EP2125199A2 - Nouveau catalyseur et hydrogénations associées - Google Patents

Nouveau catalyseur et hydrogénations associées

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Publication number
EP2125199A2
EP2125199A2 EP08707639A EP08707639A EP2125199A2 EP 2125199 A2 EP2125199 A2 EP 2125199A2 EP 08707639 A EP08707639 A EP 08707639A EP 08707639 A EP08707639 A EP 08707639A EP 2125199 A2 EP2125199 A2 EP 2125199A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
smf
zno
nanoparticles
hydrogenation
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.)
Withdrawn
Application number
EP08707639A
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German (de)
English (en)
Inventor
Werner Bonrath
Martin Grasemann
Albert Renken
Natalia Semagina
Lioubov Kiwi-Minsker
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DSM IP Assets BV
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DSM IP Assets BV
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Publication date
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Priority to EP08707639A priority Critical patent/EP2125199A2/fr
Publication of EP2125199A2 publication Critical patent/EP2125199A2/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals 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
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B01J37/0226—Oxidation of the substrate, e.g. anodisation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • 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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a structured catalyst based on sintered metal fibers (SMF) coated by a ZnO layer impregnated with Pd-nanoparticles, reactions of organic starting material with hydrogen in the presence of said catalyst and vitamins, carotinoids, perfume ingredients, and/or food or feed ingredients prepared by using this reaction.
  • SMF sintered metal fibers
  • Pd atoms of low coordination number present in small particles of 1-2 nm provide too strong alkynol adsorption diminishing turnover frequency and selectivity. This phenomena is known as a geometric or "ensemble" effect.
  • Particles of 7-10 nm size demonstrate better catalytic performance in hydrogenations of 2-butyne-l,4-diol and 2-methyl-3-butyn-2-ol (MBY) as compared to highly dispersed Pd.
  • MBE 2-methyl-3-buten-2-ol
  • alkenol can be further enhanced by addition of a second metal as a promoter.
  • the promoting effect of co-metal in alkynol hydrogenations has been shown for Pb, Mn, Cu, Bi, Sn, Au, Zn, Cd, etc.
  • Modified electronic and geometric properties of palladium affect the adsorption of alkynols and alkenols and suppress ⁇ -PdH phase formation known to catalyze direct hydrogenation of alkynol to the saturated alcohol.
  • the alkenol yield increases considerably in the presence of additives to the reaction mixture such as ammonia, quinoline, pyridine and sulfur compounds. The mechanism of their influence on activity/selectivity is still under discussion.
  • Metallic grids have a disadvantage of low geometric surface area of ⁇ 100 cm 2 /g. Fabrics of activated carbon fibers used in 2-butyne-l,4-diol hydrogenation possess low mechanical strength. Therefore, there is a need for a structured catalyst which may overcome limitations of the above-mentioned materials.
  • SMF Three-dimensional sintered metal filters (SMF) consisting of metallic microfibers were chosen as a structured catalyst support. SMF have high thermal conductivity that is a great advantage in exothermic hydrogenations, high porosity and permeability. The metal fiber matrix also acts as a micron-scale static mixer eliminating channeling. In addition, high mechanical strength, chemical and thermal stability, easy shaping make SMF promising materials for intensification of catalytic hydrogenation.
  • SMF were coated with a thin layer of ZnO known as efficient support for 2-methyl-3-butyn-2-ol hydrogenation.
  • Pd nanoparticles were deposited from the beforehand prepared sol, and the material was heated in hydrogen atmosphere to create PdZn intermediates.
  • ZnO layer acts both as a basic support and a Pd promoter.
  • the P ⁇ VZnO/SMF material was tested for mechanical stability, and its catalytic behavior was studied in MBY hydrogenation.
  • structured catalyst refers to catalysts wherein the spatial position of the catalyst is controlled. Structured catalysts are known in the art, see, e.g., Chimia 56(4), 2002, 159-163. Examples of structured catalysts are ceramic carrier constructions and fibrous structures, especially filamentous woven cloths. All types of filamentous woven cloths can be used for use in the present invention.
  • the fibers may be from organic or inorganic matter. Examples are fabrics from activated carbon fibers such as acrylonitril fibers, glass libers, ceramic fibers, metal fibers or fleece composite oxides of activated carbon fibers. Preferred are polyacrylonitril fabrics.
  • the individual fibers of the filamentous woven cloth preferably have a diameter of about 2 ⁇ m to about 100 ⁇ m, especially a diameter of no more than about 20 ⁇ m.
  • the fabrics are suitably be woven from threads consisting of a boundle of individual fibers, providing a porous size of the woven cloth of less than about 1 mm. They may be chemically treated, e.g., with nitric acid to modify the specific surface and may have a coating, e.g. of metals such as Al, Ti or Pb to improve selectivity.
  • Pd nanoparticles examples include nanoparticles of noble metals such as platinum, iridium, rhodium, ruthenium or combinations thereof.
  • the catalyst may be present on the carrier fabric in an amount up to about 10 mass%, suitably 1-10 mass%.
  • the loading of the carrier fabric is accomplished by treating with a solution of a precursor of the catalyst, e.g. a salt of the catalyst metal and subsequent drying and heating in a hydrogen atmosphere and can be controlled by the concentration of the catalyst precursor in the loading solution.
  • the hydrogenation in accordance with the present invention can be carried out under conditions conventionally used for hydrogenations of 2-butin-2,4-diol to produce 2-butene-2,4-diol.
  • the hydrogenation is carried out at a pressure of about 0.1 to about 6 MPa and at a temperature of about 350K to about 500K.
  • the hydrogenation can be carried out batch wise or in continuous mode.
  • Example 1 illustrates the invention further without limiting it.
  • Zinc acetate dihydrate (puriss. p. a., >99.5%), monoethanolamine (ethanolamine, puriss. p. a., ⁇ 99%), acetoin (3-hydroxy-2-butanone, purum, mixture of monomer and dimer), sodium molydbate dihydrate (puriss. p. a., >99%), palladium (II) chloride anhydrous (purum), nitric acid (puriss., p.a.), ethanol (purum, >99.8%), toluene (puriss. p. a., >99.7%), 2-propanol (puriss. p. a., >99.8%) were supplied by Fluka. Acetone (puriss., >99%) was purchased from Riedel-deHaen. Lindlar catalyst (5% Pd content as confirmed by AAS) was a gift of DSM Nutritional AG (Switzerland).
  • 2-Methyl-3-butyn-2-ol (purum, >99%), 2-methyl-3-buten-2-ol (purum, >97%), 2-methyl-2- butanol (purum, >98%), 1-butanol (purum, >99.5%), and quinoline (purum, >97%) were purchased from Fluka and used as received. Hydrogen (>99.99% purity) was from Carbagas, Switzerland. Demineralized-bidistilled water was used throughout this work.
  • the SMF panels were degreased with acetone, boiled in toluene for 0.5 h and air-dried.
  • SMF were oxidized in air at 1373 K for 3 h to create an ⁇ - Al 2 O 3 surface layer.
  • Such a temperature (1373-1473 K) for the treatment of FeCrAl alloy with little rare earth content is known to lead to the formation of a structured alumina film, characterized by equiaxed grains on the outer surface, while lower temperature treatment gives oxide whiskers.
  • Coating was conducted by a dip-coating procedure. The gel film thus obtained was air-dried at 383 K for 10 min and then heated at 873 K for 30 min.
  • Rapid heating was applied which is known to result in the formation of highly oriented crystals (slow heating, on the other hand, gives plicated structures).
  • the coating-heating procedure was repeated 7 times to give the weight gain of 6 wt%. ZnO.
  • the coating then was post-annealed at 1173 K for 15 min to promote the formation of island structure of ZnO grains with the increased the specific surface area.
  • Pd and Zn amounts after dissolution in hot nitric acid were determined by atomic absorption spectroscopy via Shimadzu AA-6650 spectrometer with an air-acetylene flame. ZnO loading was also determined gravimetrically.
  • the BET specific surface area and pores size distribution (PSD) of the support and the catalyst were determined using a Sorptomatic 1990 (Carlo Erba) instrument via N 2 adsorption- desorption at 77 K. PSD calculation was performed by Dollimore/Heal method.
  • the ultrasonic adherence test for the mechanical stability of the catalyst was carried out using an ultrasonic bath (Bransonic ultrasonic cleaner, Branson Ultrasonic Corp., USA).
  • the catalyst was treated in water for 20 min totally, and after each 5 min the material was dried at 393 K and weighed.
  • the surface morphology of the samples was investigated by scanning electron microscopy SEM, using a JSM-6300F, JEOL. XRD analysis was carried out in a Siemens D 500 diffractometer using CuKa radiation. The spectra were recorded in a rapid scanning mode (4.0 s/step, 20 step size of 0.04°) in a 20 range of 30-50°.
  • the GC analysis was performed using Auto System XL (Perkin Elmer) equipped with a 30 m Stabilwax (Crossbond Carbowax-PEG, Restek, USA) 0.32 mm capillary column with a 0.25 ⁇ coating.
  • the carrier gas (He) pressure was 101 kPa.
  • Injector and FID temperatures were 473 K and 523 K, respectively.
  • the oven temperature was hold for 4 min at 323 K, then increased to 473 K at a ramp of 30 7min.
  • the GC analysis conditions allowed detecting also the dimerized by-products formed during the reaction.
  • 1-Butanol was used as an internal standard (0.74 g), thus, actual quantity of the reaction mixture components could be determined.
  • catalyst was washed with water, dried at ambient conditions and stored in vacuum desiccator. Two regeneration procedures were applied: 1 ) calcination at 773 K for 2 h with subsequent reduction in hydrogen atmosphere at 773 K for 2 h as described in 2.2; 2) the catalyst was placed in a beaker with ethanol, ultrasonically treated for 10 min in the ultrasonic bath and washed with water.
  • BET specific surface area of the synthesized material was found to be ⁇ 0.7 m 2 /g with a pore specific volume of 6- 10 "3 cm 3 /g and mean pore radius of 1.2 nm. This value is in agreement with the surface area of SMF of ⁇ 1 m 2 /g and of ZnO powder (4 m 2 /g).
  • the adherence test for the mechanical stability of ZnO layer was performed via ultrasonic treatment of the ZnO/SMF in water. Cumulative weight loss of ZnO after 20 min treatment was 0.25 wt% with respect to ZnO weight.
  • the synthesized material possesses high mechanical stability and resistance in water media. This adherence could be attributed to the formation of a thin layer of mixed oxides between FeCrAl alloy and ZnO at 1173 K, like ZnAl 2 O 4 or ZnFe 2 O 4 . Oxide layer formation has been also reported for ZnO-coated ZrO 2 and SiO 2 .
  • Zn being an electron donor with respect to Pd, modifies its electronic properties and changes the alkynol/alkenol relative adsorption strength.
  • the maximum MBE yield for Pd/ZnO/SMF catalyst was achieved as 94.5%.
  • MBA and dimers concentrations were 3.9 mM and 2.3 mM, respectively. Dimers formation stops when all MBY as has been already reported for MBY hydrogenation.
  • Catalytic behavior of Pd/ZnO/SMF catalyst was compared to the one of industrially used Lindlar catalyst. Both catalysts exhibited initial selectivity of 97%.
  • the initial activity of Pd/ZnO/SMF catalyst was 0.71 mol MBY /molp d /s at 308 K and 5 bar H 2 pressure. This value is an order of magnitude higher than the one of Lindlar catalyst (0.04 mol MB ⁇ /molp d /s).
  • quinoline was added to the reaction mixtures.
  • the effect of the nitrogen organic bases is explained as i) preferential adsorption of the additive compared to alkenol, i.e., poisoning (site blocking) of the less selective sites, ii) decreasing the catalyst activity that provides extra time for the mass- transfer processes in the catalyst particles and higher selectivity, iii) electron donation from the N-atom to Pd and change the alkynol/alkenol relative adsorption strength ("ligand" effect), iv) formation of Pd ⁇ + -H ⁇ " mode on Pd surface resulting in the preferred attack of the nucleophilic H on the triple bond, or v) catalyst surface rearrangement.
  • the nitrogen base-to-Pd molar ratio used in hydrogenation reactions varies from 2 to ⁇ 1500, being 7 for the original Lindlar work.
  • Pd/ZnO/SMF catalyst shows improved catalytic performance compared to the industrially used Lindlar catalyst and does not require filtration after the reaction. Moreover, the use of metallic filters as support allows design of a bubble column staged with the catalyst layers for three-phase hydrogenation. These catalysts may be recycled without significant deactivation and/or may be regenerated. Therefore, we performed reuse of the 2-month aged Pd/ZnO/SMF catalyst and the results are presented in Table 2.
  • No. 6 of Table 2 shows the efficient catalyst regeneration via ultrasonic treatment in ethanol for 10 min (no Pd was detected afterwards in ethanol by AAS).
  • selectivity and MBE yield after the ultrasonic regeneration were fully restored to the level of the fresh catalyst, however, the activity decreased twice.
  • MBA-to-dimers molar ratio after regeneration changed from ⁇ 2 to ⁇ 1.
  • Ultrasonic treatment is known to clean the surface of heterogeneous catalysts from carbonaceous deposits and provides morphological changes leading to the improved reusability. Therefore, ultrasonic regeneration is suitable allowing the yield of the target product for the recycled catalyst as high as the yield over the fresh one.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un catalyseur structuré à base de fibres métalliques frittées (SMF) revêtues par une couche de ZnO imprégnée de nanoparticules de Pd; des réactions d'un produit de départ organique avec de l'hydrogène en présence dudit catalyseur ainsi que des vitamines, caroténoïdes, des ingrédients de parfum, et/ou des aliments ou ingrédients alimentaires préparés au moyen de cette réaction.
EP08707639A 2007-02-19 2008-02-09 Nouveau catalyseur et hydrogénations associées Withdrawn EP2125199A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08707639A EP2125199A2 (fr) 2007-02-19 2008-02-09 Nouveau catalyseur et hydrogénations associées

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07003423 2007-02-19
PCT/EP2008/000995 WO2008101603A2 (fr) 2007-02-19 2008-02-09 Nouveau catalyseur et hydrogénations associées
EP08707639A EP2125199A2 (fr) 2007-02-19 2008-02-09 Nouveau catalyseur et hydrogénations associées

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EP (1) EP2125199A2 (fr)
CN (1) CN101616733B (fr)
WO (1) WO2008101603A2 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780406B (zh) * 2009-01-19 2012-06-27 中国科学院化学研究所 一种纳米金属催化剂及其制备方法与应用
EP2528882B1 (fr) * 2010-01-28 2016-11-30 DSM IP Assets B.V. Procédé d'hydrogénation
US9101917B2 (en) 2010-07-01 2015-08-11 Dsm Ip Assets B.V. Structured catalyst
CN102503772A (zh) * 2011-10-11 2012-06-20 上海博鹤企业发展有限公司 一种生产2-甲基-3-丁烯-2-醇的方法
ES2655542T3 (es) * 2011-10-27 2018-02-20 Dsm Ip Assets B.V. Procedimiento de hidrogenación de un acetileno aplicando un catalizador de Pd/Ag soportado sobre fibras metálicas
IN2014DN07060A (fr) * 2012-02-24 2015-04-10 Dsm Ip Assets Bv
BR112014020919B1 (pt) * 2012-02-24 2020-10-27 Dsm Ip Assets B.V sistema catalítico em pó para processos de hidrogenação
US9283549B2 (en) 2012-02-24 2016-03-15 Dsm Ip Assets B.V. Metal powderdous catalyst comprising a CoCrMo-alloy
WO2013156502A1 (fr) * 2012-04-18 2013-10-24 Dsm Ip Assets B.V. Dispositif pouvant être utilisé dans le cadre de réactions d'hydrogénation (ii)
US9381489B2 (en) 2012-04-18 2016-07-05 Dsm Ip Assets B.V. Device useful for hydrogenation reactions (I)
EP2864032A1 (fr) * 2012-04-18 2015-04-29 DSM IP Assets B.V. Dispositif pouvant être utilisé dans le cadre de réactions d'hydrogénation (iii)
CN105612137B (zh) * 2013-09-30 2018-09-21 帝斯曼知识产权资产管理有限公司 用于选择性氢化三键的在勃姆石上的Pd催化体系
CN109382100A (zh) * 2018-11-12 2019-02-26 大连理工大学 一种选择加氢获取1,4-丁烯二醇的含锌金属间化合物催化剂及其制备方法
KR20220053518A (ko) * 2019-06-21 2022-04-29 커먼웰쓰 사이언티픽 앤드 인더스트리얼 리서치 오가니제이션 스캐폴드의 촉매 코팅 공정
CN114073959B (zh) * 2020-08-19 2023-08-29 中国石油化工股份有限公司 一种丁烯氧化脱氢催化剂及其制备方法和应用
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