Metal powderdous catalyst for hydrogenation processes

Abstract

The present invention is related to a new metal powder catalytic system (catalyst), its production and its use in hydrogenation processes.

Claims

1. A method for selective hydrogenation of an organic starting material comprised of a compound of formula (I): ##STR00005## wherein, R.sub.1 is linear or branched C.sub.1-C.sub.35 alkyl or linear or branched C.sub.5-C.sub.35 alkenyl moiety, wherein the C chain can be substituted, R.sub.2 is linear or branched C.sub.1-C.sub.4 alkyl, wherein the C chain can be substituted, and R.sub.3 is H or —C(CO)C.sub.1-C.sub.4alkyl, wherein the method comprises subjecting the organic starting material comprised of the compound of formula (I) to selective hydrogenation conditions in the presence of hydrogen and a powderous catalytic system comprising a metal alloy carrier which is impregnated with Pd and coated by a metal oxide layer comprised of CeO.sub.2, wherein the metal alloy carrier comprises, based on the total weight of the metal alloy: (i) 45 wt. % to 80 wt-% of Fe, (ii) 0.5 wt. % to 30 wt. % of Ni, (iii) 0 wt. % to 20 wt. % of Co, (iv) 0 wt. % to 8 wt. % of Mo, and (v) 0 wt. % to 30 wt-% of Cr.

2. The method according to claim 1, wherein the organic starting material comprises at least one compound selected from the group consisting of: ##STR00006##

3. The method according to claim 1, wherein the hydrogen of the hydrogenation step is H.sub.2 gas.

4. The method according to claim 1, wherein the metal alloy carrier comprises, based on the total weight of the metal alloy: (i) 45 wt. % to 75 wt. % of the Fe, (ii) 15 wt. % to 30 wt. % of the Ni, (iii) 5 wt. % to 20 wt. % of the Co, and (iv) 3 wt. % to 8 wt. % of the Mo.

5. The method according to claim 1, wherein the metal alloy carrier comprises, based on the total weight of the metal alloy: (i) 60 wt. % to 70 wt. % of the Fe, (ii) 15 wt. % to 25 wt. % of the Ni, (iii) 5 wt. % to 15 wt. % of the Co, and (iv) 3.5 wt. % to 7 wt. % of the Mo.

6. The method according to claim 1, wherein the metal alloy carrier comprises, based on the total weight of the metal alloy: (i) 60 wt. % to 80 wt. % of the Fe, (ii) 1 wt. % to 30 wt. % of the Cr, and (iii) 0.5 wt. % to 10 wt. % of the Ni.

7. The method according to claim 1, wherein the metal alloy carrier comprises at least one further metal selected from the group consisting of Cu, Mn, Si, Ti, Al and Nb.

8. The method according to claim 1, wherein metal alloy carrier comprises carbon.

9. The method according to claim 1, wherein the metal alloy carrier is coated with at least one further metal oxide comprising an oxide of a metal selected from the group consisting of Cr, Mn, Zn, Cu and Al.

10. A selective hydrogenation reaction system comprising: (a) an organic reactant comprised of a compound of formula (I): ##STR00007## wherein, R.sub.1 is linear or branched C.sub.1-C.sub.35 alkyl or linear or branched C.sub.5-C.sub.35 alkenyl moiety, wherein the C chain can be substituted, R.sub.2 is linear or branched C.sub.1-C.sub.4 alkyl, wherein the C chain can be substituted, and R.sub.3 is H or —C(CO)C.sub.1-C.sub.4alkyl, and (b) a metal alloy carrier which is impregnated with Pd and coated by a metal oxide layer comprised of CeO.sub.2, wherein the metal alloy carrier comprises, based on the total weight of the metal alloy: (i) 45 wt. % to 80 wt-% of Fe, (ii) 0.5 wt. % to 30 wt. % of Ni, (iii) 0 wt. % to 20 wt. % of Co, (iv) 0 wt. % to 8 wt. % of Mo, and (v) 0 wt. % to 30 wt-% of Cr.

11. The selective hydrogenation reaction system according to claim 10, wherein the metal alloy carrier comprises, based on total weight of the metal alloy: (i) 45 wt. % to 75 wt. % of the Fe, (ii) 15 wt. % to 30 wt. % of the Ni, (iii) 5 wt. % to 20 wt. % of the Co, and (iv) 3 wt. % to 8 wt. % of the Mo.

12. The selective hydrogenation reaction system according to claim 10, wherein the metal alloy carrier comprises, based on total weight of the metal alloy: (i) 60 wt. % to 70 wt. % of the Fe (ii) 15 wt. % to 25 wt. % of the Ni, (iii) 5 wt. % to 15 wt. % of the Co, and (iv) 3.5 wt. % to 7 wt. % of the Mo.

13. The selective hydrogenation system according to claim 10, wherein the metal alloy carrier comprises, based on total weight of the metal alloy: (i) 60 wt. % to 80 wt. % of the Fe, (ii) 1 wt. % to 30 wt. % of the Cr, and (iii) 0.5 wt. % to 10 wt. % of the Ni.

14. The selective hydrogenation system according to claim 10, wherein the metal alloy carrier comprises at least one further metal selected from the group consisting of Cu, Mn, Si, Ti, Al and Nb.

15. The selective hydrogenation system according to claim 10, wherein metal alloy carrier comprises carbon.

16. The selective hydrogenation reaction system according to claim 10, wherein the metal alloy carrier is coated with at least one further metal oxide comprising an oxide of a metal selected from the group consisting of Cr, Mn, Zn, Cu and Al.

Description

EXAMPLES

Example 1

Preparation of Metal Powder Catalyst

(1) The EOS MaragingSteel MS1 was heated at 450° C. for 3 h in air. For preparation of the primer solution, Ce(NO.sub.3).sub.3.6H.sub.2O (508 mmol) and 700 mL water were added to a beaker. The mixture was stirred until the salt was completely dissolved. The solution was heated to 90° C. and ZnO (508 mmol) was slowly added to the solution. The stirring was maintained at 90° C. and 65% nitric acid was added dropwise until all ZnO was completely dissolved (final c.sub.HNO3=1 M). Afterwards the solution was cooled to room temperature and filtrated through a 0.45 μm membrane filter. The deposition of ZnO/CeO.sub.2 was performed by adding thermally treated MS1 powder (10.0 g) to 25 mL of the precursor solution. This mixture was stirred at room temperature for 15 min. Afterwards the suspension was filtered via a 0.45 μm membrane filter and dried under vacuum at 40° C. for 2 h followed by calcination at 450° C. for 1 h. This process was repeated until the desired number of primer layers had been deposited.

(2) Sodium tetrachloropalladate(II) (0.48 mmol) was dissolved in 133 mL of Millipore water and PEG-MS40 (3.2 mmol) was added. The solution was heated to 60° C. and sonication was started at this temperature. A fresh prepared solution of sodium formate (16 mM, 67 mL) were added. The solution was sonicated for further 60 minutes at this temperature and then cooled to room temperature followed by addition of the coated MS1 (10.0 g). The suspension was stirred at room temperature for 60 minutes followed by filtration via a 0.45 μm membrane filter. The residue was washed with water and dried under vacuum at 40° C. for 2 h. The catalyst was subjected to a temperature treatment between 150° C.-350° C. for 4 h (temperature ramp—10°/min) under H.sub.2—Ar flow (1:9; total flow rate—450 ml/min).

Hydrogenation Examples

Selective Semi-Hydrogenation of an Alkyne to an Alkene

(3) 40.0 g of 2-methyl-3-butyne-2-ol (MBY) and the desired amount of metal powder catalyst were added to a 125 mL autoclave reactor. Isothermal conditions during the hydrogenation reaction (338 K) were maintained by a heating/cooling jacket. The reactor was equipped with a gas-entrainment stirrer. After purging with nitrogen, the reactor was purged with hydrogen and heated to the desired temperature. The pressure in the reactor (3.0 bar) was maintained during the experiments by supplying hydrogen from external reservoir. The reaction mixture was stirred at 1000 rpm. Liquid samples (200 μL) were periodically withdrawn from the reactor starting at a minimum conversion of 95% of MBY and analysed by gas-chromatography (HP 6890 series, GC-system). Selectivity is reported as amount of the desired semi-hydrogenation product (2-methyl-3-butene-2-ol (MBE)) compared to all reaction products.

(4) Tables 1a and 1b: Test Results of Different Oxide Layers, Pd-Source, Pd-Amount and Pd-Reduction

(5) The catalysts prepared according to the process described in the example above and they were thermal activated as mentioned in the preparation procedure Reaction conditions: 500 mg catalyst, 40.0 MBY, 1000 rpm, 3.0 bar H.sub.2, 65° C. Exp. 1 is a comparison example using a oxide layer known from the prior art.

(6) TABLE-US-00001 TABLE 1a Oxide Layer & Pd-source (loading Exp Layer # wt %) Pd-reduction procedure 1 Al.sub.2O.sub.3/ZnO (3) PdCl.sub.2 (0.50) H.sub.2 bubbling (25° C.) 2 CeO.sub.2/ZnO (3) Na.sub.2PdCl.sub.4 (0.50) H.sub.2 bubbling (25° C.) 3 CeO.sub.2/ZnO (5) Na.sub.2PdCl.sub.4 (0.35) HCOONa, PEG, sonication (60° C.)

(7) TABLE-US-00002 TABLE 1b Conv. Time Select. Activity Exp (%) (min) (%) (mmol/sg.sub.Pd) 1 99.9 195 95.1 247.1 2 99.7 125 96.0 315.8 3 99.7 107 97.0 535.5

(8) It can be seen that the new metal oxide powders show an improved selectivity and an improved activity.

(9) TABLE-US-00003 TABLE 2 Test results at varying metal oxide layer thickness of CeO.sub.2/ZnO and Pd-amount (Na.sub.2PdCl.sub.4 reduced with HCOONa/sonication/PEG at 60° C.), Metal oxide Pd-loading Conv Time Select. Activity Exp layers # (wt %) (%) (min) (%) (mmol/sg.sub.Pd) 4 3 0.20 99.7 119 96.64 733.6 5 3 0.35 99.6 92 96.66 582.5 6 3 0.50 99.7 134 96.33 353.0 7 5 0.20 99.6 120 96.70 630.6 8 5 0.35 99.7 112 96.84 508.8 9 5 0.50 99.6 105 96.28 366.4 10 8 0.20 99.7 151 96.73 553.1 11 8 0.35 99.7 171 96.44 474.1 12 8 0.50 99.7 157 96.22 355.8 The catalysts prepared according to the process described in the example above and they were thermal activated as mentioned in the preparation procedure Reaction conditions: 500 mg catalyst, 40.0 MBY, 1000 rpm, 3.0 bar H.sub.2, 65° C.

(10) TABLE-US-00004 TABLE 3 Test results at varying thermal activation temperatures; 5 layersCeO.sub.2/ZnO and 0.35 wt % Pd (Na.sub.2PdCl.sub.4 reduced with HCOONa/sonication/PEG at 60° C. Activation Select. Activity Exp. temp (° C.) Conv. (%) Time (min) (%) (mmol/sg.sub.Pd) 13 200 99.7 103 96.9 538.1 14 250 99.7 107 97.0 535.5 15 300 99.9 112 96.6 508.8 16 350 99.8 127 96.2 464.0 The catalysts prepared according to the process described in the example above. Reaction Conditions: 500 mg catalyst, 40.0 MBY, 1000 rpm, 3.0 bar H.sub.2, 65° C.