WO2009000526A1 - Catalyseur colloïdal et procédé pour sa production - Google Patents

Catalyseur colloïdal et procédé pour sa production Download PDF

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Publication number
WO2009000526A1
WO2009000526A1 PCT/EP2008/005167 EP2008005167W WO2009000526A1 WO 2009000526 A1 WO2009000526 A1 WO 2009000526A1 EP 2008005167 W EP2008005167 W EP 2008005167W WO 2009000526 A1 WO2009000526 A1 WO 2009000526A1
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Prior art keywords
ligand
stabilized
nanoparticles
catalytically active
catalyst
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PCT/EP2008/005167
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German (de)
English (en)
Inventor
Richard Fischer
Roland Fischer
Marie-Katrin SCHRÖTER
Martin Muhler
Shaojun Miao
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Süd-Chemie AG
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Publication of WO2009000526A1 publication Critical patent/WO2009000526A1/fr

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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a colloidal catalyst and to a process for the production thereof, wherein the catalyst according to the invention comprises a plurality of nanoparticles of a catalytically active metal, which are partially coated with a layer containing ligand-stabilized metal ions. Furthermore, the present invention relates to the use of such inventive colloidal catalysts.
  • Colloidal catalysts consisting of a multiplicity of individual nanoparticles and having their specific surfaces modified ("decorated") to modify their stability, solubility and functionality, are an increasingly important field of nanochemistry (J. Grünes et al. Chem. Commun. 2003, 2257-2260).
  • colloids are typically carried out by the reduction of a metal salt in the presence of surface-active compounds, for example by the so-called polyol process (CB Murray, Murray et al., Ann Rev. Mater, 2000, 30, 545-610) by electrochemical processes.
  • polyol process CB Murray, Murray et al., Ann Rev. Mater, 2000, 30, 545-610
  • the unpublished German Patent Application No. DE 10 2006 013794.9 proposes a process for the preparation of colloidal nanocatalysts, wherein first a soluble ligand-stabilized complex of an ion of a catalytically active metal over a defined period of time a first thermal thermal by sequential or simultaneous addition in an inert non-aqueous solvent Treatment is carried out in a certain temperature range, and then after the thermal treatment, a precursor compound of a so-called promoter compound of a metal is added, which converts at the selected temperature to the corresponding metal oxide.
  • This results in colloids which have up to 180% of the activity of conventional ternary reference catalysts in the methanol synthesis of CO and H 2 .
  • the synthesis of these colloidal nanocatalysts is relatively complicated and requires a targeted process control.
  • the object of the present invention was therefore to provide further catalysts or catalyst systems, in particular for the synthesis of methanol from CO and hydrogen on the basis of mixed metal promoter / metal nanoparticles, which are largely air and thermodynamically stable and in terms of their activity and stability can be selectively adjusted and optimized and beyond can be obtained from simple and inexpensive starting materials without complex process steps.
  • a colloidal nanocatalyst comprising a plurality of nanoparticles of a catalytically active metal, which are partially coated with a layer containing ligand-stabilized metal ions, and wherein the ligand stabilized metal ion and the catalytically active metal are different from each other.
  • the difference between metal ion and catalytically active metal means that it is thus at least two different elements of the periodic table, as will be described specifically below.
  • the term "colloidal nanocatalyst” is also used below for the catalyst according to the invention:
  • the IgG-stabilized metal ions form the so-called "promoter”.
  • the colloidal nanocatalyst according to the invention is largely stable to air.
  • the oxidized form of the catalyst i. e.g. the preferably air-stable non-reduced metal compound, which is then reacted to the catalytically active metal, can be easily reduced, preferably directly in situ in the reactor, in which the methanol synthesis can be carried out.
  • air-stable starting compounds are preferably used, so that a particularly simple access to such catalysts without complicated, e.g. under protective gas to be carried out process is possible.
  • the nanoparticles of the colloidal nanocatalyst according to the invention have an approximately spherical shape and are separated from one another. Most (about 80%) of the nanoparticles typically have a size of 6 - 10 nm, mixed with smaller particles in the size range of 4-6 and larger in the range of 11 - 15 nm.
  • the catalytically active metal particles are interspersed through them enveloping layer containing the ligand-stabilized metal ions, in particular, for example, protected from oxidation and arrange themselves in hexagonal two-dimensionally ordered lattices with a Particle spacing of about 0.9 - 2 nm on. The protective effect is achieved in particular by the ligand envelopes of the metal ions.
  • EXAFS X-ray structure absorption spectroscopy
  • the surface of the nanoparticles of the catalytically active metal is only partially enveloped or coated by the layer containing IgG-stabilized metal ions, so that the colloidal catalysts of the invention are particularly stable both thermally and kinetically and have an increased catalytic activity, since they still have some free metal sites where the catalysis is preferred.
  • the colloidal catalyst according to the invention has a higher productivity than comparable commercial ternary CuO / ZnO / Al 2 O 3 catalysts.
  • the average particle size of the nanoparticles is from 0.7 to 15 nm, which in the present case is also intended to serve as definition according to the invention of the term "nanoparticles.” This results in a very high reactivity of the catalyst achieved at the same time small particle size of the catalytically active centers. It is also possible in less preferred developments of the catalyst according to the invention that the nanoparticles are completely enveloped by a layer containing ligand-stabilized metal ions. As has been shown (see results), even in this case there is still sufficient accessibility of the catalytically active elemental metal particle, which, for reactants, is given in a catalytic reaction.
  • the distance between the individual nanoparticles is 0.9 to 2 nm, which is achieved in particular by the layer of ligand-stabilized metal ions or, in other words, by the ligands.
  • the nanoparticles of a freshly prepared catalyst according to the invention have a size of 6 to 10 nm. Even more preferably, more than 50% of the nanoparticles have a size of 8-10 nm.
  • the catalytically active metal of the nanoparticles is preferably selected from the group consisting of Cu, Ni, Pd, Pt, Ir, Ru, Rh, Re, Os, Au, Ag, Co, Fe, thus offering the possibility of different catalysts katalyti different - make accessible to shear active metals, very particularly preferred are Cu, Ni, Pd, Pt, Co and Fe.
  • binary, ternary and polynary systems of catalytically active metals such as Cu / Ni, Al / Ni, Pt / Pd, Fe / Co, Cu / Ni / Fe, etc. may also be present.
  • the preferred ligands for the ligand-stabilized metal ions are selected from substituted and unsubstituted alcoholates, carboxylates, betadicetonates, beta-chain mi stylist, mixed alkoxide betadiketonates, guanidinates and phenolates which typically give air stable compounds with the corresponding metal ions listed below so that they can be handled easily.
  • carboxylates in particular of fatty and oleic acids such as stearates, palmitates, oleates, etc.
  • the metal ion (“promoter ion”) of the ligand-stabilized metal ions is selected from among the ions of the metals of the group consisting of Ti, Zr, Zn, Al, Sn, Ca, Mg, Ba, Si and rare earths, which are particularly air-stable with the ligands mentioned above Complex and synthetically easily accessible.
  • the catalyst according to the invention is supported, in particular on a preferably porous support made of aluminum oxide, titanium oxide, zirconium oxide, silicon oxide and mixtures thereof, so that the catalyst according to the invention
  • Nanocatalysts for example, also known per se
  • Shaped body can be applied from the aforementioned materials, for example by means of a washcoat.
  • the object of the present invention is further achieved by a process for the preparation of a colloidal Catalyst dissolved, wherein the method comprises the steps that in a non-aqueous solvent-soluble ligand-stabilized complexes of an ion of a first catalytically active metal together with ligand-stabilized metal ions of a second metal of a thermal treatment at 180 ° to 25O 0 C, in particular via a Period of 1 to 10 minutes under a hydrogen atmosphere, wherein the ion of the catalytically active first metal is different from the ligand-stabilized metal ion of the second metal.
  • an air-stable ligand-stabilized complex of the ion of the catalytically active metal is used in the process according to the invention, which considerably simplifies the handling and the accessibility of the nanocatalysts obtained by the process according to the invention.
  • a completely air-stable ligand-stabilized metal ion is used, such as, for example, zinc, calcium, magnesium, zirconium, tin and silicon complexes.
  • the inert, non-aqueous solvent is selected from higher hydrocarbons, such as decane, undecane, dodecane, etc., substituted and unsubstituted aromatics, as well as polyethers, and most preferably squalane.
  • reaction mixture is free of other stabilizers such as hexadecylamine (HDA), as known from the prior art.
  • HDA hexadecylamine
  • the nanocatalyst according to the invention obtainable by means of the process according to the invention, for example, is used. example as Zn / Cu nanocatalyst in the production of methanol from CO and H 2 , or as a Raney catalyst such.
  • Raney nickel and Raney cobalt and Raney copper for the desulfurization and dehalogenation, for the hydrogenation of double and triple bonds in olefins (for example for fat hardening), alkynes and aromatics Reduction of aldehydes and ketones to alcohols as well as of nitriles, nitro compounds or oximes to amines, to the decomposition of hydrazine, to the dehydrogenation of primary and secondary alcohols to aldehydes and ketones and as a catalyst in fuel cells.
  • the Zn-stearate stabilized Cu / Ni nanocatalysts according to the invention are used in particular as hydrogenation catalysts in the production of fats.
  • FIG. 1 shows in situ ATR spectra of adsorbed CO on a Cu / Zn nanocatalyst according to the invention.
  • FIG. 2 shows the productivities of methanol over Cu / Zn stearate colloids with different Cu / Zn ratios compared to a reference catalyst at 493 K.
  • FIG. 3 shows the particle size distribution of a catalyst according to the invention before (FIG. 3a) and after (FIG. 3b) catalysis at 493 K over 72 h.
  • FIG. 4 shows TEM images of a catalyst according to the invention before (4a) and after catalysis (4b) at 493 K for 72 h.
  • the synthesis of a catalyst according to the invention is exemplified by means of a Cu / Zn stearate nanocatalyst according to the invention.
  • Zinc stearate available from Sigma-Aldrich was used without further purification. Copper stearate was prepared according to the instructions of Kimura and Taniguchi in Catal. Lett. 1996, 40, 123-130.
  • Cu (dmap) 2 can be used as the Cu source.
  • FIG. 4a A TEM image of the product is shown in Figure 4a.
  • the TEM images were taken with a Hitachi 8100 microscope.
  • Cu / Zn stearate colloids with different Cu / Zn ratios were prepared analogously.
  • the colloidal copper solution (Cu: 15.9 mmol / l in hexadecane) was measured under inert gas with the aforementioned ATR-IR system.
  • the adsorption of CO is a good indicator of the catalytic suitability of such systems, in particular for the production of methanol from CO and H 2 .
  • CO is simply adsorbed on the surface of nanocatalysts according to the invention.
  • the catalytic tests were carried out by reducing the hydrogen in the CSTR reactor (Parr, series 5102) to the synthesis gas (72% H 2 , 10% CO, 4% CO 2 , balance N 2 ) at a pressure of 2.6 MPa was converted.
  • This procedure thus enables the in-situ one-step synthesis of the catalyst according to the invention starting from air-stable educts directly in the reactor in which the catalytic reaction is to be carried out without, for example, transfer step of the catalysts in the reaction reactor.
  • the catalytic tests were carried out in a continuously operated high-pressure liquid reactor (CSTR reactor, Parr, series 5102) in squalane solution with freshly prepared inventive nanocolloids according to Example 1 at 2.6 mPa with a gas mixture of 72% H 2 , 10% CO 4% CO 2 and 14% N 2 were carried out at a flow rate of 50 ml / min -1 (so-called three-phase systems) squalane was chosen as the solvent for carrying out the experiment because it has a very good gas solubility for the gases Squalane may of course also use other suitable solvents such as higher hydrocarbons, mesytiles, benzene, toluene, etc.
  • Table 1 shows the catalytic activity of the invention Cu / Zn stearate nanocatalysts of various compositions compared with a conventional catalyst under the same conditions.
  • Table 1 Catalytic activities of Cu / Zn stearate catalysts according to the invention in comparison with a commercially available ternary Cu / Zn / Al catalyst
  • the productivity of methanol over all catalysts increased to a maximum and then settled to a standard value.
  • the activation periods ("induction period") (from start to maximum productivity) and the productivity decrease before maximum to the continuous value differed for each catalyst and depended on the respective ratio of Cu / Zn.
  • the activation period was measured mainly by the diffusion rate of the feed gas to the copper core. Although Cu nanoparticles stabilized with a lower amount of Zn stearate are more accessible to the feed gas, they are less stable.
  • a Cu / Zn stearate nanocolloid (75:25) according to the invention shows a productivity of 3,468 ⁇ mol / g Cu ⁇ H (curve 4), which was about 55.7% of the reference ternary catalyst.
  • Activity decreased rapidly as the Cu content decreased, reaching a maximum of 6,408 ⁇ mol / g Cu ⁇ H with a Cu / Zn ratio of 1 (Curve 2), which roughly corresponds to the reference catalyst (Curve 1).
  • An amount of Zn stearate in a Cu / Zn stearate nanocolloid catalyst according to the invention for a ratio of Cu / Zn of 75:25 does not appear to be sufficient to sufficiently stabilize the Cu nanoparticles because the time-on-stream Productivity decreased rapidly after peak activity, corresponding to partial precipitation of the colloid after reaction.
  • More stearate (via Zn stearate) in the colloid thus has a higher stabilizing property and the decrease in productivity is not so serious.
  • FIG. 3 shows the particle size distribution of a catalyst according to the invention before (FIG. 3 a) and after (FIG. 3 b) catalyst at 493 0 K over 72 h.
  • the ratio of copper to zinc was 50:50.
  • the particle size distribution shown in FIG. 3a is derived from freshly prepared zinc stearate-stabilized copper nanoparticles, which have also been investigated by means of TEM.
  • the particles are approximately spherical and separated, that is, isolated.
  • the majority of nanoparticles have a size of 8-10 nm.
  • there are a larger number of particles between 4 - 5 nm and 11 - 12 nm.
  • the distance between the particles was about 2 nm and the particles showed a tendency toward a two-dimensionally ordered lattice. This has also been observed in the case of hexadecylamine-stabilized copper colloids and can therefore be taken as evidence that the protection against agglomeration is mediated by the zinc stearate or by the stearate radicals.
  • SAED Selected Area Electron Diffraction

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Abstract

L'invention concerne un catalyseur colloïdal comprenant des nanoparticules métalliques catalytiquement actives qui sont enrobées par endroits d'une couche contenant un composé métallique stabilisé par des ligands. L'invention concerne également un procédé pour la production de nanocatalyseurs colloïdaux selon l'invention, selon lequel un complexe, stabilisé par des ligands et soluble dans un solvant inerte non aqueux, d'un ion du métal catalytiquement actif du nanocatalyseur est soumis, conjointement avec le composé métallique stabilisé par des ligands, à un traitement thermique à 180-250°C pendant une période de 1-10 min sous atmosphère d'hydrogène.
PCT/EP2008/005167 2007-06-25 2008-06-25 Catalyseur colloïdal et procédé pour sa production WO2009000526A1 (fr)

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Application Number Priority Date Filing Date Title
DE102007029201.7 2007-06-25
DE102007029201A DE102007029201B4 (de) 2007-06-25 2007-06-25 Kolloidaler Nanokatalysator und Verfahren zu dessen Herstellung

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP3881955A1 (fr) * 2020-03-20 2021-09-22 BASF Corporation Procédé de préparation de nanoparticules de métal de transition

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JP5410363B2 (ja) * 2010-04-28 2014-02-05 日立Ｇｅニュークリア・エナジー株式会社 水素及び酸素の再結合触媒、再結合装置及び原子力プラント

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Title
KIMURA, HIROSHI ET AL: "Reusability of the Cu/Ni-based colloidal catalysts stabilized by carboxylates of alkali-earth metals for the one-step amination of dodecyl alcohol and dimethylamine", APPLIED CATALYSIS, A: GENERAL , 292, 281-286 CODEN: ACAGE4; ISSN: 0926-860X, 2005, XP002500060 *
KIMURA: "Cu/Ni colloidal dispersions stablised by calcium and barium stearates for the amination of oxo-alcohols", CATALYSIS LETTERS, no. 40, 1996, pages 123 - 130, XP002500059 *
SCHLÜTH: "Quasi-Homogenous Methanol Synthesis over Highly Active Copper Nanoparticles", CATALYST RESEARCH, no. 44, 2005, pages 7978 - 7981, XP002500061 *
SCHRÖTER M-K ET AL: "A colloidal ZnO/Cu nanocatalyst for methanol synthesis", CHEMICAL COMMUNICATIONS - CHEMCOM, ROYAL SOCIETY OF CHEMISTRY, GB, 5 May 2006 (2006-05-05), pages 2498 - 2500, XP002436833, ISSN: 1359-7345 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3881955A1 (fr) * 2020-03-20 2021-09-22 BASF Corporation Procédé de préparation de nanoparticules de métal de transition
WO2021186021A1 (fr) * 2020-03-20 2021-09-23 Basf Corporation Procédé pour la préparation de nanoparticules de métal de transition
CN115397582A (zh) * 2020-03-20 2022-11-25 巴斯夫公司 过渡金属纳米颗粒的制备方法

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