US4565621A
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Hydrocracking with rare earth-containing Y zeolite compositions
Assignee: Honeywell UOP LLC
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Filing: 1984-01-09
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Granted: 1986-01-21
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Expires: 2004-01-09
Abstract
Abstract Y Zeolites are prepared with rare earth cations and Group VIII metal cations exchanged thereinto, such zeolites being especially useful in hydrocracking catalysts. The zeolites of the invention are prepared by exchanging a sodium Y zeolite with cations of one or more rare earth elements followed by a calcination, an ammonium ion exchange, and a Group VIII metal cation exchange. The resultant zeolite is not only highly active for catalytically promoting hydrocracking reactions but is also, after use in hydrocracking environments resulting in coke deposition, essentially completely regenerable by combustion of the coke.
Inventors
- 👤 John W. Ward
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 20:00
CPC Classifications
C; C10; C10G; C10G47/00; C10G47/02; C10G47/10; C10G47/12; C10G47/16; C10G47/18; B; B01; B01J; B01J29/00; B01J29/04; B01J29/06; B01J29/08; B01J29/10; B01J29/12; B01J29/126; C10G47/20; C10G65/00; C10G65/02; C10G65/12
Claims Analysis
Total Claims: 29
Claim 1
Independent Claim
110 words
A hydrocracking process which comprises contacting a hydrocarbon feedstock with hydrogen in the presence of a hydrocracking catalyst under hydrocracking conditions, said catalyst containing a zeolite having been prepared by a process comprising: (a) cation-exchanging a type Y crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; and (d) introducing, after said ammonium ion exchange of step (c), a metal component consisting essentially of one or more noble metal-containing cations into said zeolite by cation exchange.
Claim 2
Dependent Claim
110 words
A hydrocracking process which comprises contacting a hydrocarbon feedstock with hydrogen in the presence of a hydrocracking catalyst under hydrocracking conditions, said catalyst containing a zeolite having been prepared by a process comprising: (a) cation-exchanging a type Y crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; and (d) introducing, after said ammonium ion exchange of step (c), a metal component consisting essentially of one or more noble metal-containing cations into said zeolite by cation exchange.
Claim 3
Dependent Claim
170 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst comprising an intimate mixture of a porous refractory oxide and a type Y crystalline aluminosilicate zeolite containing a rare earth metal and a hydrogenation metal, said catalyst having been prepared by a process comprising: (a) cation-exchanging a type Y crystalline alumino-silicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) introducing, after said ammonium ion exchange of step (c), a hydrogenation metal component consisting essentially of one or more Group VIB or Group VIII metal-containing cations into said zeolite by cation exchange, and subsequently (e) mixing the zeolite from step (d) with a porous refractory oxide component and calcining the resultant mixture.
Claim 4
Dependent Claim
170 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst comprising an intimate mixture of a porous refractory oxide and a type Y crystalline aluminosilicate zeolite containing a rare earth metal and a hydrogenation metal, said catalyst having been prepared by a process comprising: (a) cation-exchanging a type Y crystalline alumino-silicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) introducing, after said ammonium ion exchange of step (c), a hydrogenation metal component consisting essentially of one or more Group VIB or Group VIII metal-containing cations into said zeolite by cation exchange, and subsequently (e) mixing the zeolite from step (d) with a porous refractory oxide component and calcining the resultant mixture.
Claim 5
Dependent Claim
25 words
A process as defined by claim 1 wherein the ammonium-exchanged zeolite from step (c) is calcined prior to introducing said metal component into said zeolite.
Claim 6
Dependent Claim
21 words
A process as defined by claim 1 or claim 2 wherein said zeolite in step (a) comprises a sodium Y zeolite.
Claim 7
Dependent Claim
42 words
A process as defined by claim 1 or 2 wherein said zeolite in step (a) initially is a sodium Y zeolite and said calcining is accomplished in the presence of water vapor at a water vapor partial pressure above about 1.0 p.s.i.a.
Claim 8
Dependent Claim
19 words
A process as defined by claim 2 wherein said hydrogenation metal component consists essentially of Group VIII metal-containing cations.
Claim 9
Dependent Claim
17 words
A process as defined by claim 6 wherein said Group VIII metal-containing cations comprise noble metal-containing cations.
Claim 10
Dependent Claim
19 words
A process as defined by claim 1 or 7 wherein said noble metal-containing cations comprise palladium or platinum-containing cations.
Claim 11
Dependent Claim
16 words
A process as defined by claim 1, 6, or 7 wherein said hydrocracking conditions are ammonia-deficient.
Claim 12
Dependent Claim
34 words
A process as defined by claim 1 or 2 wherein said calcination in the presence of water vapor is carried out at a water vapor partial pressure between about 2 and about 15 p.s.i.a.
Claim 13
Dependent Claim
31 words
A process as defined by claim 2 including the additional step of calcining the zeolite product from step (d) prior to mixing said zeolite product with said porous refractory oxide component.
Claim 14
Dependent Claim
32 words
A process as defined by claim 1 or 2 wherein the unit cell size of said zeolite after the calcination of step (b) is between about 24.20 Angstroms and about 24.64 Angstroms.
Claim 15
Dependent Claim
29 words
A process as defined by claim 4 wherein said zeolite after said ammonium ion exchange contains less than about 0.5 percent by weight sodium, calculated as Na 2 O.
Claim 16
Dependent Claim
29 words
A process as defined by claim 4 wherein said zeolite after said ammonium ion exchange contains less than about 0.05 percent by weight sodium, calculated as Na 2 O.
Claim 17
Dependent Claim
26 words
A process as defined by claim 2 wherein said calcination in step (b) is carried out in the presence of an atmosphere consisting essentially of steam.
Claim 18
Dependent Claim
73 words
A process as defined by claim 1 or 2 wherein after said ammonium ion exchange said zeolite is exchanged with noble metal cations, with the resulting zeolite containing at least about 2.0 percent by weight rare earth metals, calculated as RE 2 O 3 , less than 0.5 percent by weight sodium, calculated as Na 2 O, and at least about 0.1 percent by weight of total noble metals, calculated as the metals.
Claim 19
Dependent Claim
126 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst prepared by a process consisting essentially of: (a) cation-exchanging a type of crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) ion-exchanging the ammonium-exchanged zeolite from step (c) with Group VIII metal cations; and (e) mixing the Group VIII metal cation-exchanged zeolite from step (d) with a porous refractory oxide component and calcining the resulting mixture.
Claim 20
Dependent Claim
126 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst prepared by a process consisting essentially of: (a) cation-exchanging a type of crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) ion-exchanging the ammonium-exchanged zeolite from step (c) with Group VIII metal cations; and (e) mixing the Group VIII metal cation-exchanged zeolite from step (d) with a porous refractory oxide component and calcining the resulting mixture.
Claim 21
Dependent Claim
133 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst prepared by a process consisting essentially of: (a) cation-exchanging a type Y crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) calcining the ammonium-exchanged zeolite from step (c); (e) ion-exchanging the calcined zeolite from step (d) with Group VIII metal cations; and (f) mixing the Group VIII metal-exchanged zeolite from step (e) with a porous refractory oxide component and calcining the resulting mixture.
Claim 22
Dependent Claim
133 words
A process for hydrocracking a hydrocarbon feedstock to produce a product of lower average boiling point which process comprises contacting said hydrocarbon feedstock with molecular hydrogen under hydrocracking conditions in the presence of a catalyst prepared by a process consisting essentially of: (a) cation-exchanging a type Y crystalline aluminosilicate zeolite with rare earth-containing cations; (b) calcining the resultant rare earth-exchanged zeolite in the presence of water vapor at a water vapor partial pressure of at least about 0.2 p.s.i.a.; (c) ion-exchanging the calcined zeolite from step (b) with ammonium ions; (d) calcining the ammonium-exchanged zeolite from step (c); (e) ion-exchanging the calcined zeolite from step (d) with Group VIII metal cations; and (f) mixing the Group VIII metal-exchanged zeolite from step (e) with a porous refractory oxide component and calcining the resulting mixture.
Claim 23
Dependent Claim
19 words
A process as defined by claim 17 or 18 wherein said Group VIII metal cations comprise noble metal cations.
Claim 24
Dependent Claim
15 words
A process as defined by claim 19 where said noble metal cations comprise palladium cations.
Claim 25
Dependent Claim
42 words
A process as defined by claim 17 or 18 wherein said calcination in the presence of water vapor is carried out at a temperature between about 1100° F. and about 1350° F. and a water vapor partial pressure above about 12 p.s.i.a.
Claim 26
Dependent Claim
36 words
A process as defined by claim 1, 2, 17 or 18 wherein said rare earth cation exchange introduces a mixture of rare earth cations into said zeolite, said mixture containing cerium, lanthanum, praeseodymium, and neodymium cations.
Claim 27
Dependent Claim
48 words
A process as defined by claim 17 or 18 wherein said calcination in step (b) is carried out so as to effect at least some reduction in the unit cell size of said zeolite with the resultant unit cell size being between about 24.20 Angstroms and 24.64 Angstroms.
Claim 28
Dependent Claim
20 words
A process as defined by claim 17 or 18 wherein said zeolite in step (a) comprises a sodium Y zeolite.
Claim 29
Dependent Claim
29 words
A process as defined by claim 24 wherein said zeolite after said ammonium ion exchange contains less than about 0.5 percent by weight sodium, calculated as Na 2 O.
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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) | 1989-01-20 | 1989-07-22 | 1990-01-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1993-01-20 | 1993-07-22 | 1994-01-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1997-01-20 | 1997-07-22 | 1998-01-21 | $7700.00 | Window Closed / Lapsed |