US4138326A
Expired / Lapsed
US
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Hydrotreating process and catalyst
Assignee: Gulf Research and Development Co
•
Filing: 1977-08-23
•
Granted: 1979-02-06
•
Expires: 1997-08-23
Abstract
Abstract A catalyst comprising (1) a subgroup of a certain class of nickel and/or cobalt-substituted semicrystalline aluminosilicates which are synthetic and which are predominantly ordered in two directions (laminar clay-like materials); (2) tungsten in the form of its oxide and/or sulfide; and (3) a crystalline zeolite which has an alpha value of at least 20, which is in particulate form, and which is dispersed through the layered aluminosilicate; and processes using this catalyst.
Inventors
- 👤 Harold E. Swift
- 👤 Roger F. Vogel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 19:47
CPC Classifications
C; C10; C10G; C10G47/00; C10G47/02; C10G47/10; C10G47/12; C10G47/16; C10G47/20; B; B01; B01J; B01J23/00; B01J23/70; B01J23/76; B01J23/84; B01J23/85; B01J23/888; B01J37/00; B01J37/04
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
293 words
A catalyst composite consisting essentially of: (A) from 3 to 25 weight percent of tungsten in the form of metal oxide or metal sulfide, or any mixture thereof, calculated as the metal; (B) from 35 to 80 weight percent of a laminar 2:1 layer-lattice aluminosilicate mineral possessing layer-lattice unit cells, each cell having an inherent negative charge balanced by cations exterior to said unit cell, said mineral corresponding to the following overall formula prior to drying and calcining: [(Al3.sup.+.sub.4-ew Y.sup.2+.sub.3w).sup.VI (Q.sup.4+.sub.8-x Al.sup.3+.sub.x).sup.IV O.sub.20 (OH).sub.4-f F.sub.f ]·[dC.sup.y ] where Al is aluminum; Y is selected from the class consisting of nickel, cobalt and mixtures thereof; Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.65 A; and F is fluorine; C is at least one charge-balancing cation; and where e has a numerical value from 2 to 3 inclusive; w has a numerical value from 0.01 to 2 inclusive, with the proviso that the quantity ew have a numerical value from 0.02 to 4 inclusive; f has a value of 4 or less; x has a numerical value from 0.05 to 2.0 inclusive; y is the valence of the cation C; d is the number of cations C where the product dy = x + 3(e-2)w and wherein said first bracket represents said layer-lattice unit cell formulation and said second bracket represents said charge-balancing cations; and (C) from 5 to 50 weight percent of a crystalline zeolite having an alpha value of at least 20; and wherein said composite is formed by: (i) initially coating or impregnating component (B) with component (A); and (ii) thereafter uniformly dispersing component (C) through the mixture of components (A) and (B) formed in step (i).
Claim 2
Dependent Claim
293 words
A catalyst composite consisting essentially of: (A) from 3 to 25 weight percent of tungsten in the form of metal oxide or metal sulfide, or any mixture thereof, calculated as the metal; (B) from 35 to 80 weight percent of a laminar 2:1 layer-lattice aluminosilicate mineral possessing layer-lattice unit cells, each cell having an inherent negative charge balanced by cations exterior to said unit cell, said mineral corresponding to the following overall formula prior to drying and calcining: [(Al3.sup.+.sub.4-ew Y.sup.2+.sub.3w).sup.VI (Q.sup.4+.sub.8-x Al.sup.3+.sub.x).sup.IV O.sub.20 (OH).sub.4-f F.sub.f ]·[dC.sup.y ] where Al is aluminum; Y is selected from the class consisting of nickel, cobalt and mixtures thereof; Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.65 A; and F is fluorine; C is at least one charge-balancing cation; and where e has a numerical value from 2 to 3 inclusive; w has a numerical value from 0.01 to 2 inclusive, with the proviso that the quantity ew have a numerical value from 0.02 to 4 inclusive; f has a value of 4 or less; x has a numerical value from 0.05 to 2.0 inclusive; y is the valence of the cation C; d is the number of cations C where the product dy = x + 3(e-2)w and wherein said first bracket represents said layer-lattice unit cell formulation and said second bracket represents said charge-balancing cations; and (C) from 5 to 50 weight percent of a crystalline zeolite having an alpha value of at least 20; and wherein said composite is formed by: (i) initially coating or impregnating component (B) with component (A); and (ii) thereafter uniformly dispersing component (C) through the mixture of components (A) and (B) formed in step (i).
Claim 3
Dependent Claim
21 words
A composition according to claim 1 werein Y in said laminar 2:1 lattic-layer aluminosilicate mineral is nickel and Q is silicon.
Claim 4
Dependent Claim
23 words
A composition according to claim 2 wherein said zeolite is selected from the group consisting of X and Y zeolites or mixtures thereof.
Claim 5
Dependent Claim
68 words
A composition in accordance with claim 2 wherein said second bracket in said laminar 2:1 layer-lattic aluminosilicate formula has the composition: a M.sup.n + b Al(OH).sup.z.sub.3-z wherein an + bz = dy = x + 3(e-2)w and M is selected from the group consisting of hydrogen, ammonium, multivalent metal cations other than aluminum, and partial hydroxides of multivalent metal cations, and n is the unsatisfied valence of M.
Claim 6
Dependent Claim
24 words
A composition according to claim 4 wherein the amount of nickel in said mineral is from 0.1 to 35 weight percent of said mineral.
Claim 7
Dependent Claim
53 words
A composition according to claim 4 wherein said amount of tungsten is from 6 to 20 weight percent of the composite catalyst; said zeolite is from 10 to 35 weight percent of the composite catalyst; and said laminar 2:1 layer-lattice aluminosilicate mineral is from 40 to 70 weight percent of the composite catalyst.
Claim 8
Dependent Claim
47 words
A catalyst composition according to claim 1 wherein said tungsten component A is uniformly dispersed through said component B from an aqueous solution of a salt of tungsten which is capable of conversion to the oxide form and which salt is thereafter converted to said oxide form.
Claim 9
Dependent Claim
21 words
A composition according to claim 7 wherein Y in said laminar 2:1 layer-lattice aluminosilicate mineral is nickel and Q is silicon.
Claim 10
Dependent Claim
23 words
A composition according to claim 8 wherein said zeolite is selected from the group consisting of X and Y zeolites or mixtures thereof.
Claim 11
Dependent Claim
14 words
A composition according to claim 9 wherein said zeolite is in the hydrogen form.
Claim 12
Dependent Claim
19 words
A composition according to claim 9 wherein said zeolite has a hydrogenation metal at least partially replacing hydrogen ions.
Claim 13
Dependent Claim
12 words
A composition according to claim 11 wherein the hydrogenation metal is nickel.
Claim 14
Dependent Claim
91 words
A catalyst composite consisting essentially of: (A) from 3 to 25 weight percent of tungsten in the form of metal oxide or metal sulfide, or any mixture thereof, calculated as the metal; (B) from 35 to 80 weight percent of a laminar 2:1 layer-lattice aluminosilicate mineral possessing layer-lattice unit cells, each cell having an inherent negative charge balanced by cations exterior to said unit cell, said mineral corresponding to the following overall formula prior to drying and calcining: [(Al3.sup.+.sub.4-ew Y.sup.2+.sub.3w).sup.VI (Q.sup.4+.sub.8-x Al.sup.3+.sub.x).sup.IV O.sub.20 (OH).sub.4-f F.sub.f ]·[dC.sup.y ] where Al is aluminum;
Claim 15
Dependent Claim
91 words
A catalyst composite consisting essentially of: (A) from 3 to 25 weight percent of tungsten in the form of metal oxide or metal sulfide, or any mixture thereof, calculated as the metal; (B) from 35 to 80 weight percent of a laminar 2:1 layer-lattice aluminosilicate mineral possessing layer-lattice unit cells, each cell having an inherent negative charge balanced by cations exterior to said unit cell, said mineral corresponding to the following overall formula prior to drying and calcining: [(Al3.sup.+.sub.4-ew Y.sup.2+.sub.3w).sup.VI (Q.sup.4+.sub.8-x Al.sup.3+.sub.x).sup.IV O.sub.20 (OH).sub.4-f F.sub.f ]·[dC.sup.y ] where Al is aluminum;
Claim 16
Dependent Claim
201 words
Y is selected from the class consisting of nickel, cobalt and mixtures thereof; Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.65 A; and F is fluorine; C is at least one charge-balancing cation; and where e has a numerical value from 2 to 3 inclusive; w has a numerical value from 0.01 to 2 inclusive, with the proviso that the quantity ew have a numerical value from 0.02 to 4 inclusive; f has a value of 4 or less; x has a numerical value from 0.05 to 2.0 inclusive; y is the valence of the cation C; d is the number of cations C where the product dy = x + 3(e-2)w and wherein said first bracket represents said layer-lattice unit cell formulation and said second bracket represents said charge-balancing cations; and (C) from 5 to 50 weight percent of a crystalline zeolite having an alpha value of at least 20; and wherein said composite is formed by: (i) initially admixing component (B) and component (C); and (ii) thereafter coating or impregnating the admixture formed in step (1) of components (B) and (C) with component (A).
Claim 17
Dependent Claim
201 words
Y is selected from the class consisting of nickel, cobalt and mixtures thereof; Q is at least 0.95 mol fraction silicon ions, the remainder consisting of tetravalent ions having an ionic radius not to exceed 0.65 A; and F is fluorine; C is at least one charge-balancing cation; and where e has a numerical value from 2 to 3 inclusive; w has a numerical value from 0.01 to 2 inclusive, with the proviso that the quantity ew have a numerical value from 0.02 to 4 inclusive; f has a value of 4 or less; x has a numerical value from 0.05 to 2.0 inclusive; y is the valence of the cation C; d is the number of cations C where the product dy = x + 3(e-2)w and wherein said first bracket represents said layer-lattice unit cell formulation and said second bracket represents said charge-balancing cations; and (C) from 5 to 50 weight percent of a crystalline zeolite having an alpha value of at least 20; and wherein said composite is formed by: (i) initially admixing component (B) and component (C); and (ii) thereafter coating or impregnating the admixture formed in step (1) of components (B) and (C) with component (A).
Claim 18
Dependent Claim
81 words
A composition according to claim 3 wherein Y in said laminar 2:1 layer-lattice aluminosilicate mineral is nickel, Q is silicon, and the second bracket in said laminar 2:1 layer-lattice aluminosilicate mineral formula has the composition: aM.sup.n + b Al(OH).sub.3-z.sup.z wherein an + bz = dy = x + 3(e-2)w and M is selected from the group consisting of hydrogen, ammonium, multivalent metal cations other than aluminum, and partial hydroxides or multivalent metal cations, and n is the unsatisfied valence of M.
Claim 19
Dependent Claim
23 words
A composition according to claim 14 wherein said zeolite is selected from the group consisting of X and Y zeolites or mixtures thereof.
Claim 20
Dependent Claim
71 words
A composition according to claim 15 wherein the amount of nickel in said mineral is from 0.1 to 35 weight percent of said mineral; the laminar 2:1 layer-lattice aluminosilicate mineral is from 40 to 70 weight percent of the catalyst composite; the amount of tungsten is from 6 to 20 weight percent of the catalyst composite; and the zeolite component is from 10 to 35 weight percent of the catalyst composite.
Claim 21
Dependent Claim
51 words
A catalyst composition according to claim 13 wherein said tungsten component A is uniformly dispersed through said admixture of components B and C from an aqueous solution of a salt of tungsten which is capable of conversion to the oxide form and which salt is thereafter converted to said oxide form.
Claim 22
Dependent Claim
21 words
A composition according to claim 17 wherein Y in said laminar 2:1 layer-lattice aluminosilicate mineral is nickel, and Q is silica.
Claim 23
Dependent Claim
23 words
A composition according to claim 18 wherein said zeolite is selected from the group consisting of X and Y zeolites or mixtures thereof.
Claim 24
Dependent Claim
14 words
A composition according to claim 19 wherein said zeolite is in a hydrogen form.
Claim 25
Dependent Claim
19 words
A composition according to claim 19 wherein said zeolite has a hydrogenation metal at least partially replacing hydrogen ions.
Claim 26
Dependent Claim
12 words
A composition according to claim 21 wherein the hydrogenation metal is nickel.
Claim 27
Dependent Claim
70 words
A hydrotreating process which comprises contacting a hydrocarbon feed containing substantial amounts of materials boiling above 200° F. and selected from the group consisting of petroleum distillates, solvent deasphalted petroleum residua, shale oils and coal derived liquids or coal tar distillates in a reaction zone with hydrogen at hydrotreating conditions to obtain the conversion of at least 25 volume percent of said hydrocarbon feed with the catalyst of claim 1.
Claim 28
Dependent Claim
79 words
A process according to claim 23 wherein said hydrotreating conditions include a temperature in the range of 400° to 950° F., a pressure in the range of 800 to 3500 psig, and a liquid hourly space velocity in the range of 0.25 to 5.0 volumes of charge stock per volume of catalyst per hour, and a total hydrogen supply rate of 800 to 20,000 SCF of hydrogen per barrel of feedstock and recovering hydrotreated products from said reaction zone.
Claim 29
Dependent Claim
21 words
A process according to claim 24 wherein Y in said laminar 2:1 layer-lattice aluminosilicate mineral is nickel and Q is silicon.
Claim 30
Dependent Claim
12 words
A process according to claim 25 wherein said zeolite is a Y-zeolite.
Claim 31
Dependent Claim
14 words
A process according to claim 26 wherein said Y-zeolite is in the hydrogen form.
Claim 32
Dependent Claim
20 words
A process according to claim 26 wherein said Y-zeolite has a hydrogenation metal at least partially replacing the hydrogen ions.
Claim 33
Dependent Claim
12 words
A process according to claim 28 wherein said hydrogenation metal is nickel.
Claim 34
Dependent Claim
69 words
A process in accordance with claim 29 wherein said second bracket in said laminar 2:1 layer-lattice aluminosilicate mineral formula has the composition: a M.sup.n + b Al(OH).sup.z.sub.3-z wherein an + bz = dy = x + 3(e-2)w and M is selected from the group consisting of hydrogen, ammonium, multivalent metal cations other than aluminum, and partial hydroxides of multivalent metal cations, and n is the unsatisfied valence of M.
Claim 35
Dependent Claim
25 words
A process in accordance with claim 30 wherein said charge stock is a petroleum charge stock boiling from 400° to 1100° F. at atmospheric pressure.
Claim 36
Dependent Claim
69 words
A hydrotreating process which comprises contacting a hydrocarbon feed containing substantial amounts of materials boiling above 200° F. and selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal derived liquids or coal tar distillates in a reaction zone with hydrogen at hydrotreating conditions to obtain the conversion of at least 25 volume percent of said hydrocarbon feed with the catalyst of claim 13.
Claim 37
Dependent Claim
79 words
A process according to claim 32 wherein said hydrotreating conditions include a temperature in the range of 400° to 950° F., a pressure in the range of 800 to 3500 psig, and a liquid hourly space velocity in the range of 0.25 to 5.0 volumes of charge stock per volume of catalyst per hour, and a total hydrogen supply rate of 800 to 20,000 SCF of hydrogen per barrel of feedstock and recovering hydrotreated products from said reaction zone.
Claim 38
Dependent Claim
18 words
A process according to claim 33 wherein the conversion is from 50% to 75% of said hydrocarbon feed.
Claim 39
Dependent Claim
20 words
A process according to claim 33 wherein the hydrocarbon feed has a nitrogen content ranging from 350 to 4000 ppm.
Claim 40
Dependent Claim
30 words
A process according to claim 35 wherein the hydrocarbon feed has from 700 to 1800 ppm of nitrogen and a product is recovered having less than 10 ppm of nitrogen.
Claim 41
Dependent Claim
21 words
A process according to claim 33 wherein Y in said laminar 2:1 layer-lattice aluminosilicate mineral is nickel and Q is silicon.
Claim 42
Dependent Claim
12 words
A process according to claim 37 wherein said zeolite is a Y-zeolite.
Claim 43
Dependent Claim
14 words
A process according to claim 38 wherein said Y-zeolite is in the hydrogen form.
Claim 44
Dependent Claim
20 words
A process according to claim 38 wherein said Y-zeolite has a hydrogenation metal at least partially replacing the hydrogen ions.
Claim 45
Dependent Claim
12 words
A process according to claim 40 wherein said hydrogenation metal is nickel.
Claim 46
Dependent Claim
69 words
A process in accordance with claim 41 wherein said second bracket in said laminar 2:1 layer-lattice aluminosilicate mineral formula has the composition: a M.sup.n + b Al(OH).sup.z.sub.3-z wherein an + bz = dy = x + 3(e-2)w and M is selected from the group consisting of hydrogen, ammonium, multivalent metal cations other than aluminum, and partial hydroxides of multivalent metal cations, and n is the unsatisfied valence of M.
Claim 47
Dependent Claim
25 words
A process in accordance with claim 42 wherein said charge stock is a petroleum charge stock boiling from 400° to 1100° F. at atmospheric pressure.
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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) | 1982-02-05 | 1982-08-07 | 1983-02-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-02-05 | 1986-08-07 | 1987-02-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-02-05 | 1990-08-07 | 1991-02-06 | $7700.00 | Window Closed / Lapsed |