WO1996037297A1 - Catalysts for the selective oxidation of organic substrates and process for producing the same - Google Patents

Abstract

Compounds for catalytic oxidation in the gaseous phase have the general formula (1) QaMbRucRdXeYfSegOh * 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; 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

Catalysts for the selective oxidation of organic substrates and processes for their production

The present invention relates to novel metal oxide catalysts containing ruthenium and to a process for their production and their use.

The selective oxidation of organic substrates, both saturated and unsaturated, aliphatic and cyclic hydrocarbons and aromatics, is one of the most important processes in the chemical industry.

For example, 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 .

The use of 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.

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

SUBSTITUTE (RULE 26) 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 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.

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

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

Q _a M _b Ru _c R _d X _e Y _f Se _g O _h * H ₂ 0- (1)

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 CC ₂ -

Alkyl, especially for a C ^ Cg and C ₁₆ -C _2u alkyl, or C ^ Cg

-Cycloalkylrest or for an arylrest, in particular for one

Are methyl, ethyl, propyl or butyl; 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 or groups

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; 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

4 to 18; a process for the preparation of these compounds and their use.

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

1,5-hexadiene.

In the reactions mentioned above, 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.

In order to obtain catalysts which can be used universally, the catalysts of the present invention must have ruthenium and selenium in the ratios indicated above. In the reactions mentioned above, the presence of these elements in the metal oxidation masses leads to universal applicability in comparison with conventional catalysts. 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.

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 metal cations with alkylammonium cations, the catalyst syntheses 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 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 readily soluble selenium compounds. Selenic acid H ₂ SeO ₃ , selenic acid H ₂ SeO ₄ or their alkali and alkaline earth metal and ammonium salts, but also the selenium halides, in particular chlorides and bromides, may be mentioned here, for example. In the above formula, g is preferably in the range of 0.02 to 5.

If 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.

Like ruthenium, selenium is present in the metal oxide catalysts according to the invention in higher oxidation states and in oxidic form.

Due to its simple commercial availability, 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. In addition, 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 .

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 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.

For example, particularly good selectivities are achieved in the epoxidation of propene in the gas phase if the KCI content (Q = K) is increased during the catalyst preparation. In this way, 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). Conversely, 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. 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. 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 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 coordinated with the application of the catalyst. 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 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 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.

In a further preferred embodiment, 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.

In this way it is possible to reduce the extent of undesirable side reactions and to increase the selectivity for the desired product.

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. 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 .

Thus, 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. At lower temperatures the reaction rates are too slow for a reasonable conversion, at higher temperatures there is an increased degree of combustion reactions. In general, 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%.

Using the example of the oxidative dehydrodimerization of propene, 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. Here, too, 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%.

Examples

Example 1 :

A catalyst with the empirical formula ^a 2.5 ^κ i2, ιS ^e o, θ6 ^w i5, ι ^Ru ι, o ^c, 6.5 ^* * - * ^* 4i, 6 ^{x 1} ^ ' ^{7 H} 2 ^ was as follows manufactured:

To a solution of 7.92 g Na ₂ WO ₄ 2H ₂ O and 0.43 g H ₂ SeO ₄ (dissolved at 35 ° C.) in 40 ml H ₂ O is a solution of 0.78 g RuCI ₃ xH ₂ 0 in 24 ml of 1N hydrochloric acid, the solution is stirred at room temperature for 3.5 hours and then an excess of solid potassium chloride is added to precipitate the soluble catalyst, and the product is crystallized, filtered off, washed and dried.

Example 2

A catalyst with the empirical formula

Na _{1 7} K _{7 5} Se-, -, W _{10 3} Ru _{1 0} CI _{4 7} O _{36 6} x 10.7 H ₂ O was prepared as follows:

A solution of 0.41 g RuCl ₃ xH ₂ O in 15 ml 1 N hydrochloric acid is added dropwise to a solution of 6.25 Na ₂ WO ₄ 2H ₂ O and 0.26 g H ₂ SeO3 in 25 ml H ₂ O. After stirring for several hours at room temperature, the reaction solution is mixed with an excess of solid potassium chloride for precipitation, crystallized, filtered off, washed and dried. Example 3

A catalyst with the empirical formula

Na _{9 | 2} ((C ₂ H ₅ ) ₄ N) _{1 8} Se _0/1 W _{16 # 5} Ru _{1 # 0} CI _{5 6} Br _{0 6} O _51/5 x 17, 1 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 0.22 g H ₂ SeO ₄ in 20 ml H ₂ O. It is stirred for 2 hours at room temperature and then the

Reaction solution with 0.32 g tetraethylammonium bromide and the

Crystallized catalyst, washed and dried.

Example 4

A catalyst with the empirical formula

Na ₄ , - | ((C ₂ H _{5) 4} N) _4, 2Se ₂ W _{4 18, 2} ^R <Jι _f0 ^c h o 8 ^Br, ι ° 7i, 5 ^{x 7 '7 H} 2 ° ^Wurd e ^¬ following reasonably prepared:

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.

Example 5

A catalyst with the empirical formula

Na _6f0 ((C ₂ H ₅ ) ₄ N) _2/7 Se _{0 | 2} Mo _{16 (2} Ru _{2 (0} CI _3/5 Br _{0 2} O _{53f 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, washed and dried. Example 6

A catalyst with the empirical formula

Na _{βr 1} ((C ₂ H ₅ ) ₄ N) _{2f l} Sβ _{1 f7} Mo _{17 # 2} Ru _0f2 Cl _{l f5} Br _{0f 1} O _48/9 x 22.8 H ₂ O was prepared as follows:

A solution of 0.39 g RuCl ₃ 3H ₂ O is added dropwise to a solution of 2.90 g Na ₂ MoO ₄ 2H ₂ O and 0.19 g H ₂ SeO ₃ in 10 ml H ₂ O. After two hours

Stirring at room temperature, the reaction solution with 0.32 g

Tetraethylammoniumbromid added and the catalyst crystallized, washed and dried.

Example 7

1 g of the water-soluble catalyst from Example 1 to be heterogenized is dissolved in 20 ml of H ₂ O and 5 g of silica gel are added in portions with vigorous stirring. The slurry is completely dried and used in powder form after crushing.

Example 8

5 g of neutral aluminum oxide are added to a reaction solution analogous to Example 1 before the addition of a concentrated potassium chloride solution, filtered off and dried after washing.

Example 9

The catalyst from Example 1 is 2 hours at 200 ° C and then 2

Calcined for hours at 400 ° C. Example 10

The catalyst from Example 2 is calcined for 2 hours at 200 ° C and then for 2 hours at 450 C ^β. The mass obtained in this way is impregnated with an aqueous solution of H ₂ SeO ₃ and then dried at 120 ° C.

Example 11

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.

Table 1

Activity tests of the catalysts produced

No. Kataly¬ Tempe¬ propene product total sensor from temperature ^* C conversion lectivity Ex.

1 1 300> 25% propylene 10% lenoxide

2 2,460 5.5% propylene 7% lenoxide

3 3 390 22% acrolein 31%

4 4 420 25.2% acrolein 37%

5 5 450 18.4% acrolein 41% 6 6 330 18.5% acrolein 35%

7 6 360 22.6% acrolein 30%

8 * 5 360 2% acrolein 70%

18% propene / 28.5% air / 53.5% N2 mixture It can be seen from the table that, in comparison with the prior art, a high selectivity to propylene oxide is achieved with high propene conversion; the CO ₂ selectivity here is <9%. Depending on the catalyst composition, different main products can be realized with medium conversions.

Claims

claims 1. Compounds of the general formula (1) for catalytic oxidation in the gas phase Q _a M _b Ru _c R _d X _e Y _f Se _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 ₁ -C o -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; 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, 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 is the number of oxygen atoms required for the stoichiometric compensation of the oxide formation; is a number ranging from 0 to 25; 2. Compounds according to claim 1, characterized in that they are selective oxidation catalysts in the presence of oxygen or oxygen-containing gases for the oxidation of saturated and unsaturated hydrocarbons to ketones, acids or aldehydes, for the epoxidation of aliphatic and cyclic olefins 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 alkanes, alkenes or of alkyl aromatics. 3. Compounds according to claim 1, characterized in that they are applied to a corresponding support material and are used as regularly or irregularly shaped support bodies or in powder form as heterogeneous oxidation catalysts. 4. 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. 5. Process for the preparation of compounds of the general formula (1) Q _a M _b Ru _c R _d X _e Y _f Se _g O _h * H ₂ Oi (1) 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 RR ³ R ^{4 +} , Be, Mg, Ca, Sr, Ba, where R ¹ , R ² , R ³ and R ^{4 are} independent from each other for hydrogen, a C _j ^ r _j - alkyl or C ₁ -C ₈ cycloalkyl radical, an aryl radical, in particular for represent 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, Ge, SnJS, Se, Te, P, As, Sb, Bi; a is a number in the range from 1 to 30 ; b is a number in the range of 5 to 50; c is a number in the range of 0.1 to 10; d is a number in the range of 0 to 10; e is a number in the range of 0 to 20; f is a Number in the range from 0 to 10; g is a number in the range from 0.01 to 10; h is the number of oxygen atoms required for the stoichiometric compensation of the oxide formation; i is a number in the range from 0 to 25; by preparing a slurry containing the individual starting components and reacting the resulting mixtures at a temperature in the range from 15 to 50 ° C. and then reacting the solution thus obtained with 0.2 to 30 equivalents of an alkali metal or alkyammonium halide, based on the ruthenium component and crystallization of the resulting catalyst. 6. The method according to claim 5, characterized in that the resulting catalyst is dried and pulverized and then calcined. 7. The method according to claim 6, characterized in that is calcined in a temperature range of 200 to 1000 ° C, in the presence of nitrogen, oxygen or an oxygen-containing gas 0.5 to 24 hours. 8. The method according to claim 5, characterized in that the resulting catalyst is impregnated in an organic solvent or an aqueous solution with an organic or inorganic compound of one or more components of the groups R, X and Y.