Process for the preparation of saturated organic compounds

Process for the preparation of completely or partly saturated organic compounds by catalytic hydrogenation of unsaturated organic compounds with hydrogen or hydrogen-containing gas mixtures in the presence of a shaped Raney catalyst as the hydrogenation catalyst, wherein the Raney catalyst is in the form of hollow bodies. Nickel, cobalt, copper, iron, platinum, palladium or ruthenium are preferably used as catalytically active constituents.

USE EXAMPLE 1 The catalytic activity &lsqb;sic&rsqb; of the catalyst of examples 1 to 7 during hydrogenation of butinediol (BID) to 1,4-butanediol (BDO) and butenediol (BED) were compared. For this purpose, 40 ml catalyst (from 35 to 73 grams of the corresponding catalysts) were introduced into a tube reactor and tested in a trickle phase. The temperature of the reaction was 150° C., the concentration of butinediol in water was 50 wt. %, the pH of the reaction solution was brought to 7 with NaHCO 3 and the pressure of the reaction was from 35 to 60 bar. The throughput of hydrogen was 82.5 l/h and the throughput of butinediol was 0.20 to 1.7 g butinediol/h·ml of catalyst. The product mixture was analysed by GC. 
 EXAMPLE 1 A free-flowing, pelletable catalyst mixture was prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst of 1000 grams of 50% Ni and 50% Al alloy powder (this alloy was melted in an induction furnace and sprayed with water), 75 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The shaped articles were calcined at 700° C. for 2 hours. After the calcining, the tables were activated for 2 hours at 80° C. in 20% sodium hydroxide solution. 40 ml (66.6 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 1. 1 TABLE 1 The results of example 1 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 35 0.20 99.4 75.7 85.5 2.389 3.977 60 0.20 99.7 63.1 70.3 2.994 4.984 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 2 A free-flowing, pelletable catalyst mixture was prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst of 1000 grams of 50% Ni and 50% Al alloy powder (this alloy was melted in an induction furnace and sprayed with water), 75 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The shaped articles were calcined at 700° C. for 2 hours. After the calcining, the tables were activated for 2 hours at 80° C. in 20% sodium hydroxide solution. This catalyst was doped with a sodium molybdate solution and the Mo content of the catalyst at the end was 0.2%. 40 ml (72.8 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 2. 2 TABLE 2 The results of example 2 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 35 0.40 97.4 55.6 73.5 0.37 0.67 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 3 A coating solution was prepared by suspending 1730 grams of 53% Ni and 47% Al alloy powder and 130 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) in 1557 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of poylstyrene &lsqb;sic&rsqb; beads with a diameter of about approx. 2 mm, while these were suspended in a stream of air directed upwards. 1 liter of these beads was coated further with an alloy solution. The solution for the second layer comprised 1203 grams of 53% Ni and 47% Al alloy powder, 90 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 1083 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of the abovementioned polystyrene beads precoated with Ni/Al, while these were suspended in a stream of air (nitrogen and other gases can also be used) directed upwards. After the polystyrene beads had been coated with the abovementioned solutions, the beads were heated to 500° C. in order to burn out the polystyrene. The Ni/Al hollow spheres were then heated to 800° C. in order to sinter together the alloy particles and nickel powder. The hollow spheres were then activated in a 20 wt. % sodium hydroxide solution for approx. 1.5 h at 80° C. The activated hollow spheres obtained had a diameter of about approx. 3.3 mm and a shell thickness of about approx. 700 &mgr;m. This catalyst was doped with a sodium molybdate solution and the Mo content of the catalyst at the end was 0.3%. 40 ml (36.07 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 3. 3 TABLE 3 The results of example 3 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0.80 99.8 83.0 89.5 0.89 0.798 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 4 A coating solution was prepared by suspending 1730 grams of 48.5% Ni, 50.1% Al, 0.9% Cr and 0.5% Fe alloy powder alloy powder and 130 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) in 1557 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of poylstyrene &lsqb;sic&rsqb; beads with a diameter of about approx. 2 mm, while these were suspended in a stream of air directed upwards. 1 liter of these beads was coated further with an alloy solution. The solution for the second layer comprised 1203 grams of 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe alloy powder, 90 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 1083 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of the abovementioned polystyrene beads precoated with Ni/Al/Cr/Fe, while these were suspended in a stream of air (nitrogen and other gases can also be used) directed upwards. After the polystyrene beads had been coated with the abovementioned solutions, the beads were heated to 500° C. in order to burn out the polystyrene. The Ni/Al/Cr/Fe hollow spheres were then heated to 800° C. in order to sinter together the alloy particles and nickel powder. The hollow spheres were then activated in a 20 wt. % sodium hydroxide solution for approx. 1.5 h at 80° C. The activated hollow spheres obtained had a diameter of about approx. 3.3 mm and a shell thickness of about approx. 700 &mgr;m. 40 ml (32.88 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 4. 4 TABLE 4 The results of example 4 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0.80 96.12 63.14 79.23 0.94 0.774 60 0.80 94.13 63.00 82.93 0.92 0.754 60 1.60 71.63 48.10 74.17 1.40 1.149 60 1.60 78.28 49.53 73.66 1.53 1.256 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 5 A free-flowing, pelletable catalyst mixture was prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst of 1000 grams of 50% Ni and 50% Al alloy powder (this alloy was melted in an induction furnace and sprayed with water), 75 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The shaped articles were calcined at 700° C. for 2 hours. After the calcining, the tables were activated for 2 hours at 80° C. in 20% sodium hydroxide solution. 40 ml (70.3 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 5. 5 TABLE 5 The results of example 5 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0.80 83.6 36.6 66.3 0.38 0.669 60 0.80 88.2 36.8 65.7 0.40 0.706 60 1.60 62.8 28.6 56.3 0.57 1.005 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 6 A free-flowing, pelletable catalyst mixture was prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst of 1000 grams of 50% Ni and 50% Al alloy powder (this alloy was melted in an induction furnace and sprayed with water), 75 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The shaped articles were calcined at 700° C. for 2 hours. After the calcining, the tables were activated for 2 hours at 80° C. in 20% sodium hydroxide solution. This catalyst was doped with a sodium molybdate solution and the Mo content of the catalyst at the end was 0.2%. 40 ml (70.9 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 6. 6 TABLE 6 The results of example 6 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0.80 95.3 51.4 75.1 0.43 0.763 60 0.80 92.1 47.5 73.1 0.42 0.737 60 1.60 71.4 28.9 48.5 0.64 1.142 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 EXAMPLE 7 A coating solution was prepared by suspending 1730 grams of 53% Ni and 47% Al alloy powder and 130 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) in 1557 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of polystyrene beads with a diameter of about approx. 2 mm, while these were suspended in a stream of air directed upwards. 1 liter of these beads was coated further with an alloy solution. The solution for the second layer comprised 1203 grams of 53% Ni and 47% Al alloy powder, 90 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 1083 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of the abovementioned polystyrene beads precoated with Ni/Al, while these were suspended in a stream of air (nitrogen and other gases can also be used) directed upwards. After the polystyrene beads had been coated with the abovementioned solutions, the beads were heated to 500° C. in order to burn out the polystyrene. The Ni/Al hollow spheres were then heated to 800° C. in order to sinter together the alloy particles and nickel powder. The hollow spheres were then activated in a 20 wt. % sodium hydroxide solution for approx. 1.5 h at 80° C. The activated hollow spheres obtained had a diameter of about approx. 3.3 mm and a shell thickness of about approx. 700 &mgr;m. 40 ml (34.62 grams) of this catalyst were tested in accordance with use example 1 and the results of this experiment are shown in table 7. 7 TABLE 7 The results of example 7 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0.80 99.5 71.0 81.0 0.920 0.796 60 1.60 91.3 44.7 67.9 1.688 1.461 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 USE EXAMPLE 2 The catalytic activities of the catalyst of example 8 during hydrogenation of butinediol (BID) to 1,4-butanediol (BDO) and butenediol (BED) were investigated. For this purpose, 40 ml of catalyst were introduced into a tube reactor and tested in a bubble column process. The temperature of the reaction was 150° C., the concentration of butinediol in water was 50 wt. %, the pH of the reaction solution was brought to 7 with NaHCO 3 and the pressure of the reaction was 60 bar. The throughput of hydrogen was 82.5 l/h and the throughput of butinediol was 0.40 g butinediol/h·ml of catalyst. The product mixture was analysed by GC. 
 EXAMPLE 8 A free-flowing, pelletable catalyst mixture was prepared in accordance with the instructions in EP 0 648 534 A1 for a catalyst of 1000 grams of 50% Ni and 50% Al alloy powder (this alloy was melted in an induction furnace and sprayed with water), 75 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The shaped articles were calcined at 700° C. for 2 hours. After the calcining, the tables were activated for 2 hours at 80° C. in 20% sodium hydroxide solution. This catalyst was doped with a sodium molybdate solution and the Mo content of the catalyst at the end was 0.2%. 40 ml (72.8 grams) of this catalyst were tested in accordance with use example 2 and the results of this experiment are shown in table 8. 8 TABLE 8 The results of example 8 Sel. Activity Activity Pressure Throughput Sel. Without per per &lsqb;bar&rsqb; &lsqb;g BID/ (h · ml cat.)&rsqb; Conversion &lsqb;%&rsqb; &lsqb;%&rsqb; A BED &lsqb;%&rsqb; B weight C volume D 60 0,40 99,4 75,7 85,5 2,18 3,97 60 0,40 99,7 63,1 70,3 2,74 4,99 A % selectivity B % selectivity, where the amount of BED is not counted C Activity per weight &equals; &lsqb;g BDO/h · g cat&rsqb; D Activity per volume &equals; &lsqb;g BDO/h · ml cat&rsqb; 
 USE EXAMPLE 3 The catalytic activity &lsqb;sic&rsqb; of the catalyst of examples 9 and 10 during hydrogenation of a mixture of aromatics from benzene were compared. For this purpose, 11.6 to 11.0 grams of catalyst were introduced into a flask in an autoclave and tested in a liquid phase. The temperature of the reaction was 180° C., the amount of aromatics was 200 grams, The solution was stirred at 1000 rpm and the pressure of the reaction was 35 bar. The activity was calculated by H 2 uptake. 
 EXAMPLE 9 11 . 6 grams of a commercial 10%NI/Al 2 O 3 catalyst were tested in accordance with use example 3. This catalyst showed an activity per catalyst volume of 15.81 ml H 2 /ml cat·h and an activity per catalyst weight of 18.82 ml H 2 /g cat·h. 
 EXAMPLE 10 A coating solution was prepared by suspending 1730 grams of 53% Ni and 47% Al alloy powder and 130 grams of pure nickel powder (99%.Ni and d50&equals;21 &mgr;m) in 1557 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of polystyrene beads with a diameter of about approx. 2 mm, while these were suspended in a stream of air directed upwards. 1 liter of these beads was coated further with an alloy solution. The solution for the second layer comprised 1203 grams of 53% Ni and 47% Al alloy powder, 90 grams of pure nickel powder (99% Ni and d50&equals;21 &mgr;m) and 1083 ml of an aqueous solution with a content of approx. 2 wt. % polyvinyl alcohol. This suspension was then sprayed on to 1,000 ml of the abovementioned polystyrene beads precoated with Ni/Al, while these were suspended in a stream of air (nitrogen and other gases can also be used) directed upwards. After the polystyrene beads had been coated with the abovementioned solutions, the beads were heated to 500° C. in order to burn out the polystyrene. The Ni/Al hollow spheres were then heated to 800° C. in order to sinter together the alloy particles and nickel powder. The hollow spheres were then activated in a 20 wt. % sodium hydroxide solution for approx. 1.5 h at 80° C. The activated hollow spheres obtained had a diameter of about approx. 3.3 mm and a shell thickness of about approx. 700 &mgr;m. 11.0 grams of this catalyst were tested in accordance with use example 3. This catalyst showed an activity per catalyst volume of 29.16 ml H 2 /ml cat·h and an activity per catalyst weight of 36.45 ml H 2 /g cat h.