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WO1996037297A1 - Catalyseurs d'oxydation selective de substrats organiques et leur procede de production - Google Patents

Catalyseurs d'oxydation selective de substrats organiques et leur procede de production Download PDF

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WO1996037297A1
WO1996037297A1 PCT/EP1996/001961 EP9601961W WO9637297A1 WO 1996037297 A1 WO1996037297 A1 WO 1996037297A1 EP 9601961 W EP9601961 W EP 9601961W WO 9637297 A1 WO9637297 A1 WO 9637297A1
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range
oxide
elements selected
catalyst
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Rolf Schulz
Bernd Scharbert
Georges Gelbard
Jacques Vedrine
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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
    • B01J23/38—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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
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    • 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
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    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C07C2/82—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling
    • C07C2/84—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen oxidative coupling catalytic
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • 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
    • C07D301/08—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 gaseous 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
    • C—CHEMISTRY; METALLURGY
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    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Definitions

  • the present invention relates to novel metal oxide catalysts containing ruthenium and to a process for their production and their use.
  • the epoxidation of cyclic or straight-chain olefins the oxidation of saturated and unsaturated hydrocarbons to saturated or unsaturated aldehydes, acids or ketones, the ammoxidation of alkanes and alkenes to nitriles and oxidative dehydrogenations for the production of alkenes, dienes and alkenyl aromatics are of great technical importance .
  • metal oxide catalysts plays an important role in carrying out the above-mentioned reactions. Even the smallest change in the activity and / or selectivity of a catalyst, caused by a different composition or a special pretreatment, can determine the economic efficiency of a process.
  • EP-A-0 404 529 describes metal oxides based on iron, antimony and phosphorus, which are particularly suitable as catalysts for the ammoxidation of methanol.
  • the metal oxide compositions described here are less suitable.
  • the oxidative dehydrodimerization can be carried out on contact with the basic components NaBiO 3 / CeO 2 (US Pat. No. 4,484,017) or on a Bi 48 ZnO 73 phase (Catal. Lett. 15 (4) (1992) 393-400) become.
  • the catalysts known to date from the literature are unsatisfactory in terms of their universal applicability.
  • the catalysts are mostly either only for the oxidation of unsaturated or saturated hydrocarbons, for example for the oxidation of propene to acrolein or propylene oxide, or for the ammoxidation, for example of propene to acrylonitrile, or for the oxidative dehydrogenation, e.g. Butene to butadiene, can be used.
  • Poor reproducibility and poor physical properties for example with regard to industrial recycling and insufficient catalyst life, also pose problems.
  • the object of the present invention is therefore to provide new, universally usable catalyst systems.
  • the present invention solves this problem and relates to compounds of the general formula (1) for catalytic oxidation in the gas phase
  • Alkyl especially for a C ⁇ Cg and C 16 -C 2u alkyl, or C ⁇ Cg
  • M stands for one or more of the following elements V, Mo, Wo
  • R stands for one or more elements selected from the following group Sc, Y, La, Ce, Ti, Zr, Nb, Ta, V, Cr, Mn, Re, Fe,
  • Y stands for one or more elements selected from the following group Ga, In, Ge, Sn, S, Se, Te, P, As, Sb, Bi; a is a number ranging 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 number of oxygen atoms required for stoichiometric compensation of the oxide formation; i is a number in the range from 0 to 25, preferably in the range from
  • the compounds according to the invention with the basic constituents ruthenium, selenium and oxygen and, as further elements, molybdenum and / or vanadium and / or tungsten are suitable as selective oxidation catalysts, in particular for the following reactions: for the oxidation of saturated and unsaturated hydrocarbons
  • Ketones acids or aldehydes, for example for the oxidation of
  • Propene to acrolein for the epoxidation of both aliphatic and cyclic olefins, e.g. for gas phase oxidation of propene to propylene oxide; for the ammoxidation of saturated and unsaturated both aliphatic and cyclic hydrocarbons as well as aromatics and alcohols, and for the oxidative dehydrogenation and dehydrodimerization of alkenes or of alkyl aromatics, e.g. Ethylbenzene to styrene or propene too
  • oxygen or oxygen-containing gases are always used in a heterogeneously catalyzed gas phase reaction.
  • the catalysts according to the invention are particularly preferred for the selective oxidation of linear and branched C 2 -C 10 alkanes and alkenes or mixtures thereof, cyclic C 5 -C 10 hydrocarbons or C 8 -C 10 alkylene and alkenyl aromatics.
  • the catalysts of the present invention must have ruthenium and selenium in the ratios indicated above.
  • the present compounds are particularly preferably suitable as oxidation catalysts for the epoxidation of alkenes, ie for selective oxidation while avoiding allyl oxidation with good selectivities and high yields with a reduced proportion of total combustion in comparison to the known catalysts.
  • the catalyst syntheses 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 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 readily soluble selenium compounds.
  • g is preferably in the range of 0.02 to 5.
  • the selenium 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 content exceeds the specified upper limit, the catalyst activity is restricted and the physical properties deteriorate.
  • selenium is present in the metal oxide catalysts according to the invention in higher oxidation states and in oxidic form.
  • ruthenium trichlorohydrate is particularly suitable as the starting compound for introducing the ruthenium, but also other compounds of trivalent metal, such as Ru-III bromide, acetonylacetonate, nitrosyl chloride, nitrosyl nitrate, K 2 RuCI 5 , Ru (NH 3 ) 6 CI 3 and H 3 Ru (SO 3 ) 2 OH have proven their worth.
  • compounds of ruthenium in other oxidation states are also suitable, such as Ru (NH 3 ) 6 CI 2 , (NH 4 ) 2 RuCI 6 , Ru (C 10 H 8 N 2 ) 2 CI 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 ruthenium as essential elements.
  • the other optional elements are selected according to the desired field of application of the catalyst. In this way, the contact can be optimized for the desired oxidation reaction.
  • By varying the ratio to one another it is possible in this way to specifically influence the physical properties of the catalyst and the selectivity for the corresponding end product, to increase the yields, to control the undesired total oxidation and to suppress side reactions.
  • the selectivity in the formation of epoxides increases to 45%, particularly up to 30%, in particular up to 6 to 15%, with a propene conversion of 2 to 75%, particularly 2 to 40%, in particular 2 to 25 % (see Table 1, Example 1).
  • particularly good yields are achieved in the oxidation of organic compounds to aldehydes if tetraethyl monium bromide is used in the synthesis of the catalyst (cf. Example 4).
  • the metal oxide catalyst according to the invention can be used without a corresponding support material or can be applied to such.
  • the usual carrier materials such as silicon dioxide, porous or non-porous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, are suitable.
  • 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 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 coordinated with the application of the catalyst.
  • An acidic, aqueous solution is preferably prepared.
  • the salt is preferably dissolved in hydrochloric acid and added dropwise to the reaction solution.
  • 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 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 an oxygen
  • the time is from 0.5 to 24 hours, and such a 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 in an organic solvent or an aqueous solution with an organic or inorganic compound of one or more components of groups R, X and Y impregnated.
  • the catalyst according to the invention can be used for all oxidation reactions, in particular for the oxidation of propene to propylene oxide, for the selective oxidation of unsaturated hydrocarbons, e.g. Propene or isobutene to acrolein or methacrolein in the gas phase.
  • unsaturated hydrocarbons e.g. Propene or isobutene to acrolein or methacrolein in the gas phase.
  • the catalysts described are also suitable for the ammoxidation of saturated and unsaturated both aliphatic and cyclic hydrocarbons as well as aromatics and alcohols, and for the oxidative dehydrogenation or dehydrodimerization of alkenes or of alkyl aromatics, in particular for the dehydrodimerization of propene to 1, 5-hexadiene .
  • the catalyst used in the fixed bed in the epoxidation of propene for example, at a temperature in the range 250 to 480 is contacted * C with the oxygen-containing feed gas and propene at a pressure in the range of 1 to 10 bar.
  • the reaction rates are too slow for a reasonable conversion, at higher temperatures there is an increased degree of combustion reactions.
  • propene / nitrogen / oxygen or propene / air mixtures are reacted, preferably those in which the olefin concentration is below 2% or above 17%.
  • the propene conversions are in the range from 2 to 75%, particularly in the range from 2 to 40%, in particular in the range from 2 to 25%, the selectivity to propylene oxide is in the range from 2 to 45%, particularly in the range from 5 to 30% , especially in the range of 6 to 15%.
  • the catalyst used in the fixed bed is at a temperature in the range from 300 to 500 ° C. with the starting gas containing oxygen and propene at a pressure contacted in the range of 1 to 10 bar.
  • the reaction rates are too low for a reasonable conversion at lower temperatures, while an increased degree of combustion reactions occurs at higher temperatures.
  • the olefin concentration is in the same range as for epoxidation.
  • the propene conversions are in the range of 2 to 30%, the selectivities for 1,5-hexadiene in the range of 15 to 60%.
  • a catalyst with the empirical formula a 2.5 ⁇ i2, ⁇ S e o, ⁇ 6 w i5, ⁇ Ru ⁇ , o c, 6.5 * * - * * 4i, 6 x 1 ⁇ ' 7 H 2 ⁇ was as follows manufactured:
  • a solution of 0.39 g RuCI 3 3H 2 O in 12 ml 1 N hydrochloric acid is added dropwise to a solution of 3.95 g Na 2 WO 4 2H 2 O and 0.19 g H 2 SeO 3 in 20 ml H 2 O.
  • the solution is stirred for 2 hours at room temperature and then mixed with 0.32 g of tetraethylammonium bromide and the catalyst crystallizes out, washed and dried.
  • Tetraethylammoniumbromid added and the catalyst crystallized, washed and dried.
  • the catalyst from Example 1 is 2 hours at 200 ° C and then 2
  • the catalyst from Example 2 is calcined for 2 hours at 200 ° C and then for 2 hours at 450 C ⁇ .
  • the mass obtained in this way is impregnated with an aqueous solution of H 2 SeO 3 and then dried at 120 ° C.
  • the catalyst of Example 9 is calcined for 2 hours at 300 "C and then for 2 hours at 600 * C.
  • the material thus obtained is impregnated with an aqueous solution of H 2 SeO 3, and then dried at 120 ° C.
  • Table 1 provides an overview of some activity tests that have been carried out. Unless otherwise stated, an 18% propene / air mixture was always used.

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Abstract

L'invention concerne des composés d'oxydation catalytique en phase gazeuse qui répondent à la formule générale (1) QaMbRucRdXeYfSegOh * 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, où R?1, R2, R3 et R4¿ désignent 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; 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/EP1996/001961 1995-05-24 1996-05-09 Catalyseurs d'oxydation selective de substrats organiques et leur procede de production WO1996037297A1 (fr)

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DE19519004.1 1995-05-24
DE19519004A DE19519004A1 (de) 1995-05-24 1995-05-24 Neue selen- und rutheniumhaltige Metalloxidkatalysatoren sowie ein Verfahren zu ihrer Herstellung und ihre Verwendung

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001087867A1 (fr) * 2000-05-18 2001-11-22 Bayer Aktiengesellschaft Procede pour epoxyder des hydrocarbures
US6350716B1 (en) 1998-04-02 2002-02-26 Bp Chemicals Limited Catalyst and process for the oxidation of ethane and/or ethylene
EP1283206A3 (fr) * 2001-08-10 2004-01-02 Bayer Ag Procédé pour l'époxydation d'hydrocarbures
CN114950462A (zh) * 2022-06-23 2022-08-30 万华化学集团股份有限公司 一种甲醇氨氧化制备hcn的催化剂及其制备方法
CN118527137A (zh) * 2024-07-23 2024-08-23 山东海科创新研究院有限公司 一种用于合成环氧丙烷用钼铋负载型催化剂及制备方法和应用

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DE1543029A1 (de) * 1964-11-09 1969-09-11 Halcon International Inc Verfahren zur Herstellung von Oxiranverbindungen
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 (2)

* 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
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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6350716B1 (en) 1998-04-02 2002-02-26 Bp Chemicals Limited Catalyst and process for the oxidation of ethane and/or ethylene
WO2001087867A1 (fr) * 2000-05-18 2001-11-22 Bayer Aktiengesellschaft Procede pour epoxyder des hydrocarbures
EP1283206A3 (fr) * 2001-08-10 2004-01-02 Bayer Ag Procédé pour l'époxydation d'hydrocarbures
SG113429A1 (en) * 2001-08-10 2005-08-29 Bayer Ag A process for the epoxidation of hydrocarbons
CN114950462A (zh) * 2022-06-23 2022-08-30 万华化学集团股份有限公司 一种甲醇氨氧化制备hcn的催化剂及其制备方法
CN114950462B (zh) * 2022-06-23 2024-04-09 万华化学集团股份有限公司 一种甲醇氨氧化制备hcn的催化剂及其制备方法
CN118527137A (zh) * 2024-07-23 2024-08-23 山东海科创新研究院有限公司 一种用于合成环氧丙烷用钼铋负载型催化剂及制备方法和应用
CN118527137B (zh) * 2024-07-23 2024-09-20 山东海科创新研究院有限公司 一种用于合成环氧氯丙烷用钼铋负载型催化剂及制备方法和应用

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