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US4548705A
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US
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Hydrocracking with catalytically active amorphous silica and zeolites
Assignee: Honeywell UOP LLC
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Filing: 1984-08-29
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Granted: 1985-10-22
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Expires: 2004-08-29
Abstract
Abstract Catalytically active amorphous silicas are prepared by dehydrating a silica hydrogel or precipitate prepared from an acidified aqueous silicate solution containing an amine of pK a above 10 or a cation containing either a nitrogen or phosphorus atom bonded to four carbon atoms. The resultant amorphous silica is catalytically active for, among other chemical reactions, the isomerization of orthoxylene and the cracking of hydrocarbons.
Inventors
- 👤 Dean A. Young
- 👤 Jeffery W. Koepke
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 06:02
CPC Classifications
C; C10; C10G; C10G11/00; C10G11/02; C10G11/04; B; B01; B01J; B01J21/00; B01J21/06; B01J21/08; C07; C07C; C07C5/00; C07C5/22; C07C5/27; C07C5/2729; C07C5/2732; C07C5/2756; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/52
Claims Analysis
Total Claims: 55
Claim 1
Independent Claim
106 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions including an elevated temperature and pressure with a catalyst prepared by a method comprising forming a hydrogel or precipitate in a reaction mixture comprising water, silicate anions and an organic reactant selected from the group consisting of amines having a pK a value above about 10.0, quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, quaternary phosphonium cations having a phosphorus atom bonded to four carbon atoms, precursors of the foregoing and mixtures thereof, and dehydrating the resultant hydrogel or precipitate to yield a product containing amorphous silica.
Claim 2
Dependent Claim
106 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions including an elevated temperature and pressure with a catalyst prepared by a method comprising forming a hydrogel or precipitate in a reaction mixture comprising water, silicate anions and an organic reactant selected from the group consisting of amines having a pK a value above about 10.0, quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, quaternary phosphonium cations having a phosphorus atom bonded to four carbon atoms, precursors of the foregoing and mixtures thereof, and dehydrating the resultant hydrogel or precipitate to yield a product containing amorphous silica.
Claim 3
Dependent Claim
17 words
The process defined in claim 1 wherein said hydrocracking conditions include a temperature above about 900° F.
Claim 4
Dependent Claim
29 words
The process defined in claim 1 wherein said catalyst further comprises at least one hydrogenation metal component selected from the group consisting of Group VIB and Group VIII metals.
Claim 5
Dependent Claim
22 words
The process defined in claim 1 wherein said catalyst further comprises at least one hydrogenation component and at least one zeolite component.
Claim 6
Dependent Claim
15 words
The process defined in claim 4 wherein said zeolite component comprises a stabilized Y zeolite.
Claim 7
Dependent Claim
37 words
The process defined in claim 1 wherein said organic reactant is a quaternary ammonium cation and said carbon atoms in said quaternary ammonium cation are each members of alkyl groups containing between 1 and 6 carbon atoms.
Claim 8
Dependent Claim
33 words
A method as defined in claim 1 wherein the pH of the reaction mixture is between about 8 and 12 and wherein the reaction mixture producing said hydrogel is maintained below 100° C.
Claim 9
Dependent Claim
63 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising forming a hydrogel in a reaction mixture comprising water, silicate anions and quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, and dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 10
Dependent Claim
63 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising forming a hydrogel in a reaction mixture comprising water, silicate anions and quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, and dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 11
Dependent Claim
24 words
The process defined in claim 8 wherein said hydrocracking conditions include a temperature above about 900° F. and a pressure above about 500 p.s.i.g.
Claim 12
Dependent Claim
29 words
The process defined in claim 8 wherein said catalyst further comprises at least one hydrogenation metal component selected from the group consisting of Group VIB and Group VIII metals.
Claim 13
Dependent Claim
23 words
The process defined in class 8 wherein said catalyst further comprises at least one hydrogenation metal component and at least one zeolite component.
Claim 14
Dependent Claim
23 words
The process defined in class 8 wherein said catalyst further comprises at least one hydrogenation metal component and at least one zeolite component.
Claim 15
Dependent Claim
15 words
The process defined in claim 8 wherein said zeolite component comprises a stabilized Y zeolite.
Claim 16
Dependent Claim
105 words
A method as defined in claim 8 wherein said quaternary ammonium cation is introduced into said reaction mixture by addition of one or more precursors thereof, said precursors being selected from the group consisting of (1) quaternary ammonium compounds containing a nitrogen atom bonded to four carbon atoms and having at least some solubility in water and (2) amines or ammonia in combination with an emulsifying agent and one or more alkyl compounds containing a halide or sulfate, said alkyl compounds being present in an amount at least sufficient to bond at least one nitrogen atom of the amines or ammonia to four carbon atoms.
Claim 17
Dependent Claim
33 words
A method as defined in claim 8 wherein the pH of the reaction mixture is between about 8 and 12 and wherein the reaction mixture producing said hydrogel is maintained below 100° C.
Claim 18
Dependent Claim
86 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising acidifying a reaction mixture comprising sodium silicate, water and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, allowing a hydrogel to form in the reaction mixture, separating the hydrogel from the reaction mixture and removing one or more metals from said hydrogel, and dehydrating said hydrogel to produce a product containing a substantial proportion of amorphous silica gel.
Claim 19
Dependent Claim
86 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising acidifying a reaction mixture comprising sodium silicate, water and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, allowing a hydrogel to form in the reaction mixture, separating the hydrogel from the reaction mixture and removing one or more metals from said hydrogel, and dehydrating said hydrogel to produce a product containing a substantial proportion of amorphous silica gel.
Claim 20
Dependent Claim
14 words
The process defined in claim 15 wherein said catalyst further comprises a hydrogenation component.
Claim 21
Dependent Claim
13 words
The process defined in claim 15 wherein said catalyst further comprises a zeolite.
Claim 22
Dependent Claim
17 words
The process defined in claim 15 wherein said hydrocracking conditions include a temperature above about 900° F.
Claim 23
Dependent Claim
42 words
A method as defined in claim 15 wherein said reaction mixture contains sodium as essentially the only alkali or alkaline earth metal therein, and after said sodium removal, said hydrogel contains sodium to silicon in an atom ratio less than about 0.10.
Claim 24
Dependent Claim
40 words
A method as defined in claim 15 wherein said acidifying produces in the reaction mixture a pH between about 10 and 12, and during the formation of said hydrogel, the reaction mixture is maintained at a temperature below 100° C.
Claim 25
Dependent Claim
163 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising (a) forming a hydrogel in a reaction mixture comprising water, silicate anions and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, said quaternary ammonium cation is introduced into said reaction mixture by addition of one or more precursors thereof, said precursors being selected from the group consisting of (1) quaternary ammonium compounds containing a nitrogen atom bonded to four carbon atoms and having at least some solubility in water and (2) amines or ammonia in combination with an emulsifying agent and one or more alkyl compounds containing a halide or sulfate, said alkyl compounds being present in an amount at least sufficient to bond at least one nitrogen atom of the amines or ammonia to four carbon atoms, and (b) dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 26
Dependent Claim
163 words
A hydrocracking process comprising contacting a hydrocarbon in the presence of hydrogen under hydrocracking conditions with a catalyst prepared by a method comprising (a) forming a hydrogel in a reaction mixture comprising water, silicate anions and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, said quaternary ammonium cation is introduced into said reaction mixture by addition of one or more precursors thereof, said precursors being selected from the group consisting of (1) quaternary ammonium compounds containing a nitrogen atom bonded to four carbon atoms and having at least some solubility in water and (2) amines or ammonia in combination with an emulsifying agent and one or more alkyl compounds containing a halide or sulfate, said alkyl compounds being present in an amount at least sufficient to bond at least one nitrogen atom of the amines or ammonia to four carbon atoms, and (b) dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 27
Dependent Claim
17 words
The process defined in claim 21 wherein said hydrocracking conditions include a temperature above about 900° F.
Claim 28
Dependent Claim
29 words
The process defined in claim 21 wherein said catalyst further comprises at least one hydrogenation metal component selected from the group consisting of Group VIB and Group VIII metals.
Claim 29
Dependent Claim
22 words
The process defined in class 21 wherein said catalyst further comprises at least one hydrogenation component and at least one zeolite component.
Claim 30
Dependent Claim
22 words
The process defined in class 21 wherein said catalyst further comprises at least one hydrogenation component and at least one zeolite component.
Claim 31
Dependent Claim
15 words
The process defined in claim 21 wherein said zeolite component comprises a stabilized Y zeolite.
Claim 32
Dependent Claim
94 words
A hydrodewaxing process comprising contacting a hydrocarbon under hydrodewaxing conditions with a catalyst prepared by a method comprising forming a hydrogel or precipitate in a reaction mixture comprising water, silicate anions and an organic reactant selected from the group consisting of amines having a pK a value above 10.0, quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, quaternary phosphonium cations having a phosphorus atom bonded to four carbon atoms, precursors of the foregoing and mixtures thereof, and dehydrating the resultant hydrogel or precipitate to yield a product containing amorphous silica.
Claim 33
Dependent Claim
94 words
A hydrodewaxing process comprising contacting a hydrocarbon under hydrodewaxing conditions with a catalyst prepared by a method comprising forming a hydrogel or precipitate in a reaction mixture comprising water, silicate anions and an organic reactant selected from the group consisting of amines having a pK a value above 10.0, quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, quaternary phosphonium cations having a phosphorus atom bonded to four carbon atoms, precursors of the foregoing and mixtures thereof, and dehydrating the resultant hydrogel or precipitate to yield a product containing amorphous silica.
Claim 34
Dependent Claim
17 words
The process defined in claim 26 wherein said hydrodewaxing conditions include a pressure above about 500 p.s.i.g.
Claim 35
Dependent Claim
29 words
The process defined in claim 26 wherein said catalyst further comprises at least one hydrogenation metal component selected from the group consisting of Group VIB and Group VIII metals.
Claim 36
Dependent Claim
22 words
The process defined in claim 26 wherein said catalyst further comprises at least one hydrogenation component and at least one zeolite component.
Claim 37
Dependent Claim
14 words
The process defined in claim 29 wherein said zeolite component comprises a ZSM-5-type zeolite.
Claim 38
Dependent Claim
37 words
The process defined in claim 26 wherein said organic reactant is a quaternary ammonium cation and said carbon atoms in said quaternary ammonium cation are each members of alkyl groups containing between 1 and 6 carbon atoms.
Claim 39
Dependent Claim
12 words
The process defined in claim 26 wherein said catalyst further comprises silicalite.
Claim 40
Dependent Claim
18 words
The process defined in claim 26 wherein said catalyst further comprises nickel and tungsten hydrogenation components and silicalite.
Claim 41
Dependent Claim
33 words
A process as defined in claim 26 wherein the pH of the reaction mixture is between about 8 and 12 and wherein the reaction mixture producing said hydrogel is maintained below 100° C.
Claim 42
Dependent Claim
163 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising (a) forming a hydrogel in a reaction mixture comprising water, silicate anions and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, said quaternary ammonium cation is introduced into said reaction mixture by addition of one or more precursors thereof, said precursors being selected from the group consisting of (1) quaternary ammonium compounds containing a nitrogen atom bonded to four carbon atoms and having at least some solubility in water and (2) amines or ammonia in combination with an emulsifying agent and one or more alkyl compounds containing a halide or sulfate, said alkyl compounds being present in an amount at least sufficient to bond pat least one nitogen atom of the amines or ammonia to four carbon atoms, and (b) dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 43
Dependent Claim
163 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising (a) forming a hydrogel in a reaction mixture comprising water, silicate anions and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, said quaternary ammonium cation is introduced into said reaction mixture by addition of one or more precursors thereof, said precursors being selected from the group consisting of (1) quaternary ammonium compounds containing a nitrogen atom bonded to four carbon atoms and having at least some solubility in water and (2) amines or ammonia in combination with an emulsifying agent and one or more alkyl compounds containing a halide or sulfate, said alkyl compounds being present in an amount at least sufficient to bond pat least one nitogen atom of the amines or ammonia to four carbon atoms, and (b) dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 44
Dependent Claim
17 words
The process defined in claim 35 wherein said hydrodewaxing conditions include a pressure above about 500 p.s.i.g.
Claim 45
Dependent Claim
29 words
The process defined in claim 35 wherein said catalyst further comprises at least one hydrogenation metal component selected from the group consisting of Group VIB and Group VIII metals.
Claim 46
Dependent Claim
23 words
The process defined in claim 35 wherein said catalyst further comprises at least one hydrogenation metal component and at least one zeolite component.
Claim 47
Dependent Claim
14 words
The process defined in claim 38 wherein said zeolite component comprises a ZSM-5-type zeolite.
Claim 48
Dependent Claim
12 words
The process defined in claim 35 wherein said catalyst further comprises silicalite.
Claim 49
Dependent Claim
18 words
The process defined in claim 35 wherein said catalyst further comprises nickel and tungsten hydrogenation components and silicalite.
Claim 50
Dependent Claim
42 words
A process as defined in claim 35 wherein said reaction mixture contains sodium as essentially the only alkali or alkaline earth metal therein, and after said sodium removal, said hydrogel contains sodium to silicon in an atom ratio less than about 0.10.
Claim 51
Dependent Claim
40 words
A process as defined in claim 35 wherein said acidifying produces in the reaction mixture a pH between about 10 and 12, and during the formation of said hydrogel, the reaction mixture is maintained at a temperature below 100° C.
Claim 52
Dependent Claim
63 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising forming a hydrogel in a reaction mixture comprising water, silicate anions and quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, and dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 53
Dependent Claim
63 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising forming a hydrogel in a reaction mixture comprising water, silicate anions and quaternary ammonium cations having a nitrogen atom bonded to four carbon atoms, and dehydrating the hydrogel to yield a product containing a substantial proportion of amorphous silica gel.
Claim 54
Dependent Claim
88 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising acidifying a reaction mixture comprising sodium silicate, water and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, forming a hydrogel in the reaction mixture, separating the hydrogel from the reaction mixture, separating the hydrogel from the reaction mixture and removing sodium from said hydrogel, and dehydrating said hydrogel to produce a product containing a substantial proportion of amorphous silica gel.
Claim 55
Dependent Claim
88 words
A hydrodewaxing process comprising contacting a hydrocarbon in the presence of hydrogen under hydrodewaxing conditions with a catalyst prepared by a method comprising acidifying a reaction mixture comprising sodium silicate, water and a quaternary ammonium cation having a nitrogen atom bonded to four carbon atoms, forming a hydrogel in the reaction mixture, separating the hydrogel from the reaction mixture, separating the hydrogel from the reaction mixture and removing sodium from said hydrogel, and dehydrating said hydrogel to produce a product containing a substantial proportion of amorphous silica gel.
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| 3.5 Years (Year 4) | 1988-10-21 | 1989-04-22 | 1989-10-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-10-21 | 1993-04-22 | 1993-10-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-10-21 | 1997-04-22 | 1997-10-22 | $7700.00 | Window Closed / Lapsed |