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WO1999038615A1 - Colloides aqueux de metal precieux et leur utilisation - Google Patents

Colloides aqueux de metal precieux et leur utilisation Download PDF

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Publication number
WO1999038615A1
WO1999038615A1 PCT/EP1999/000290 EP9900290W WO9938615A1 WO 1999038615 A1 WO1999038615 A1 WO 1999038615A1 EP 9900290 W EP9900290 W EP 9900290W WO 9938615 A1 WO9938615 A1 WO 9938615A1
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WO
WIPO (PCT)
Prior art keywords
precious metal
metal
mmol
sol
noble metal
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.)
Ceased
Application number
PCT/EP1999/000290
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German (de)
English (en)
Inventor
Daniel-Gordon Duff
Jörg-Dietrich Jentsch
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Priority to AU26190/99A priority Critical patent/AU2619099A/en
Publication of WO1999038615A1 publication Critical patent/WO1999038615A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0026—Preparation of sols containing a liquid organic phase
    • B01J13/003—Preparation from aqueous sols
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles

Definitions

  • the invention relates to precious metal colloids, i.e. in the nanometer range, highly disperse, ultra-fine precious metal particles; They are used in a variety of ways as precursors to supported catalysts.
  • J. Colloid Interface Sei. 131 (1989), 186 and in J. Colloid Interface Sci. HO (1986), 82 describes the preparation of stabilized colloids of precious metals, their application to ion exchange resins and their use as hydrogenation catalysts.
  • dissolved noble metal salts are reduced with NaBH4 in the presence of surface-active detergents and the resulting noble metal hydrosols are brought onto the ion exchange resins.
  • noble metal colloids with a noble metal concentration of at most 0.5 mmol / 1 can be produced.
  • JP 1/100 545 describes the production of a palladium hydrosol likewise containing 0.5 mmol / l by reduction of dissolved PdCl2 with ascorbic acid in the presence of poly-N-vinylpyrrolidone.
  • JP 2/179 881 describes the preparation of a Pd hydrosol containing up to 10 mmol / l, PdCl2 being reduced by reduction with NaBH4 in the presence of water-soluble polymers.
  • hydrosols with more than 10 mmol / 1 cannot be produced. Furthermore, these hydrosols are produced in the presence of alkaline earth chlorides. From J. Phys. Chem.
  • the invention relates to aqueous precious metal colloids in the form of a sol with metal particles of a size from 0.5 to 100 nm, which are obtained by reducing noble metal compounds with the aid of organic reducing agents and which are characterized by - 3 -
  • the invention further relates to a process for producing aqueous precious metal colloids with metal particles with a size of 0.5 to 100 nm, which is characterized in that an aqueous solution of a precious metal salt or
  • complex adds one or more water-soluble polymers and then the noble metal cation to the metallic state by adding an organic reducing agent from the group of C j -C 4 alcohols, C 1 -C 4 aldehydes, formic acid, ascorbic acid, citric acid, urea or others to the person skilled in the art known organic reducing agents or a mixture of several of them reduced, with a metal content of more than 10 mmol / 1 to 500 mmol / 1, calculated as elemental metal, an amount of the water-soluble polymer of 0.1 to 20 wt .-%, all based on the total weight of the aqueous solution.
  • organic reducing agent from the group of C j -C 4 alcohols, C 1 -C 4 aldehydes, formic acid, ascorbic acid, citric acid, urea or others to the person skilled in the art known organic reducing agents or a mixture of several of them reduced, with a metal content of more than 10 mmol / 1 to 500 mmol
  • the invention further relates to a process for the preparation of noble metal supported catalysts, which is characterized in that a catalyst support is brought into contact with a sol of the above type containing a noble metal colloid, the noble metal is drawn onto the support, so that the finished supported catalyst 1 to 20% by weight of precious metal, based on the total weight of the carrier - 4 -
  • lysators contains, removes the precious metal-depleted sol and dries the supported catalyst.
  • Precious metals in the sense of the invention are the elements of the so-called platinum group and group Ib of the periodic table (Mendeleev). The following may be mentioned in detail:
  • the metal particles can also be doped with non-reducible metal components in the dispersion state.
  • Such metals are, for example, Ti, Zn, Zr, Mo, Hf, Re, Ce, Lu, Ni, Cu.
  • Ni 2+ or Cu + are preferred. These metals can be introduced as a solution of their salts. The amount of these doping metals is 0 to 100% by weight, preferably 0 to 30% by weight, based on the weight of the noble metal and calculated as metal.
  • Suitable water-soluble polymers are, for example, polymers and copolymers of monomers with polar groups, such as the hydroxyl, the amino, the carboxyl and the sulfonic acid group. They can be copolymerized with monomers without a polar group or with a less polar group such as the ester group to such an extent that the water solubility of the copolymer is retained.
  • Such monomers are for example N-vinyl-pyrrolidone, acrylic acid, methacrylic acid, aspartic acid, styrenesulfonic acid, (meth) acrylic acid-C j-C4 alkyl ester with a hydroxyl, amino or C j -C 4 - (di) alkylamino group, the fictional monomer vinyl alcohol, N-vinyl caprolactam, vinyl pyridine, vinylamine, N-vinyl imidazole, N-vinyl methylimidazole;
  • Comonomers that can be used are, for example
  • (Meth) acrylic acid -CC-C4-alkyl ester and vinyl acetate are known to the person skilled in the art.
  • Preferred polymers are, for example, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol, polyaspartic acid, particularly preferably poly-N-vinylpyrrolidone.
  • the polymers have molecular weights (weight average) of - 5 -
  • Organic solvents which can be present in the noble metal colloid solutions according to the invention are water-soluble and are, for example, alcohols,
  • Carboxylic acids, ketones and nitriles with up to 4 carbon atoms such as methanol, ethanol, propanol, i-propanol, butanol, acetic acid, propionic acid, acetone, methyl ethyl ketone, acetonitrile.
  • solvents can be used if precious metal complexes which are sparingly soluble in water are used.
  • the quantity range for the solvents therefore has zero as the lower limit and is 0 to 10% by weight, based on the total weight of the sol.
  • some of the organic solvents in question can serve as organic reducing agents.
  • the invention is furthermore preferably characterized by a content of polyvalent anions in the aqueous noble metal colloids.
  • Polyvalent anions of this type are, for example: citrate, phosphate, polyphosphate.
  • Such multivalent anions are present in an amount of 0.1 to 10%, based on the total weight of the aqueous noble metal colloids.
  • the noble metal colloid solutions according to the invention are aqueous-based. The remainder is therefore 100% by weight and thus the predominant proportion of water.
  • Organic reducing agents for the preparation of novel aqueous noble metal colloids are well known in the art and are, for example C1-C 4 - alcohols, particularly methanol or ethanol, C j -C 4 - aldehydes, especially formaldehyde or acetaldehyde, formic acid, ascorbic acid, citric acid, urea or a mixture of several from them.
  • ascorbic acid Preferably used: ascorbic acid,
  • Citric acid Citric acid, methanol, ethanol or a mixture of several of them. you will be - 6 -
  • stoichiometric requirement is known to the person skilled in the art.
  • aqueous noble metal colloids for example, an aqueous solution of a noble metal salt or a water-soluble noble metal complex is added, one or more water-soluble polymers and one or more salts with polyvalent anions are added, and the mixture is reduced with one of the reducing agents mentioned. If the solubility ratios require it, one or more of the organic solvents mentioned can also be used. The order of presence and addition can also be varied as desired, but the reducing agent is preferably used at the end.
  • the noble metal is in the form of the halides (fluorides, chlorides, bromides, iodides), nitrates, sulfates or in the form of salts of carboxylic acids, which are also by
  • Amino or halogen can be used; further possibilities of using the noble metals are the use of their metal alcoholates, metal phenolates, metal acetylacetonates and other noble metal compounds familiar to the person skilled in the art. Such noble metal compounds can also be used in the form of their complexes; Complexes range from simple double salts, such as
  • Na2PdCl 4 or H 2 PtCl 6 up to complex compounds with organic ligands, such as palladium acetylacetonate.
  • Carboxylic acids the noble metal salts of which can be used, as mentioned above, have 1 to 20 C atoms, are linear, branched or cyclic, are furthermore saturated or unsaturated and have 1 to 3 carboxyl groups.
  • carboxylic acids are: formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, citric acid, lactic acid, amino acids, such as lysine or aspartic acid. - 7 -
  • the metal particles are in a size of 0.5 to 100 nm, preferably 1 to 30 nm.
  • the noble metal content in the aqueous noble metal colloids according to the invention is always above 10 mg-atom / 1, preferably above 50 mg-atom / 1, and reaches values of up to 250 mg-atom / 1, in many cases up to 500 mg Atom / 1.
  • Such an aqueous noble metal colloid according to the invention can be brought into contact with a catalyst support, such as an ion exchange resin, activated carbon, Al 2 O 3 , SiO 2 and other supports familiar to the person skilled in the art.
  • a catalyst support such as an ion exchange resin, activated carbon, Al 2 O 3 , SiO 2 and other supports familiar to the person skilled in the art.
  • the precious metal colloid spontaneously pulls onto the catalyst carrier.
  • the amount and concentration of the aqueous noble metal colloid in comparison to the amount of the offered carrier can be calculated in a simple and known manner so that the finished supported catalyst contains 0.1 to 20% by weight of noble metal, based on the total weight of the supported catalyst.
  • the support can be brought into contact with the aqueous precious metal colloid by introducing the support into this aqueous precious metal colloid, but also by other methods known to the person skilled in the art, such as by spraying on or by adding the aqueous precious metal colloid to the catalyst support, which is moved in a pelletizing drum, until the support , recognizable by its moisture state, is saturated with precious metal colloid. After each of the described contacts, the precious metal-depleted sol is removed and the supported catalyst is dried.
  • this noble metal colloid sol i.e. this Pt nanoparticle dispersion
  • this Pt nanoparticle dispersion could be used for the production of heterogeneously supported catalysts.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des colloïdes aqueux de métal précieux sous forme de sol comportant des particules métalliques de taille comprise entre 0,5 et 100 nm, qui présentent une teneur en métal précieux supérieure à 10 mmol/l de sol. Ces colloïdes peuvent être obtenus par réduction d'un sel ou d'un complexe de métal précieux dissous dans l'eau, au moyen d'un agent de réduction organique. Selon l'invention, on opère en présence d'un polymère hydrosoluble et, le cas échéant, en présence d'anions polyvalents. Ces colloïdes aqueux de métal précieux servant à produire des catalyseurs dont le support est un métal précieux, par mise en contact de ces colloïdes avec un support de catalyseur, le métal précieux prenant spontanément sur le support.
PCT/EP1999/000290 1998-01-31 1999-01-19 Colloides aqueux de metal precieux et leur utilisation Ceased WO1999038615A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU26190/99A AU2619099A (en) 1998-01-31 1999-01-19 Aqueous precious metal colloids and the use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803891A DE19803891A1 (de) 1998-01-31 1998-01-31 Wäßrige Edelmetallkolloide und ihre Verwendung
DE19803891.7 1998-01-31

Publications (1)

Publication Number Publication Date
WO1999038615A1 true WO1999038615A1 (fr) 1999-08-05

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/000290 Ceased WO1999038615A1 (fr) 1998-01-31 1999-01-19 Colloides aqueux de metal precieux et leur utilisation

Country Status (3)

Country Link
AU (1) AU2619099A (fr)
DE (1) DE19803891A1 (fr)
WO (1) WO1999038615A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2491988C2 (ru) * 2008-01-28 2013-09-10 Басф Кэталистс Ллк Способ получения водной суспензии коллоида благородного металла

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19911504B4 (de) 1999-03-16 2006-02-23 Südzucker AG Mannheim/Ochsenfurt Verfahren zur industriellen Oxidation von Alkoholen, Aldehyden oder Polyhydroxyverbindungen
DE10037071A1 (de) 2000-07-29 2002-02-21 Omg Ag & Co Kg Edelmetall-Nanopartikel, Verfahren zu ihrer Herstellung und Verwendung
EP1236512A1 (fr) * 2001-02-28 2002-09-04 Council Of Scientific And Industrial Research Catalyseur de métal précieux à taille nano et procédé de préparation sélective de 1,4 butènediol
DE10116315A1 (de) * 2001-04-02 2002-10-10 Giesecke & Devrient Gmbh Farbcodierung zur Kennzeichnung von Gegentänden
JP4771366B2 (ja) * 2003-07-17 2011-09-14 旭化成メディカル株式会社 金属コロイド溶液
KR20070030158A (ko) * 2003-08-22 2007-03-15 코세 코퍼레이션 일중항산소 소거제 및 그것을 사용한 조성물
DE102006025148A1 (de) * 2006-05-30 2007-12-06 Süd-Chemie AG Verfahren zur Herstellung eines geträgerten Metallkatalysators
DE102013108664A1 (de) * 2013-08-09 2015-02-12 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Oberflächenmodifizierte Metallkolloide und ihre Herstellung
CN114797870B (zh) * 2022-04-14 2023-06-09 浙江师范大学 一种用于间苯二甲腈加氢制备间苯二甲胺的催化剂及其制备方法和应用

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DE4443705A1 (de) * 1994-12-08 1996-06-13 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren
WO1997024224A1 (fr) * 1995-12-28 1997-07-10 Heath James R Nanocristaux de metal monodisperses organiquement fonctionnalises
EP0879642A2 (fr) * 1997-05-23 1998-11-25 Hoechst Research & Technology Deutschland GmbH & Co. KG Nanoparticules contenant du palladium et stabilisées par une polybétaine, leur procédé de préparation ainsi que le catalyseur ainsi préparé pour la production d'acétate de vinyle

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DE4443705A1 (de) * 1994-12-08 1996-06-13 Studiengesellschaft Kohle Mbh Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren
WO1997024224A1 (fr) * 1995-12-28 1997-07-10 Heath James R Nanocristaux de metal monodisperses organiquement fonctionnalises
EP0879642A2 (fr) * 1997-05-23 1998-11-25 Hoechst Research & Technology Deutschland GmbH & Co. KG Nanoparticules contenant du palladium et stabilisées par une polybétaine, leur procédé de préparation ainsi que le catalyseur ainsi préparé pour la production d'acétate de vinyle

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ANTONIETTI M: "SYNTHESIS AND CHARACTERIZATION OF NOBLE METAL COLLOIDS IN BLOCK COPOLYMER MICELLES**", ADVANCED MATERIALS, vol. 7, no. 12, 1 December 1995 (1995-12-01), pages 1000 - 1005, XP000547224 *
NAOKI TOSHIMA ET AL: "POLYMER-PROTECTED PALLADIUM-PLATINUM BIMETALLIC CLUSTERS: PREPARATION, CATALYTIC PROPERTIES AND STRUCTURAL CONSIDERATIONS", JOURNAL OF THE CHEMICAL SOCIETY. FARADAY TRANSACTIONS, vol. 89, no. 14, 21 July 1993 (1993-07-21), pages 2537 - 2543, XP000381461 *
YUAN WANG ET AL: "IMMOBILIZATION OF POLYMER-PROTECTED METAL COLLOID CATALYSTS BY THE FORMATION OF POLYMER HYDROGEN BOND COMPLEXES", POLYMERS FOR ADVANCED TECHNOLOGIES, vol. 7, no. 8, 1 August 1996 (1996-08-01), pages 634 - 638, XP000623415 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2491988C2 (ru) * 2008-01-28 2013-09-10 Басф Кэталистс Ллк Способ получения водной суспензии коллоида благородного металла

Also Published As

Publication number Publication date
AU2619099A (en) 1999-08-16
DE19803891A1 (de) 1999-08-05

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