WO1996037295A1

WO1996037295A1 - New ruthenium- and selenium- or sulphur-containing metal oxide catalysts, process for producing the same and their use

Info

Publication number: WO1996037295A1
Application number: PCT/EP1996/001960
Authority: WO
Inventors: Bernd Scharbert; Rolf Schulz
Original assignee: Hoechst Aktiengesellschaft
Priority date: 1995-05-24
Filing date: 1996-05-09
Publication date: 1996-11-28
Also published as: DE19519008A1

Abstract

Compounds for catalytic oxidation in the liquid phase have the general formula (1): QaMbRucRdXeYfZgOh * H2Oi, in which the symbols Q, M, R, X, Y, a, b, c, d, e, f, g, h and i have the following meanings: Q stands for one or several elements selected in the group Na, K, Rb, Cs, NR?1R2R3R4+¿, Be, Mg, Ca, Sr, Ba, in which R?1, R2, R3 and R4¿ represent independently from each other hydrogen, a C¿1?-C20 alkyl or C1-C8 cycloalkyl residue, an aryl residue, in particular a methyl, ethyl, propyl or butyl residue; M stands for one or several elements among V, Mo, Wo; R stands for one or several elements selected in the group Sc, Y, La, Ce, Ti, Zr, Nb, Ta, V, Cr, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu; X stands for one or several elements among F, Cl, Br, J, NO3?-, SO¿42-; Y stands for one or several elements selected in the group Ga, In, Ge, Sn, S, Se, Te, P, As, Sb, Bi; Z stands for S or Se; a equals 1 to 30; b equals 5 to 50; c equals 0.1 to 10; d equals 0 to 10; e equals 0 to 20; f equals 0 to 10; g equals 0.01 to 10; h equals the number of oxygen atoms required to stochiometrically compensate for oxide formation; i equals 0 to 25.

Description

New metal oxide catalysts containing ruthenium and be or sulfur, as well as a process for their preparation and their use

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 (oxiranes) are compounds of considerable industrial importance. They are used in the production of a large number of economically important products.

For example, 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.

The reaction of epoxides with alcohols leads to glycol ethers, e.g. B. find use as a polar solvent.

Many different processes have been developed for the production of epoxides, which are intended to allow selective epoxidation of alkenes. It was found that metal oxide compositions as catalysts in a gas phase oxidation have an insufficient selectivity for the epoxides.

For example, 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. With regard to the selective oxidation, in particular the epoxidation of olefins, and the oxidative dehydrogenations, the metal oxide masses described here are less suitable.

REPLACEMENT BLAΠ (RULE 26) the metal oxide compositions described here are less suitable.

Systems containing bismuth are known catalysts for oxidation in the allyl position. Bismuth-molybdenum oxides are the basis of numerous known catalyst systems, in particular for the oxidation of propene to acrolein and for the ammoxidation (US Pat. No. 4,414,134). EP-B-468 290 describes

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.

The epoxidation of alkenes is carried out in numerous cases on silver or silver oxide contact (EP-A-036 392). The disadvantage of the process described here is the limitation to alkenes without allylic hydrogen atoms, since otherwise the combustion predominates.

Oxidation processes that were developed in the liquid phase use the technically most interesting and cheapest oxidizing agent, molecular oxygen, only in exceptional cases.

For example, 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. However, there is no economic application of the method disclosed here, since 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.

The epoxidation of propylene with atmospheric oxygen in the presence of catalysts containing tungsten or molybdenum is described in DE-C-22 35 229. The epoxidation reaction is carried out in a solvent that coexists with Oxygen can be oxidized to form hydroperoxides. In subsequent reactions, however, the hydroperoxides formed lead to oxygen-containing by-products, generally alcohols, which are obtained as reaction coupling products.

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)). Compounds such as MoO ₂ (8-hydroxyquinoline) ₂ , MoO ₂ (phenylene-bis-salicylimine) (= MoO ₂ (salphen)), MoO ₂ (salicylaldoxime) ₂ and MoO ₂ (5-nitroso- 8-hydroxyquinoline) ₂ called. 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.

The processes for the epoxidation of alkenes described in the prior art have the disadvantage that, in addition to the desired end product of the epoxide, a number of undesirable by-products are also obtained, i.e. the reaction cannot be controlled selectively. Furthermore, in addition to the catalyst used, it is often necessary to use a further oxidation agent (generally a hydroperoxide), the end product of which must be disposed of after the reaction has been carried out.

The oxidation of olefins with air or oxygen as the oxidizing agent would be of great technical advantage since the oxidizing agent is available inexpensively and the reaction could proceed without the formation of reduced by-products.

A process for the production of epoxides in the catalyzed Liquid phase oxidation of olefins with molecular oxygen or air is described in DD-B-159 075. 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. The most active compounds here are those that contain HMPT as donor ligands, with HMPT being known as a carcinogen.

In the case of the epoxidation of oct-1 -es, 34% epoxide selectivity is found in the presence of molybdenum acetylacetonate and 28% in the presence of MoO ₃ [J. practical chem. 334 (1992) 165-75, Table 1, 7th column].

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 _a M _b Ru _c R _d X _e Y _f Z _fl O _h * H ₂ 0, where the symbols Q, M, R, X, Y, a, b, c, d, e, f, g, h and i have the following meaning:

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

Group Sc, Y, La, Ce, Ti, Zr, Nb, Ta, V, Cr, Mn, Re, Fe, Ru, Os, Co, Rh,

Ir, Ni, Pd, Pt, Cu; X stands for one or more of the following elements F, Cl, Br, J, NO ₃ ^" ,

SO ₄ ^{2 "} Y stands for one or more elements selected from the following

Group Ga, In, S, Ge, Sn, Se, Te, P, As, Sb, Bi; Z stands for S or Se 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

18th

a process for the preparation of these compounds and their use. 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.

To obtain catalysts that provide good selectivities for epoxide formation, the catalysts of the present invention must have ruthenium and selenium and / or sulfur in the ranges given above.

It has proven to be advantageous in the synthesis of the metal oxide catalysts to start from the starting compounds which are soluble or not readily soluble in aqueous solution, with particular preference given to the halides, nitrates, sulfates, hydroxides and acids, and some oxy compounds, such as sodium molybdate or sodium tungstate.

By replacing the metalations with alkylammonium cations, the catalyst theses can also be carried out in organic solvents. Dichloromethane, ethers, alcohols and other polar solvents are particularly suitable for this.

In the formula given above, 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.

In a preferred embodiment, 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. In the above formula, g is preferably in the range of 0.02 to 5.

If 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. In addition, 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 .

If the proportion of ruthenium increases above the limits specified above, the proportion of total combustion increases. 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.

In the epoxidation of higher alkenes (> C ₈ ), Mo is generally preferred when Z = S, while W and V are preferred when Z = Se. Furthermore, particularly good selectivities are achieved, for example, in the epoxidation of oct-1-ene in the liquid phase if the potassium content (Q = K) is increased in the preparation of the catalyst. This is particularly advantageous if M = Mo. On the other hand, increased selectivities are achieved when using R ₄ NBr in the case of M = W or V.

In the epoxidation of lower alkenes (<C ₃ ), the use of R ₄ NBr has proven itself, especially when M = Mo. By varying the ratio of the individual components to one another, it is possible in this way to specifically influence the physical properties of the catalyst and the selectivity in accordance with the starting compounds used.

In this way it is possible to increase yields and undesirable ones

Side reactions, e.g. Suppress total oxidation.

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. After shaping, the catalyst can be used as a regularly or irregularly shaped support body or in powder form as a heterogeneous oxidation catalyst.

The metal oxide catalysts according to the invention are prepared by preparing a slurry, preferably an aqueous solution, which contains the individual starting components.

In the event that M is molybdenum or tungsten, it is advisable to use the corresponding molybdates or tungstates as starting compounds due to the commercial availability; Examples are Na ₂ WO ₄ and Na ₂ MoO ₄ .

In a preferred embodiment, 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. When using ruthenium chloride, 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. For example, saturated and unsaturated, aliphatic, cyclic and aromatic solvents, which preferably contain oxygen, and halogenated hydrocarbons can be used. In a preferred embodiment, 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.

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.

In the event that 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.

In a further preferred embodiment, 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. In general, 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.

For example, 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.

The liquid phase oxidation takes place either in pure olefin or diluted in an oxidation-stable solvent. Examples of suitable solvents include the following groups: 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.

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.

Furthermore, the 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.

In the case of a continuous procedure, 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. In the batch process, 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.

With the aid of the catalysts according to the invention, epoxy yields of> 35%, in particular in the range of 35-50%, are achieved. Compared to the prior art, 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.

Examples

example 1

A catalyst with the empirical formula

Na _{4 l} ((C ₂ H ₅ ) ₄ N) _{2 (8} Se _{2 (4} W _{l 8/2} Ru _{1 # 0} CI _{1 8} Br ₀ -, 0 ₇ ^ 5 x 7.7 H ₂ O was prepared as follows :

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

The solution is stirred for 2 hours at room temperature, 0.32 g of tetraethylammonium bromide is then added and the catalyst is crystallized out, filtered off, washed and dried. Example 2

A catalyst with the empirical formula

Na _{6 0} ((C ₂ H ₅ ) ₄ N) _{2 0} Se _{0 (2} Mo _{16 2} Ru _{2 # 0} CI _{3 5} Br _{0 2} O _{53 1} x 10.5 H ₂ O was prepared as follows:

A solution of 0.39 g RuCl ₃ 3 H ₂ O in 12 ml 1 N hydrochloric acid becomes a solution of 2.90 g Na ₂ MoO ₄ 2H ₂ O and 0.22 g H ₂ SeO ₄ in 10 ml H ₂ O. dripped. It is stirred for 2 hours at room temperature, the reaction solution with 0.32 g

Tetraethylammoniumbromid added and the catalyst crystallized out, filtered off, washed and dried.

Example 3

A catalyst with the empirical formula

^N ai.8 7.6 ^S 1.2 ^M Ol8 ₍ 5 ^Ru 1.0 ^CI 4.4θ ₄ 8.3 ^{x 1} 3.8 H ₂ O was prepared as follows:

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 2.9 g Na ₂ MoO ₄ 2H ₂ O and 1.5 mmol H ₂ SO ₄ in 10 ml H ₂ O. . After stirring for two hours at room temperature, an excess of solid potassium chloride is added to the reaction solution for precipitation, and the catalyst is crystallized out, filtered off, washed and dried.

Example 4

A catalyst with the empirical formula

₅ Na ₈ ((C ₂ H ₅₎ ₄ N) _2, ₆ S ₀ 03 18.3 ^Mθ ^Ru 0, 2 ^Cl 2, 4 ° 64.1 ^{x 8} '° 2 ° ^H ^was prepared as follows:

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 2.9 g Na ₂ MoO ₄ 2H ₂ O and 1.5 mmol H ₂ SO ₄ in 10 ml H ₂ O. . After stirring for two hours at room temperature, 0.32 g of tetraethylammonium bromide is added to the reaction solution, and the catalyst is crystallized out, filtered off, washed and dried. Example 5

A reaction solution analogous to Example 4 is concentrated before adding a

Solution of 0.32 g tetraethylammonium bromide 5g neutral aluminum oxide added. The reaction mixture is filtered and washed and then dried.

General working instructions for the epoxidation of oct-1s

Examples 6-12

In a ^β at 100 C tempered 10 ml reactor (septum,

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.

Example No. Catalyst time to take up epoxide selectivity from e.g. 10 ml O ₂

6 (cf.) Na ₂ WO ₄ 300 min 24%

7 (See) Na ₂ MoO ₄ 230 min 32%

8 1 1 10 min 41%

9 2 125 min 41%

10 3 200 min 46%

1 1 4 170 min 45%

12 5 145 min 46% Oxidation of propene

Examples 13, 14

In a 200 ml autoclave, 200 mg of catalyst are slurried in 20 ml of chlorobenzene and 25 g of propene are condensed in at -20 ° C. The

The 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.

Example 13:

Catalyst from Example 3: Selectivity for 1,2-epoxypropane is 27%

35% sales.

Example 14:

Catalyst from Example 2: selectivity for 1, 2-epoxypropane is 30%

35% sales.

Claims

1. Compounds of the general formula (1) for catalytic oxidation in the liquid phase

Q _a M _b Ru _c R _d X _e Y _f Z _g O _h * H ₂ Oi (D

where the symbols Q, M, R, X, Y, a, b, c, d, e, f, g, h and i follow

Have meaning:

Q stands for one or more elements selected from the group Na, K, Rb, Cs, NR ¹ R ² R ³ R ^{4 +} , Be, Mg, Ca, Sr, Ba, where R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, a C ₁ -C ₈ -alkyl or C ₁ -C ₈ -cycloalkyl radical, an 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 group Sc, Y, La, Ce, Ti, Zr, Nb, Ta, V, Cr, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu;

X represents one or more of the following elements F, Cl, Br, J, NO ₃ \ SO ₄ ^{2 '} ;

Y stands for one or more elements selected from the following group Ga, In, Ge, Sn, S, Se, Te, P, As, Sb, Bi;

Z stands for S or Se; 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 ranging from 0 to 25;

Compounds according to Claim 1, characterized in that they are suitable as selective oxidation catalysts in the presence of oxygen or oxygen-containing gases for the epoxidation of aliphatic, optionally branched and alicyclic C ₂ -C ₃₀ olefins and cyclic olefins having 5 to 12 carbon atoms.

Compounds according to at least one of claims 1 and 2, characterized in that they are applied to a corresponding carrier material and are used as regularly or irregularly shaped carrier bodies or in powder form as heterogeneous oxidation catalysts.

Compounds according to claim 3, characterized in that the carrier material is 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 nitride or silicon carbide is used.

Process for the selective epoxidation of aliphatic, optionally branched, and alicyclic C ₂ -C ₃₀ olefins and cyclic olefins having 5 to 12 carbon atoms with atmospheric oxygen or an oxygen-containing gas in the liquid phase in the presence of a catalyst of the general formula (1)

Q _a M _b Ru _c R _d X _e Y _f Z _g O _h * H ₂ O _j (1)

where the symbols Q, M, R, X, Y, a, b, c, d, e, f, g, h and i have the following meaning: Q stands for one or more elements selected from the group Na, K, Rb, Cs, NR ¹ R ² R ³ R ^{4 +} , Be, Mg, Ca, Sr, Ba, where R ¹ , R ² , R ³ and R ⁴ independently of one another represent hydrogen, a C, -C ₂₀ -alkyl or C.-C ₈ -cycloalkyl radical, an aryl radical, in particular a methyl, ethyl, propyl or butyl radical;

M stands for one or more of the following elements V, Mo, Wo;

X represents one or more of the following elements F, Cl, Br, J, NO ₃ ^" , SO ₄ ^2" ;

Z stands for S or Se; a is a number m ranging from 1 to 30; b is a number m ranging from 5 to 100; c is a number m ranging from 0.1 to 10; d is a number m ranging from 0 to 10; e is a number m ranging from 0 to 20; f is a number m ranging from 0 to 10; g is a number m range from 0.01 to 10; h stands for the number of oxygen atoms required for stoichiometric compensation of the oxide formation; i is a number ranging from 0 to 10;

A method according to claim 5, characterized in that the oxygen used as the oxidizing agent is used in pure form or is diluted with an inert gas.

A method according to claim 5, characterized in that the reaction temperature in the oxidation of C ₆ -C _{1 2} -alkenes in the range of 30 to 300 "C and in the oxidation of C ₂ -C ₅ -alkenes in the range is from 120 to 230 ° C and the pressure is selected so that the reaction takes place in the liquid phase.

8. The method according to claim 5, characterized in that the oxidation takes place without solvent, in the pure olefin.

9. The method according to claim 5, characterized in that the oxidation in a solvent selected from the group of halogenated aromatics, the halogenated or non-halogenated hydrocarbons, the C ..- C ₁₂ alcohols or in water is carried out.

10. The method according to claim 5, characterized in that an activator and / or a radical initiator is added to the reaction mixture.

1 1. The method according to claim 10, characterized in that the activator is added in stoichiometric amounts, based on the catalyst.

12. The method according to claim 5, characterized in that the epoxy yields are> 35%.