Process for the condensation of aldehydes

• US 4,701,562 A
• Filed: 06/25/1986
• Issued: 10/20/1987
• Est. Priority Date: 06/25/1986
• Status: Expired due to Fees

• Current Assignee: UOP Des Plaines IL A NY General Partnership
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Olson, Kurt D.
• Primary Examiner(s): Reamer, James H.
• Application Number:
  US06/878,201
• Time in Patent Office: 482 Days
• Field of Search: 568/390, 568/391, 568/345, 568/313, 568/400, 568/401, 568/462, 568/463, 568/464, 568/465, 568/396, 568/347, 568/350, 568/353, 568/461
• US Class Current: 568/390
• CPC Class Codes: C07C 45/002 by dehydrogenation
• CPC Class Codes: C07C 45/62 by hydrogenation of carbon-to-carbon double or triple bonds
• CPC Class Codes: C07C 45/73 combined with hydrogenation
• CPC Class Codes: C07C 45/74 combined with dehydration
• CPC Class Codes: C07C 45/75 Reactions with formaldehyde

Abstract

Aldehydes can be condensed with ketones or aldehydes to produce higher aldehydes or ketones by contacting the materials to be condensed with a nonzeolitic molecular sieve. The condensation may be carried out in the presence of hydrogen to give as product a saturated aldehyde or ketone. The ketone and/or aldehyde may be generated in situ by dehydrogenation of an alcohol, and the hydrogen thus liberated used to effect hydrogenation of the immediate unsaturated product of the condensation, thereby producing as the final product a saturated aldehyde or ketone. The non-zeolitic molecular sieves can achieve improved conversion rates and selectivities as compared with conventional catalysts for the reaction.

Claims

1. A process for condensing an aldehyde with a carbonyl compound selected from the group consisting of ketones and aldehydes, which process comprises contacting the aldehyde and the carbonyl compound with a non-zeolitic molecular sieve, the contacting of the aldehyde and the carbonyl compound with the non-zeolitic molecular sieve being effected under conditions effective to cause condensation of the aldehyde and the carbonyl compound.

2. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises a silicoaluminophosphate molecular sieve as claimed in U.S. Pat. No. 440,871.

3. A process according to claim 2 wherein the silicoaluminophosphate molecular sieve comprises any one or more of SAPO-5, SAPO-11, SAPO-31, SAPO-34, SAPO-36, SAPO-37, SAPO-40 and SAPO-41.

4. A process according to claim 3 wherein the silicoaluminophosphate molecular sieve comprises SAPO-5.

5. A process according to claim 3 wherein the silicoaluminophosphate molecular sieve comprises SAPO-11.

6. A process according to claim 3 wherein the silicoaluminophosphate molecular sieve comprises SAPO-34.

7. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises a silicoaluminophosphate molecular sieve comprising at least one element capable of forming a framework tetrahedral oxide and selected from the group consisting of arsenic, beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium and zinc.

8. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a titanium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of titanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39. ______________________________________

9. A process according to claim 8 wherein the titanium silicoaluminophosphate molecular sieve comprises TiAPSO-5.

10. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a magnesium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.39 0.59 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

11. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a manganese silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of manganese, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

12. A process according to claim 11 wherein the silicoaluminophosphate molecular sieve comprises MnAPSO-31.

13. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a cobalt silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of cobalt, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

14. A process according to claim 13 wherein the aluminophosphate molecular sieve comprises CoAPSO-34.

15. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a zinc silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of zinc, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

16. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is an iron silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of iron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

17. A process according to claim 16 wherein the silicoaluminophosphate molecular sieve comprises FeAPSO-5.

18. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a cobalt/manganese silicoaluminophosphate molecular sieve wherein the mole fractions "u", "v", "x", "y" and "z" of cobalt, manganese, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "u", "v", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z", where w=u+v:

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.37 0.03 B 0.37 0.60 0.03 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39. ______________________________________

19. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a cobalt/manganese/magnesium silicoaluminophosphate molecular sieve wherein the mole fractions "t", "u", "v", "x", "y" and "z" of cobalt, manganese, magnesium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "t", "u", "v", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z" (where w=t+u+v):

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.36 0.04 B 0.36 0.60 0.04 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39. ______________________________________

20. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is an arsenic silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of arsenic, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

21. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a boron silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of boron, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

22. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a beryllium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of beryllium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

23. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a chromium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y"and "z" of chromium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

24. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a gallium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of gallium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

25. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a germanium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of germanium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

26. A process according to claim 7 wherein the silicoaluminophosphate molecular sieve is a lithium silicoaluminophosphate molecular sieve wherein the mole fractions "w", "x", "y" and "z" of lithium, aluminum, phosphorus and silicon, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "w", "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, said points A, B, C, D and E representing the following values for "w", "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y (z + w) ______________________________________ A 0.60 0.38 0.02 B 0.38 0.60 0.02 C 0.01 0.60 0.39 D 0.01 0.01 0.98 E 0.60 0.01 0.39 ______________________________________

27. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises an aluminophosphate molecular sieve as claimed in U.S. Pat. No. 4,310,440.

28. A process according to claim 27 wherein the aluminophosphate molecular sieve comprises any one or more of AlPO₄ -5, AlPO₄ -11, AlPO₄ -18, and AIPO₄ -31.

29. A process according to claim 28 wherein the aluminophosphate molecular sieve comprises AlPO₄ -11.

30. A process according to claim 28 wherein the aluminophosphate molecular sieve comprises AlPO₄ -18.

31. A process according to claim 28 wherein the aluminophosphate molecular sieve comprises AlPO₄ -31.

32. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises an aluminophosphate molecular sieve as claimed in U.S. Pat. No. 4,567,029.

33. A process according to claim 32 wherein the aluminophosphate molecular sieve comprises MgAPO-36.

34. A process according to claim 32 wherein the aluminophosphate molecular sieve comprises CoAPO-5.

35. A process according to claim 32 wherein the aluminophosphate molecular sieve comprises MnAPO-41.

36. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises an iron aluminophosphate molecular sieve as claimed in U.S. Pat. No. 4,554,143.

37. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises a titanium aluminophosphate molecular sieve as claimed in U.S. Pat. No. 4,500,651.

38. A process according to claim 1 wherein the non-zeolitic molecular sieve comprises an aluminophosphate molecular sieve containing at least one element "M" capable of forming a framework tetrahedral oxide, the element "M" being selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium and lithium, subject to the proviso that, when "M" denotes two elements the second element is selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium, cobalt, iron, magnesium, manganese, titanium and zinc.

39. A process according to claim 38 wherein the aluminophosphate molecular sieve is an arsenic aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of arsenic, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the hexagonal compositional area defined by points A, B, C, D, E and F, said points A, B, C, D, E and F representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.39 0.01 0.60 D 0.60 0.01 0.39 E 0.60 0.39 0.01 F 0.39 0.60 0.01. ______________________________________

40. A process according to claim 38 wherein the aluminophosphate molecular sieve is a boron aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of boron, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, the points A, B, C, D and E representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.02 0.60 0.38 B 0.02 0.38 0.60 C 0.39 0.01 0.60 D 0.98 0.01 0.01 E 0.39 0.60 0.01. ______________________________________

41. A process according to claim 38 wherein the aluminophosphate molecular sieve is a beryllium aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of beryllium, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the hexagonal compositional area defined by points A, B, C, D, E and F, the points A, B, C, D, E and F representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.39 0.01 0.60 D 0.60 0.01 0.39 E 0.60 0.39 0.01 F 0.39 0.60 0.01. ______________________________________

42. A process according to claim 38 wherein the aluminophosphate molecular sieve is a chromium aluminophosphate molecular sieve wherein the mole fraction of chromium is at least 0.01.

43. A process according to claim 38 wherein the aluminophosphate molecular sieve is a gallium aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of gallium, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the hexagonal compositional area defined by points A, B, C, D, E and F, the points A, B, C, D, E and F representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.34 0.65 C 0.34 0.01 0.65 D 0.60 0.01 0.39 E 0.60 0.39 0.01 F 0.39 0.60 0.01. ______________________________________

44. A process according to claim 38 wherein the aluminophosphate molecular sieve is a germanium aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of germanium, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, the points A, B, C, D and E representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.47 0.52 C 0.94 0.01 0.05 D 0.98 0.01 0.01 E 0.39 0.60 0.01. ______________________________________

45. A process according to claim 38 wherein the aluminophosphate molecular sieve is a lithium aluminophosphate molecular sieve wherein the mole fractions "x", "y" and "z" of lithium, aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.01, the mole fractions "x", "y" and "z" being within the hexagonal compositional area defined by points A, B, C, D, E and F, the points A, B, C, D, E and F representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.01 0.60 0.39 B 0.01 0.39 0.60 C 0.39 0.01 0.60 D 0.60 0.01 0.39 E 0.60 0.39 0.01 F 0.39 0.60 0.01. ______________________________________

46. A process according to claim 38 wherein the aluminophosphate molecular sieve is a mixed-element aluminophosphate molecular sieve having a framework structure of MO₂ⁿ, AlO₂^- and PO₂⁺ tetrahedral units, wherein MO₂ⁿ represents at least two different elements present as tetrahedral units "MO₂ⁿ " with charge "n", where "n" may be -3, -2, -1, 0 or +1, one of the elements "M" being selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium, while a second one of the elements "M" is selected from the group consisting of cobalt, iron, magnesium, manganese, titanium and zinc, and wherein the mole fractions "x", "y" and "z" of the elements "M", aluminum and phosphorus, respectively, present as tetrahedral oxides each have a value of at least 0.02, 0.01 and 0.01, respectively, the mole fractions "x", "y" and "z" being within the pentagonal compositional area defined by points A, B, C, D and E, the points A, B, C, D and E representing the following values for "x", "y" and "z":

space="preserve" listing-type="tabular">______________________________________ Mole Fraction Point x y z ______________________________________ A 0.02 0.60 0.38 B 0.02 0.38 0.60 C 0.39 0.01 0.60 D 0.98 0.01 0.01 E 0.39 0.60 0.01. ______________________________________

47. A process according to claim 1 wherein the carbonyl compound is an aldehyde.

48. A process according to claim 47 wherein each aldehyde contains from one to eight carbon atoms, and the condensation product contains less than about 10 carbon atoms.

49. A process according to claim 48 wherein both the aldehyde and the carbonyl compound are acetaldehyde and the condensation product comprises crotonaldehyde.

50. A process according to claim 49 which is carried out at a pressure of from about atmospheric pressure to about 1000 psig.

51. A process according to claim 49 which is carried out at a temperature of from about 150°

C. to about 400°

C.

52. A process according to claim 49 which is carried out at a weight hourly space velocity of liquid acetaldehyde in the range of from about 0.2 to about 5.0.

53. A process according to claim 49 which is carried out with the acetaldehyde in the gaseous phase.

54. A process according to claim 49 which is carried out at an acetaldehyde conversion of at least about 10%.

55. A process according to claim 49 which is carried out at a selectivity to crotonaldehyde of at least about 90%.

56. A process according to claim 48 wherein both the aldehyde and the carbonyl compound are n-butyraldehyde and the condensation product comprises 2-ethylhex-2-enal.

57. A process according to claim 56 wherein the non-zeolitic molecular sieve has, in its calcined form, an adsorption of isobutane of at least about 2 percent by weight of the non-zeolitic molecular sieve at a partial pressure of 500 torr and a temperature of 20°

C.

58. A process according to claim 57 wherein the non-zeolitic molecular sieve has, in its calcined form, an adsorption of isobutane of at least about 4 percent by weight of the non-zeolitic molecular sieve at a partial pressure of 500 torr and a temperature of 20°

C.

59. A process according to claim 56 which is carried out at a temperature of from about 150°

C. to about 300°

C.

60. A process according to claim 56 which is carried out with the n-butyraldehyde in the gaseous phase.

61. A process according to claim 1 wherein the carbonyl compound is a ketone.

62. A process according to claim 61 wherein both the aldehyde and the carbonyl compound contain not more than eight carbon atoms, and the condensation product contains less than about ten carbon atoms.

63. A process according to claim 62 wherein the aldehyde is n-butaraldehyde, the ketone is acetone, and the condensation product comprises hept-3-en-2-one.

64. A process according to claim 63 which is carried out at a pressure of from about atmospheric pressure to about 1000 psig.

65. A process according to claim 63 which is carried out at a temperature of from about 150°

C. to about 300°

C.

66. A process according to claim 65 which is carried out at a temperature of from about 175°

C. to about 225°

C. and at substantially atmospheric pressure.

67. A process according to claim 63 which is carried out at a weight hourly space velocity in the range of from about 0.1 to about 50.

68. A process according to claim 67 which is carried out at a weight hourly space velocity in the range of from about 0.5 to about 5.0.

69. A process according to claim 62 wherein the aldehyde is acetaldehyde, the ketone is acetone, and the condensation product comprises pent-3-en-2-one.

70. A process according to claim 62 wherein the aldehyde is formaldehyde, the ketone is acetone, and the condensation product comprises methyl vinyl ketone.

71. A process according to claim 62 wherein the ketone is cyclohexanone and the condensation product comprises a methylene cyclohexanone.

72. A process according to claim 1 which is carried out in the presence of hydrogen and of a hydrogenation catalyst capable of catalyzing the hydrogenation of the unsaturated immediate product of the condensation, thereby producing, as the final product of the condensation, a saturated aldehyde or ketone.

73. A process according to claim 72 wherein the hydrogenation catalyst comprises a transition metal selected from the group consisting of copper, nickel, cobalt, palladium, platinum, rhodium and iridium.

74. A process according to claim 73 wherein the transition metal catalyst comprises nickel or platinum.

75. A process according to claim 73 wherein the transition metal catalyst comprises palladium.

76. A process according to claim 73 wherein the transition metal catalyst is incorporated into the non-zeolitic molecular sieve.

77. A process according to claim 76 wherein the transition metal catalyst is palladium and is present in the non-zeolitic molecular sieve in an amount of from about 0.01 to about 5 per cent by weight of the non-zeolitic molecular sieve.

78. A process according to claim 77 wherein the palladium is present in the non-zeolitic molecular sieve in an amount of from about 0.1 to about 1 per cent by weight of the non-zeolitic molecular sieve.

79. A process according to claim 72 wherein the carbonyl compound is an aldehyde.

80. A process according to claim 79 wherein each of the aldehydes contains not more than eight carbon atoms, and the condensation product contains less than about ten carbon atoms.

81. A process according to claim 80 wherein both the aldehyde and the carbonyl compound are acetaldehyde and the condensation product comprises at least one of n-butyraldehyde.

82. A process according to claim 81 which is carried out with the acetaldehyde in the gaseous phase.

83. A process according to claim 80 wherein both the aldehyde and the carbonyl compound are n-butyraldehyde and the condensation product comprises 2-ethylhexaldehyde.

84. A process according to claim 83 which is carried out at a temperature of from about 150°

C. to about 300°

C.

85. A process according to claim 83 which is carried out with the n-butyraldehyde in the gaseous phase.

86. A process according to claim 72 wherein the carbonyl compound is a ketone.

87. A process according to claim 86 wherein each of the aldehyde and the carbonyl compound contains not more than eight carbon atoms, and the condensation product contains less than about ten carbon atoms.

88. A process according to claim 87 wherein the aldehyde is n-butyraldehyde, the ketone is acetone, and the condensation product comprises methyl amyl ketone.

89. A process according to claim 88 which is carried out at a pressure of from about atmospheric pressure to about 1000 psig.

90. A process according to claim 88 which is carried out at a temperature of from about 150°

C. to about 300°

C.

91. A process according to claim 90 which is carried out at a temperature of from about 175°

C. to about 225°

C. and at substantially atmospheric pressure.

92. A process according to claim 88 which is carried out at a weight hourly space velocity in the range of from about 0.1 to about 50.

93. A process according to claim 92 which is carried out at a weight hourly space velocity in the range of from about 0.3 to about 5.0.

94. A process according to claim 87 wherein the aldehyde is acetaldehyde, the ketone is acetone, and the condensation product comprises methyl propyl ketone.

95. A process according to claim 87 wherein the ketone is acetone, the aldehyde is formaldehyde and the condensation product comprises methyl ethyl ketone.

96. A process according to claim 1 wherein at least one of the aldehyde and the carbonyl compound is formed in situ by feeding to the process a precursor compound capable of being converted to the aldehyde or the carbonyl compound and providing a precursor catalyst effective, under the reaction conditions, to convert the precursor compound to the said at least one of the aldehyde and the carbonyl compound.

97. A process according to claim 96 wherein the precursor compound comprises a compound capable of being dehydrogenated to yield the said at least one of the aldehyde and the carbonyl compound, and the precursor catalyst comprises a dehydrogenation catalyst.

98. A process according to claim 97 wherein the precursor compound comprises a primary alcohol which is dehydrogenated to form an aldehyde.

99. A process according to claim 98 wherein the precursor compound comprises ethanol.

100. A process according to claim 97 wherein the precursor compound comprises a secondary alcohol which is dehydrogenated to form a ketone.

101. A process according to claim 97 wherein the non-zeolitic molecular sieve used to catalyze the condensation of the aldehyde and the carbonyl compound incorporates a hydrogenation catalyst capable of catalyzing the hydrogenation of the unsaturated immediate product of the condensation, whereby the hydrogen generated by the dehydrogenation of the precursor compound is reincorporated into the unsaturated immediate product of the condensation, thereby producing, as the final product of the condensation, a saturated aldehyde or ketone.

102. A process according to claim 1 wherein the aldehyde and the carbonyl compound are mixed with an inert carrier gas while being contacted with the non-zeolitic molecular sieve.

103. A process according to claim 102 wherein the inert carrier gas is nitrogen.