions.
  • Iridium acetate, among others, is mentioned as iridium compound suitable for this purpose.
  • platinum group metal salts are, among others, the acetates of palladium and rhodium obtained from the hydroxides dissolved in glacial acetic acid by reaction with acetic anhydride.
  • EP 0 844 251 relates to the production of ruthenium carboxylate solutions from ruthenium(IV) oxide by reduction with hydrazine derivative in the presence of a carboxylic acid.
  • the production of ruthenium oxide, in particular its filtration, is highly time consuming.
  • iridium hydroxide is precipitated from an aqueous solution of an chloroiridium compound with an aqueous solution of an alkali metal hydroxide, alkali metal carbonate or alkali metal hydrogen carbonate, the precipitated iridium hydroxide is separated off and reacted with acetic acid or a mixture of acetic acid/acetic anhydride to form a solution containing iridium acetate, and the iridium acetate is isolated from the solution as solid.
  • the noble metal carboxylate compounds produced according to the process, in particular the acetate compounds, should be catalytically as highly effective as possible.
  • the compounds should also have a high purity and, in particular, have a low chlorine, sulphur, sodium and potassium content.
  • a melt or fusion mass exhibiting noble metal and alkaline earth peroxide is dissolved in a carboxylic acid, if necessary with an addition of water, and subsequently filtered. From the filtered solution, the alkaline earth ions introduced by the alkaline earth peroxide are separated as salt of oxalic acid or salt of oxalic acid derivatives.
  • Oxalate derivatives in the case of which an organic radical is arranged between the carboxyl groups have the same effect as oxalates. This process is highly efficient and circumvents time consuming BaSO 4 precipitation and the filtration of barium sulphate according to the Watson process.
  • the purified noble metal carboxylate solution can be concentrated, it being possible to adjust the concentration increase to a desired concentration or to carry it out up to the isolation of the solid.
  • the methods corresponding to the state of the art such as evaporation of the reaction solution, spray drying or precipitation at a low temperature or addition of a suitable solvent are used.
  • the catalytic properties are particularly good when a noble metal carboxylate solution, in particular an acetic acid solution of ruthenium acetate or iridium acetate originates from the process using the precipitation of the alkaline earth metal as salt of oxalic acid or salt of oxalic acid derivatives.
  • the mass of oxalic acid and/or salts of oxalic acids or corresponding derivatives is smaller or equal to the mass of noble metal.
  • the noble metals are digested with calcium peroxide or barium peroxide.
  • Ruthenium and iridium are preferred noble metals.
  • Acetate is the preferred carboxylate.
  • the digested noble metal mixture dissolved in aqueous acetic acid is correspondingly preferred.
  • the proportion of alkaline earth metal, in particular calcium, strontium or barium amounts to 100 ppm to 10% by weight, in particular 500 ppm to 0.5% by weight, based on the noble metal, following precipitation as salt of oxalic acid or salt of oxalic acid derivatives.
  • the calcium, strontium and barium content can be considerably reduced by fractional crystallisation.
  • the mixture is transferred into a nickel crucible and heated for 15 hours at 850° C.
  • 150 ml of a mixture of acetic acid and water in a ratio of 2:1 are heated to 50° C. in a 200 ml three-necked flask.
  • the reaction mixture of ruthenium powder and barium peroxide is introduced into the three-necked flask.
  • the mixture heats up to 80° C. by exothermic reaction.
  • the mixture is heated to boiling temperature and stirred at boiling temperature for 3 hours.
  • the solution is cooled to room temperature and filtered through a membrane filter.
  • the filter cake is washed with a little acetic acid/water mixture (2:1).
  • the mixture is transferred into a nickel crucible and heated for 15 hours at 850° C.
  • 150 ml of a mixture of acetic acid and water in a ratio of 2:1 are heated to 50° C. in a 200 ml three-necked flask.
  • the reaction mixture of ruthenium powder and barium peroxide is introduced into the three-necked flask.
  • the mixture heats up to 76° C. by exothermic reaction.
  • the mixture is heated to boiling temperature and stirred at boiling temperature for 3 hours.
  • the solution is cooled to room temperature and filtered through a membrane filter. The filter cake is washed with a little acetic acid.
  • the suspension adopted a brown colour within approximately 5 minutes.
  • the barium was precipitated as salt with 51.453 grams of oxalic acid dehydrate and stirred for a further hour whereupon a yellow liquid was filtered off via a suction filter using a blue band filter. The filtrate was concentrated in a rotation evaporator at a temperature of 75° C.
  • the rhodium acetate was dried up to mass constancy and ground using a mortar. The dried yield of rhodium acetate was 11.012 g. The rhodium content was determined by ICP analysis as being 34.43% by weight.
  • Iridium is digested with barium peroxide according to the Watson process and dissolved with acetic acid.
  • the barium from the Watson process is precipitated with oxalic acid in a manner analogous to the above example 1 to 3 and filtered off.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US12/531,795 2007-03-26 2008-03-19 Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au Abandoned US20100113258A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/294,672 US20140274670A1 (en) 2007-03-26 2014-06-03 Catalytically highly effective precious metal-carboxylate compounds of ir, ru, rh, pd and au
US15/879,681 US11045795B2 (en) 2007-03-26 2018-01-25 Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd and Au

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007014914A DE102007014914B4 (de) 2007-03-26 2007-03-26 Katalytisch hochwirksame Edelmetall-Carboxylat-Verbindungen von Ir, Ru, Rh, Pd, Pt und Au
DE102007014914.1 2007-03-26
PCT/EP2008/002186 WO2008116585A1 (de) 2007-03-26 2008-03-19 Katalytisch hochwirksame edelmetall-carboxylat-verbindungen von ir, ru, rh, pd, pt und au

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/002186 A-371-Of-International WO2008116585A1 (de) 2007-03-26 2008-03-19 Katalytisch hochwirksame edelmetall-carboxylat-verbindungen von ir, ru, rh, pd, pt und au

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/294,672 Division US20140274670A1 (en) 2007-03-26 2014-06-03 Catalytically highly effective precious metal-carboxylate compounds of ir, ru, rh, pd and au

Publications (1)

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US20100113258A1 true US20100113258A1 (en) 2010-05-06

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US12/531,795 Abandoned US20100113258A1 (en) 2007-03-26 2008-03-19 Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au
US14/294,672 Abandoned US20140274670A1 (en) 2007-03-26 2014-06-03 Catalytically highly effective precious metal-carboxylate compounds of ir, ru, rh, pd and au
US15/879,681 Active 2029-01-24 US11045795B2 (en) 2007-03-26 2018-01-25 Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd and Au

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US14/294,672 Abandoned US20140274670A1 (en) 2007-03-26 2014-06-03 Catalytically highly effective precious metal-carboxylate compounds of ir, ru, rh, pd and au
US15/879,681 Active 2029-01-24 US11045795B2 (en) 2007-03-26 2018-01-25 Catalytically highly effective precious metal-carboxylate compounds of Ir, Ru, Rh, Pd and Au

Country Status (10)

Country Link
US (3) US20100113258A1 (ko)
EP (1) EP2125209B1 (ko)
JP (1) JP5383646B2 (ko)
KR (1) KR101332498B1 (ko)
CN (1) CN101678344A (ko)
BR (1) BRPI0809300B1 (ko)
DE (1) DE102007014914B4 (ko)
RU (1) RU2482916C2 (ko)
WO (1) WO2008116585A1 (ko)
ZA (1) ZA200906692B (ko)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN115536520A (zh) * 2022-11-02 2022-12-30 金川集团股份有限公司 一种醋酸钌的制备方法

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CN102381957A (zh) * 2010-08-31 2012-03-21 中国石油化工股份有限公司 乙酸钌的制备方法
RU2565423C1 (ru) * 2014-11-06 2015-10-20 Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) Оксоацетатные соединения платины для изготовления гетерогенных катализаторов
US20180215697A1 (en) * 2015-07-28 2018-08-02 Umicore Ag & Co. Kg Bis(oxalato) platinum acid "on the rocks"
CN108409554B (zh) * 2018-03-28 2021-04-20 西安瑞鑫科金属材料有限责任公司 一种醋酸铱的合成方法
CN115141093A (zh) * 2022-06-28 2022-10-04 浙江微通催化新材料有限公司 一种醋酸钌的制备方法

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GB8605034D0 (en) * 1986-02-28 1986-04-09 Shell Int Research Carbonylation of compounds
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GB9306409D0 (en) 1993-03-26 1993-05-19 Bp Chem Int Ltd Process
FR2730229B1 (fr) * 1995-02-02 1997-04-11 Rhone Poulenc Chimie Procede de preparation de carboxylates d'iridium et leur utilisation comme catalyseurs
ZA9710220B (en) 1996-11-26 1999-05-12 Bp Chem Int Ltd Process for the production of ruthenium (III) acetate solution
GB9626429D0 (en) * 1996-12-19 1997-02-05 Bp Chem Int Ltd Process
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GB2413323A (en) * 2004-04-22 2005-10-26 Johnson Matthey Plc Improvements to processes for the preparation of iridium acetate
CN1733599B (zh) 2004-08-13 2010-04-28 中国人民解放军63971部队 过渡金属氧化物或氢氧化物湿凝胶的制备方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536520A (zh) * 2022-11-02 2022-12-30 金川集团股份有限公司 一种醋酸钌的制备方法

Also Published As

Publication number Publication date
US11045795B2 (en) 2021-06-29
DE102007014914A1 (de) 2008-10-02
JP2010522221A (ja) 2010-07-01
US20140274670A1 (en) 2014-09-18
KR20090127284A (ko) 2009-12-10
CN101678344A (zh) 2010-03-24
ZA200906692B (en) 2010-05-26
KR101332498B1 (ko) 2013-11-26
WO2008116585A1 (de) 2008-10-02
DE102007014914B4 (de) 2013-09-12
US20180147570A1 (en) 2018-05-31
BRPI0809300B1 (pt) 2019-04-24
RU2009139264A (ru) 2011-05-10
EP2125209B1 (de) 2017-09-06
RU2482916C2 (ru) 2013-05-27
EP2125209A1 (de) 2009-12-02
JP5383646B2 (ja) 2014-01-08
BRPI0809300A2 (pt) 2014-10-14

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WALTER, RICHARD;MEYER, HORST;VOSS, STEFFEN;AND OTHERS;SIGNING DATES FROM 20091124 TO 20091130;REEL/FRAME:023693/0486

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Owner name: HERAEUS PRECIOUS METALS GMBH & CO. KG, GERMANY

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