US4269737A
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Method for preparing a group IVB, VB or VIB metal oxide on inorganic refractory oxide support catalyst and the product prepared by said method
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1979-10-05
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Granted: 1981-05-26
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Expires: 1999-10-05
Abstract
Abstract An acid catalyst comprising a catalytic component selected from the group consisting of oxides of tungsten, niobium and mixtures thereof and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide on an inorganic refractory oxide support is prepared by depositing by means known in the art a metal oxide precursor salt on an inorganic refractory metal oxide which is not itself an acid cracking catalyst or by intimately mixing a metal oxide precursor salt with a refractory metal oxide support precursor salt, converting the salt or salts to the respective metal oxides and subjecting the resultant combination to steaming at elevated temperatures prior to use. Catalysts prepared in this manner exhibit enhanced activity and selectivity as compared to conventional acid catalysts. They also exhibit remarkable resistance to coke make.
Inventors
- 👤 Dane C. Grenoble
- 👤 Chang J. Kim
- 👤 Lawrence L. Murrell
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 16:19
CPC Classifications
B; B01; B01J; B01J21/00; B01J21/06; B01J21/066; B01J21/063; B01J21/12; B01J23/00; B01J23/16; B01J23/20; B01J23/24; B01J23/26; B01J23/30; B01J37/00; B01J37/08; B01J37/10
Claims Analysis
Total Claims: 69
Claim 1
Independent Claim
126 words
In an acid catalyst preparation method wherein a catalytic component is deposited upon an inorganic refractory metal oxide support which is not itself an acid cracking catalyst so as to result in a supported catalyst which is pretreated prior to use in acid catalyzed hydrocarbon conversion processes, the improvements comprising: (a) using as the catalytic component a metal oxide selected from the group consisting of the oxides of niobium, tungsten, and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide, and (b) subjecting the supported catalyst prior to use to a steam atmosphere at a temperature of from 600° to 1200° C.
Claim 2
Dependent Claim
126 words
In an acid catalyst preparation method wherein a catalytic component is deposited upon an inorganic refractory metal oxide support which is not itself an acid cracking catalyst so as to result in a supported catalyst which is pretreated prior to use in acid catalyzed hydrocarbon conversion processes, the improvements comprising: (a) using as the catalytic component a metal oxide selected from the group consisting of the oxides of niobium, tungsten, and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide, and (b) subjecting the supported catalyst prior to use to a steam atmosphere at a temperature of from 600° to 1200° C.
Claim 3
Dependent Claim
22 words
The catalyst preparation method of claim 1 wherein the steam atmosphere comprises from 0.1 to 100% steam, the balance being inert gas.
Claim 4
Dependent Claim
25 words
The catalyst preparation method of claim 1 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxide and niobium oxide.
Claim 5
Dependent Claim
35 words
The catalyst preparation method of claim 1 wherein the inorganic refractory metal oxide support which is not an acid cracking catalyst is alumina, zirconia, boria, thoria, magnesia, zirconium-titanate, titania, chromia, silica, kieselguhr and mixtures thereof.
Claim 6
Dependent Claim
25 words
The catalyst preparation method of claim 4 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxide and niobium oxide.
Claim 7
Dependent Claim
15 words
The catalyst preparation method of claim 1 wherein the refractory metal oxide support is alumina.
Claim 8
Dependent Claim
25 words
The catalyst preparation method of claim 6 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxide and niobium oxide.
Claim 9
Dependent Claim
16 words
The catalyst preparation method of claim 6 wherein the catalytic metal oxide component is tungsten oxide.
Claim 10
Dependent Claim
17 words
The catalyst preparation method of claim 1 wherein step (b) is conducted outside the catalytic process reactor.
Claim 11
Dependent Claim
19 words
The catalyst preparation method of claim 1 wherein step (b) is conducted in situ in the catalytic process reactor.
Claim 12
Dependent Claim
33 words
The catalyst preparation method of claim 9 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxide and niobium oxide and the refractory inorganic oxide support is alumina.
Claim 13
Dependent Claim
142 words
An acid catalyst comprising a catalytic metal oxide component selected from the group consisting of oxides of tungsten, niobium and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide supported on an inorganic refractory metal oxide base which is not itself an acid cracking catalyst prepared by the process of contacting a catalytic metal oxide precursor salt with an inorganic refractory metal oxide base or metal oxide base precursor salt, converting the salt or salts to cataltic metal oxide and refractory metal oxide base respectively and steaming the resulting composite at a temperature of from 600° to 1200° C., the steaming being conducted in a steam atmosphere comprising from 0.1 to 100% steam, the balance being inert gas.
Claim 14
Dependent Claim
142 words
An acid catalyst comprising a catalytic metal oxide component selected from the group consisting of oxides of tungsten, niobium and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide supported on an inorganic refractory metal oxide base which is not itself an acid cracking catalyst prepared by the process of contacting a catalytic metal oxide precursor salt with an inorganic refractory metal oxide base or metal oxide base precursor salt, converting the salt or salts to cataltic metal oxide and refractory metal oxide base respectively and steaming the resulting composite at a temperature of from 600° to 1200° C., the steaming being conducted in a steam atmosphere comprising from 0.1 to 100% steam, the balance being inert gas.
Claim 15
Dependent Claim
25 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide is selected from the group consisting of the oxides of tungsten and niobium.
Claim 16
Dependent Claim
42 words
The catalyst prepared as in claim 12 wherein the inorganic refractory metal oxide base which is not itself an acid cracking catalyst is selected from the group consisting of alumina, titania, zirconia, boria, thoria, magnesia, zirconium-titanate, chromia, silica, kieselguhr and mixtures thereof.
Claim 17
Dependent Claim
23 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide is tungsten and the inorganic nonacidic refractory metal oxide is alumina.
Claim 18
Dependent Claim
22 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide comprises from 0.5 to 25 wt.% of the total catalyst.
Claim 19
Dependent Claim
20 words
The catalyst prepared as in claim 16 wherein the catalytic metal oxide comprises from 2-10 wt.% of the total catalyst.
Claim 20
Dependent Claim
25 words
The catalyst prepared as in claim 14 wherein the catalytic metal oxide is selected from the group consisting of the oxides of tungsten and niobium.
Claim 21
Dependent Claim
15 words
The catalyst prepared as in claim 18 wherein the catalytic metal oxide is tungsten oxide.
Claim 22
Dependent Claim
22 words
The catalyst prepared as in claim 15 wherein the catalytic metal oxide comprises from 0.5 to 25 wt.% of the total catalyst.
Claim 23
Dependent Claim
22 words
The catalyst prepared as in claim 20 wherein the catalytic metal oxide comprises from 2 to 10 wt.% of the total catalyst.
Claim 24
Dependent Claim
21 words
The catalyst prepared as in claim 12 wherein the steaming is conducted at a temperature of from 800° to 1200° C.
Claim 25
Independent Claim
123 words
A method for preparing an acid catalyst, which catalyst comprises a catalytic metal oxide component selected from the group consisting of oxides of niobium, tungsten, and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide supported on an inorganic refractory metal oxide support, which is not itself an acid cracking catalyst, which method comprises depositing on the refractory metal oxide support a catalytic metal oxide precursor salt, converting the catalytic metal oxide precursor salt to metal oxide and subjecting the supported catalyst composite prior to use to a steam atmosphere at a temperature of from 600° to 1200° C.
Claim 26
Independent Claim
123 words
A method for preparing an acid catalyst, which catalyst comprises a catalytic metal oxide component selected from the group consisting of oxides of niobium, tungsten, and mixtures thereof, and tungsten or niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide supported on an inorganic refractory metal oxide support, which is not itself an acid cracking catalyst, which method comprises depositing on the refractory metal oxide support a catalytic metal oxide precursor salt, converting the catalytic metal oxide precursor salt to metal oxide and subjecting the supported catalyst composite prior to use to a steam atmosphere at a temperature of from 600° to 1200° C.
Claim 27
Dependent Claim
44 words
The method of claim 23 wherein the refractory metal oxide is itself in initially a precursor salt wherein the catalytic metal oxide precursor salt and the refractory metal oxide support precursor salt are intimately mixed and the mixture is converted to the respective oxides.
Claim 28
Dependent Claim
16 words
The method of claim 23 wherein the catalytic metal oxide is tungsten oxide and niobium oxide.
Claim 29
Dependent Claim
26 words
The method of claim 23 wherein the catalytic metal oxide precursor salts are deposited on the inorganic refractory metal oxide support from aqueous or nonaqueous solution.
Claim 30
Dependent Claim
25 words
The method of claim 23 wherein the catalytic metal oxide precursor salt is deposited on the refractory metal oxide support from aqueous or alcohol solution.
Claim 31
Dependent Claim
24 words
The method of claim 23 wherein the steaming is conducted in an atmosphere comprising from 0.1 to 100% steam, the balance being inert gas.
Claim 32
Dependent Claim
24 words
The method of claim 23 wherein the inorganic refractory metal oxide support has a surface area of from 10 to 500 m 2 /g.
Claim 33
Dependent Claim
34 words
The method of claim 23 wherein the refractory metal oxide support is selected from the group consisting of η-alumina, γ-alumina, α-alumina, zirconia, boria, thoria, magnesia, zirconium titanate, titania, chromia, silica, kieselguhr and mixtures thereof.
Claim 34
Dependent Claim
13 words
The method of claim 30 wherein the refractory metal oxide support is alumina.
Claim 35
Dependent Claim
19 words
The catalyst preparation method of claim 1 wherein said steaming temperature ranges from between about 800° and 1200° C.
Claim 36
Dependent Claim
27 words
The catalyst preparation of claim 32 wherein said catalyst contains one or more promoter materials selected from the group consisting of oxides of barium, calcium and magnesium.
Claim 37
Dependent Claim
27 words
The acid catalyst of claim 12 wherein said catalyst contains one or more promoter materials selected from the group consisting of oxides of barium, calcium and magnesium.
Claim 38
Dependent Claim
17 words
The method of claim 31 wherein said steaming temperature ranges from between about 800° and 1200° C.
Claim 39
Dependent Claim
26 words
The method of claim 35 wherein the catalyst contains one or more promoter materials selected from the group consisting of oxides of barium, calcium and magnesium.
Claim 40
Dependent Claim
77 words
The catalyst preparation method of claim 1 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide, and niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 41
Dependent Claim
48 words
The catalyst preparation method of claim 1 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 42
Dependent Claim
48 words
The catalyst preparation method of claim 1 wherein the catalytic metal oxide component is selected from the group consisting of niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 43
Dependent Claim
18 words
The catalyst preparation method of claim 37, 38 or 39 wherein the inorganic refractory oxide support is alumina.
Claim 44
Dependent Claim
77 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide, and niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 45
Dependent Claim
48 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 46
Dependent Claim
48 words
The catalyst prepared as in claim 12 wherein the catalytic metal oxide component is selected from the group consisting of niobium oxide in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 47
Dependent Claim
19 words
The catalyst prepared as in claims 35, 36 or 37 wherein the inorganic refractory metal oxide base is alumina.
Claim 48
Dependent Claim
27 words
The catalyst prepared as in claim 35 wherein the ratio of tungsten oxide or niobium oxide to the additional metal oxide is in the order of 1:1.
Claim 49
Dependent Claim
16 words
The catalyst prepared as in claim 45 wherein the ratio is in the order of 9:1.
Claim 50
Dependent Claim
24 words
The catalyst prepared as in claim 42 wherein the ratio of tungsten oxide to the additional metal oxide is in the order of 1:1.
Claim 51
Dependent Claim
24 words
The catalyst prepared as in claim 42 wherein the ratio of tungsten oxide to the additional metal oxide is in the order of 9:1.
Claim 52
Dependent Claim
24 words
The catalyst prepared as in claim 43 wherein the ratio of niobium oxide to the additional metal oxide is in the order of 1:1.
Claim 53
Dependent Claim
24 words
The catalyst prepared as in claim 43 wherein the ratio of niobium oxide to the additional metal oxide is in the order of 9:1.
Claim 54
Dependent Claim
27 words
The catalyst prepared as in claim 44 wherein the ratio of tungsten oxide or niobium oxide to the additional metal oxide is in the order of 1:1.
Claim 55
Dependent Claim
27 words
The catalyst prepared as in claim 44 wherein the ratio of tungsten oxide or niobium oxide to the additional metal oxide is in the order of 9:1.
Claim 56
Dependent Claim
75 words
The method of claim 23 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide, and niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide and zirconium oxide.
Claim 57
Dependent Claim
46 words
The method of claim 23 wherein the catalytic metal oxide component is selected from the group consisting of tungsten oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide, and zirconium oxide.
Claim 58
Dependent Claim
46 words
The method of claim 23 wherein the catalytic metal oxide component is selected from the group consisting of niobium oxides in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide, and zirconium oxide.
Claim 59
Independent Claim
16 words
The method of claims 53, 54, or 55 wherein the inorganic refractory oxide support is alumina.
Claim 60
Dependent Claim
62 words
An acid catalyst comprising a catalytic metal oxide component selected from the group consisting of tungsten oxide or niobium oxide in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide, and zirconium oxide, supported on an inorganic refractory metal oxide base which is not itself an acid cracking catalyst.
Claim 61
Dependent Claim
62 words
An acid catalyst comprising a catalytic metal oxide component selected from the group consisting of tungsten oxide or niobium oxide in combination with one or more additional metal oxides selected from the group consisting of tantalum oxide, hafnium oxide, chromium oxide, titanium oxide, and zirconium oxide, supported on an inorganic refractory metal oxide base which is not itself an acid cracking catalyst.
Claim 62
Dependent Claim
19 words
The catalyst of claim 57 wherein the metal oxide in combination with the additional metal oxide is tungsten oxide.
Claim 63
Dependent Claim
19 words
The catalyst of claim 57 wherein the metal oxide in combination with the additional metal oxide is niobium oxide.
Claim 64
Dependent Claim
17 words
The catalyst of claims 57, 58 or 59 wherein the inorganic refractory metal oxide support is alumina.
Claim 65
Dependent Claim
27 words
The catalyst of claim 57 wherein the ratio of tungsten oxide or niobium oxide to the additional metal oxide is in the order of 1:1 to 9:1.
Claim 66
Dependent Claim
24 words
The catalyst of claim 58 wherein the ratio of tungsten oxide to the additional metal oxide is in the order of 1:1 to 9:1.
Claim 67
Dependent Claim
24 words
The catalyst of claim 59 wherein the ratio of niobium oxide to the additional metal oxide is in the order of 1:1 to 9:1.
Claim 68
Dependent Claim
27 words
The catalyst of claim 60 wherein the ratio of tunsten oxide or niobium oxide to the additional metal oxide is in the order of 1:1 to 9:1.
Claim 69
Dependent Claim
26 words
The acid catalyst of claim 57 which additionally contains one or more promoter materials selected from the group consisting of oxides of barium, calcium and magnesium.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-05-25 | 1984-11-24 | 1985-05-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-05-25 | 1988-11-24 | 1989-05-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-05-25 | 1992-11-24 | 1993-05-26 | $7700.00 | Window Closed / Lapsed |