DE10059319A1 - Hydrogenation catalyst for reducing functional groups and process for its preparation - Google Patents

Abstract

The present invention relates to a hydrogenation catalyst for the reduction of functional groups and processes for its production. As the catalytically active metal, the hydrogenation catalyst contains nickel and finally or cobalt, which is applied to a support containing TiO¶2¶.

Description

The invention relates to a catalyst which for the hydrogenation of functional groups organi shear compounds in neutral acidic or basic media, especially for the hydrogenation of Nitro groups in nitro aromatics to the corresponding Amines, for the hydrogenation of aldehydes and keto NEN to the corresponding alcohols for which hyd nitriles to the amines and for the re ductile amination of aldehydes and ketones can be set and a process for its manufacture position.

These hydrogenations are both in the fixed bed reactor as well as carried out in the batch reactor. Most frequently technically these hydrogenations are in the liquid phase with suspended catalyst, the process being characterized by the reaction temperature temperature, pressure, catalyst, solvent and art distinguish the reaction procedure.

The catalytic hydrogenation of glucose to sorbitol with a Ni-SiO ₂ -Al ₂ O ₃ catalyst is disclosed in NL 8 102 190. The use of Ni-Cu supported catalysts for glucose hydrogenation is described in DD 217 996. SiO ₂ , Al ₂ O ₃ and SiO ₂ Al ₂ O ₃ are used as carriers. DD 156 175 describes the production of sorbitol by hydrogenation of glucose in the presence of a Ni-SiO ₂ catalyst. According to the patent specification SU 565 040, the hydrogenation to sorbitol on Raney-Ni runs with a catalyst concentration of 5-6%, temperatures of 110 to 150 ° C. and pressures of 40 to 60 bar after 1 to 2 hours with good yields. US 4,694,113 describes a two-stage process for the hydrogenation of glucose to sorbitol: in the first stage, about 95% of the glucose is hydrogenated to sorbitol in the presence of a Ni catalyst; after removal of the Ni catalyst, the rest of the glucose is hydrogenated to sorbitol using an Ru catalyst.

The hydrogenation of 2,4-dinitrotoluene in the presence of the catalysts Pd / C, Raney cobalt, respectively Platinum black is disclosed in patent J 551 33 33 beard. A Ni-diatomaceous earth supported catalyst is used for the hydrogenation of di-nitrobenzophenone to the diamine disclosed in EP 98 681. In EP 3 537 247 A is the hydrogenation of di-nitro compounds to the Diamines in the presence of modified Raney Nickel catalysts described. The preferred In addition to Ni, Fe, Cr, Mo, the catalyst system contains W, V, Ti, Nb, Re, Ru, Zr and / or Hf.

EP 0 335 222 teaches the use of Ni-Al ₂ O ₃ / ZrO _{2 supported} catalysts for the hydrogenation of nitriles, aromatics, nitro compounds and olefins. The simultaneous precipitation of Ni, Zr and Al is particularly claimed on supports at 50-120 ° C. and at pH 7.3-9, with activated carbon, Al ₂ O ₃ , SiO ₂ , and diatomaceous earth being used, among other things, as a support , Particular attention is paid to a homogeneous precipitation of the components.

Ni-Al ₂ O ₃ / ZrO ₂ catalysts are disclosed in SU-PS 28 31 85. They are made by precipitation of Ni and Al ₂ O ₃ on ZrO ₂ . According to the teaching of US Pat. No. 2,564,331, a Ni-ZrO ₂ catalyst is produced by precipitating a nickel and zirconium carbonate mixture with subsequent washing, drying and reducing at 250 to 350 ° C. The catalyst contains a maximum of 10% by mass of ZrO ₂ .

DE-AS 12 57 753 also describes the precipitation of the insoluble carbonates. The precipitation process is triggered by evaporation of CO ₂ and NH ₃ from a mixed salt solution of ammonium zirconyl carbonate and nickel amine carbonate.

EP 0 672 452 discloses catalysts for hydrogenating organic compounds which are essentially 65 to 80% by mass of Ni, calculated as NiO, 10 to 25% by mass of SiO ₂ , 2 to 10% by mass of Zr, calculated as ZrO ₂ and 0 to 10% by mass of Al, calculated as Al ₂ O ₃ , the sum of the content of SiO ₂ and Al ₂ O _{3 being} at least 15% by mass. These catalysts are prepared by adding an acidic aqueous solution of Ni, Zr and, if desired, aluminum compounds. During the precipitation, the pH is first reduced to 4.0 to 6.5 and subsequently adjusted to 7 to 8. The precipitate is dried, cal ciniert and deformed.

For the hydrogenation of nitriles to amines preferably described Raney-Ni catalysts. The FR 2722710 discloses a Raney Ni catalyst, that with elements of the 4th, 5th and 6th subgroup do is.

Raney-Ni and Raney-Co catalysts are used in the WO 9527695 for the reductive amination of hydro xyaldehyden to hydroxyamines disclosed.

The use of Co-TiO _{2 supported} catalysts with additions of SiO ₂ and ZrO ₂ is disclosed in US Pat. No. 5,169,821 for the Fischer-Tropsch synthesis, the catalyst preparation being carried out in two stages: precipitation of the TiO ₂ with subsequent calculation of the Carrier and subsequent precipitation of the Co ²⁺ carbonate.

The previously known Ni, Co and Co-Ni hydrogenation Catalysts have the crucial disadvantage on that under alkaline and acidic reaction conditions conditions a relatively rapid aging of the kata analyzer entry. Basic investigations erga that aging in particular to rapid Ni crystallite growth is attributable.

The invention therefore has the technical problem basis, nickel and / or cobalt-containing carrier ka To provide catalysts that are under acid or basic reaction conditions a higher life have duration.

This problem is solved according to the invention in that a catalyst which, in particular for the hydrogenation of functional groups in organic compounds, in particular for the hydrogenation of nitro groups in nitroaromatics to the corresponding amines, for the hydrogenation of aldehydes and ketones to the corresponding alcohols , for the hydrogenation of nitriles to the amines and for the reductive amination of aldehydes and ketones, containing nickel and / or cobalt on a TiO ₂ -containing carrier, the catalyst being reduced or reduced and stabilized, metal crystallites with crystallite sizes <120 Å, in the reduced and passivated state a Ni and / or Co content of 20 to 80 mass% (based on the total mass of the catalyst), a TiO ₂ content of 10-80 mass%, an SiO ₂ content of 0 to 20 mass%, a ZrO ₂ content of 0-60 mass%, an HfO ₂ content of 0-5 mass% (in each case based on the total mass of the K atalysers) and after a one-hour post-reduction at 100 ° C has a degree of reduction of at least 55%.

The invention thus provides for a catalyst which has nickel, cobalt or nickel and cobalt as catalytically active metal, ie contains nickel and / or cobalt metal, these metals or this metal being supported on a support comprising TiO ₂ , The TiO ₂ content, based on the total mass of the catalyst, is 10 to 80% by mass, preferably 20 to 80% by mass, based on the total mass of the catalyst (including support). According to the invention, it is provided in a particularly preferred embodiment that the carrier containing TiO ₂ additionally has SiO ₂ and / or ZrO ₂ and / or HfO ₂ . In a particularly preferred embodiment, the SiO ₂ content, based on the total mass of the catalyst (ie including the support), can be up to 20% by mass. In a further preferred embodiment, the ZrO ₂ content can be up to 60 mass%, based on the total mass of the catalyst. In a further preferred embodiment, the HfO ₂ content can be up to 5% by mass (based on the total mass of the catalyst).

The degree of reduction is after an hour Reduction of the stabilized catalyst 100 ° C in hydrogen flow (load: 1000 v / vh) certainly. In connection with the present Er is called the degree of reduction Proportion of metallic Ni and / or Co in total Ni and Co content understood.

In a particularly preferred embodiment The invention provides that the aforementioned Kata analyzer with metal contents of nickel, cobalt or Nickel and cobalt <50% by mass an average metal crystallite size of <100 Å. In a white teren preferred embodiment provides the inventor the catalyst at metal contents of nickel, cobalt or nickel and cobalt <50 mas an average metal crystallite size of <60 Å.

In a particularly preferred embodiment of the Invention are the reduced and not stabili or the reduced and stabilized Ka Talysators entered in a suitable medium.  

Depending on the application, water, Alcohols, fatty amines or other protective agents be applied.

However, the catalysts can also be reduced and stabilized form as powder with grain sizes from 1 to 200 µm, preferably from 1 to 30 µm, be used. The catalysts themselves understandably also be designed as moldings.

The catalysts of the invention stand out advantage over conventional catalysts more dangerous and surprising due to their length extended life with improved catalytic Activity for the target products from, in particular, if alkaline or acidic reaction conditions available. Apparently, according to the invention production of Ni and / or Co phases, that are particularly active and stable catalysts to lead. The catalyst according to the invention is for the hydrogenation of functional groups organi shear connections in neutral, but especially especially in acidic or basic media suitable. The invention also solves this problem by providing a method of manufacture position of such a catalyst.

In another embodiment, the invention also relates to a process for the preparation of the above-mentioned catalyst, wherein by precipitation from a salt solution containing a) Ni ²⁺ and Ti ⁴⁺ , b) Ni ²⁺ , Co ²⁺ and Ti ⁴⁺ or c ) Co ²⁺ and Ti ⁴⁺ by adding a basic solution, in particular a solution of NaOH, NaHCO ₃ , Na ₂ CO ₃ or a mixture of at least two of these substances, up to a pH of 7 to 9.5 a precipitate is obtained, which is washed after filtration, then dried at temperatures from 80 ° C to 150 ° C, then calcined at temperatures from 250 to 700 ° C, optionally thereafter rendered inert and then with hydrogen at temperatures from 300 ° C to 550 ° C is reduced, if necessary rendered inert and finally stabilized or added to a medium.

In a particularly preferred embodiment of the present invention it can be provided that the solution containing a mixture of salts, ie the salt solution, containing a) Ni ²⁺ and Ti ⁴⁺ , b) Ni ²⁺ , Co ²⁺ and Ti ⁴⁺ or c) Co ²⁺ and Ti ⁴⁺ additionally contains Zr ⁴⁺ . In a further preferred embodiment it can be provided that the solution contains a mixture of salts in addition to the aforementioned components also Hf ⁴⁺ . In a further preferred embodiment, a soluble Si ⁴⁺ compound, for example water glass, is added to the basic solution of NaOH, NaHCO ₃ , Na ₂ CO ₃ or a mixture of at least two of these substances.

In a particularly preferred form, the solution containing a mixture of salts contains proportions of TiO ₂ or TiO ₂ -ZrO ₂ mixtures or TiO ₂ -ZrO ₂ -SiO ₂ mixtures, preferably in suspended form, where in the reduced catalyst prepared in accordance with the invention the proportion of the carrier from the oxidic additives in a particularly preferred embodiment does not exceed 80% by mass (based on the mass of the carrier). A maximum of 80% of the mass of the carrier comes from the addition of solid TiO ₂ , ZrO ₂ or SiO ₂ . The remaining portions of the carrier originate from the precipitation from the Ti ⁴⁺ and Zr ⁴⁺ salt solutions.

The invention therefore provides in a particularly preferred embodiment that the substances used as carriers, such as TiO ₂ , ZrO ₂ or SiO _{2, can be used} in the precipitation solution both in solid and in dissolved form.

The precipitation product is thus prepared by adding the basic solution mentioned to the Ni ²⁺ - or / and Co ²⁺ - and Ti ⁴⁺ - or Ti ⁴⁺ - and Zr ⁴⁺ - salt solution, which optionally contains TiO ₂ or TiO ₂ - Contains ZrO ₂ mixtures or TiO ₂ -ZrO ₂ -SiO ₂ mixtures, this addition taking place until and until the precipitation suspension reaches a final pH of 7.5-9.5. In a further preferred embodiment it is provided that a soluble Si ⁴⁺ compound, for example water glass, is added to the basic solution mentioned.

Furthermore, the invention sees in a preferred th embodiment that the precipitation at Tem temperatures from 65 ° C to 100 ° C. In preferred embodiment can be provided that after reaching the final pH Precipitation suspension, for example, for 0.5 to 4 hours is stirred before further processing follows. The reduction and passivation or the one support of the Ni and / or Co-containing supported catalyst tors in a protective medium can usually be in front  be taken and is in the execution examples len described.

Further advantageous embodiments of the invention result from the subclaims.

The object of the invention is at the following case play illustrated.

Example 1

8 l of water are placed in a heatable precipitation container provided with a stirrer and then 1.2 kg of soda are added. After adding the soda, the suspension is heated to a temperature of 80-90 ° C. with stirring. After the soda has been completely dissolved, the dosing of a solution that contains solid titanium oxide in addition to nickel and titanium in the form of nitrate or oxysulfate begins. The molar ratio of nickel to TiO ₂ is approximately 4. The mass ratio of TiO _{2 present} as titanyl sulfate in solution to fes th TiO ₂ is about 3. The precipitation is about 85 ° C. The precipitation is complete when a pH of 8-8.5 is reached. The total fall time is approx. 2 hours. Following the precipitation, the suspension is stirred for a further approx. 2 h at the above temperatures, then filtered and washed with alkali-free water until the Na ₂ O content in the filter cake is <0.3%, based on the residue on ignition of the 800 ° C tempered filter cake. The filter cake is then dried for approx. 15 h at temperatures of 120-150 ° C and calcined at 450 ° C.

After the calcination, the intermediate product is ground, tabletted, reduced in a hydrogen stream at 420 ° C. for 6 h and treated in a CO ₂ / nitrogen stream with an oxygen content of 0.1 to 1% by volume at temperatures below 80 ° C.

The reduced and stabilized catalyst contains approx. 65% nickel and 20% TiO ₂ based on the total catalyst. It has a degree of nickel reduction, expressed by the ratio of metallic nickel to total nickel of approx. 80%. The mean nickel primary particle size is 59 Å.

Example 2

8 l of water are placed in a heatable precipitation container and then a solution containing nickel, ZrO ₂ and TiO ₂ is added. The molar ratio of nickel to ZrO ₂ to TiO ₂ is 1: 0.07: 0.11. The zirconium oxide was added both in solid and in dissolved form as a ZrO ₂ or zirconyl nitrate solution. The mass ratio of solution to solid zircon in the precipitation was approx. 3. After adding the solution, the mixture was heated to 80 ° C. with stirring and then with a soda solution (150 g soda / l solution) until pH value of 8-8.5 precipitated. The precipitation and subsequent stirring times were also 2 hours each.

The catalyst was further processed as in Example 1. The reduction of the catalyst  precursor was 6 h at a temperature of 450 ° C. performed.

The finished catalyst had a nickel content of approx. 66%, a ZrO ₂ and a TiO ₂ content of approx. 10% each. The degree of reduction was around 85%. The mean nickel primary particle size was 80 Å.

Example 3

8 l of water are placed in a heatable precipitation container provided with a stirrer and then a solution is added which contains cobalt and titanium in the form of nitrate or oxysulfate. The molar ratio of cobalt to TiO ₂ in the metal solution is approximately 2. After the solution has been added, the mixture is heated to a temperature of 80 ° C. with stirring and then precipitation is started after the temperature has been reached. An aqueous soda solution with a Na ₂ CO ₃ concentration of approx. 180 g / l serves as the precipitant. The precipitation time and subsequent stirring time at temperatures of 80-90 ° C are each about 2 hours. The precipitation was complete after setting a pH of 8.5-8.8.

The drying of the catalyst was carried out as described in game 1. The calcination was carried out at temperatures of 350 ° C. Following the calcination, the granular intermediate product was roughly ground and then loosely tabletted with the addition of graphite. The reduction in the hydrogen flow was carried out at 350 ° C. and then the catalyst was stabilized in the CO ₂ / nitrogen flow with O ₂ contents of 0.1-0.5% by volume.

The finished catalyst contains approx. 50% cobalt and 35% TiO ₂ . The degree of reduction was approx. 60% and the average crystallite size was 115 Å.

The reduced and stabilized catalysts Examples 1 to 3 according to the invention are based on a grain size of <63 microns ground and then for the suspension phase hydrogenation of glucose 135 ° C and 125 bar (Example 1-3) used. The Catalysts of Examples 1 and 2 are also catalyzed in the nitrobenzene hydrogenation table tested.

Example 4

8 l of water are placed in the precipitation container and then about 1.4 kg of NaHCO _{3 are} added with stirring. Thereafter, the mixture is heated to a temperature of approx. 80 ° C and, after the bicarbonate has been completely dissolved, precipitation begins. The metal solution used contains nickel, zirconium and titanium in the form of nitrate, oxynitrate and oxysulfate. The molar ratio of nickel to ZrO ₂ to TiO ₂ in the solution is 1: 0.143: 0.22. The precipitation is carried out at a temperature of 80 ° C up to a pH of 8.8. The precipitation and subsequent stirring times are identical to those mentioned in the previous examples. The Fällsus pension is then filtered and the filter cake is washed with ultrapure condensate. The filter cake is then redispersed in water and the slurry thus produced is sprayed in a spray dryer. The resulting powdery dry product is peptized using water, HNO ₃ and a suitable binder and then extruded to 2 mm full strands. After drying and calcination at temperatures of 130 ° C and 400 ° C, the moldings are reduced at a temperature of 420 ° C in the hydrogen stream. The stabilization is carried out as described in Example 1.

The finished catalyst has a nickel content of approx. 55%, the ZrO ₂ and TiO ₂ content were approx. 17% each. The hafnium content (calculated as HfO ₂ ) is approximately 0.5%. The degree of reduction is approx. 80%, the average crystallite size is 52 Å and the edge strength of the extrudates is approx. 8 N / mm. The hafnium content results from the contamination of the Zr ⁴⁺ salt solution.

The catalyst is used for the hydrogenation of glucose in a fixed bed process at a temperature of 105-120 ° C and a pressure of 220 bar. Ver a 40% glucose solution was used.

Example 5

As described in Example 1, water is placed in the precipitation container and then soda is added with stirring. After the soda has been dissolved, solid TiO ₂ with an average grain size of 7 μm is added to the solution and then heated to a temperature of 90-95 ° C. The precipitation is carried out using a combined nickel, cobalt nitrate and titanium oxysulfate solution up to a pH of 8.5. The precipitation and subsequent stirring times are 1.5 hours each. The molar ratio of nickel to cobalt to TiO ₂ in the precipitation solution is 1: 0.33: 0.65. The mass ratio between solid and dissolved TiO ₂ is 1.

After completion of the precipitation, as already be wrote, filtered, washed and the filter ku Chen redispersed and sprayed in water. The average grain size of the sprayed material at 10 µm. The dry product is reduced at 380 ° C. After the reduction is complete, the stream of inert gas cooled and then the pyrophoric, reduced Ka Talysatorpulver in a han with exclusion of air standard hardened tallow fatty amine (distearyl amine).

The reduced (not listed) catalyst has a composition of 40% nickel, 13% cobalt and 33% TiO ₂ . The degree of reduction is 85%, the average metal crystallite size is 93 Å.

The catalyst was used for the hydrogenation of fat acid nitriles to primary amines in the Suspensi onsphase tested.

Example 6 (comparative example)

305.76 g of Ni (NO ₃ ) ₂ 6 H ₂ O and 29.52 g of Al (NO ₃ ) ₃ 9H ₂ O are dissolved in 1760 ml of distilled water and 2.32 g of zirconium carbonate in 9 ml of HNO ₃ (56% by mass ) solved. Both solutions are combined and heated to 101 ° C. This mixed salt solution is uniformly added over 3 minutes to a 100 ° C hot and intensely stirred soda solution which has been prepared from 147.04 g of soda and 1416 ml of distilled water. 27.76 g of diatomaceous earth are stirred into the freshly precipitated suspension and the resulting mixture is stirred for a further 3 minutes. The precipitate is then filtered and washed with hot water until the alkali content of the wash water is about 20 mg Na ₂ O / l. The filter cake obtained in this way is suspended in 70 ° C. hot water (quantitative ratio filter cake to water = 1: 1), stirred for 60 minutes and then filtered again. The resulting filter cake is extruded into cylindrical shaped bodies (diameter 5 mm, length 8 to 10 mm) and then with increasing temperature (50 to 60 ° C) with air to a residual water content <10 mass%, based on ge dried mass, dried. The dried material is heated in a hydrogen stream after prior inerting in a nitrogen stream (1000 v / vh, 30 minutes) with a load of 400 v / vh and a heating time of 5 ° C / min to 470 ° C and over a period of Reduced 4 h at this temperature. The stabilization was carried out as in the examples according to the invention.

The catalysts were characterized catalytically as follows:

• A) Hydrogenation of glucose with a 0.5 l agitation toklav and a hydrogen consumption measurement at constant pressure:
  Reaction mixture: 120 g glucose, 90 g water and 1.2 g catalyst (particle size <63 µm)
  Pressure: 125 bar
  Reaction temperature: 135 ° C
  Stirring speed: 2000 revolutions / minute
  The measure of activity is the reaction time required to hydrogenate 98.5% of the glucose.
• B) Hydrogenation of nitrobenzene to aniline in a 0.5 l autoclave with hydrogen consumption measurement at constant reaction pressure:
  Reaction mixture: 80 g nitrobenzene, 40 g water and 0.25 g catalyst (particle size <63 µm)
  Reaction pressure: 25 bar
  Reaction temperature: 120 ° C
  Stirring speed: 2000 revolutions / minute
  The measure of the hydrogenation activity was the time in which 100% of the nitrobenzene had been converted.
• C) Process hydrogenation of glucose to sorbitol in a fixed bed
  Before the start of the hydrogenation, the catalysts are activated in a stream of hydrogen at 180 ° C. for 4 h. The reaction temperature, which must be set to achieve a conversion of 99.8%, and the sorbito yield serve as a measure of activity and selectivity.
• D) Hydrogenation of oleyl nitrile to oleylamine
  batch process
  Reaction mixture: 150 g oleyl nitrile, 33 g ammonia and 2.5 g catalyst (entered in fat); Weight: without fat
  Reaction temperature: 140 ° C
  Reaction pressure: 75 bar
  Stirring speed: 2100 revolutions / minute
  Hydrogenation time: 130 minutes

The stability of the catalysts was determined by the average metal crystallite size after a 100-hour treatment in the reaction mixture after hydrogenation of the nitro benzene under the pressure and temperature conditions the hydrogenation stops.

The mean metal crystal size was determined using a measuring station from Rich. Seifart & Co. Freiberger-Präzisionsmechanik GmbH determined by taking the scatter curve sections for nickel and for cubic crystallized Co perpendicular to the (200) network plane or for hexagonally crystallized Co perpendicular to the (101) network plane from the interference line broadening under the following conditions are.

The catalysts are supported by the data from fol characterized tables:  

Table 1

Results of the catalytic test in nitro benzene and glucose hydrogenation (suspension method)

Table 2

Results of the catalytic test in glucose hydrogenation (fixed bed method)

Table 3

Results of the catalytic test for the hydrogenation of oleyl nitrile to oleylamine

The advantages of the catalysts according to the invention are due to the high catalytic activity and high stability. The better ones Stabilities are due to the small increases in Metal crystallite size confirmed.

Claims (22)

1. Catalyst, in particular for the hydrogenation of functional groups of organic compounds containing nickel and / or cobalt on a support containing TiO ₂ , the catalyst being reduced, metal crystallites with crystal sizes of <120 Å, in the reduced and passivated state a total Content of 20 to 80% by mass (based on the total mass of the catalyst) of nickel, cobalt or nickel and cobalt, a TiO ₂ content of 10-80% by mass, and after a one-hour reduction at 100 ° C a degree of reduction of at least 55%. 2. Catalyst according to claim 1, wherein the TiO ₂ -containing support has a SiO ₂ content of at most 20% by mass (based on the total mass of the catalyst). 3. Catalyst according to claim 1 or 2, wherein the TiO ₂ -containing support has a ZrO ₂ content of at most 60% by mass (based on the total mass of the catalyst). 4. Catalyst according to one of claims 1 to 3, wherein the TiO ₂ -containing support has an HfO ₂ content of at most 5% by mass (based on the total mass of the catalyst). 5. The catalyst of claim 1, wherein the reducer te catalyst is stabilized. 6. Catalyst according to one of the preceding An say, the catalyst is a total metal content of cobalt and / or nickel <50% by mass and an average metal crystallite size of <100 Å. 7. Catalyst according to one of claims 1 to 5, wherein the catalyst has a metal content of cobalt and nickel <50 mass% and an average Metal crystallite size of <60 Å. 8. Catalyst according to one of claims 2 to 4, the catalyst in reduced and stabili form as powder with grain sizes from 1 to 200 µm is present. 9. A catalyst according to claim 5, wherein the catalyst tor as powder with grain sizes from 1 to 30 µm lies. 10. Catalyst according to one of claims 1 to 8, the catalyst in the form of extrudates, Ku gel or tablets. 11. Catalyst according to one of the preceding An say, the catalyst in a suitable Medium selected from the group consisting of what water, alcohols, fatty amines or other protective agents is present. 12. A process for the preparation of a Ni and / or Co-containing supported catalyst, in particular for the hydrogenation of functional groups of organic compounds, in particular according to one of claims 1 to 11, wherein a solution containing a mixture of salts is selected by precipitation from the group consisting of a) Ni ²⁺ and Ti ⁴⁺ , b) Ni ²⁺ and Co ²⁺ and Ti ⁴⁺ , and c) Co ²⁺ and Ti ⁴⁺ with a basic solution, in particular a solution of NaOH, NaHCO ₃ or Na ₂ CO ₃ or a mixture of at least two of these substances, up to a pH of 7 to 9.5, a precipitate is obtained, which is washed after filtration, then at temperatures of 80 ° C to 150 ° C dried, calcined at temperatures from 250 to 700 ° C, and reduced with hydrogen at temperatures from 300 ° C to 550 ° C. 13. The method according to claim 12, wherein the catalyst is rendered inert after the calcination. 14. The method according to any one of claims 12 or 13, the catalyst being inerti after the reduction is settled. 15. The method according to any one of claims 13 or 14, the reduced and optionally inert related catalyst after the reduction inertization is stabilized. 16. The method according to any one of claims 13 to 15, the catalyst after the reduction and counter if necessary, inertization was carried out directly in a Medium is entered.   17. The method according to any one of claims 12 to 16, wherein the solution contains a mixture of salts Zr ⁴⁺ . 18. The method according to any one of claims 12 to 17, wherein the solution containing a mixture of salts contains proportions of TiO ₂ or TiO ₂ -ZrO ₂ mixtures or TiO ₂ - ZrO ₂ -SiO ₂ mixtures, preferably in suspended form, the proportion of the TiO ₂ -containing carrier in the reduced catalyst from the oxidic additives is a maximum of 80%. 19. The method according to any one of claims 12 to 18, the precipitation at temperatures from 65 ° C to 100 ° C is made. 20. The method according to any one of claims 12 to 19, after receiving the final pH value ne precipitation suspension stirred for 0.5 to 4 hours before further processing takes place. 21. The method according to any one of claims 12 to 20, wherein a soluble Si ⁴⁺ compound is added to the basic solution. 22. The method of claim 21, wherein the soluble Si ⁴⁺ compound is water glass.