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US3897327A
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Hydrocracking process with stabilized y-zeolite catalysts
Assignee: Union Oil Company of California
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Filing: 1973-10-15
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Granted: 1975-07-29
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Expires: 1993-10-15
Abstract
Abstract Highly active, hydrothermally stable and ammonia-stable Y zeolite compositions are disclosed, which compositions are useful as adsorbents, hydrocarbon conversion catalysts, and as acidic supports for catalytic metals. The stabilized Y zeolite composition is prepared from a sodium Y zeolite by a novel sequence of: (1) partial exchange of ammonium ions for sodium ions, (2) steam calcination under controlled conditions of time, temperature and steam partial pressure, and (3) further ion exchange of ammonium ions for sodium ions to reduce the final Na2O content to below about one weight-percent.
Inventors
- 👤 John W Ward
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 19:48
CPC Classifications
C; C10; C10G; C10G47/00; C10G47/02; C10G47/10; C10G47/12; C10G47/16; B; B01; B01J; B01J20/00; B01J20/02; B01J20/10; B01J20/16; B01J20/18; B01J29/00; B01J29/04; B01J29/06; B01J29/064; B01J29/068; B01J29/08; B01J29/084; B01J29/10; B01J29/14; B01J29/146; B01J29/16; B01J29/166; B01J29/60; B01J29/64; C10G11/00; C10G11/02; C10G11/04; C10G11/05; C10G35/00; C10G35/04; C10G35/06; C10G35/095; C10G45/00; C10G45/58; C10G45/60; C10G45/64; B01J2229/00; B01J2229/10; B01J2229/26; B01J2229/30; B01J2229/36; B01J2229/40; B01J2229/42
Claims Analysis
Total Claims: 38
Claim 1
Independent Claim
65 words
CALCINING AN AMMONIUM-SODIUM Y ZEOLITE CONTAINING ABOUT 0.6 - 5 WEIGHT-PERCENT OF SODIUM AS NA2O, SAID CALCINING BEING CARRIED OUT AT A TEMPERATURE BETWEEN ABOUT 600* AND 1650*F IN CONTACT WITH AT LEAST ABOUT 00.2 PSI OF WATER VAPOR FOR A SUFFICIENT TIME TO SUBSTANTIALLY REDUCE THE UNIT CELL ZSIZE OF SAID ZEOLITE AND BRING IT TO A VALUE BETWEEN ABOUT 24.40 AND 24.64 A,
Claim 2
Dependent Claim
65 words
CALCINING AN AMMONIUM-SODIUM Y ZEOLITE CONTAINING ABOUT 0.6 - 5 WEIGHT-PERCENT OF SODIUM AS NA2O, SAID CALCINING BEING CARRIED OUT AT A TEMPERATURE BETWEEN ABOUT 600* AND 1650*F IN CONTACT WITH AT LEAST ABOUT 00.2 PSI OF WATER VAPOR FOR A SUFFICIENT TIME TO SUBSTANTIALLY REDUCE THE UNIT CELL ZSIZE OF SAID ZEOLITE AND BRING IT TO A VALUE BETWEEN ABOUT 24.40 AND 24.64 A,
Claim 3
Dependent Claim
71 words
A PROCESS FOR THE HYDROCRACKING OF A HYDROCARBON FEEDSTOCK TO PRODUCE A LOWER BOILING HYDROCARBON PRODUCE, WHICH COMPRISES SUBJECTING SAID FEEDSTOCK PLUS ADDED HYDROGEN TO HYDROCRACKING CONDITIONS OF PRESSURE AND TEMPERATURE IN CONTACT WITH A CATALYST COMPRISING A GROUP VIB AND/OR GROUP VIII METAL, METAL OXIDE OR METAL SULFIDE HYDROGENATING COMPONENT INTIMATELY DISPERSED IN A STABILIZED METAL-CATION-DEFICIENT Y ZEOLITE CRACKING BASE, SAID CRACKING BASE HAVING BEEN PREPARED BY THE STEPS OF:
Claim 4
Dependent Claim
71 words
A PROCESS FOR THE HYDROCRACKING OF A HYDROCARBON FEEDSTOCK TO PRODUCE A LOWER BOILING HYDROCARBON PRODUCE, WHICH COMPRISES SUBJECTING SAID FEEDSTOCK PLUS ADDED HYDROGEN TO HYDROCRACKING CONDITIONS OF PRESSURE AND TEMPERATURE IN CONTACT WITH A CATALYST COMPRISING A GROUP VIB AND/OR GROUP VIII METAL, METAL OXIDE OR METAL SULFIDE HYDROGENATING COMPONENT INTIMATELY DISPERSED IN A STABILIZED METAL-CATION-DEFICIENT Y ZEOLITE CRACKING BASE, SAID CRACKING BASE HAVING BEEN PREPARED BY THE STEPS OF:
Claim 5
Dependent Claim
15 words
A process as defined in claim 1 wherein said hydrogenating component is palladium and/or platinum.
Claim 6
Dependent Claim
40 words
subjecting the calcined zeolite to further ammonium ion exchange under conditions adjusted to replace at least about 25 percent of its residual zeolitic sodium ions with ammonium ions and produce a final product containing less than about 1 weight-percent Na2O;
Claim 7
Dependent Claim
40 words
subjecting the calcined zeolite to further ammonium ion exchange under conditions adjusted to replace at least about 25 percent of its residual zeolitic sodium ions with ammonium ions and produce a final product containing less than about 1 weight-percent Na2O;
Claim 8
Dependent Claim
40 words
SUBJECTING THE CALCINED ZEOLITE TO FURTHER AMMONIUM ION EXCHANGE UNDER CONDITIONS ADJUSTED TO REPLACE AT LEAST ABOUT 25 PERCENT OF ITS RESIDUAL ZEOLITIC SODIUM IONS WITH AMMONIUM IONS AND PRODUCE A FINAL PRODUCE CONTAINING LESS THAN ABOUT 1 WEIGHT-PERCENT NA2O,
Claim 9
Dependent Claim
40 words
SUBJECTING THE CALCINED ZEOLITE TO FURTHER AMMONIUM ION EXCHANGE UNDER CONDITIONS ADJUSTED TO REPLACE AT LEAST ABOUT 25 PERCENT OF ITS RESIDUAL ZEOLITIC SODIUM IONS WITH AMMONIUM IONS AND PRODUCE A FINAL PRODUCE CONTAINING LESS THAN ABOUT 1 WEIGHT-PERCENT NA2O,
Claim 10
Dependent Claim
40 words
subjecting the calcined zeolite to further ammonium ion exchange under conditions adjusted to replace at least about 70 percent of its residual zeolitic sodium ions with ammonium ions and produce a final product containing less than about 0.6 weight-percent Na2O;
Claim 11
Dependent Claim
40 words
subjecting the calcined zeolite to further ammonium ion exchange under conditions adjusted to replace at least about 70 percent of its residual zeolitic sodium ions with ammonium ions and produce a final product containing less than about 0.6 weight-percent Na2O;
Claim 12
Dependent Claim
36 words
consolidating the product from step (2) into granules having intimately admixed therein a finely divided hydrous oxide selected from the class consisting of alumina, silica, magnesia, titania, zirconia, thoria, beryllia, chromia, clays and mixtures thereof; and
Claim 13
Dependent Claim
36 words
consolidating the product from step (2) into granules having intimately admixed therein a finely divided hydrous oxide selected from the class consisting of alumina, silica, magnesia, titania, zirconia, thoria, beryllia, chromia, clays and mixtures thereof; and
Claim 14
Dependent Claim
36 words
CONSOLIDATING THE PRODUCT FROM STEP (2) INTO GRANULES HAVING INTIMATELY ASMIXED THEREIN A FINELY DIVIDED HYDROUS OXIDE SELECTED FROM THE CLASS CONSISTING OF ALUMINA, SILICA, MAGNESIA, TITANIA, ZIRCONIA, THORIA, BERYLLIA, CHROMIA, CLAYS AND MIXTURES THEREOF, AND
Claim 15
Dependent Claim
36 words
CONSOLIDATING THE PRODUCT FROM STEP (2) INTO GRANULES HAVING INTIMATELY ASMIXED THEREIN A FINELY DIVIDED HYDROUS OXIDE SELECTED FROM THE CLASS CONSISTING OF ALUMINA, SILICA, MAGNESIA, TITANIA, ZIRCONIA, THORIA, BERYLLIA, CHROMIA, CLAYS AND MIXTURES THEREOF, AND
Claim 16
Dependent Claim
21 words
A process as defined in claim 1 wherein said hydrogenating component comprises nickel and molybdenum as free metals, oxides or sulfides.
Claim 17
Dependent Claim
36 words
consolidating the product from step (2) into granules having intimately admixed therein a finely divided hydrous oxide selected from the class consisting of alumina, silica, magnesia, titania, zirconia, thoria, beryllia, chromia, clays and mixtures thereof; and
Claim 18
Dependent Claim
36 words
consolidating the product from step (2) into granules having intimately admixed therein a finely divided hydrous oxide selected from the class consisting of alumina, silica, magnesia, titania, zirconia, thoria, beryllia, chromia, clays and mixtures thereof; and
Claim 19
Dependent Claim
35 words
calcining the granules at a temperature between about 600* and 1500*F for a time sufficient to effect substantial deammoniation, but insufficient to reduce the unit cell size of the zeolite to below about 24.40 A.
Claim 20
Dependent Claim
35 words
calcining the granules at a temperature between about 600* and 1500*F for a time sufficient to effect substantial deammoniation, but insufficient to reduce the unit cell size of the zeolite to below about 24.40 A.
Claim 21
Dependent Claim
35 words
CALCINING THE GRANULES AT A TEMPERATURE BETWEEN ABOUT 600* AND 1500*F FOR A TIME SUFFICIENT TO EFFECT SUBSTANTIAL DEAMMONIATION, BUT INSUFFICIENT TO REDUCE THE UNIT CELL SIZE OF THE ZEOLITE TO BELOW ABOUT 24.40 A.
Claim 22
Dependent Claim
35 words
CALCINING THE GRANULES AT A TEMPERATURE BETWEEN ABOUT 600* AND 1500*F FOR A TIME SUFFICIENT TO EFFECT SUBSTANTIAL DEAMMONIATION, BUT INSUFFICIENT TO REDUCE THE UNIT CELL SIZE OF THE ZEOLITE TO BELOW ABOUT 24.40 A.
Claim 23
Dependent Claim
31 words
A process as defined in claim 1 wherein said feedstock is a mineral oil fraction boiling predominantly above 400*F, and said hydrocarbon product comprises gasoline and/or turbine fuel and/or diesel fuel.
Claim 24
Dependent Claim
35 words
calcining the granules at a temperature between about 800* and 1500*F for a time sufficient to effect substantial deammoniation, but insufficient to reduce the unit cell size of the zeolite to below about 24.40 A.
Claim 25
Dependent Claim
35 words
calcining the granules at a temperature between about 800* and 1500*F for a time sufficient to effect substantial deammoniation, but insufficient to reduce the unit cell size of the zeolite to below about 24.40 A.
Claim 26
Dependent Claim
17 words
A process as defined in claim 1 wherein step (4) is carried out under substantially dry conditions.
Claim 27
Dependent Claim
14 words
A process as defined in claim 1 wherein said hydrous oxide is essentially alumina.
Claim 28
Dependent Claim
15 words
A process as defined in claim 6 wherein said hydrogenating component is palladium and/or platinum.
Claim 29
Dependent Claim
21 words
A process as defined in claim 6 wherein said hydrogenating component comprises nickel and molybdenum as free metals, oxides or sulfides.
Claim 30
Dependent Claim
71 words
A process for the hydrocracking of a hydrocarbon feedstock to produce a lower boiling hydrocarbon product, which comprises subjecting said feedstock plus added hydrogen to hydrocracking conditions of pressure and temPerature in contact with a catalyst comprising a Group VIB and/or Group VIII metal, metal oxide or metal sulfide hydrogenating component intimately dispersed in a stabilized metal-cation-deficient Y zeolite cracking base, said cracking base having been prepared by the steps of:
Claim 31
Dependent Claim
71 words
A process for the hydrocracking of a hydrocarbon feedstock to produce a lower boiling hydrocarbon product, which comprises subjecting said feedstock plus added hydrogen to hydrocracking conditions of pressure and temPerature in contact with a catalyst comprising a Group VIB and/or Group VIII metal, metal oxide or metal sulfide hydrogenating component intimately dispersed in a stabilized metal-cation-deficient Y zeolite cracking base, said cracking base having been prepared by the steps of:
Claim 32
Dependent Claim
15 words
A process as defined in claim 9 wherein said hydrogenating component is palladium and/or platinum.
Claim 33
Dependent Claim
21 words
A process as defined in claim 9 wherein said hydrogenating component comprises nickel and molybdenum as free metals, oxides or sulfides.
Claim 34
Dependent Claim
31 words
A process as defined in claim 9 wherein said feedstock is a mineral oil fraction boiling predominantly above 400*F, and said hydrocarbon product comprises gasoline and/or turbine fuel and/or diesel fuel.
Claim 35
Dependent Claim
17 words
A process as defined in claim 9 wherein step (4) is carried out under substantially dry conditions.
Claim 36
Dependent Claim
14 words
A process as defined in claim 9 wherein said hydrous oxide is essentially alumina.
Claim 37
Dependent Claim
15 words
A process as defined in claim 14 wherein said hydrogenating component is palladium and/or platinum.
Claim 38
Dependent Claim
21 words
A process as defined in claim 14 wherein said hydrogenating component comprises nickel and molybdenum as free metals, oxides or sulfides.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-07-28 | 1979-01-27 | 1979-07-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-07-28 | 1983-01-27 | 1983-07-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-07-28 | 1987-01-27 | 1987-07-29 | $7700.00 | Window Closed / Lapsed |