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1. WO2011056247 - CATALYSEURS POUR FABRIQUER DE L'ÉTHANOL À PARTIR D'ACIDE ACÉTIQUE

Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

[ EN ]

A catalyst comprising a first metal, a silicaceous support, and at least one metasilicate support modifier.

The catalyst of claim 1 , wherein the at least one metasilicate support modifier is selected from the group consisting of (i) alkaline earth metal metasilicates, (ii) alkali metal metasilicates, (iii) Group IIB metal metasilicates, (iv) Group IIIB metal metasilicates, and mixtures thereof.

The catalyst of claim 1 , wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten.

The catalyst of claim 1, wherein the first metal is present in an amount of from 0.1 to 25 wt.%, based on the total weight of the catalyst.

The catalyst of claim 1, wherein the at least one metasilicate support modifier is selected from metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, and zinc.

The catalyst of claim 1 , wherein the at least one metasilicate support modifier comprises CaSi03.

The catalyst of claim 1, wherein the at least one metasilicate support modifier is present in an amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.

The catalyst of claim 1, wherein the silicaceous support is present in an amount of 25 wt.% to 99 wt.%, based on the total weight of the catalyst.

The catalyst of claim 1, wherein the silicaceous support has a surface area of from 50 m2/g to 600 m2/g.

10. The catalyst of claim 1, wherein the silicaceous support is selected from the group consisting of silica, silica alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof.

11. The catalyst of claim 10, wherein the silicaceous support contains less than 1 wt.% of aluminum, based on the total weight of the catalyst.

12. The catalyst of claim 1 , wherein the first metal is selected from the group consisting of Group IB, IIB, IIIB, IVB, VB, VIB, VIIB, or VIII transitional metal, a lanthanide metal, an actinide metal or a metal from any of Groups IIIA, IV A, VA, or VIA.

13. The catalyst of claim 12, further comprising a second metal different from the first metal.

14. The catalyst of claim 13, wherein the first metal is platinum and the second metal is tin.

15. The catalyst of claim 14, wherein the molar ratio of platinum to tin is from 0.4:0.6 to 0.6:0.4.

16. The catalyst of claim 13 , wherein the first metal is palladium and the second metal is rhenium.

17. The catalyst of claim 16, wherein the molar ratio of rhenium to palladium is from

0.7:0.3 to 0.85:0.15.

18. The catalyst of claim 13, wherein the second metal is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel.

19. The catalyst of claim 13, wherein the second metal is present in an amount of from 0.1 to 10 wt.%, based on the total weight of the catalyst.

20. The catalyst of claim 13, wherein the catalyst further comprises a third metal different from the first metal and the second metal.

21. The catalyst of claim 20, wherein the third metal is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin, and rhenium.

22. The catalyst of claim 20, wherein the third metal is present in an amount of 0.05 and 4 wt.%, based on the total weight of the catalyst.

23. The catalyst of claim 1, wherein the catalyst is suitable for use as a hydrogenation catalyst in converting acetic acid to ethanol and yields an acetic acid conversion of at least 10%.

24. The catalyst of claim 23, wherein the catalyst has a selectivity to ethanol of at least 80%.

25. The catalyst of claim 24, wherein the catalyst has a selectivity to methane, ethane, and carbon dioxide of less than 4%.

26. The catalyst of claim 24, wherein the catalyst has a productivity that decreases less than 6% per 100 hours of catalyst usage.

27. A catalyst satisfying the formula:

PtvPdwRexSnyCapSiqOr,

wherein:

(i) the ratio of v.y is between 3:2 and 2:3, and/or (ii) the ratio of w:x is between 1:3 and 1:5; and

p and q are selected such that p:q is from 1 :20 to 1 :200 with r being selected to satisfy valence requirements and v and w being selected such that:

0.005 < (3 5v + L75m ) < 0.05 .

28. The catalyst of claim 27, wherein the ratio of v.y is between 3:2 and 2:3.

29. The catalyst of claim 27, wherein the ratio of w:x is between 1 :3 and 1 :5.

30. A catalyst satisfying the formula:

PtvPdwRexSnyAlzCapSiqOr,

wherein:

(i) v and y are between 3 :2 and 2:3; and/or (ii) w and x are between 1 :3 and 1 :5; and

p and z and the relative locations of aluminum and calcium atoms present are controlled such that Bransted acid sites present upon the surface thereof are balanced by a support modifier; and

p and q are selected such that p:q is from 1 :20 to 1 :200 with r being selected to satisfy valence requirements, and

v and w are selected such that:

0 005≤ (3.25v + 1.75w)≤() Q5

q

31. The catalyst of claim 30, wherein the ratio of v:y is between 3:2 and 2:3.

32. The catalyst of claim 30, wherein the ratio of w:x is between 1 :3 and 1 :5.

33. The catalyst of claim 30, wherein the at least one support modifier is selected from the group consisting of (i) alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alkaline earth metal metasilicates, (iv) alkali metal metasilicates, (v) Group IIB metal oxides, (vi) Group IIB metal metasilicates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal metasilicates, and mixtures thereof.

34. A catalyst, comprising a first metal, a second metal, a silicaceous support, and at least one support modifier, the first metal being selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten, and the second metal being selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium, and nickel, wherein the second metal is different than the first metal.

35. The catalyst of claim' 34, wherein the at least one support modifier is selected from the group consisting of (i) alkaline earth metal metasilicates, (ii) alkali metal metasilicates, (iii) Group IIB metal metasilicates, (iv) Group IIIB metal metasilicates, and mixtures thereof.

36. The catalyst of claim 34, wherein the first metal is present in an amount of from 0.1 to 25 wt.%, based on the total weight of the catalyst.

37. The catalyst of claim 34, wherein the at least one support modifier is selected from

metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, and zinc.

38. The catalyst of claim 34, wherein the at least one support modifier comprises CaSi03.

39. The catalyst of claim 34, wherein the at least one support modifier is present in an

amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.

40. The catalyst of claim 34, wherein the silicaceous support is present in an amount of 25 wt.% to 99 wt.%, based on the total weight of the catalyst.

41. The catalyst of claim 34, wherein the silicaceous support has a surface area of from 50 m2/g to 600 m2/g.

42. The catalyst of claim 34, wherein the silicaceous support is selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof.

43. The catalyst of claim 42, wherein the silicaceous support contains less than 1 wt.% of aluminum, based on the total weight of the catalyst.

44. The catalyst of claim 34, wherein the first metal is platinum and the second metal is tin.

45. The catalyst of claim 44, wherein the molar ratio of platinum to tin is from 0.4:0.6 to 0.6:0.4.

46. The catalyst of claim 34, wherein the first metal is palladium and the second metal is rhenium.

47. The catalyst of claim 46, wherein the molar ratio of rhenium to palladium is from

0.7:0.3 to 0.85:0.15.

48. The catalyst of claim 34, wherein the second metal is present in an amount of from 0.1 to 10 wt.%, based on the total weight of the catalyst.

49. The catalyst of claim 34, wherein the catalyst further comprises a third metal different from the first metal and the second metal.

50. The catalyst of claim 49, wherein the third metal is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin, and rhenium.

51. The catalyst of claim 49, wherein the third metal is present in an amount of 0.05 and 4 wt.%, based on the total weight of the catalyst.

52. The catalyst of claim 34, wherein the catalyst is suitable for use as a hydrogenation catalyst in converting acetic acid to ethanol and yields an acetic acid conversion of at least 10%.

53. The catalyst of claim 52, wherein the catalyst has a selectivity to ethanol of at least 80%.

54. The catalyst of claim 53, wherein the catalyst has a selectivity to methane, ethane, and carbon dioxide of less than 4%.

55. The catalyst of claim 53, wherein the catalyst has a productivity that decreases less than 6% per 100 hours of catalyst usage.

56. A process for preparing a catalyst, the process comprising the steps of:

(a) contacting a first metal precursor to a first metal with a modified silicaceous support to form an impregnated support, wherein the modified silicaceous support comprises a silicaceous material and at least one metasilicate support modifier; and

(b) heating the impregnated support under conditions effective to reduce the first metal and form the catalyst.

57. The process of claim 56, further comprising the steps of:

(c) contacting the at least one metasilicate support modifier or a precursor thereof with the silicaceous material to form a modified support precursor;

(d) heating the modified support precursor under conditions effective to form the modified support.

58. The process of claim 56, wherein the heating occurs under a reducing atmosphere, at least in part.

59. The process of claim 56, further comprising the step of calcining the catalyst.

60. The process of claim 56, wherein the at least one metasilicate support modifier is

selected from the group consisting of (i) alkaline earth metal metasilicates, (ii) alkali metal metasilicates, (iii) Group IIB metal metasilicates, (iv) Group IIIB metal metasilicates, and mixtures thereof.

61. The process of claim 56, wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium, molybdenum, and tungsten.

62. The process of claim 56, wherein the catalyst comprises the first metal is present in an amount of from 0.1 to 25 wt.%, based on the total weight of the catalyst.

63. The process of claim 56, wherein the at least one metasilicate support modifier is

selected from metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, and zinc.

64. The process of claim 56, wherein the at least one metasilicate support modifier

comprises CaSi03.

65. The process of claim 56, wherein the at least one metasilicate support modifier is

present in the catalyst in an amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.

66. The process of claim 56, wherein the modified silicaceous support is present in the catalyst in an amount from 25 wt.% to 99 wt.%, based on the total weight of the catalyst.

67. The process of claim 56, wherein the silicaceous material has a surface area of from 50 m2/g to 600 m2/g.

68. The process of claim 56, wherein the silicaceous material is selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof.

69. The process of claim 68, wherein the silicaceous material contains less than 1 wt.% of aluminum, based on the total weight of the catalyst.

70. The process of claim 56, wherein the first metal is selected from the group consisting of Group IB, IIB, IIIB, IVB, VB, VIB, VIIB, or VIII transitional metal, a lanthanide metal, an actinide metal or a metal from any of Groups IIIA, IV A, VA, or VIA.

71. The process of claim 56, further comprising the steps of impregnating and reducing a second metal precursor to a second metal different from the first metal on the support either before, after, or concurrently with steps (a) and (b).

72. The process of claim 71 , wherein the first metal is platinum and the second metal is tin.

73. The process of claim 72, wherein the molar ratio of platinum to tin in the catalyst is from 0.4:0.6 to 0.6:0.4.

74. The process of claim 71 , wherein the first metal is palladium and the second metal is rhenium.

75. The process of claim 74, wherein the molar ratio of rhenium to palladium in the catalyst is from 0.7:0.3 to 0.85:0.15.

76. The process of claim 71 , wherein the second metal is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, ruthenium, rhenium, gold, and nickel.

77. The process of claim 71, wherein the second metal is present in the catalyst in an

amount of from 0.1 to 10 wt.%, based on the total weight of the catalyst.

78. The process of claim 71, further comprising the steps of impregnating and reducing a third metal precursor to a third metal different from the first metal and the second metal on the support either before, after, or concurrently with steps (a) and (b).

79. The process of claim 78, wherein the third metal is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin, and rhenium.

80. The process of claim 78, wherein the third metal is present in the catalyst in an amount from 0.05 and 4 wt.%, based on the total weight of the catalyst.

81. A process for preparing a catalyst, the process comprising the steps of:

(a) contacting a first metal precursor to a first metal with a modified silicaceous support comprising at least one support modifier, wherein the first metal is selected from the group consisting of copper, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, chromium, rhenium,

molybdenum, and tungsten;

(b) contacting a second metal precursor to a second metal, different from the first metal, with the modified silicaceous support, wherein the second metal is selected from the group consisting of copper, molybdenum, tin, chromium, iron, cobalt, vanadium, tungsten, palladium, platinum, lanthanum, cerium, manganese, rhenium, and nickel; and

(c) heating the modified silicaceous support under conditions effective to reduce the first metal and the second metal and form the catalyst.

82. The process of claim 81, wherein the heating occurs after steps (a) and (b).

83. The process of claim 81, wherein the heating occurs between steps (a) and (b) to reduce the first metal and after steps (a) and (b) to reduce the second metal.

84. The process of claim 81 , further comprising the steps of:

(d) contacting at least one metasilicate support modifier or a precursor thereof with the silicaceous material to form a modified support precursor; and

(e) heating the modified support precursor under conditions effective to form the modified silicaceous support.

85. The process of claim 81, wherein the heating occurs under a reducing atmosphere, at least in part.

86. The process of claim 81, further comprising the step of:

(d) calcining the catalyst.

87. The process of claim 86, wherein the calcining occurs after steps (a) and (b).

88. The process of claim 86, wherein the calcining occurs between steps (a) and (b) and after steps (a) and (b).

89. The process of claim 81 , wherein the at least one support modifier is selected from the group consisting of (i) alkaline earth metal metasilicates, (ii) alkali metal metasilicates, (iii) Group IIB metal metasilicates, (iv) Group IIIB metal metasilicates, and mixtures thereof.

90. The process of claim 81 , wherein the first metal is present in an amount of from 0.1 to 25 wt.%, based on the total weight of the catalyst.

91. The process of claim 81 , wherein the at least one support modifier is selected from metasilicates of a metal selected from the group consisting of sodium, potassium, magnesium, scandium, yttrium, and zinc.

92. The process of claim 81 , wherein the at least one support modifier comprises CaSi03.

93. The process of claim 81 , wherein the at least one support modifier is present in an

amount of 0.1 wt.% to 50 wt.%, based on the total weight of the catalyst.

94. The process of claim 81 , wherein the modified silicaceous support is present in an

amount of 25 wt.% to 99 wt.%, based on the total weight of the catalyst.

95. The process of claim 81, wherein the modified silicaceous support has a surface area of from 50 m2/g to 600 m2/g.

96. The process of claim 81, wherein the modified silicaceous support further comprises a support material selected from the group consisting of silica, silica/alumina, calcium metasilicate, pyrogenic silica, high purity silica and mixtures thereof.

97. The process of claim 96, wherein the modified silicaceous support contains less than 1 wt.% of aluminum, based on the total weight of the catalyst.

98. The process of claim 81 , wherein the first metal is platinum and the second metal is tin.

99. The catalyst of claim 98, wherein the molar ratio of platinum to tin is from 0.4:0.6 to 0.6:0.4.

100. The process of claim 81 , wherein the first metal is palladium and the second metal is rhenium.

101. The process of claim 100, wherein the molar ratio of rhenium to palladium is from 0.7:0.3 to 0.85:0.15.

102. The process of claim 81 , wherein the second metal is present in an amount of from 0.1 to 10 wt.%, based on the total weight of the catalyst.

103. The process of claim 81 , further comprising the steps of impregnating and reducing a third metal precursor to a third metal different from the first metal and the second metal on the modified silicaceous support.

104. The process of claim 103, wherein the third metal is selected from the group consisting of cobalt, palladium, ruthenium, copper, zinc, platinum, tin, and rhenium.

105. The process of claim 103, wherein the third metal is present in an amount of 0.05 and 4 wt.%, based on the total weight of the catalyst.