Catalyst for light olefins and LPG in fludized catalytic units
View Patent ↗A catalyst composition comprising at least about 10% by weight pentasil, at least about 12% by weight Y-type zeolite at a pentasil to Y zeolite ratio of at least 0.25, and wherein the pentasil and Y zeolite comprise at least about thirty-five percent of the catalyst have been shown to optimize light olefin yields and LPG from FCC processes. Embodiments having matrix surface areas greater than 25 m 2 /g, phosphorous and rare earth are preferred. The compositions of this invention are particularly useful in typical fluid catalytic cracking (FCC) processes.
1. A catalyst composition comprising
a. about twelve to about sixty percent by weight Y-type zeolite;
b. at least about ten percent by weight pentasil and wherein pentasil and Y-type zeolite is present in a weight ratio (pentasil:Y-type zeolite) of at least 0.25 and no more than 2.3; and
c. the Y-type zeolite and pentasil comprises at least about thirty-five percent by weight of the catalyst composition; and wherein the pentasil and the Y-type zeolite are contained in separate particles, and the separate particles of Y-type zeolite comprise two to eight percent by weight rare earth (measured as rare earth oxide) based on the Y type zeolite.
2. A catalyst composition according to claim 1 wherein the composition further comprises phosphorus.
3. A catalyst composition according to claim 2 wherein the composition comprises up to about 12% by weight phosphorus, as measured by the content of P 2 O 5 .
4. A catalyst composition according to claim 1 wherein the composition further comprises matrix having a surface area of at least 25 m 2 /g.
5. A catalyst composition according to claim 2 wherein the pentasil-containing particles comprise phosphorus.
6. A catalyst composition according to claim 5 wherein the pentasil-containing particles comprises phosphorus in amounts in the range of about six to about twenty-four % by weight, as measured by the content of P 2 O 5 .
7. A catalyst composition according to claim 2 wherein the Y-type zeolite-containing particles comprise phosphorus.
8. A catalyst composition according to claim 7 wherein the Y-type zeolite-containing particles comprise 0.01 to about 3 weight percent phosphorus as measured by P 2 O 5 .
9. A catalyst composition according to claim 1 wherein the composition has a surface area of at least 150 m 2 /g.
10. A catalyst composition according to claim 1 wherein the composition has a surface area of at least 150 m 2 /g after being treated at 816° C. for 4 hours with 100% steam.
11. A catalyst composition according to claim 1 comprising about ten percent to about fifty percent by weight pentasil.
12. A catalyst composition according to claim 1 having a Davison Attrition Index of about 20 or less.
13. A catalyst composition according to claim 1 having a Davison Attrition Index of about 10 or less.
14. A catalyst composition according to claim 1 having a Davison Attrition Index of about 5 or less.
15. A catalyst composition according to claim 1 wherein (a) the pentasil-containing particles comprise phosphorous, and (b) the catalyst further comprises matrix having a surface area of at least 25 m 2 /g.
16. A catalyst composition according to claim 15 comprising about one to about twelve percent by weight phosphorous.
17. A catalyst composition according to claim 15 comprising matrix having a surface area in the range of about 45 to about 130 m 2 /g.
18. A catalyst composition according to claim 15 having a total surface area of at least about 150 m 2 /g.
19. A catalyst composition according to claim 16 having a surface area of at least about 150 m 2 /g.
20. A catalyst composition according to claim 15 comprising about ten to about fifty weight percent pentasil.
21. A catalyst composition according to claim 20 wherein the pentasil is ZSM-5 or ZSM-11.
22. A catalyst composition according to claim 16 wherein the Y-type zeolite is exchanged with cerium cations, lanthanum cations, neodymium cation, praseodymium cations, or mixtures thereof.
23. A catalyst composition according to claim 1 wherein the catalyst composition has a kinetic conversion activity of at least about 2.3.
24. A catalyst composition according to claim 1 wherein the catalyst composition has a kinetic conversion activity of at least about 3.
25. A catalyst composition according to claim 1 wherein the catalyst composition has a kinetic conversion activity in the range of about 3.5 to about 5.5.
26. A catalyst composition according to claim 1 wherein the catalyst composition has a kinetic conversion activity in the range of about 4 to about 5.
27. A catalytic cracking process comprising:
a. introducing a hydrocarbon feedstock into a reaction zone of a catalytic cracking unit comprised of a reaction zone, stripping zone, and a regeneration zone, which feedstock is characterized as having an initial boiling point from about 120° C. with end points up to about 850° C.;
b. catalytically cracking said feedstock in said reaction zone at a temperature from about 400° C. to about 700° C., by causing the feedstock to be in contact with a cracking catalyst comprising:
i. about twelve to about sixty percent by weight Y-type zeolite;
ii. two to eight percent by weight rare earth (measured as rare earth oxide) based on the Y-type zeolite;
iii. at least about ten percent by weight pentasil and wherein pentasil and Y-type zeolite is present in a weight ratio pentasil:Y-type zeolite of at least 0.25 and no more than 2.3;
iv. the Y-type zeolite and pentasil comprises at least about thirty-five percent by weight of the catalyst composition; and wherein the pentasil and the Y-type zeolite are contained in separate particles, and the separate particles of Y-type zeolite comprise two to eight percent by weight rare earth (measured as rare earth oxide) based on the Y type zeolite; and
c. stripping recovered used catalyst particles with a stripping fluid in a stripping zone to remove therefrom some hydrocarbonaceous material; and
d. recovering stripped hydrocarbonaceous material from the stripping zone and circulating stripped used catalyst particles to the regenerator or regeneration zone; and
e. regenerating said coked catalyst in a regeneration zone by burning-off a substantial amount of the coke on said catalyst, and with any added fuel component to maintain the regenerated catalyst at a temperature which will maintain the catalytic cracking reactor at a temperature from about 400° C. to about 700° C.; and
f. recycling said regenerated hot catalyst to the reaction zone.
28. A process according to claim 27 wherein the catalyst in step (b) further comprises phosphorous.
29. A process according to claim 27 wherein the catalyst in step (b) further comprises matrix having a surface area of at least 25 m 2 /g.
30. A process according to claim 27 wherein the process is a fluidized catalytic cracking process.
31. A process according to claim 30 wherein the pentasil-containing particles comprise phosphorus.
32. A process according to claim 31 wherein the Y-type zeolite-containing particles comprise phosphorus.
33. A process according to claim 31 wherein the catalyst in step (b) comprises phosphorous in amounts in the range of about one to about twelve % by weight, as measured by the content of P 2 O 5 .
34. A process according to claim 31 wherein the pentasil-containing particles comprises phosphorus in amounts in the range of about six to about twenty-four % by weight, as measured by the content of P 2 O 5 .
35. A process according to claim 27 wherein the catalyst in step (b) has a surface area of at least 150 m 2 /g.
36. A process according to claim 27 wherein the catalyst in step (b) has a surface area of at least 150 m 2 /g after being treated at 1500° F. for 4 hours with 100% steam.
37. A process according to claim 27 wherein the catalyst in step (b) comprises about ten percent to about fifty percent by weight pentasil.
38. A process according to claim 27 wherein the catalyst in step (b) has a Davison Attrition Index of about 20 or less.
39. A process according to claim 27 wherein the catalyst in step (b) has a Davison Attrition Index of about 10 or less.
40. A process according to claim 27 wherein the catalyst in step (b) has a Davison Attrition Index of about 5 or less.
41. A process according to claim 30 wherein the catalyst in step (b) comprises (a) pentasil-containing particles comprising phosphorous, and (b) matrix having a surface area of at least 25 m 2 /g.
42. A process according to claim 41 wherein the catalyst in step (b) comprises about one to about twelve percent by weight phosphorous.
43. A process according to claim 41 wherein the catalyst in step (b) comprises matrix having a surface area in the range of about 45 to about 130 m 2 /g.
44. A process according to claim 41 wherein the catalyst in step (b) has a surface area of at least about 150 m 2 /g.
45. A process according to claim 43 wherein the catalyst in step (b) has a surface area of at least about 150 m 2 /g.
46. A process according to claim 41 wherein the catalyst in step (b) comprises about ten to about fifty weight percent pentasil.
47. A process according to claim 46 wherein the catalyst in step (b) comprises pentasil that is ZSM-5.
48. A process according to claim 46 wherein the catalyst in step (b) comprises pentasil that is ZSM-11.
49. A process according to claim 41 wherein the catalyst in step (b) comprises Y-type zeolite that is exchanged with cerium cations, lanthanum cations, neodymium cations, praseodymium cations, or mixtures thereof.
50. A process according to claim 41 wherein step (b) of said process produces a product comprising at least about ten percent by weight propylene.
51. A process according to claim 41 wherein step (b) of said process produces a product comprising at least about 12 percent by weight propylene.
52. A process according to claim 41 wherein step (b) of said process produces a product comprising at least about 15 percent by weight propylene.
53. A process according to claim 41 wherein step (b) of said process produces a product comprising at least about 16 percent by weight propylene.
54. A process according to claim 27 wherein step (b) of said process produces a product comprising light olefins comprising C 3 and C 4 olefins.
55. A process according to claim 27 wherein step (b) of said process produces at least 25% by weight liquefied petroleum gas based on the weight of the feedstock.
56. A process according to claim 27 wherein the temperature of step (b) is in the range of about 500 to about 550° C.
57. A process according to claim 30 wherein the temperature of step (b) is in the range of about 500 to about 550° C.
58. A process according to claim 27 wherein the temperature of step (b) is in the range of about 505 to about 575° C.
59. A process according to claim 27 wherein the temperature of step (b) is in the range of about 560 to about 650° C.
60. A process according to claim 27 wherein the temperature of step (b) is in the range of about 550 to about 570° C.
61. A process according to claim 27 wherein the yield in gasoline is less than forty four percent by weight the hydrocarbon feedstock.
62. A process according to claim 27 wherein the yield in gasoline is less than forty two percent by weight the hydrocarbon feedstock.
63. A process according to claim 27 wherein the yield in gasoline is less than forty percent by weight the hydrocarbon feedstock.
64. A process according to claim 27 wherein the hydrocarbon feedstock has a fifty percent point of at least about 315° C.
65. A process according to claim 27 wherein the hydrocarbon feedstock comprises at least 100 ppm natural nitrogen.
66. A process according to claim 27 the catalyst in step (b) has a kinetic conversion activity of at least about 2.3.
67. A process according to claim 27 the catalyst in step (b) has a kinetic conversion activity of at least about 3.
68. A process according to claim 27 the catalyst in step (b) has a kinetic conversion activity in the range of about 3.5 to about 5.5.
69. A process according to claim 30 the catalyst in step (b) has a kinetic conversion activity in the range of about 3.5 to about 5.5.
70. A catalytic cracking process comprising:
a. introducing a hydrocarbon feedstock into a reaction zone of a catalytic cracking unit comprised of a reaction zone, stripping zone, and a regeneration zone, which feedstock is characterized as having: an initial boiling point from about 120° C. with end points up to about 850° C.;
b. catalytically cracking said feedstock in said reaction zone at a temperature from about 400° C. to about 700° C., by causing the feedstock to be in contact with a cracking catalyst having a Davison Index of about 20 or less and a kinetic conversion activity of at least about 2.3 and comprising:
i. about twelve to about sixty percent by weight Y-type zeolite;
ii. at least about ten percent by weight pentasil wherein said pentasil and Y-type zeolite is present in a weight ratio (pentasil:Y-type zeolite) of at least 0.25 and no more than 2.3; wherein the Y-type zeolite and pentasil are contained in separate particles, and the Y-type zeolite and pentasil comprise at least thirty-five percent by weight of the catalyst composition;
iii. about one to about twelve percent phosphorus as measured by P 2 O 5 content;
iv. the separate particles of Y-type zeolite comprise about 2 to about 8% by weight rare earth, based on Y type zeolite, as measured by rare earth oxide content; and
v. matrix having a surface area of at least 25 m 2 /g;
c. stripping recovered used catalyst particles with a stripping fluid in a stripping zone to remove therefrom some hydrocarbonaceous material; and
d. recovering stripped hydrocarbonaceous material from the stripping zone and circulating stripped used catalyst particles to the regenerator or regeneration zone; and
e. regenerating said coked catalyst in a regeneration zone by burning-off a substantial amount of the coke on said catalyst, and with any added fuel component to maintain the regenerated catalyst at a temperature which will maintain the catalytic cracking reactor at a temperature from about 400° C. to about 700° C.; and
f. recycling said regenerated hot catalyst to the reaction zone.
71. A process according to claim 70 wherein the catalyst in step (b) has a Davison Index of less than about 10, an activity of at least about 3.0 and a total surface area of at least about 150 m 2 /g and comprises at least about 25% by weight Y-type zeolite; and about 10 to about 30% pentasil.
72. A process according to claim 71 wherein the catalyst in step (b) has a kinetic conversion activity in the range of about 3.5 to about 5.5 and comprises at least about 30% by weight percent Y-type zeolite; and about 10 to about 20% by weight pentasil.
73. A process according to claim 70 wherein the temperature in step (b) is in the range of about 500 to about 550° C.
74. A process according to claim 73 wherein step (b) produces a product comprising C 3 and C 4 olefins.
75. A process according to claim 73 wherein step (b) produces at least 25% by weight liquefied petroleum gas based on weight of feedstock.
76. A process according to claim 73 wherein step (b) produces at least 12% by weight propylene.
77. A process according to claim 75 wherein step (b) produces at least 12% by weight propylene.
78. A process according to claim 77 wherein step (b) produces about 42% by weight or less gasoline.
79. A process according to claim 70 wherein the hydrocarbon feedstock in step (a) comprises at least about 100 ppm nitrogen.