WO1996037295A1 - Nouveaux catalyseurs d'oxyde metallique contenant du ruthenium et du selenium ou du soufre, leur procede de preparation et leur utilisation - Google Patents

Nouveaux catalyseurs d'oxyde metallique contenant du ruthenium et du selenium ou du soufre, leur procede de preparation et leur utilisation Download PDF

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Publication number
WO1996037295A1
WO1996037295A1 PCT/EP1996/001960 EP9601960W WO9637295A1 WO 1996037295 A1 WO1996037295 A1 WO 1996037295A1 EP 9601960 W EP9601960 W EP 9601960W WO 9637295 A1 WO9637295 A1 WO 9637295A1
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stands
ranging
oxidation
oxide
oxygen
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PCT/EP1996/001960
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German (de)
English (en)
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Bernd Scharbert
Rolf Schulz
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Hoechst Aktiengesellschaft
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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
    • B01J31/26—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
    • 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
    • B01J23/007—Mixed 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
    • B01J23/38—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
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • 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
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation

Definitions

  • the present invention relates to new ruthenium and be or sulfur-containing metal oxide catalysts and a process for their preparation and their use.
  • Epoxies are compounds of considerable industrial importance. They are used in the production of a large number of economically important products.
  • epoxides can be hydrolyzed to glycols, which are used as deicing agents or as reactive monomers for the production of condensation polymers.
  • Polyether polyols produced by ring opening polymerization of epoxides, are commonly used as intermediates in the production of polyurethane foams, elastomers, coatings, sealants or similar articles.
  • glycol ethers e.g. B. find use as a polar solvent.
  • EP-A-0 404 529 describes metal oxides based on iron, antimony and phosphorus, which are particularly suitable as catalysts in the ammoxidation of methanol.
  • the metal oxide masses described here are less suitable.
  • REPLACEMENT BLA ⁇ (RULE 26) the metal oxide compositions described here are less suitable.
  • Molybdenum bismuth iron catalysts which are only recommended for the gas phase oxidation of propene or isobutene to acrolein or methacrolein. All of the catalysts described here are unsuitable for the epoxidation of propene.
  • Oxidation processes that were developed in the liquid phase use the technically most interesting and cheapest oxidizing agent, molecular oxygen, only in exceptional cases.
  • Huybrecht J. Mol. Catal. 71, 129 (1992); EP-A-31 1983 describes the epoxidation of olefins with hydrogen peroxide in the presence of titanium silicate compounds as a catalyst.
  • hydrogen peroxide is on the one hand a relatively expensive oxidizing agent and on the other hand cannot be used completely because it partly decomposes to water and oxygen.
  • a process for the epoxidation of ethylene with tert-butyl hydroperoxide (TBHP) in the presence of molybdenum complexes as a catalyst is described by Kelly et al. (Polyhedron, Vol. 5, 271-275, (1986)).
  • the actual active catalyst is a molybdenum complex that has already added TBHP and one equivalent of epoxy.
  • the process proceeds with high selectivity, but an expensive oxidation agent is used. Furthermore, there are problems with reproducibility, which prevents the method from being used industrially.
  • Epoxidation-active transition metal salts or complexes of molybdenum are used as catalysts, for example chlorine, carbonyl or chloronitrosyl complexes which also contain donor ligands such as hexamethylphosphoric triamide (HMPT), triphenyl phosphite or acetonitrile.
  • HMPT hexamethylphosphoric triamide
  • the most active compounds here are those that contain HMPT as donor ligands, with HMPT being known as a carcinogen.
  • the catalysts known to date from the literature are unsatisfactory in terms of selective epoxidation.
  • the catalysts for the oxidation of olefins in the gas phase usually achieve satisfactory selectivities only for oxidation in the allyl position (e.g. propene to acrolein) or for ammoxidation (propene to acrylonitrile) or for oxidative dehydrogenation (butene to butadiene).
  • the catalysts for the oxidation of olefins in the liquid phase only achieve unsatisfactory epoxide selectivities when molecular oxygen is used, or use carcinogens to prepare the catalysts.
  • the object of the present invention is therefore to provide new catalyst systems which lead to good selectivities in the oxidation of olefins to the corresponding epoxides by means of molecular oxygen or atmospheric oxygen.
  • the present invention solves this problem and relates to compounds of the general formula
  • Q stands for one or more elements selected from the group Na, K,
  • Rb Cs, NR 1 R 2 R 3 R +, Be, Mg, Ca, Sr, Ba, wherein R 1, R 2, R 3 and R 4 independently represent hydrogen, a C, -. C 2C N-alkyl -, especially for a C r C 8 - and C 16 -C 20 alkyl, or C r C 8 cycloalkyl radical, one
  • Aryl radical in particular a methyl, ethyl, propyl or butyl radical;
  • M stands for one or more of the following elements V, Mo, Wo;
  • R stands for one or more elements selected from the following
  • Ir, Ni, Pd, Pt, Cu; X stands for one or more of the following elements F, Cl, Br, J, NO 3 " ,
  • a is a number in the range from 1 to 30; b is a number ranging from 5 to 50; c is a number ranging from 0.1 to 10; d is a number ranging from 0 to 10; e is a number ranging from 0 to 20; f is a number ranging from 0 to 10; g is a number in the range of 0.01 to 10; h stands for the stoichiometric compensation of the oxide formation
  • Number of oxygen atoms; i is a number in the range from 0 to 25, preferably in the range from 4 to
  • the compounds according to the invention with the basic building blocks of ruthenium, selenium or sulfur and oxygen, and as further elements molybdenum and / or vanadium and / or tungsten are suitable as selective catalysts for the epoxidation of olefins.
  • Oxygen or oxygen-containing gases are always heterogeneous or homogeneous catalyzed liquid phase reaction are used.
  • the catalysts of the present invention must have ruthenium and selenium and / or sulfur in the ranges given above.
  • the catalyst theses can also be carried out in organic solvents. Dichloromethane, ethers, alcohols and other polar solvents are particularly suitable for this.
  • Q in particular represents Na, K, Cs and NR 1 R 2 R 3 R 4 + , the index a preferably being in the range from 5 to 20.
  • M stands for at least one or more elements from the group Mo, W and vanadium, in particular for Mo and W.
  • Mo and W are preferably in the form of their water-soluble compounds, particularly preferably in oxidation state VI. Examples are (NH 4 ) 6 Mo 7 O 24 , Na 2 MoO 4 , Na 2 WO 4 , Na 6 W 12 O 39 but also MoOCI 4 , MoO 2 CI 2 , MoF 6 , WOCI 4 , WO 2 CI 2 , WCI 6 and WF 6 as well as NaVO 3 , VOSO 4 and VOF 3 can be used.
  • the index b is preferably in the range from 10 to 30.
  • R is preferably an element selected from the group consisting of V, Ru, Os, Cu, Ti and Ce; the index d is in the range from 0 to 5.
  • X is Cl or Br and Y is selected in particular from the group S, Se, Te, P, Sb and Bi.
  • the indices e and f are in particular in the range from 1 to 10 for e and from 0 to 5 for f.
  • Component Y plays a role in particular with regard to an increase in selectivity and in terms of suppressing total oxidation.
  • the preparation of the catalysts is preferably based on the soluble or more soluble selenium and sulfur compounds.
  • Examples include selenic acid H 2 SeO 3 and sulfurous acid H 2 SO 3 , selenic acid H 2 SeO 4 or sulfuric acid H 2 SO 4 or SO 3 or their alkali and alkaline earth metal and ammonium salts.
  • g is preferably in the range of 0.02 to 5.
  • the selenium or sulfur content of the metal oxide is below the range given above (g ⁇ 0.01), the proportion of total oxidation products increases considerably and the selectivity of the reaction drops drastically. On the other hand, if the selenium / sulfur content exceeds the specified upper limit, the catalyst activity is restricted and the physical properties deteriorate.
  • Selenium and sulfur, like ruthenium, are present in the metal oxide catalysts according to the invention in higher oxidation states and in oxidic form.
  • the starting compound for introducing the ruthenium is particularly suitable due to its simple commercial availability Ruthenium trichlorohydrate, but also other compounds of the trivalent metal, such as Ru-III-bromide, acetone acetonate, nitrosyl chloride, nitrosyl nitrate, K 2 RuCI 5 , Ru (NH 3 ) 6 CI 3 and H 3 Ru (SO 3 ) 2 OH proven itself.
  • compounds of ruthenium in other oxidation states are also suitable, such as Ru (NH 3 ) 6 Cl 2 , (NH 4 ) 2 RuCl 6 , Ru (C 10 H 8 N 2 ) 2 Cl 2 , (2,2'-bipy ) and all-trans-Ru (O) 2 (OAc) 2 Py 2 .
  • the index c is therefore in particular in the range from 0.1 to 5.
  • Metal oxide catalysts according to the present invention contain selenium and / or sulfur and ruthenium as essential elements. In order to achieve an increased epoxide selectivity in the oxidation of alkenes, at least one of the two elements S or Se must be present in the metal oxide compositions according to the invention within the limits specified above.
  • the other optional elements are selected in their selection and their exact composition according to the desired field of application of the catalyst. In this way, the catalyst can be optimized for the desired epoxidation.
  • the metal oxide catalyst according to the invention can without a corresponding
  • Carrier material are used or applied to such.
  • the usual carrier materials such as silicon dioxide, porous or non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitrate, are suitable or silicon carbide.
  • Preferred carrier materials have a surface area of less than 20 m 2 / g.
  • Preferred carrier materials are silicon dioxide and aluminum dioxide with a low specific surface area.
  • the metal oxide catalysts according to the invention are prepared by preparing a slurry, preferably an aqueous solution, which contains the individual starting components.
  • M is molybdenum or tungsten
  • Examples are Na 2 WO 4 and Na 2 MoO 4 .
  • one of these substances is used in an aqueous solution.
  • a soluble selenium compound and, depending on the field of use of the catalyst, a soluble compound of one or more elements from group Y are then added to this solution.
  • the ruthenium component is also dissolved separately, if appropriate with a compound of a cation from the group R which is matched to the catalyst application.
  • An acidic, aqueous solution is preferably prepared.
  • the salt is preferably dissolved in hydrochloric acid and added dropwise to the reaction solution.
  • the resulting mixture is stirred for 2 to 6 hours, preferably 3 to 5 hours at 15 to 50 ° C., in particular at 20 to 30 ° C.
  • Organic solvents are also suitable for the synthesis of the metal oxide catalysts according to the invention, provided that the compounds to be dissolved have a sufficiently high solubility in the corresponding solvents.
  • saturated and unsaturated, aliphatic, cyclic and aromatic solvents, which preferably contain oxygen, and halogenated hydrocarbons can be used.
  • dichloromethane, alcohols, ethers or ketones and organic acids are used.
  • the solution is then mixed with 0.2 to 30 equivalents, in particular 0.5 to 25 equivalents, based on the ruthenium component, alkali metal or ammonium halide, in particular potassium chloride or tetramethyl or tetraethylammonium bromide, and the catalyst crystallizes out.
  • alkali metal or ammonium halide in particular potassium chloride or tetramethyl or tetraethylammonium bromide
  • the mass obtained in this way is dried at 20 to 100 ° C., preferably at 25 to 40 ° C. for 1 to 48 hours, in particular 6 to 24 hours.
  • the pH of the mass to be dried should preferably not be above 7, especially in the range from pH 1 to 4.
  • the mixed oxide catalyst obtained is subsequently subjected to a calcination process, it is advisable to use the dried and pulverized catalyst at a temperature in the range from 200 to 1000 ° C., in particular 350 to 800 ° C. in the presence of nitrogen, oxygen or one to calcine oxygen-containing gas.
  • the time period is 0.5 to 24 hours.
  • Such calcination of the catalyst according to the invention is particularly preferred in the case of mixed oxide catalysts in which (alkyl) ammonium compounds have been used as starting materials.
  • the catalyst obtained by the process according to the invention is impregnated with an organic or inorganic compound of one or more components of the groups R, X and Y either before or after the calcination in an organic solvent or an aqueous solution.
  • the catalyst according to the invention can be used for all epoxidation reactions in the liquid phase, in particular for the epoxidation of linear terminal olefins.
  • Aliphatic, optionally branched and alicyclic C 2 -C 30 olefins preferably linear olefins having 2 to 12 carbon atoms and cyclic olefins having 5 to 12 carbon atoms are epoxidized with a high selectivity using the catalysts according to the invention.
  • Oxygen serves as the oxidizing agent, which can be diluted in pure form or with an inert gas such as CO 2 , N 2 , noble gases or methane.
  • the oxidation conditions are chosen so that a noticeable oxidation occurs even without the addition of catalyst, in which case the selectivity of the epoxide formation is low.
  • the temperature at which the reaction can be carried out is in the range from 30 to 500 ° C.
  • the pressure range can be varied from normal pressure to 200 bar and is preferably not more than 100 bar.
  • the temperature / pressure range should be chosen so that neither temperature nor pressure assume extremely high values, since the reaction is more difficult to handle under these conditions.
  • a temperature range of 30 to 300 ° C and a pressure in the range of normal pressure to 30 bar has proven to be advantageous in the oxidation of C 6 -C 1 -alkenes, while the epoxidation of alkenes with less than 6 carbon atoms preferably at lower Temperatures in the range of 120 to 230 "C and pressures in the range of 30 to 100 bar. It is carried out so that the oxidation always takes place in the liquid phase.
  • halogenated aromatics such as chlorobenzene, 1-chloro-4-bromobenzene, bromobenzene, halogenated and non-halogenated hydrocarbons, such as chloroform, chloropropanol, dichloromethane, 1, 2-dichloroethane, trichlorethylene, ketones , such as acetone, and ethers, furthermore alcohols, in particular C 12 -C 12 alcohols, such as ethanol, methanol or propanol, and higher alcohols, esters, such as alkyl benzoates, and water.
  • halogenated aromatics such as chlorobenzene, 1-chloro-4-bromobenzene, bromobenzene
  • halogenated and non-halogenated hydrocarbons such as chloroform, chloropropanol, dichloromethane, 1, 2-dichloroethane, trichlorethylene
  • ketones such as acetone
  • ethers furthermore alcohols, in particular C
  • the oxidation can be carried out continuously or in a batch process.
  • the catalyst can be added in bulk.
  • the catalyst can also be generated in situ during catalysis, e.g. according to the manufacturing instructions from the individual components.
  • reaction can be accelerated by adding stoichiometric amounts, based on the catalyst, of an activator such as hydroperoxides, hydrogen peroxide or peracids and / or by adding a radical initiator such as azobisisobutyronitrile.
  • an activator such as hydroperoxides, hydrogen peroxide or peracids and / or by adding a radical initiator such as azobisisobutyronitrile.
  • the addition of oxygen is metered in such a way that a residence time in the reactor is less than 60 minutes, preferably less than 1 minute results.
  • the oxygen uptake can take place until the alkene has completely converted, but preference is given to oxygen up to an alkene conversion of 50%.
  • the reaction product is worked up and purified, for example by distillation. This also applies to the continuous procedure.
  • epoxy yields of> 35%, in particular in the range of 35-50%, are achieved.
  • the epoxy yields are improved when using metal oxide catalysts and the use of carcinogenic substances for the production can be dispensed with.
  • the oxygen used as an oxidizing agent in the process according to the invention is available inexpensively and there is no formation of reduced by-products which have to be disposed of after the epoxidation reaction.
  • Tetraethylammoniumbromid added and the catalyst crystallized out, filtered off, washed and dried.
  • reaction solution analogous to Example 4 is concentrated before adding a
  • Reflux gas burette are added exactly 2.0 ml (12.6 mmol) of oct-1-ene and 200 mg of catalyst.
  • the apparatus is rinsed with O 2 and filled with a pure O 2 atmosphere (1 bar). The time until an O 2 intake of 10 ml (0.45 mmol) is measured. It is then cooled, 1 ml of the reaction solution is mixed with exactly 0.050 ml of heptane (external GC standard) and the selectivity for 1, 2-epoxyoctane is determined by gas chromatography.
  • reaction mixture is brought to 150 ° C., 15 bar of air are pressed in at this temperature and the mixture is stirred for 10 minutes.
  • the reaction is then stopped by cooling, a gas and a liquid sample are taken at 20 ° C. and both are analyzed by gas chromatography.

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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)
  • Epoxy Compounds (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des composés d'oxydation catalytique en phase liquide, de formule générale (1): QaMbRucRdXeYfZgOh * H2Oi, dans laquelle les symboles Q, M, R, X, Y, a, b, c, d, e, f, g, h et i ont la signification suivante: Q désigne un ou plusieurs éléments sélectionnés dans le groupe constitué par Na, K, Rb, Cs, NR?1R2R3R4+¿, Be, Mg, Ca, Sr, Ba, R?1, R2, R3 et R4¿ désignant indépendamment les uns des autres hydrogène, un reste alkyle C¿1?-C20 ou cycloalkyle C1-C8, un reste aryle, notamment un reste méthyle, éthyle, propyle ou butyle; M désigne un ou plusieurs éléments parmi V, Mo, Wo; R désigne un ou plusieurs éléments sélectionnés dans le groupe constitué par Sc, Y, La, Ce, Ti, Zr, Nb, Ta, V, Cr, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu; X désigne un ou plusieurs éléments parmi F, Cl, Br, J, NO3?-, So¿42-; Y désigne un ou plusieurs éléments sélectionnés dans le groupe constitué par Ga, In, Ge, Sn, S, Se, Te, P, As, Sb, Bi; Z désigne S ou Se; a vaut 1 à 30; b vaut 5 à 50; c vaut 0,1 à 10; d vaut 0 à 10; e vaut 0 à 20; f vaut 0 à 10; g vaut 0,01 à 10; h désigne le nombre d'atomes d'oxygène requis pour compenser stoechiométriquement la formation d'oxydes; i vaut 0 à 25.
PCT/EP1996/001960 1995-05-24 1996-05-09 Nouveaux catalyseurs d'oxyde metallique contenant du ruthenium et du selenium ou du soufre, leur procede de preparation et leur utilisation WO1996037295A1 (fr)

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Application Number Priority Date Filing Date Title
DE1995119008 DE19519008A1 (de) 1995-05-24 1995-05-24 Neue ruthenium- und selen- oder schwefelhaltige Metalloxidkatalysatoren sowie ein Verfahren zu ihrer Herstellung und ihre Verwendung
DE19519008.4 1995-05-24

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL120942A0 (en) 1997-05-29 1997-09-30 Yissum Res Dev Co A process for the epoxidation of alkenes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1543029A1 (de) * 1964-11-09 1969-09-11 Halcon International Inc Verfahren zur Herstellung von Oxiranverbindungen
FR2279706A1 (fr) * 1974-07-22 1976-02-20 Standard Oil Co Procede d'oxydation d'olefines utilisant des catalyseurs contenant divers elements activateurs
EP0475351A1 (fr) * 1990-09-10 1992-03-18 Nitto Chemical Industry Co., Ltd. Composition catalytique à base de fer, d'antimoine et de molybdère et procédé pour sa préparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1543029A1 (de) * 1964-11-09 1969-09-11 Halcon International Inc Verfahren zur Herstellung von Oxiranverbindungen
FR2279706A1 (fr) * 1974-07-22 1976-02-20 Standard Oil Co Procede d'oxydation d'olefines utilisant des catalyseurs contenant divers elements activateurs
EP0475351A1 (fr) * 1990-09-10 1992-03-18 Nitto Chemical Industry Co., Ltd. Composition catalytique à base de fer, d'antimoine et de molybdère et procédé pour sa préparation

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