Hydrogenation Catalyst And Process For Production Thereof By The Use Of Uncalcined Starting Material

• US 20150314273A1
• Filed: 09/25/2013
• Published: 11/05/2015
• Est. Priority Date: 09/28/2012
• Status: Active Grant

• Current Assignee: Clariant International AG (Clariant AG)
• Original Assignee: Clariant International AG (Clariant AG)
• Inventors: PAULUS, Martin, GROSSMANN, Frank, STADLER, Karl-Heinz
• Granted Patent: US 10,035,137 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 33/00 Protection of catalysts, e.g. by coating
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/69 bimodal
• CPC Class Codes: B01J 37/0009 Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/0063 Granulating
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/18 with gases containing free hydrogen
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/125 containing five to twenty-two carbon atoms

Abstract

The invention relates to a process for preparing a shaped Cu—Al catalyst body for the hydrogenation of organic compounds containing a carbonyl function. More particularly, the shaped catalyst body is suitable for the hydrogenation of aldehydes, ketones and of carboxylic acids or esters thereof, specifically of fatty acids or esters thereof, such as fatty acid methyl esters, to the corresponding alcohols such as butanediol. The present invention further relates to Cu—Al catalysts obtainable by the preparation process.

Claims

1. A process for producing a tableted shaped catalyst body, which comprises the steps of:

(a) combining of (i) at least one aqueous solution of copper compounds, aluminum compounds and optionally transition metal compounds and (ii) at least one aqueous carbonate-containing solution to form a precipitate, isolation of the precipitate, optionally washing of the isolated precipitate and drying of the isolated precipitate to give a dried precipitate, and

(b) tableting of the dried precipitate obtained in step (a).

2. The process according to claim 1, wherein step (b) comprises:

(b1) calcination of dried precipitate obtained in step (a) at a temperature in the range from 250 to 900°

C., to give a calcined precipitate,

(b2) mixing of dried precipitate obtained in step (a) with calcined precipitate obtained in step (b1) in a weight ratio of dried precipitate to calcined precipitate in the range from 2;

98 to 98;

2, to give a mixture, and

(b3) tableting of the mixture obtained in step (b2).

3. The process according to claim 2, wherein a lubricant is added to the uncalcined precipitate obtained from step (a) or to the mixture obtained from step (b2) in an amount of from 0.1 to 5% by weight, based on the total weight of the composition to be tableted, before tableting.

4. The process according to claim 3, wherein the lubricant is added in an amount of from 0.5 to 5% by weight, based on the total weight of the composition to be tableted.

5. The process according to claim 3, wherein the lubricant is graphite.

6. The process according to claim 1, wherein the pore volume of the tableted shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.1 to 0.6 cm³/g.

7. The process according to claim 1, which comprises the following step:

(c) after-calcination of the tableted shaped catalyst body at a temperature in the range from 250 to 900°

C., to give an after-calcined shaped catalyst body.

8. The process according to claim 7, wherein the pore volume of the after-calcined shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.15 to 0.70 cm³/g.

9. The process according to claim 6, which comprises the following step:

(d) reduction of the tableted shaped catalyst body obtained from step (b) and/or the after-calcined shaped catalyst body obtained from step (c) to give a reduced shaped catalyst body.

10. The process according to claim 9, wherein reduction is effected by means of hydrogen.

11. The process according to claim 9, wherein reduction is carried out at a temperature in the range from 150°

C. to 400°

C.

12. The process according to claim 9, wherein reduction is carried out over a period of from 1 hour to 10 days.

13. The process according to claim 9, wherein

(a) the reduced shaped catalyst body is covered with a liquid with exclusion of air after reduction, where the liquid is selected from the group consisting of isodecanol, Nafol, fatty alcohols, hexadecane, 2-ethylhexanol, propylene glycol and mixtures thereof, or

(b) a mixture of an oxygen-containing gas and an inert gas, wherein the oxygen-containing gas is oxygen and the inert gas is argon or nitrogen is fed into the reduction reactor containing the reduced shaped catalyst body, preferably at a reactor temperature of less than 100°

C. where the concentration of oxygen in the mixture during introduction is from 0.001% by volume to 50% by volume and is increased from about 0.02% by volume to about 21% by volume.

14. The process according to claim 1, wherein the precipitate obtained in step (a) has a carbonate content of up to 20% by weight inclusive, based on the total weight of the dried precipitate obtained in step (a).

15. The process according to claim 1, wherein the precipitate obtained in step (a) contains at least 5% by weight of Cu hydroxocarbonate.

16. The process according to claim 1, wherein the copper compound is selected from the group consisting of copper, copper oxide (Cu₂O and/or CuO), copper nitrate, copper sulfate, copper carbonate, copper hydroxocarbonate, copper acetate, copper halides copper chloride, copper bromide or copper iodide and mixtures thereof.

17. The process according to claim 1, wherein the aluminum compound is selected from the group consisting of aluminum, aluminum hydroxide, aluminum oxide hydrate (boehmite), alkali metal aluminates, aluminum oxide (Al₂O₃), aluminum nitrate, aluminum sulfate, aluminum halides and mixtures thereof.

18. The process according to claim 1, wherein the transition metal compound is selected from the group consisting of Zn, Ti, Mn, Ni, Cr, Fe, Co, Mo, Ce and Zr and mixtures thereof.

19. The process according to claim 1, wherein the carbonate-containing solution is obtainable using at least one alkali metal carbonate, alkaline earth metal carbonate and/or ammonium carbonate and/or at least one alkali metal hydrogen carbonate, alkaline earth metal hydrogen carbonate and/or ammonium hydrogen carbonate.

20. A shaped catalyst body obtained by a process according to claim 1.

21. A reduced shaped catalyst body which has been obtained by a process according to claim 1 and has a pore volume of from 0.20 to 0.80 cm³/g.

22. The shaped catalyst body according to claim 21 which contains Cu(0) in a proportion in the range from 5 to 70% by weight, based on the shaped catalyst body.

23. The shaped catalyst body according to claim 20 which has a bimodal pore radius distribution which has a first maximum in the range from 10 to 30 nm and/or a second maximum in the range from 500 to 2500 nm.

24. The shaped catalyst body according to claim 23, wherein from 5 to 30 of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 500 to 2500 nm and/or from 40 to 90%, of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.

26. A shaped catalyst body according to any of claim 20 for the hydrogenation of organic compounds.

27. The shaped catalyst body according to claim 26 for hydrogenation, wherein the organic compounds have at least one carbonyl group.

28. The shaped catalyst body according to claim 26 for the hydrogenation of aldehydes, ketones or monocarboxylic, dicarboxylic and polycarboxylic acids and/or esters thereof.

29. The process according to claim 2, wherein step (b1) calcination of dried precipitate obtained in step (a) at a temperature in the range from 300 to 750°

C., to give a calcined precipitate.

30. The process according to claim 2, wherein step (b1) calcination of dried precipitate obtained in step (a) at a temperature in the range from 600 to 750°

C., to give a calcined precipitate.

31. The process according to claim 2, wherein the weight ratio of dried precipitate to calcined precipitate is in the range of from 10:

90 to 90;

10 to give a mixture.

32. The process according to claim 2, wherein the weight ratio of dried precipitate to calcined precipitate is in the range of from 15:

85 to 85;

15 to give a mixture.

33. The process according to claim 2, wherein the weight ratio of dried precipitate to calcined precipitate is in the range of from 20:

80 to 50;

50 to give a mixture.

34. The process according to claim 3, wherein the lubricant is added in an amount of from 1 to 4% by weight, based on the total weight of the composition to be tableted.

35. The process according to claim 1, wherein the pore volume of the tableted shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.13 to 0.40 cm³/g.

36. The process according to claim 1, wherein the pore volume of the tableted shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.15 to 0.25 cm³/g.

37. The process according to claim 6, wherein the step (c) takes place at a temperature in the range from 300 to 750°

C.

38. The process according to claim 6, wherein the step (c) takes place at temperature in the range of 600 to 750°

C.

39. The process according to claim 6, wherein the step (c) takes places at at temperature of about 750°

C.

40. The process according to claim 7, wherein the pore volume of the after-calcined shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.17 to 0.50 cm³/g.

41. The process according to claim 7, wherein the pore volume of the after-calcined shaped catalyst body, determined by the Hg intrusion method in accordance with DIN 66133, is from 0.19 to 0.4 cm³/g.

42. The process according to claim 9, wherein reduction is carried out at a temperature in the range from 180°

C. to 250°

C.

43. The process according to claim 9, wherein reduction is carried out at a temperature in the range from 190°

C. to 210°

C.

44. The process according to claim 9, wherein reduction is carried out at a temperature of about 200°

C.

45. The process according to claim 9, wherein reduction is carried out over a period of from 2 hours to 72 hours.

46. The process according to claim 9, wherein reduction is carried out over a period of from 24 to 48 hours.

47. The process according to claim 9, wherein (a) the reduced shaped catalyst body is covered with a liquid with exclusion of air after reduction, where the liquid is isodecanol.

48. The process according to claim 13, wherein the step (b) a mixture of an oxygen-containing gas and an inert gas, wherein the oxygen-containing gas is oxygen and the inert gas is argon or nitrogen, is fed into the reduction reactor containing the reduced shaped catalyst body, preferably at a reactor temperature in the range from 30°

C. to 50°

C., where the concentration of oxygen in the mixture during introduction is from 0.001% by volume to 50% by volume and is increased from about 0.02% by volume to about 21% by volume.

49. The process according to claim 1, wherein the precipitate obtained in step (a) has a carbonate content range from 5% by weight to 18% by weight, based on the total weight of the dried precipitate obtained in step (a).

50. The process according to claim 1, wherein the precipitate obtained in step (a) has a carbonate content in the range from 6% by weight to 15% by weight, based on the total weight of the dried precipitate obtained in step (a).

53. The process according to claim 1, wherein the precipitate obtained in step (a) contains from 15 to 70% by weight, of Cu hydroxocarbonate.

54. The process according to claim 1, wherein the copper compound is selected from the group consisting of copper oxide, copper nitrate, copper chloride, copper carbonate, copper hydroxocarbonate, copper acetate, copper sulfate and mixtures thereof.

55. The process according to claim 1, wherein the aluminum compound is selected from the group consisting of aluminum nitrate, aluminum hydroxide, aluminum oxide hydrate, aluminum chloride, sodium aluminate, aluminum oxide and mixtures thereof.

56. The process according to claim 1, wherein the transition metal compound is selected from the group consisting of Mn, Zn, Ce, Zr and mixtures thereof.

57. The process according to claim 1, wherein the transition metal compound is from among compounds of Mn.

58. The process according to claim 1, wherein the carbonate-containing solution is obtainable using sodium carbonate and/or sodium hydrogen carbonate.

59. A reduced shaped catalyst body which has been obtained by a process according to claim 1 and has a pore volume of from 0.22 to 0.70 cm³/g.

60. A reduced shaped catalyst body which has been obtained by a process according to claim 1 and has a pore volume of from 0.25 to 0.35 cm³/g.

61. The shaped catalyst body according to claim 21 which contains Cu(0) in a proportion in the range from 10 to 70% by weight, based on the shaped catalyst body.

62. The shaped catalyst body according to claim 21 which contains Cu(0) in a proportion in the range from 20 to 50% by weight, based on the shaped catalyst body.

63. The shaped catalyst body according to claim 20 which has a bimodal pore radius distribution which has a first maximum in the range from 15 to 25 nm and in particular at about 20 nm, and/or a second maximum in the range from 700 to 2000 nm.

64. The shaped catalyst body according to claim 20 which has a bimodal pore radius distribution with a first maximum in at about 20 nm, and/or a second maximum in the range from 800 to 1000 nm.

65. The shaped catalyst body according to claim 23, wherein from 10 to 25%, of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 500 to 2500 nm and/or from 45 to 80% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.

66. The shaped catalyst body according to claim 23, wherein from 15 to 25%, of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 50 to 70% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.

25. A tableted shaped catalyst body containing copper, aluminum and optionally a transition metal selected from the group consisting of Zn, Si, Ti, Mn, Ni, Cr, Fe, Co, Mo, Ca, Ba, Ce and Zr and mixtures thereof,

wherein from 5 to 30 of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 500 to 2500 nm and/or from 40 to 90% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.

51. The process according to, wherein the precipitate obtained in step (a) has a carbonate content in the range from 8 to 12% by weight, based on the total weight of the dried precipitate obtained in step (a).

52. The process according to, wherein the precipitate obtained in step (a) contains from 10 to 80% by weight, of Cu hydroxocarbonate.

67. A tableted shaped catalyst body containing copper, aluminum and optionally a transition metal selected from the group consisting of Mn, Zn, Ce, Zr and mixtures thereof,

wherein from 10 to 25% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 500 to 2500 nm and/or from 45 to 80% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.

68. A tableted shaped catalyst body containing copper, aluminum and optionally a transition metal selected from the group consisting of Mn, Zn, Ce, Zr and mixtures thereof,

wherein from 15 to 25% of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 500 to 2500 nm and/or from 50 to 70%, of the pore volume of the shaped catalyst body is formed by pores having a pore radius in the range from 5 to 50 nm.