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1. (WO1986003138) CATALYSEURS DE CRAQUAGE ET PROCEDE DE CRAQUAGE UTILISANT DES SYSTEMES CATALYSEURS MIXTES
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

WHAT IS CLAIMED IS:
1. The process for cracking a crude oil feedstock to produce lower boiling hydrocarbons comprising contacting at effective catalytic
cracking conditions a crude oil feedstock with a conversion catalyst comprising effective amounts of at least one zeolitic aluminosilicate and at least one silicoaluminophosphate molecular sieve of U.S. Patent No. 4,449,871 characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C.

2. The process of claim 1 wherein said silicoaluminophosphate is further characterized in its calcined form by an adsorption of triethylamine of less than 5 percent by weight at a pressure of 2.6 torr and a temperature of 22°C.

3. The process of claim 1 wherein said catalyst comprises a weight ratio between about 1:10 and about 500:1 of said zeolitic aluminosilicate cracking component to said silicoaluminophosphate molecular sieve and from 0 and about 99 weight percent of at least one inorganic oxide matrix component, based on the total weight of said
catalyst.

4. The process of claim 3 wherein the weight ratio of zeolitic aluminosilicate to said silicoaluminophosphate is between about 1:2 and about 50:1.

5. The process of claim 4. wherein the weight ratio of zeolitic aluminosilicate to said silicoaluminophosphate is between about 1:1 and about 20:1.

6. The process of claim 3 wherein
inorganic oxide component is present in an amount between about 5 and about 95 percent by weight, based on the total weight of said catalyst.

7. The process according to claim 1 wherein said zeolite component of the conversion catalyst contains an effective amount of a cation selected from the group consisting of ammonium, Group IIA, Group IIIA, Groups IIIB to VIIB, cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and mixtures thereof.

8. The process of claim 1 wherein said silicoaluminophosphate has at least part of its cations as hydrogen-forming species.

9. The process of claim 8 wherein said hydrogen-forming species is NH4+ or H+.

10. The cracking process of claim 1 wherein the process is carried out by contacting crude oil feedstock boiling between 420°F and about 1800°F with the conversion catalyst at a temperature between about 400°F and about 1300°F, at a pressure between about 14.7 psia to about 100 psia.

11. The process of claim 7 wherein said conversion catalyst contains between about 0.1 percent and about 20 weight percent of said
multivalent cations.

12. The process of claim 6 wherein said inorganic oxide matrix component is selected from the group consisting of clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesia, alumina-borias, alumina-titanias and mixtures thereof.

13. The process of claim 1 or 2 wherein said silicoaluminophosphate is characterized as microporous crystalline silicoaluminophosphates the pores of which are uniform and have nominal
diameters of greater than about 3 Angstroms and whose essential empirical chemical composition in the as-synthesized and anhydrous form is
mR:(SixAlyPz)O2
wherein "R" represents at least one organic
templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (SixAlyPz)O2; "m" has a value of
from 0.02 to 0.3; "x", "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points ABCD and E of the ternary diagram which is FIG. 1 of the drawings of U.S. Patent No. 4,440,871.

14. The process of claim 1 or 2 wherein said silicoaluminophosphate is characterized as having a three-dimensional microporous framework structure of PO+2, AlO2- and SiO2
tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is:
mR:(SixAlyPz)O2
wherein "R" represents at least one organic
templating agent present in the intracrystalline pore sys.tem; "m" represents the moles of "R" present per mole of (SixAlyPz)O2 and has a value of
from zero to 0.3; "x", "y" and "z" represent
respectively, the mole fractions of silicon,
aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG. 1, said
silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables I, III, V, VII, IX, XII, XVII, XXI, XXIII or XXV of U.S. Patent No. 4,440,871.

15. The process of claim 1 or 2 wherein said silicoaluminophosphate is at least one selected from the group consisting of SAPO-5, SAPO-11,
SAPO-31, SAPO-37, SAPO-40 and SAPO-41.

16. The process of claim 15 wherein the silicoaluminophosphate is SAPO-5.

17. The process of claim 15 wherein the silicoaluminophosphate is SAPO-11.

18. The process of claim 15 wherein the silicoaluminophosphate is SAPO-31.

19. The process of claim 15 wherein the silicoaluminophosphate is SAPO-40.

20. The process of claim 15 wherein the silicoaluminophosphate is SAP0-41.

21. The process of claim 1 wherein said crude oil feedstock is selected from the group consisting of distillate gas oils, heavy vacuum gas oils, VGO, atmospheric resids, vacuum resids, syncrudes, pulverized coal and mixtures thereof.

22. The process of claim 1 wherein said zeolitic aluminosilicate is selected from the group consisting of zeolite Y, zeolite X, zeolite beta, zeolite KZ-20, faujasite, LZ-210, LZ-10, ZSM-type zeolites and mixtures thereof.

23. The process of claim 3 wherein said zeolitic aluminosilicate is selected from the group consisting of zeolite Y, zeolite X, zeolite beta, zeolite KZ-20, faujasite, LZ-210, LZ-10, ZSM-type zeolities and mixtures thereof.

24. The process for the preparation of a catalyst comprising:
a) forming a mixture of at least one zeolitic aluminosilicate and at least one
silicoaluminophosphate of U.S. Patent No. 4,449,871 characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C at a weight ratio of between about 1:10 and about 500:1, respectively;

b) forming a mixture of the product of step a) and at least one inorganic oxide matrix component to form a catalyst.

25. The process for the preparation of a catalyst comprising:
a) forming a mixture of at least one inorganic oxide matrix component and at least one zeolitic aluminosilicate;
b) forming a mixture of at least one inorganic oxide matrix component and at least one silicoaluminophosphate of U.S. Patent No. 4,449.871 characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C; and
c) forming a mixture of the products of steps a) and b) to form a catalyst having a weight ratio of zeolitic aluminosilicate to
silicoaluminophosphate between about 1:10 and about 500:1.

26. The catalyst prepared by the process of claim 24.

27. The catalyst prepared by the process of claim 25.

28. A cracking catalyst comprising at least one zeolitic aluminosilicate having cracking activity at effective cracking conditions and at least one silicoaluminophosphate molecular sieve of U.S. Patent No. 4, 449, 871, characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C, wherein the weight ratio of said aluminosilicate to silicialuminophosphate is between about 1:10 and about 500:1.

29. The catalyst of claim 28 wherein said silicoaluminophosphate molecular sieve is further characterized in its calcined form by an adsorption of triethylamine of less than 5 percent by weight at a pressure of 2.6 torr and a temperature of 22°C.

30. The catalyst of claim 27 or 28 wherein said silicoaluminophosphate is characterized as microporous crystalline silicoaluminophosphates the pores of which are uniform and have nominal
diameters of greater than about 3 Angstroms and whose essential empirical chemical composition in the as-synthesized and anhydrous form is
mR: (SiχAlyPz)O2
wherein "R" represents at least one organic
templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (SixAlyPz)O2; "m" has a value of
from 0.02 to 0.3; "x" , "y" and "z" represent the mole fractions of silicon, aluminum and phosphorus respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points ABCD and E of the ternary diagram which is FIG. 1 of the drawings of U.S. Patent No. 4,440,871.

31. The catalyst of claim 28 or 29 wherein said silicoaluminophosphate is characterized as having a three-dimensional microporous framework structure of PO2+, AlO2- and SiO2
tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is:
mR:(SixAlyPz)O2
wherein "R" represents at least one organic
templating agent present in the intracrystalline pore system; "m" represents the moles of "R" present per mole of (SixAlyPx)O2 and has a value of
from zero to 0.3; "x", "y" and "z" represent
respectively, the mole fractions of silicon,
aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG. 1, said
silicoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables I, III, V, VII, IX, XII, XVII, XXI, XXIII or XXV of U.S. Patent No. 4,440,871.

32. The catalyst of claim 28 or 29 wherein said zeolitic aluminosilicate is selected from the group consisting of zeolite Y, zeolite X, zeolite beta, zeolite KZ-20, faujasite, LZ-210, LZ-10,
ZSM-type zeolites and mixtures thereof.

33. The catalyst of claim 32 wherein said catalyst contains from 0 to 99 percent by weight of at least inorganic oxide matrix component.

34. The catalyst of claim 33 wherein the inorganic oxide matrix component is selected from the group consisting of clays, silicas, aluminas, silica-aluminas, silicas-zirconias, silica-magnesia, alumina-borias, alumina-titanias and mixtures thereof.

35. The catalyst of claim 28 wherein said silicoaluminophosphate is selected from the group consisting of SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40, SAPO-41 and mixtures thereof.

36. The catalyst of claim 28 wherein said zeolitic aluminosilicate is selected from the group consisting of Y zeolite, LZ-210, LZ-10 and mixtures thereof and said silicoaluminophosphate is selected from the group consisting of SAPO-5, SAPO-11,
SAPO-31, SAPO-41 and mixtures thereof.

37. The catalyst of claim 28 wherein said zeolitic aluminosilicate contains between about 0.1 and about 20 percent by weight of a cation selected from the group consisting of ammonium, Group IIA, Group IIA, Groups II B to VII B, rare earth and mixtures thereof.

38. A cracking catalyst comprising of at least one cracking catalyst having cracking activity at effective cracking conditions and an effective amount of at least one silicoaluminophosphate molecular sieve of U.S. Patent No. 4,449,871
characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C.

39. The catalyst of claim 38 wherein the weight ratio of said cracking catalyst to said silicoaluminophosphate is between about 1:10 and about 500:1.

40. The catalyst of claim 38 wherein said cracking catalyst consists at least one zeolitic aluminosilicate.

41. The catalyst of claim 38 wherein said cracking catalyst consists essentially of a
silica-alumina.

42. The catalyst of claim 38 wherein said silicoaluminophosphate is further characterized in its calcined form by an adsoption of triethylamine of less than 5 percent by weight at a pressure of 2.6 torr and a temperature of 22°C.