Patent US4288422A successfully refreshed from Google Patents.
US4288422A
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Method of preparing chalcogenides of group VIII by low temperature precipitation from monaqueous solution, the products produced by said method and their use as catalysts
Assignee: ExxonMobil Technology and Engineering Co
•
Filing: 1980-06-16
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Granted: 1981-09-08
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Expires: 2000-06-16
Abstract
Abstract A method is described for the preparation of chalcogenides of ruthenium, rhodium, osmium and iridium transition metals of the Periodic Table of the Elements which comprises mixing in the absence of an aqueous solvent a Group VIII transition metal salt with a source of chalcogenide, said chalcogenide being selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, yielding a precipitate of the formula MXy wherein M is selected from the group consisting of ruthenium, rhodium, osmium and iridium, X is sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 0.1 to about 3, preferably 0.1 to about 2.5. By the practice of the nonaqueous synthesis technique, Group VIII chalcogenides are prepared which are finely divided, have a high surface area, small particle size and small crystallite size which are also free of excess sulfur, water and/or hydrolysis products. Layered stoichiometric osmium disulfide is prepared by this technique. The precipitates may be cleansed of any anion salt coproduct by any technique common to the art. Compounds of the formula MXy thus prepared are superior sulfur-tolerant catalysts in catalytic processes, for example, hydrodesulfurization, hydrodenitrogenation, hydroconversion, hydrogenation.
Inventors
- 👤 Russell R. Chianelli
- 👤 Theresa A. Pecoraro
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 16:50
CPC Classifications
C; C01; C01B; C01B19/00; C01B19/04; B; B01; B01J; B01J27/00; B01J27/02; B01J27/04; B01J27/043; B01J27/045; B01J27/057; B01J27/0573; B01J27/0576; B82; B82Y; B82Y30/00; C01G; C01G55/00; C01P; C01P2002/00; C01P2002/02; C01P2002/20; C01P2002/22; C01P2002/60; C01P2002/70; C01P2002/77; C01P2004/00; C01P2004/60; C01P2004/64; C01P2006/00; C01P2006/12; C01P2006/80; Y; Y10; Y10S; Y10S505/00; Y10S505/80; Y10S505/81
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
73 words
Chalcogenides amorphous to x-ray, having a particle size of less than 0.1 micron and a crystallite size of about 50 A×100 A or less of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 0.1 to about 3.
Claim 2
Dependent Claim
73 words
Chalcogenides amorphous to x-ray, having a particle size of less than 0.1 micron and a crystallite size of about 50 A×100 A or less of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 0.1 to about 3.
Claim 3
Dependent Claim
13 words
Chalcogenides of claim 1 wherein the particle size is less than 0.05 micron.
Claim 4
Dependent Claim
9 words
Chalcogenides of claim 1 wherein the chalcogenide is sulfur.
Claim 5
Dependent Claim
14 words
Chalcogenides of claim 1 wherein the metal is ruthenium, and the chalcogenide is sulfur.
Claim 6
Dependent Claim
182 words
Chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 0.1 to about 3, prepared by mixing in the absence of aqueous protic solvent solutions of: (a) metal salts, the metal being selected from the group consisting of ruthenium, rhodium, iridium and osmium, and (b) sources of sulfur, selenium, tellurium ions and mixtures thereof selected from the group consisting of Li 2 X, Na 2 X, K 2 X, KHX, NaHK, (NH 4 ) 2 X, (RNH 3 ) 2 X, (RR'NH 2 ) 2 X, LiHX, (RR'R"NH) 2 X, wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 to C 20 alkyl and C 6 to C 20 aryl groups and X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, at a temperature of between 0° to 400° C.
Claim 7
Dependent Claim
182 words
Chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, and y is a number ranging from about 0.1 to about 3, prepared by mixing in the absence of aqueous protic solvent solutions of: (a) metal salts, the metal being selected from the group consisting of ruthenium, rhodium, iridium and osmium, and (b) sources of sulfur, selenium, tellurium ions and mixtures thereof selected from the group consisting of Li 2 X, Na 2 X, K 2 X, KHX, NaHK, (NH 4 ) 2 X, (RNH 3 ) 2 X, (RR'NH 2 ) 2 X, LiHX, (RR'R"NH) 2 X, wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 to C 20 alkyl and C 6 to C 20 aryl groups and X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, at a temperature of between 0° to 400° C.
Claim 8
Dependent Claim
15 words
Chalcogenides prepared as in claim 5, further comprising the use of a nonaqueous aprotic solvent.
Claim 9
Dependent Claim
12 words
Chalcogenides prepared as in claim 5 wherein X is sulfur and selenium.
Claim 10
Dependent Claim
10 words
Chalcogenides prepared as in claim 5 wherein X is sulfur.
Claim 11
Dependent Claim
19 words
Chalcogenides prepared as in claim 5 wherein M is selected from the group consisting of ruthenium, rhodium, and iridium.
Claim 12
Dependent Claim
70 words
Chalcogenides prepared as in claim 6 wherein the nonaqueous solvent is selected from the group consisting of acetonitrile, benzonitrile, propionitrile, acetone, propylene carbonate, C 1 -C 20 alkylhalides, C 6 -C 20 arylhalides, 1,2-dimethoxyethane, diglyme, N-methyl formamide, dimethylformamide, C 6 -C 20 aromatics, pyridine, sulfolane, tributylphosphate, anhydrous acids, dimethylsulfite, C 1 -C 20 amines, C 5 -C 12 alkanes, C 4 -C 8 ethers and C 4 -C 8 esters.
Claim 13
Dependent Claim
17 words
Chalcogenides prepared as in claim 5, wherein the temperature of reaction is between 25° to 300° C.
Claim 14
Dependent Claim
42 words
Chalcogenides prepared as in claim 5 wherein the anion of the metal salt is selected from the group comprising halides, sulfates, nitrates, carboxylates, perfluorocarboxylates wherein the carbonaceous moiety of the anion is a C 1 to C 8 hydrocarbon or fluorocarbon radical.
Claim 15
Dependent Claim
30 words
Chalcogenides prepared as in claim 6 wherein the nonaqueous aprotic solvent is selected from the group consisting of propylene carbonate, dimethylformamide (DMF), pyridine, acetonitrite, benzonitrite, propionitrite, 1,2-dimethoxyethane, diglyme and n-methyl-formamide.
Claim 16
Dependent Claim
202 words
Homogeneous dispersions of chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 0.1 to about 3 prepared by mixing in the presence of a nonaqueous solvent selected from the group consisting of propylene carbonate, dimethylformamide (DMF), pyridine, acetonitrile, benzonitrile, propionitrile, 1,2 dimethoxyethane, diglyme and n-methylformamide solutions of: (a) metal salts, the metal being selected from the group consisting of ruthenium, rhodium, iridium and osmium, and (b) sources of sulfur, selenium, tellurium ions and mixtures thereof selected from the group consisting of Li 2 X, Na 2 X, K 2 XNaHX, LiHX, KHX(NH 4 ) 2 X, (RNH 3 ) 2 X, (RR'NH 2 ) 2 X, (RR'R"NH) 2 X, wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 to C 20 alkyl and C 6 to C 20 aryl groups and X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, at a temperature of between 0° to 400° C.
Claim 17
Dependent Claim
202 words
Homogeneous dispersions of chalcogenides of the formula MX y wherein M is a metal selected from the group consisting of ruthenium, rhodium, iridium and osmium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof and y is a number ranging from about 0.1 to about 3 prepared by mixing in the presence of a nonaqueous solvent selected from the group consisting of propylene carbonate, dimethylformamide (DMF), pyridine, acetonitrile, benzonitrile, propionitrile, 1,2 dimethoxyethane, diglyme and n-methylformamide solutions of: (a) metal salts, the metal being selected from the group consisting of ruthenium, rhodium, iridium and osmium, and (b) sources of sulfur, selenium, tellurium ions and mixtures thereof selected from the group consisting of Li 2 X, Na 2 X, K 2 XNaHX, LiHX, KHX(NH 4 ) 2 X, (RNH 3 ) 2 X, (RR'NH 2 ) 2 X, (RR'R"NH) 2 X, wherein R, R' and R" are the same or different and are selected from the group consisting of C 1 to C 20 alkyl and C 6 to C 20 aryl groups and X is selected from the group consisting of sulfur, selenium, tellurium and mixtures thereof, at a temperature of between 0° to 400° C.
Claim 18
Dependent Claim
46 words
The homogeneous dispersions of chalcogenides of claim 14 wherein the anion of the metal salts of (a) is selected from the group comprising halides, sulfates, nitrates, carboxylates, perfluorocarboxylates wherein the carbonaceous moiety of the anion is a C 1 to C 8 hydrocarbon or fluorocarbon radical.
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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) | 1984-09-07 | 1985-03-09 | 1985-09-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-09-07 | 1989-03-09 | 1989-09-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-09-07 | 1993-03-09 | 1993-09-08 | $7700.00 | Window Closed / Lapsed |