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US4192777A
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Preparation and use of supported potassium (or rubidium)-Group VIII-metal cluster catalysts in CO/H2 Fischer-Tropsch synthesis reactions
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1978-03-01
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Granted: 1980-03-11
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Expires: 1998-03-01
Abstract
Abstract This invention relates to unique supported potassium (or rubidium) - Group VIII-metal cluster catalysts which are useful in CO/H2 reactions (Fischer-Tropsch synthesis reactions). The novel catalysts of the instant invention are prepared by depositing well characterized potassium (or rubidium) - Group VIII-metal carbonyl cluster complexes onto high surface area supports. Following a subsequent reduction, the precursor bimetallic cluster complexes are decomposed on the support surface forming a potassium (or rubidium) promoted Group VIII-metal cluster catalyst in which the potassium (or rubidium) and Group VIII metals are intimately associated. These unique, highly promoted cluster catalysts have been found to demonstrate high Group VIII-metal dispersions and enhanced Fischer-Tropsch activities and selectivities for producing olefinic and paraffinic hydrocarbons. In addition methane formation is dramatically reduced over the supported bimetallic cluster catalysts of the instant invention when compared to conventionally prepared supported potassium (or rubidium) promoted Group VIII-metal catalysts.
Inventors
- 👤 Gary B. McVicker
- 👤 M. Albert Vannice
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 11:42
CPC Classifications
C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C1/0425; C07C1/043; C07C1/0435; B; B01; B01J; B01J23/00; B01J23/38; B01J23/54; B01J23/56; B01J23/58; B01J23/70; B01J23/76; B01J23/78; C07C2521/00; C07C2521/02; C07C2521/04; C07C2523/00; C07C2523/02; C07C2523/04; C07C2523/38; C07C2523/40; C07C2523/42; C07C2523/44; C07C2523/46; C07C2523/54; C07C2523/56; C07C2523/58; C07C2523/70; C07C2523/74; C07C2523/745; C07C2523/75; C07C2523/755; C07C2523/76; C07C2523/78; C07C2531/00; C07C2531/16; C07C2531/20
Claims Analysis
Total Claims: 42
Claim 1
Independent Claim
101 words
Supported, highly dispersed, high activity potassium or rubidium-Group VIII metal cluster catalysts demonstrating improved selectivity to olefinic and paraffinic hydrocarbons in CO/H 2 reactions prepared by the process which comprises depositing known, well-characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes and mixtures thereof on a high surface area support material, drying the carbonyl cluster complex impregnated support in the absence of oxygen, and reducing the supported complex at elevated temperatures to effect the essentially complete reduction of the supported potassium or rubidium-Group VIII metal carbonyl cluster complexes to discrete potassium or rubidium-Group VIII clusters of metals on the support surface.
Claim 2
Dependent Claim
101 words
Supported, highly dispersed, high activity potassium or rubidium-Group VIII metal cluster catalysts demonstrating improved selectivity to olefinic and paraffinic hydrocarbons in CO/H 2 reactions prepared by the process which comprises depositing known, well-characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes and mixtures thereof on a high surface area support material, drying the carbonyl cluster complex impregnated support in the absence of oxygen, and reducing the supported complex at elevated temperatures to effect the essentially complete reduction of the supported potassium or rubidium-Group VIII metal carbonyl cluster complexes to discrete potassium or rubidium-Group VIII clusters of metals on the support surface.
Claim 3
Dependent Claim
23 words
The supported, highly dispersed metal cluster catalysts prepared as in claim 1 wherein the metals cluster comprises potassium and the Group VIII metals.
Claim 4
Dependent Claim
23 words
The supported, highly dispersed metal cluster catalysts prepared as in claim 1 wherein the metals cluster comprises rubidium and the Group VIII metals.
Claim 5
Dependent Claim
31 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the support is selected from the group consisting of refractory inorganic oxides and carbon.
Claim 6
Dependent Claim
40 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the support is selected from the group consisting of alumina, silica, titania, zirconia, hafnia, tantala, niobia, vanadia, tungsten oxide, silica-alumina, magnesia, chromia, molybdena.
Claim 7
Dependent Claim
33 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the support is selected from the group consisting of alumina, silica-alumina, titania, magnesia, hafnia and zirconia.
Claim 8
Dependent Claim
31 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the support is selected from the group consisting of alumina, silica-alumina, magnesia and titania.
Claim 9
Dependent Claim
39 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the known well-characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes are deposited on a high surface area support material from solution.
Claim 10
Dependent Claim
43 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the well-characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes are deposited on a high surface area support material from solution, wherein the solution is aqueous.
Claim 11
Dependent Claim
43 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the well-characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes are deposited on a high surface area support material from solution, wherein the solution is nonaqueous.
Claim 12
Dependent Claim
26 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the reducing temperature ranges from 200° to 800° C.
Claim 13
Dependent Claim
26 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the reducing temperature ranges from 350° to 600° C.
Claim 14
Dependent Claim
26 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the reducing temperature ranges from 400° to 500° C.
Claim 15
Dependent Claim
29 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalyst prepared as in claim 1 wherein the Group VIII-metal constitutes 0.1 to 50% by weight of the catalyst.
Claim 16
Dependent Claim
33 words
The supported, highly dispersed potassium or rubidium-Group VIII metal cluster catalysts prepared as in claim 1 wherein the Group VIII metal to potassium or rubidium mole ratio ranges from between 0.33 to 20.
Claim 17
Dependent Claim
35 words
The supported, highly dispersed potassium-Group VIII metal cluster catalysts prepared as in claim 2 wherein the Group VIII metal is selected from the group consisting of ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum and iron.
Claim 18
Dependent Claim
30 words
The supported, highly dispersed potassium-Group VIII metal cluster catalysts prepared as in claim 2 wherein the Group VIII metal is selected from the group consisting of iron, ruthenium and iridium.
Claim 19
Dependent Claim
21 words
The supported, highly dispersed potassium-Group VIII metal cluster catalysts prepared as in claim 2 wherein the Group VIII metal is iron.
Claim 20
Dependent Claim
27 words
The supported, highly dispersed potassium-iron metal cluster catalyst prepared as in claim 18 wherein the potassium to iron mole ratio is 2 and the support is alumina.
Claim 21
Dependent Claim
35 words
The supported, highly dispersed rubidium-Group VIII metal cluster catalysts prepared as in claim 3 wherein the Group VIII metal is selected from the group consisting of ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum and iron.
Claim 22
Dependent Claim
30 words
The supported, highly dispersed rubidium-Group VIII metal cluster catalysts prepared as in claim 3 wherein the Group VIII metal is selected from the group consisting of iron, ruthenium and iridium.
Claim 23
Independent Claim
89 words
A method for the preparation of supported potassium or rubidium Group VIII metal cluster catalysts which comprises depositing known, well characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes and mixtures thereof, on a high surface area support material, drying the carbonyl cluster complex impregnated support in the absence of oxygen, and reducing the supported complex at elevated temperatures to effect the essentially complex reduction of the supported potassium or rubidium-Group VIII metal carbonyl cluster complexes to discrete potassium or rubidium-Group VIII clusters of metals on the support surface.
Claim 24
Independent Claim
89 words
A method for the preparation of supported potassium or rubidium Group VIII metal cluster catalysts which comprises depositing known, well characterized potassium or rubidium-Group VIII metal carbonyl cluster complexes and mixtures thereof, on a high surface area support material, drying the carbonyl cluster complex impregnated support in the absence of oxygen, and reducing the supported complex at elevated temperatures to effect the essentially complex reduction of the supported potassium or rubidium-Group VIII metal carbonyl cluster complexes to discrete potassium or rubidium-Group VIII clusters of metals on the support surface.
Claim 25
Dependent Claim
19 words
The process of claim 22 wherein the metal carbonyl cluster complex comprises a potassium-Group VIII metal carbonyl cluster complex.
Claim 26
Dependent Claim
19 words
The process of claim 22 wherein the metal carbonyl cluster complex comprises a rubidium-Group VIII metal carbonyl cluster complex.
Claim 27
Dependent Claim
20 words
The process of claim 22 wherein the support is selected from the group consisting of refractory inorganic oxides and carbon.
Claim 28
Dependent Claim
23 words
The process of claim 22 wherein the potassium or rubidium-Group VIII metal carbonyl cluster complexes are deposited on the support from aqueous solution.
Claim 29
Dependent Claim
23 words
The process of claim 22 wherein the potassium or rubidium-Group VIII metal carbonyl cluster complexes are deposited on the support from nonaqueous solution.
Claim 30
Dependent Claim
15 words
The process of claim 22 wherein the reduction temperature ranges from 200° to 800° C.
Claim 31
Dependent Claim
13 words
The process of claim 22 wherein the reduction temperature ranges from 350°-600° C.
Claim 32
Dependent Claim
19 words
The process of claim 22 wherein the Group VIII metal constitutes 0.1 to 50% by weight of the catalyst.
Claim 33
Dependent Claim
22 words
The process of claim 22 wherein the Group VIII metal to potassium or rubidium mole ratio ranges from between 0.33 to 20.
Claim 34
Dependent Claim
27 words
The process of claim 23 wherein the Group VIII metal component is selected from the group consisting of ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum and iron.
Claim 35
Dependent Claim
13 words
The process of claim 23 wherein the Group VIII metal component is iron.
Claim 36
Dependent Claim
10 words
The process of claim 23 wherein the support is alumina.
Claim 37
Dependent Claim
27 words
The process of claim 24 wherein the Group VIII metal component is selected from the group consisting of ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum and iron.
Claim 38
Dependent Claim
13 words
The process of claim 24 wherein the group VIII metal component is iron.
Claim 39
Dependent Claim
10 words
The process of claim 24 wherein the support is alumina.
Claim 40
Dependent Claim
19 words
The process of claim 33 wherein the potassium to iron mole ratio is 2 and the support is alumina.
Claim 41
Dependent Claim
33 words
The process of claim 25 wherein the refractory inorganic oxide support is selected from the group consisting of alumina, silica, titania, zirconia, hafnia, tantala, niobia, vanadia, tungsten oxide, silica-alumina, magnesia, chromia and molybdena.
Claim 42
Dependent Claim
20 words
The process of claim 39 wherein the support is selected from the group consisting of alumina, silica-alumina, magnesia and titania.
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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) | 1983-03-11 | 1983-09-10 | 1984-03-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-03-11 | 1987-09-10 | 1988-03-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-03-11 | 1991-09-10 | 1992-03-11 | $7700.00 | Window Closed / Lapsed |