US4879019A
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US
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Hydrocarbon conversion process for selectively making middle distillates
Assignee: Honeywell UOP LLC
•
Filing: 1988-04-04
•
Granted: 1989-11-07
•
Expires: 2008-04-04
Abstract
Abstract A hydrocarbon conversion catalyst useful for converting hydrocarbon feeds to midbarrel products is prepared by extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity to form extrudates which are broken into particles normally ranging in length between 1/16 and 1/2 inch. The extruded particles are then calcined in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a., preferably greater than about 5.0 p.s.i.a. The calcination step is carried out in the presence of sufficient added steam for a sufficient amount of time at a sufficient temperature to convert the crystalline aluminosilicate zeolite in the extrudates into an ultrahydrophobic zeolite having a unit cell size between about 24.20 and about 24.45 Angstroms and a sorptive capacity for water vapor less than about 5 weight percent of the zeolite at 25° C. and a p/p° value of 0.10.
Inventors
- 👤 John W. Ward
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 23:22
CPC Classifications
B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/08; B01J29/084; C; C10; C10G; C10G47/00; C10G47/02; C10G47/10; C10G47/12; C10G47/16
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
121 words
A hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a hydrocarbon conversion catalyst under hydrocarbon conversion conditions to convert said feedstock into hydrocarbon conversion reaction products, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity to form extrudates, wherein said zeolite is selected from the group consisting of Y zeolites, and X zeolites; and (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms.
Claim 2
Dependent Claim
121 words
A hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a hydrocarbon conversion catalyst under hydrocarbon conversion conditions to convert said feedstock into hydrocarbon conversion reaction products, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity to form extrudates, wherein said zeolite is selected from the group consisting of Y zeolites, and X zeolites; and (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms.
Claim 3
Dependent Claim
29 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) has a silica-to-alumina mole ratio between about 3 and about 10.
Claim 4
Dependent Claim
79 words
A hydrocarbon conversion process as defined by claim 1 wherein the water vapor partial pressure of said added steam and the temperature and time of said calcination are such that, if said aluminosilicate zeolite is calcined in steam alone without first being mixed and extruded with said refractory oxide component, the water vapor sorptive capacity of said aluminosilicate zeolite will be less than about 5 weight percent of said zeolite at 25° C. and a p/p° value of 0.10.
Claim 5
Dependent Claim
21 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) comprises LZY-82 zeolite.
Claim 6
Dependent Claim
21 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) comprises LZ-210 zeolite.
Claim 7
Dependent Claim
131 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) is prepared by a process comprising the steps of (1) ammonium exchanging a sodium Y zeolite to a sodium content between about 0.6 and about 5 weight percent, calculated as Na 2 O (2) calcining the ammonium-exchanged zeolite at a temperature between about 600° F. and about 1650° F. in the presence of steam at a water vapor partial pressure of at least about 0.2 p.s.i.a. to reduce the unit cell size of said ammonium-exchanged zeolite to a value in the range between about 24.40 and 24.64 Angstroms, and (3) ammonium exchanging the steam-calcined zeolite to reduce the sodium content of the zeolite below about 0.6 weight percent, calculated as Na 2 O.
Claim 8
Dependent Claim
113 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) is prepared by a process comprising (1) ammonium exchanging a sodium Y zeolite to a sodium content between about 0.6 and about 5 weight percent, calculated as Na 2 O, (2) calcining the ammonium-exchanged zeolite at a temperature between about 600° F. and about 1650° F. in the presence of steam at a water vapor partial pressure of at least about 0.2 p.s.i.a. to reduce the unit cell size of said ammonium-exchanged zeolite to a value in the range between about 24.40 and about 24.64 Angstroms, and (3) leaching the steam-calcined zeolite with an acid.
Claim 9
Dependent Claim
38 words
A hydrocarbon conversion process as defined by claim 1 wherein said extrudates are formed by extruding a mixture of a porous, inorganic refractory oxide component, a crystalline aluminosilicate zeolite having cracking activity and at least one hydrogenation component.
Claim 10
Dependent Claim
23 words
A hydrocarbon conversion process as defined by claim 1 wherein said water vapor partial pressure is between about 5 and about 35 p.s.i.a.
Claim 11
Dependent Claim
38 words
A hydrocarbon conversion process as defined by claim 1 wherein said hydrocarbon conversion process is selected from the group consisting of catalytic cracking, isomerization of n-paraffins to isoparaffins, isomerization of alkyl aromatics, alkylation and transalkylation of alkyl aromatics.
Claim 12
Dependent Claim
29 words
A hydrocarbon conversion process as defined by claim 1 wherein said crystalline aluminosilicate zeolite used in step (a) has a silica-to-alumina mole ration between about 3 and about 6.
Claim 13
Dependent Claim
18 words
A hydrocarbon conversion process as defined by claim 2 wherein said crystalline aluminosilicate zeolite comprises a Y zeolite.
Claim 14
Dependent Claim
135 words
A hydroconversion process which comprises contacting a hydroconversion feedstock under hydroconversion reaction conditions with a hydroconversion catalyst in the presence of added hydrogen to convert said feedstock into hydroconversion reaction products, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity to form extrudates, wherein said zeolite is selected from the group consisting of Y zeolites and X zeolites; (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms; and (c) impregnating said calcined extrudates with at least one hydrogenation component.
Claim 15
Dependent Claim
135 words
A hydroconversion process which comprises contacting a hydroconversion feedstock under hydroconversion reaction conditions with a hydroconversion catalyst in the presence of added hydrogen to convert said feedstock into hydroconversion reaction products, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity to form extrudates, wherein said zeolite is selected from the group consisting of Y zeolites and X zeolites; (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms; and (c) impregnating said calcined extrudates with at least one hydrogenation component.
Claim 16
Dependent Claim
78 words
A hydroconversion process as defined by claim 13 wherein the water vapor partial pressure of said added steam and the temperature and time of said calcination are such that, if said aluminosilicate zeolite is calcined in steam alone without first being mixed and extruded with said refractory oxide component, the water vapor sorptive capacity of said aluminosilicate zeolite will be less than about 5 weight percent of said zeolite at 25° C. and a p/p° value of 0.10.
Claim 17
Dependent Claim
28 words
A hydroconversion process as defined by claim 13 wherein said calcined extrudates are impregnated with a Group VIA metal hydrogenation component and a Group VIII metal hydrogenation component.
Claim 18
Dependent Claim
38 words
A hydroconversion process as defined by claim 15 wherein said Group VIA metal hydrogenation component comprises a tungsten component or a molybdenum component and said Group VIII metal hydrogenation component comprises a nickel component or a cobalt component.
Claim 19
Dependent Claim
14 words
A hydroconversion process as defined by claim 13 wherein said hydroconversion process comprises hydrocracking.
Claim 20
Dependent Claim
20 words
A hydroconversion process as defined by claim 13 wherein said crystalline aluminosilicate zeolite used in step (a) comprises LZY-82 zeolite.
Claim 21
Dependent Claim
28 words
A hydroconversion process as defined by claim 13 wherein said crystalline aluminosilicate zeolite used in step (a) has a silica-to-alumina mole ratio between about 3.0 and about 20.
Claim 22
Dependent Claim
125 words
A hydrocracking process for selectively producing middle distillates which comprises contacting a hydrocarbon feedstock with a hydrocracking catalyst in the presence of added hydrogen under hydrocracking conditions, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate Y zeolite having cracking activity to form extrudates, (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms; and (c) impregnating said calcined extrudates with a Group VIII metal hydrogenation component and a Group VIA metal hydrogenation component.
Claim 23
Dependent Claim
125 words
A hydrocracking process for selectively producing middle distillates which comprises contacting a hydrocarbon feedstock with a hydrocracking catalyst in the presence of added hydrogen under hydrocracking conditions, wherein said catalyst is prepared by the process comprising: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate Y zeolite having cracking activity to form extrudates, (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.35 Angstroms; and (c) impregnating said calcined extrudates with a Group VIII metal hydrogenation component and a Group VIA metal hydrogenation component.
Claim 24
Dependent Claim
38 words
A hydrocracking process as defined in claim 20 wherein said Group VIA metal hydrogenation component comprises a tungsten component or a molybdenum component and said Group VIII metal hydrogenation component comprises a nickel component or a cobalt component.
Claim 25
Dependent Claim
23 words
A hydrocracking process as defined in claim 21 wherein said porous, inorganic refractory oxide component comprises a dispersion of silica-alumina in gamma alumina.
Claim 26
Dependent Claim
21 words
A hydrocracking process as defined by claim 22 wherein said crystalline aluminosilicate Y zeolite used in step (a) comprises LZY-82 zeolite.
Claim 27
Dependent Claim
79 words
A hydrocracking process as defined by claim 20 wherein the water vapor partial pressure of said added steam and the temperature and time of said calcination are such that, if said aluminosilicate Y zeolite is calcined in steam alone without first being mixed and extruded with said refractory oxide component, the water vapor sorptive capacity of said aluminosilicate zeolite will be less than about 5 weight percent of said zeolite at 25° C. and a p/p° value of 0.10.
Claim 28
Dependent Claim
125 words
A hydrocracking process as defined by claim 20 wherein said crystalline aluminosilicate zeolite used in step (a) is prepared by a process comprising (1) ammonium-exchanging a sodium Y zeolite to a sodium content between about 0.6 and about 5 weight percent, calculated as Na 2 O, (2) calcining the ammonium-exchanged zeolite at a temperature between about 600° F. and 1650° F. in the presence of steam at a water vapor partial pressure of at least about 0.2 p.s.i.a. to reduce the unit cell size of said ammonium-exchanged zeolite to a value in the range between about 24.40 and 24.64 Angstroms, and (3) ammonium-exchanging the steam calcined zeolite to reduce the sodium content of the zeolite below about 0.6 weight percent, calculated as Na 2 O.
Claim 29
Dependent Claim
131 words
A hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a hydrocarbon conversion catalyst under hydrocarbon conversion conditions to convert said feedstock into hydrocarbon conversion reaction products, wherein said catalyst is prepared by the process consisting essentially of: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity and a silica-to-alumina mole ratio between about 3 and about 20 to form extrudates; and (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.335 Angstroms; and (c) impregnating said calcined extrudates with at least one hydrogenation component.
Claim 30
Dependent Claim
131 words
A hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a hydrocarbon conversion catalyst under hydrocarbon conversion conditions to convert said feedstock into hydrocarbon conversion reaction products, wherein said catalyst is prepared by the process consisting essentially of: (a) extruding a mixture of a porous, inorganic refractory oxide component and a crystalline aluminosilicate zeolite having cracking activity and a silica-to-alumina mole ratio between about 3 and about 20 to form extrudates; and (b) calcining said extrudates in the presence of added steam at a water vapor partial pressure greater than about 2.0 p.s.i.a. under conditions such that the unit cell size of said crystalline aluminosilicate zeolite is reduced to a value between about 24.20 and about 24.335 Angstroms; and (c) impregnating said calcined extrudates with at least one hydrogenation component.
Claim 31
Dependent Claim
79 words
A hydrocarbon conversion process as defined by claim 26 wherein the water vapor partial pressure of said added steam and the temperature and time of said calcination are such that, if said aluminosilicate zeolite is calcined in steam alone without first being mixed and extruded with said refractory oxide component, the water vapor sorptive capacity of said aluminosilicate zeolite will be less than about 5 weight percent of said zeolite at 25° C. and a p/p° value of 0.10.
Claim 32
Dependent Claim
29 words
A hydrocarbon conversion process as defined by claim 26 wherein said crystalline aluminosilicate zeolite used in step (a) has a silica-to-alumina mole ratio between about 3 and about 10.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1992-11-06 | 1993-05-08 | 1993-11-07 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-11-06 | 1997-05-08 | 1997-11-07 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-11-06 | 2001-05-08 | 2001-11-07 | $7700.00 | Window Closed / Lapsed |