DE4308120A1 - Oxidn. hydrogenation or hardening catalyst obtd. from metal oxide mixt. - contains catalytic crystallites of varying size, esp. for hydrogenating oil, fat or fatty acid - Google Patents

Abstract

Catalyst (I) for oxidn., hydrogenation or hardening of cpds., esp. hydrogenation of oils, fats, fatty acids and/or their derivs., contains at least 2 metal oxides, one of which may be CuO, and has at least 30 (wt.)% catalytic crystallites (II) with size varying between 20 and 300 A. (I) pref. has 50-90, pref. at least 70% (II), which have sizes from 100 to 200 A. (II) are mainly on the surface of (I) and embedded in a solid matrix. (II) consist of CuO and (mix) oxide(s) of Ti, Ni, Co, V, Mo, Fe, Sn, Ag, Cr, Si, Al, Y, Ba, La, Sr, Bi and/or Zn and/or metallic Pt, Pd and/or Re; esp. CuO or an oxide of Ni, Co and/or V and also TiO2, Cr2O3, SiO2, Al2O3 and/or ZnO. 40-100, pref. 80-90% of (II) consist of a chemical reaction prod. of the oxides, esp. of CuAl2O4 and/or Cu2Al2O5 or of CuTiO3. (I) is prepd. by treating a solid with the oxide starting amterials (pref. with a particle size of 30-300, esp. 60-120 microns), mixing and crushing mechanically for 1 s to 60 min., pref. 5-15 min. to particles finer than 10 microns, pref. finer than 4 microns, esp. 0.1-4 microns and partic. to a narrow particle size distribution d50 of 0.1-1 micron. The starting materials are heated, pref. to 30-400 deg.C during crushing, pref. in a reactor with an energy density of 0.5-500, esp. 10-200 kW/l reactor vol. Mixing and/or crushing are carried out in a liq. pref. water. The oxidic catalyst is reduced with H2. ADVANTAGE - The formation of coloured by-prods. during oxidn., hydrogenation and hardening is avoided and high yields are obtd., esp. in hydrogenation. In an example, stoichiometric amts. of CuO and TiO2 were ground for 7 min. to particles finer than 10 microns (spectrum 8-1 microns), using an energy density of 30 kW/l reactor vol. The resultant catalyst consisted mainly of CuTiO3 and also contained Cu2TiO3, Cu4TiO4 and small amts. of mix oxides, esp. CuOTiO2 and Cu2OTiO2. This catalyst (IA) had fine crystallites (70%) with a particle size range of 100-200 A on its surface, embedded in a solid matrix of the reactants. (IA) was used in the hydrogenation of methyl laurate (III) to lauryl alcohol (IV) (and MeOH) at 300 deg.C and 280 bar H2, using 3% (IA) w.r.t. (III). After 60 min., a 90% yield of colourless (IV) was obtd. Apart from MeOH and unreacted (III), only one unidentified by-prod. was formed. If a conventional Cu chromite catalyst was used under the same conditions, the (IV) yield was 85% and 2% by-prod. were formed, whilst the (IV) obtd. was intensely coloured by the formation of coloured Cu salts and required purificn. before use

Description

The present invention relates to a catalyst for the Oxidation, hydrogenation or hardening of compounds after the The preamble of claim 1 and a method for Production of such a catalyst.

Catalysts for the oxidation, hydrogenation or hardening of Compounds, especially for the hydrogenation of oils, fet ten, fatty acids and / or derivatives are different known chemical composition. For example, describes as the DE-OS 37 06 658 an acid-resistant copper chromite Spinel catalyst based on copper-II chromite is constructed. The catalytic converter known from DE-OS 39 42 064 tor, which is also used for the hydrogenation of carboxylic acids to alcohol len is used in addition to copper chromite and copper oxide as well as colloidal silica.  

In DE-OS 39 06 586 a corresponding catalyst is be wrote of an alloy of metals, preferably from the metals copper and silicon or nickel and silicon, consists.

The known catalysts mentioned above contain a lot fold the disadvantage that when used for the hydrogenation of Oils, fats or fatty acids colored by-products arise that an additional workup of the hydrogenated Connections required.

The present invention has for its object a To provide catalyst of the given type, the one Oxidation, hydrogenation or hardening of compounds without Allows colored by-products to emerge.

This task is accomplished by a catalyst with the characteristics of claim 1 solved.

The catalyst according to the invention for the oxidation, hydrogenation or hardening of compounds, especially for hydrogenation of oils, fats, fatty acids and / or their derivatives in addition to copper oxide or another metal oxide at least another metal oxide, the catalyst being at least 30 % By weight has catalytically active crystallites, the cri stallite sizes vary between 20 angstroms and 300 angstroms. In other words, the catalytic converter according to the invention thus comprises tor at least two metal oxides in the form of at least 30  % By weight of crystallites are present whose crystallite sizes are between 20 angstroms and 300 angstroms vary.

It was surprisingly found that with the inventive catalyst, the at least two metal includes oxides in the form of crystallites, oxidation, hydrie Curing or curing reactions of compounds, in particular of organic compounds of the aforementioned type can be performed without colored reaction products are created. This in turn leads to use of the catalyst according to the invention for the aforementioned Re actions no longer open the resulting connections agile must be worked up, which is a special ders economical use of the Kataly invention sators leads. As a further, particularly advantageous property this catalyst according to the invention has been found that in the hydrogenation of oils, fats, fatty acids and / or their derivatives when using the catalyst according to the invention tors only a single by-product, which is the case with the conventional known catalysts is not the case. This in turn leads to the catalyst according to the invention having a enables particularly economical hydrogenation and also to leads particularly pure hydrogenation products, since this resulting by-product usually not separated must become.

A particularly suitable embodiment of the invention The catalyst provides that the catalyst is between 50% by weight and 90% by weight, preferably at least 70% by weight, of the be  wrote crystallites with the crystallite size mentioned there eats. Such a catalyst then allows hydration tion reactions, which are characterized by a particularly high yield award.

A further improvement in the yield of the hydrogenation reaction NEN is achieved when the catalyst of the invention Has crystallites in the aforementioned% by weight, the Crystallite sizes between 100 angstroms and 200 angstroms vary.

Preferably, in the catalyst according to the invention previously described crystallites arranged on the surface, d. H. the actual catalyst thus consists of a fe most matrix, the copper oxide, the other metal oxide and / or which contains further metal oxides, being in this solid matrix the oxidic crystallites are integrated.

In the context of the present application, the term Catalyst understood such catalysts that are pure, effective catalysts are present, d. H. thus the Weight data given above for the crystallites on the pure catalyst substance. If, however, the Catalyst on a carrier substance, for example ceramic or cement balls, or an adsorbent material, in particular other silica gel, diatomaceous earth or the like, are applied, so are the weight percentages given above depend on the crystallites of the mass ratios of the active catalyst substance and  to be calculated according to the carrier used in each case nen.

Regarding the chemical composition of the crystallites, the form the catalyst of the invention is here to note that this generally depends on which Compounds should be oxidized, hydrogenated or hardened. The catalyst according to the invention preferably has crystals lite on, in addition to copper oxide, oxides and / or mixed oxides of titanium, nickel, cobalt, vanadium, molybdenum, iron, tin, Silver, chrome, silicon, aluminum, yttrium, barium, lanthanum, Strontium, bismuth and / or zinc and / or metallic platinum, include metallic palladium and / or metallic rhenium.

Especially when the crystallites of the invention Catalyst copper oxide or in the place of copper oxide still as another metal oxide, nickel oxide, cobalt oxide and / or vanadi umoxid and as a further oxide titanium oxide, chromium oxide, silicon contain oxide, aluminum oxide and / or zinc oxide, can this catalyst is excellent for hydrogenation or hardening processing of oils, fats, fatty acids and / or their derivatives deploy.

In another embodiment of the kata according to the invention lysators consist of 40% to 100% by weight of the crystallites, preferably 80% to 90% by weight on a chemical re Action product of the oxides forming the catalyst these oxides depending on the starting products and the chosen  crushing conditions as mixed oxides, multiple oxides and / or preferably as spinels.

A particularly suitable embodiment of the catalyst according to the invention provides that the crystallites contain 40% by weight to 100% by weight, preferably 80% to 90% by weight of a mixed oxide, in particular a spinel, of copper oxide and aluminum oxide, consist in particular of an oxide of the general formula CuAl ₂ O ₄ and / or Cu ₂ Al ₂ O ₅ , or of a mixed oxide of copper oxide and titanium oxide, in particular of a mixed oxide with the formula CuTiO ₃ . With regard to the hydrogenation or hardening of fats, oils, fatty acids and / or their derivatives, these catalysts are distinguished by the fact that they bring about a high yield in the desired hydrogenation or hardening reactions which cannot be achieved with the known catalysts. Furthermore, the two types of catalysts mentioned above have a high selectivity and acid resistance, so that they can also be used in particular for the hydrogenation or curing of fatty acids without undesired colored by-products being formed in these reactions.

The present invention further relates to a method for Preparation of the aforementioned catalyst.

In the inventive method for producing the previously Catalysts are described as solids present and the catalyst forming oxidic Aus materials that are in addition to copper oxides or a other metal oxide at least one more metal oxide  acts, mixed together. Simultaneously or subsequently become the starting materials or the mixture of the starting materials mechanically crushed to a grain size smaller than 10 µ. In other words, the Ver drive the catalysts described above in a solid produced per reaction.

Surprisingly, it was found that the Solid-state reaction carried out according to the invention the desired catalyst with the oxidic starting materials high yield arises. This is the case with the invention Process attributed to that for manufacturing the activation energy required for the catalyst It is made available that the oxi used dischen raw materials to a relatively small grain size be scaled down, causing a huge increase in surface area and thus an intimate contact of the oxidic used Leads. Furthermore, the for manufacturing activation energy required in the form of mechanical energy into the respective system (oxidic off gear materials) introduced. Thus, the very fine size reduction of the oxide starting materials to a grain size smaller than 10 µ a reduction in the shares required for the production vation energy, so that then when crushing the Mechanical materials introduced into the system sufficient to produce the catalyst. As a result of Comminution of the oxidic starting materials to a grain size of less than 10 µ and due to the associated enormous Surface enlargement becomes the speed for the fro  position of the catalysts described above increased so that correspondingly short shredding times and extremely good off booties result in the inventive method.

The method according to the invention has a number of advantages on. So it should first be noted that the invention The process is extremely environmentally friendly, as this is due to the solvents required in the prior art, in which it is, for example, water, aqueous systems, acids, Ba sen, oxidizing agents, reducing agents or other solutions acts medium, can be dispensed with. Also join the The inventive method no significant emissions on what is always the case with conventional methods if appropriate catalysts after roasting or in the melt can be represented. As previously described the method according to the invention is also distinguished ren compared to the known methods by special short implementation times and particularly high yields. Fer ner, the method according to the invention opens up a completely new one Class of manufacturing processes and thus leads to completely new catalysts that are not according to conventional processes are producible. This is expressed, for example, in that the manufactured by the inventive method and Catalysts described above microcrystallites in egg A size between 20 angstroms and 300 angstroms, preferably between 100 Angstroms and 200 Angstroms in size sen, with these catalytically active microcrystallites preferably located on the surface of these catalysts are and in particular in a fixed matrix of the respective  oxidic starting materials and / or those produced therefrom Catalyst are involved. This in turn is explained Lich that such catalysts have a much better Ka catalyst effect in relation to oxidation, hydrogenation or Have hardening compounds that are in corresponding higher yields and the emergence of none or only one express a small number of undesirable by-products.

A first embodiment of the method according to the invention provides that the oxidic starting materials on a grain size smaller than 4 µ, preferably to a grain size between between 0.1 µ and 4 µ, mechanically crushed.

Particularly high yields and particularly short production times can be achieved in the process according to the invention by mechanically comminuting the oxidic starting materials in such a way that they are present in a narrow grain size distribution with ad ₅₀ value between 0.1 μ and 1 μ. Here, the d ₅₀ value is defined in such a way that at least 50% of the starting materials are smaller than the specified d ₅₀ value, ie in the case mentioned above, they are smaller than 0.1 μ to 1 μ.

The embodiments described above are preferred performed the method according to the invention such that here the oxidic Aus required for the production mixed materials and simultaneously on the grain sizes specified above are crushed, as these Process variant is most economical to carry out.  

Of course, it is also possible to start with the Mix the starting materials together and then the perform mechanical comminution.

With regard to the implementation of the invention Process crushing required there are several Opportunities.

So looks a particularly suitable and economical successful embodiment of the method according to the invention rens that the mechanical comminution by a appropriate mechanical grinding of the oxidic output substances is brought about.

There is also the possibility of the required mechanical Comminution of the oxidic starting materials and the ver bring bound energy input into the system that you do an ultrasound treatment.

Furthermore, you can in the process of the invention required shredding of the raw materials and the achieved energy input by at least one two, accelerated and opposite currents of the can collide oxidic starting materials, so that the for carrying out the method according to the invention energy to overcome the activation energy as kinetic energy is provided. The one for this required acceleration of the oxidic starting materials can, for example, via appropriate magnetic fields, electri  cal fields or via suitable accelerated fluid flows, in which feed in the oxidic starting materials be performed.

The chopping required in the method according to the invention time during which the raw materials come into contact with each other brought and charged with an appropriate energy depends on the one to be manufactured Catalyst. Usually this time varies between 1 se customer and 60 minutes, preferably between 5 minutes and 15 Minutes.

In another embodiment of the invention Process, the oxidic starting materials are heated. Be with regard to the temperature used, it should be noted that this temperature depends on the one to be carried out Response, d. H. depending on the catalyst to be manufactured, aimed and usually varies between 30 ° C and 400 ° C. If the mechanical Zer reduction of the oxide starting materials by grinding can be brought about, so it can possibly in special cases be required to remove the heat generated during grinding ren, so that in this case the starting materials during the cer not heated up but cooled instead.

The system in each case in the method according to the invention Mechanical energy to be applied is generally determined spoken after the raw materials used and here from catalysts to be produced. Preferably, the  Energy density in the method according to the invention between 0.5 kW and 500 kW per liter of reactor volume, especially between 10 kW and 200 kW per liter reactor volume.

A particularly suitable form of the method according to the invention provides that the oxidic starting materials before the Vermi to a grain size between 30 µ and 300 µ, preferably between 60 µ and 120 µ, crushed and especially crushed len. This ensures that the corresponding order setting further accelerated and the achieved in the implementation Yield of catalysts is increased.

In another embodiment of the invention The process uses the oxidic raw materials at Vermi and / or apply a fluid during comminution strikes. This fluid can be preferred wise is water, on the one hand used for heat transport are set and / or the mechanical comminution accelerate or improve the oxidation of the starting materials ser.

If in the process according to the invention the oxidic Aus grinding materials for comminution, so it makes sense to use as a fluid in particular a liquid. Preferential An inert liquid becomes wise, for example the aforementioned water, used so as to prevent that an undesirable oxidation or reduction of the hereafter manufactured catalysts occurs.  

Another embodiment of the method according to the invention provides that the mechanical comminution to the end an additional substance is added. Here should be achieved by adding the additional substance, that especially when grinding no reagglomeration of the zer ground and, if necessary, correspondingly electrically charged output substances occurs.

Concerning the concentration of at least one additional one It should be noted that this concentration is between 0.1 % By weight and 3% by weight, based on the mass of the starting materials, varies.

Such an additional substance is preferably selected which, as already mentioned above, reagglomerates the crushed raw materials prevented. As an example of particularly suitable additional substances are antistatic agents, Polyelectrolytes, such as in particular polysaccharides, polyvinylal alcohols, polyvinyl acetates, derivatives of polyvinyl alcohols and / or polyvinyl acetates, polymeric phosphates, interfaces active esters and humanites. Is that fiction according process for the preparation of catalysts in Be rich in fat hardening can be used, so can as an additional substance for grinding oils and / or fats are added, these oils and / or fats then in their The composition corresponds to the oils and / or fats that come with Then use of a catalyst prepared in this way are to be hardened. This can then lead to a separation these fats added in the preparation of the catalyst  and / or oils after catalyst manufacture who the. Furthermore, the causes at least one additional Fabric that during drying, that in the design variants of the method according to the invention is necessary in which working with a liquid, an undesirable reag glomeration of the shredded raw materials occurs.

In a particularly suitable embodiment of the The inventive method is used in the crushing of the Starting materials, especially when grinding the starting material substances, water added, as already briefly above thinks is. This prevents the shredder undesirable dust development arises because the Starting materials when crushing in an aqueous suspension or dispersion. After shredding, the inorganic compounds or Mixtures from the suspension and / or the dispersion by Flo separation, coagulation and / or precipitation adsorption separated, which on the one hand prevents the aforementioned Reagglomeration occurs and on the other hand a relatively volumi nöses end product, for example, a significant has improved catalyst activity. Depending on the type and opening construction of the manufactured by the inventive method End product are used for coagulation as a coagulation aid medium flocculants, such as salts of iron, Salts of silicon or salts of aluminum, or polymeric Flocculants, such as, in particular, starch, glue, polyacrylamide, Polyacrylates, polyethyleneimine and / or polyethylene oxide inserted puts. Anion-active surfactants,  cationic surfactants and / or amphoteric surfactants used be the usual for precipitation adsorption known adsorbents, such as aluminum oxide, Ak Carbon, silica gel and / or diatomaceous earth can be used.

Of course, however, in the case of the process uses a gas or gas mixture as a fluid the, especially when the crushing of the oxidic Starting materials is brought about by the fact that the oxidic Starting materials in two oppositely aligned fluid flows are fed in, as already above is described.

The choice of oxidic starting materials is based on the process according to the invention, which catalyst each to be manufactured.

In particular, are used as oxidic starting materials Copper oxide than other metal oxides, nickel oxide, cobalt oxide and / or vanadium oxide used, the aforementioned Oxides with titanium oxide, chromium oxide, silicon oxide, aluminum oxide and / or zinc oxide by the process according to the invention be set.

A particularly suitable embodiment, which is particularly suitable for the production of highly effective hydrogenation or curing catalysts, provides that copper oxide (CuO) and aluminum oxide (Al ₂ O ₃ ) or copper oxide (CuO) and titanium dioxide (TiO ₂ ) starts. This then ent results in the first case, microcrystalline catalysts of the type described at the outset, the catalytically active microcrystallites then consisting of 40% by weight to 100% by weight, preferably 80% by weight to 90% by weight, of CuTiO ₃ . In the second case, 40% by weight to 100% by weight, preferably 80% by weight to 90% by weight, of catalytically active microcrystallites are formed in the process according to the invention and are present as CuAl ₂ O ₄ or Cu ₂ Al ₂ O ₅ .

As already described several times above, the inventive method the mechanical comminution of oxidic starting materials preferably by grinding brought about. Depending on the respective conditions of the me mechanical shredding and the raw materials used form catalytically in the process according to the invention active crystallites, which are preferably intermediate compounds genes, multiple oxides, mixed oxides, spinels, mixed crystals and / or represent chemical compounds.

A further development of the method according to the invention provides that you reduce the oxidic catalyst with hydrogen, so that such a reduced catalyst then directly into especially for hydrogenation or hardening, preferably of Oils, fats, fatty acids and / or their derivatives can be.

Advantageous developments of the catalytic converter according to the invention tors and the inventive method are in the Subclaims specified.

The method according to the invention is described below with reference to two exemplary embodiments explained in more detail.

Embodiment 1

Stoichiometric amounts of copper oxide (CuO) and titanium dioxide (TiO ₂ ) were ground to a grain size smaller than 10 µ (grain size spectrum between 8 µ and 1 µ). The meal was 7 minutes. The energy density applied to the aforementioned reaction partners was 30 kW per liter of reactor volume.

X-ray structure analysis (XRD) showed that the resulting catalyst consisted predominantly of CuTiO ₃ . Furthermore, by-products Cu ₂ TiO ₃ , Cu ₄ TiO ₄ and mixed oxides, in particular CuOTiO ₂ and Cu ₂ OTiO ₂ , were produced to a minor extent.

The catalyst thus produced had on its surface a fine crystalline structure, the crystallite sizes in the order of magnitude varied between 100 and 200 angstroms. These crystallites (70% by weight) were in a solid matrix Reactant or the catalyst embedded.

The one produced by the previously described method Catalyst was used for the hydrogenation of lauric acid ethyl ester to lauryl alcohol (and methanol as a by-product)  used. This hydrogenation was carried out at a temperature of 300 ° C and a hydrogen pressure of 280 bar, the weight of the catalyst weighed 3% by weight of the lauric acid methyl ester. The hydrogenation time was 60 minutes.

The conversion to lauryl alcohol was 90% (% by weight).

The lauryl alcohol so produced was colorless. Furthermore could next to methanol and unreacted Lauric acid methyl ester a single, not identified by-product can be detected by gas chromatography.

The hydrogenation described above was compared with a conventional copper chromite catalyst below otherwise identical conditions carried out. Here was the yield of the hydrogenation 85 wt.%, with this conv tional hydrogenation a mixture of by-products (2% by weight) was incurred. The resulting lauryl alcohol was due to the bil of colored copper salts intensely colored, so here Appropriate cleaning takes place before further processing had to.

Embodiment 2

Stoichiometric amounts of copper oxide (CuO) and aluminum oxide (Al ₂ O ₃ ) were ground to a grain size smaller than 5 µ (grain size spectrum between 5 µ and 1 µ).

The meal was 10 minutes. The previous ones energy applied density was 150 kW per liter of reactor volume.

X-ray structure analysis (XRD) showed that the catalyst formed consisted predominantly of CuAl ₂ O ₄ or Cu ₂ Al ₂ O ₅ . This catalyst had on its surface 60% by weight of microcrystallites of the aforementioned two compounds, which had a grain size between 100 angstroms and 200 angstroms. These crystallites were embedded in a solid matrix of the reactants or the catalyst formed during the reaction.

The one produced by the previously described method Catalyst was used for the hydrogenation of lauric acid ethyl ester to lauryl alcohol (and methanol as a by-product) used. This hydrogenation was carried out at a temperature of 320 ° C and a hydrogen pressure of 300 bar, the weight of the catalyst weighed 3% by weight of the lauric acid methyl ester. The hydrogenation time was 50 minutes.

The conversion to lauryl alcohol was 92% (% by weight).

The lauryl alcohol so produced was colorless. Furthermore could in addition to methanol and unreacted lauric acid thylester a single, unspecified secondary pro be detected by gas chromatography.  

Also in the case of the one produced according to embodiment 2 The previously described hydrology became a catalyst tion with a conventional copper chromite catalyst otherwise carried out identical conditions. Here was the yield of the hydrogenation 83 wt.%, with this conv tional hydrogenation in addition to unreacted lauric acid thylester a mixture of by-products (2.5% by weight) was obtained. In comparison, the hydrogenation with the copper Aluminum oxide catalyst (according to the invention) 1.5% by weight addition products.

The lauryl alcohol produced in the conventional process was intense due to the formation of colored copper salts colored while using the of copper-aluminum Umoxid catalyst (according to the invention) Laurylalko hol was colorless, so that ver appropriate cleaning could be waived.

Claims (24)

1 catalyst for the oxidation, hydrogenation or curing of compounds, in particular for the hydrogenation of oils, fats, fatty acids and / or their derivatives, characterized in that the catalyst contains at least one further metal oxide in addition to copper oxide or another metal oxide and that the catalyst has at least 30% by weight of catalytically active crystallites, the crystallite sizes of which vary between 20 angstroms and 300 angstroms. 2. Catalyst according to claim 1, characterized in that the catalyst is preferably between 50% and 90% by weight has at least 70% by weight of crystallites. 3. Catalyst according to claim 1 or 2, characterized in that that the catalyst has crystallites whose crystallite size vary between 100 angstroms and 200 angstroms.   4. Catalyst according to one of the preceding claims, characterized characterized in that the crystallites predominantly on the Surface of the catalyst arranged and in a fixed Ma trix are involved. 5. Catalyst according to one of the preceding claims, characterized characterized in that the crystallites in addition to copper oxide Oxides and / or mixed oxides of titanium, nickel, cobalt, vanadium, Molybdenum, iron, tin, silver, chrome, silicon, aluminum, Yttrium, barium, lanthanum, strontium, bismuth and / or zinc and / or metallic platinum, metallic palladium and / or include metallic rhenium. 6. Catalyst according to claim 5, characterized in that the crystallites other than copper oxide or an oxide of nickel, Cobalt and / or vanadium as another oxide or titanium oxide, Chromium oxide, silicon oxide, aluminum oxide and / or zinc oxide as contain further oxide. 7. Catalyst according to one of the preceding claims, characterized characterized in that the crystallites are 40% by weight to 100% by weight, preferably 80% to 90% by weight, from a chemical Reaction product of the oxides forming the catalyst stands. 8. Catalyst according to one of the preceding claims, characterized in that the crystallites from 40% by weight to 100% by weight, preferably from 80% by weight to 90% by weight, of CuAl ₂ O ₄ and / or Cu ₂ Al ₂ O ₅ exist. 9. Catalyst according to one of the preceding claims 1 to 7, characterized in that the crystallites are 40% by weight to 100% by weight, preferably 80% by weight to 90% by weight, of CuTiO ₃ . 10. Process for the preparation of the catalyst according to one of the preceding claims, characterized in that the present as a solid and forming the catalyst oxi dical raw materials, which are in addition to copper oxide or another metal oxide at least one more Metal oxide acts, mixed together and simultaneously or then the oxides to a grain size smaller than 10 µ mechanically crushed. 11. The method according to claim 10, characterized in that the starting materials have a particle size of less than 4 μ, preferably to a grain size between 0.1 µ and 4 µ, mecha niche crushed. 12. The method according to claim 10 or 11, characterized in that the starting materials are comminuted such that they are present in a narrow grain size distribution with ad ₅₀ value between 0.1 u and 1 u. 13. The method according to any one of claims 10 to 12, characterized characterized in that the starting materials between 1 second and 60 minutes, preferably between 5 minutes and 15 minutes mechanically crushed.   14. The method according to any one of claims 10 to 13, characterized characterized in that the starting materials during the Crushing warmed up. 15. The method according to claim 14, characterized in that the starting materials to a temperature between 30 ° C and 400 ° C heated. 16. The method according to any one of claims 10 to 15, characterized characterized in that the starting materials in a reactor arranges and there with an energy density between 0.5 kW and 500 kW per liter of reactor volume, preferably with one Energy density between 10 kW and 200 kW per liter reactor volume men, crushed. 17. The method according to any one of claims 10 to 16, characterized characterized in that the starting materials are mixed before mixing a grain size between 30 μ and 300 μ, preferably between 60 µ and 120 µ, crushed. 18. The method according to any one of claims 10 to 17, characterized characterized in that when mixing and / or in the Zer reduction applied a fluid to the raw materials. 19. The method according to claim 18, characterized in that a liquid, preferably water, is used as the fluid.   20. The method according to any one of claims 10 to 19, characterized characterized in that copper, nickel, Cobalt, vanadium, molybdenum, iron, tin, silver, chrome, Silicon, aluminum, yttrium, barium, lanthanum, strontium Bismuth and / or zinc oxide and / or metallic platinum, metallic palladium and / or metallic rhenium. 21. The method according to any one of claims 10 to 20, characterized in that copper oxide (CuO) and titanium dioxide (TiO ₂ ) are used as starting materials. 22. The method according to any one of claims 10 to 21, characterized in that copper oxide (CuO) and aluminum oxide (Al ₂ O ₃ ) are used as starting materials. 23. The method according to any one of claims 10 to 22, characterized characterized in that the starting materials for comminution mechanically ground. 24. The method according to any one of claims 10 to 23, characterized ge indicates that the oxidic catalyst with water fabric reduced.