Patent US4065484A successfully refreshed from Google Patents.
US4065484A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Methanation process with intermittent reactivation of catalyst
Assignee: Union Oil Company of California
•
Filing: 1976-12-06
•
Granted: 1977-12-27
•
Expires: 1996-12-06
Abstract
Abstract A process is provided for the hydrogenation of carbon monoxide and/or carbon dioxide to form methane (methanation), using certain sulfur-sensitive nickel-alumina catalysts having a relatively low ratio of nickel surface area to nickel mass. It has been found that when such catalysts become deactivated as a result of sulfur poisoning, they can be reactivated to substantially fresh activity by reduction with hydrogen. Other nickel-alumina methanation catalysts having higher nickel surface areas are found to be essentially non-regenerable by hydrogen reduction following sulfur deactivation.
Inventors
- 👤 Harry H. Dobashi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 18:28
CPC Classifications
C; C07; C07C; C07C1/00; C07C1/02; C07C1/04; C07C1/0485; C07C1/049; B; B01; B01J; B01J23/00; B01J23/70; B01J23/74; B01J23/755; C07C1/0425; C07C1/043; C07C1/0435; C07C1/045; C07C1/12; C07C2521/00; C07C2521/02; C07C2521/04; C07C2523/00; C07C2523/70; C07C2523/74; C07C2523/755; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/584
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
97 words
A methanation process wherein: 1. a stream of contaminated feed gas comprising hydrogen and carbon monoxide and/or carbon dioxide is contacted with a nickel-alumina catalyst at temperatures between about 600° and 1500° F to produce methane; 2. said catalyst has a total nickel content between about 15 and 60% by weight, calculated as Ni, one portion of said nickel content being in an active metallic state, and another portion thereof being nickel aluminate, the nickel specific surface area of said catalyst in its freshly reduced state being between about 5 and 50 m 2 /gm of Ni;
Claim 2
Dependent Claim
97 words
A methanation process wherein: 1. a stream of contaminated feed gas comprising hydrogen and carbon monoxide and/or carbon dioxide is contacted with a nickel-alumina catalyst at temperatures between about 600° and 1500° F to produce methane; 2. said catalyst has a total nickel content between about 15 and 60% by weight, calculated as Ni, one portion of said nickel content being in an active metallic state, and another portion thereof being nickel aluminate, the nickel specific surface area of said catalyst in its freshly reduced state being between about 5 and 50 m 2 /gm of Ni;
Claim 3
Dependent Claim
95 words
said feed gas is contaminated with H 2 S or a sulfur compound which yields H 2 S upon hydrogenation, whereby said catalyst becomes at least partially deactivated; 4. said deactivated catalyst is reactivated with essentially no removal of sulfur therefrom by contacting the same with a substantially sulfur-free stream of reactivating gas consisting essentially of hydrogen, said reactivation contacting being carried out at between about 800° and 1500° F and continued for at least about 5 hours; and 5. the resulting reactivated catalyst is again placed on-stream for methanation as defined in (1) above.
Claim 4
Dependent Claim
95 words
said feed gas is contaminated with H 2 S or a sulfur compound which yields H 2 S upon hydrogenation, whereby said catalyst becomes at least partially deactivated; 4. said deactivated catalyst is reactivated with essentially no removal of sulfur therefrom by contacting the same with a substantially sulfur-free stream of reactivating gas consisting essentially of hydrogen, said reactivation contacting being carried out at between about 800° and 1500° F and continued for at least about 5 hours; and 5. the resulting reactivated catalyst is again placed on-stream for methanation as defined in (1) above.
Claim 5
Dependent Claim
19 words
A process as defined in claim 1 wherein said reactivation contacting is continued for at least about 12 hours.
Claim 6
Dependent Claim
30 words
A process as defined in claim 1 wherein said stream of reactivating gas contacts said catalyst in an opposite flow direction from the flow direction of said feed gas stream.
Claim 7
Dependent Claim
97 words
A process as defined in claim 1 wherein said catalyst is prepared by the steps of: 1. forming at a relatively low temperature a homogeneous aqueous solution of an aluminum salt, a nickel salt and urea; 2. heating said aqueous solution to a sufficiently high temperature to bring about hydrolysis of said urea with resultant gradual increase in pH of said solution and formation of a coprecipitate of basic compounds of nickel and aluminum; 3. separating said coprecipitate from said solution before the latter reaches a pH above about 8; and 4. drying and calcining said coprecipitate.
Claim 8
Dependent Claim
23 words
A process as defined in claim 4 wherein said catalyst contains between about 25 and 50% by weight of nickel, calculated as Ni.
Claim 9
Dependent Claim
27 words
A process as defined in claim 4 wherein the nickel specific surface area of said catalyst is between about 10 and 35 m 2 /g of Ni.
Claim 10
Dependent Claim
97 words
A methanation process wherein: 1. a stream of contaminated feed gas comprising hydrogen and carbon monoxide and/or carbon dioxide is contacted with a nickel-alumina catalyst at temperatures between about 600° and 1500° F to produce methane; 2. said catalyst has a total nickel content between about 25 and 50% by weight, calculated as Ni, one portion of said nickel content being in an active metallic state, and another portion thereof being nickel aluminate, the nickel specific surface area of said catalyst in its freshly reduced state being between about 10 and 35 m 2 /gm of Ni;
Claim 11
Dependent Claim
97 words
A methanation process wherein: 1. a stream of contaminated feed gas comprising hydrogen and carbon monoxide and/or carbon dioxide is contacted with a nickel-alumina catalyst at temperatures between about 600° and 1500° F to produce methane; 2. said catalyst has a total nickel content between about 25 and 50% by weight, calculated as Ni, one portion of said nickel content being in an active metallic state, and another portion thereof being nickel aluminate, the nickel specific surface area of said catalyst in its freshly reduced state being between about 10 and 35 m 2 /gm of Ni;
Claim 12
Dependent Claim
94 words
said feed gas is contaminated with H 2 S or a sulfur compound which yields H 2 S upon hydrogenation, whereby said catalyst becomes at least partially deactivated; 4. said deactivated catalyst is reactivated with essentially no removal of sulfur therefrom by contacting the same with a substantially sulfur-free stream of reactivating gas consisting essentially of hydrogen, said reactivation contacting being carried out at between about 800° and 1500° F and continued for at least about 5 hours; and 5. the resulting catalyst is again placed on-stream for methanation as defined in (1) above.
Claim 13
Dependent Claim
94 words
said feed gas is contaminated with H 2 S or a sulfur compound which yields H 2 S upon hydrogenation, whereby said catalyst becomes at least partially deactivated; 4. said deactivated catalyst is reactivated with essentially no removal of sulfur therefrom by contacting the same with a substantially sulfur-free stream of reactivating gas consisting essentially of hydrogen, said reactivation contacting being carried out at between about 800° and 1500° F and continued for at least about 5 hours; and 5. the resulting catalyst is again placed on-stream for methanation as defined in (1) above.
Claim 14
Dependent Claim
19 words
A process as defined in claim 7 wherein said reactivation contacting is continued for at least about 50 hours.
Claim 15
Dependent Claim
30 words
A process as defined in claim 7 wherein said stream of reactivating gas contacts said catalyst in an opposite flow direction from the flow direction of said feed gas stream.
Claim 16
Dependent Claim
97 words
A process as defined in claim 7 wherein said catalyst is prepared by the steps of: 1. forming at a relatively low temperature a homogeneous aqueous solution of an aluminum salt, a nickel salt and urea; 2. heating said aqueous solution to a sufficiently high temperature to bring about hydrolysis of said urea with resultant gradual increase in pH of said solution and formation of a coprecipitate of basic compounds of nickel and aluminum; 3. separating said coprecipitate from said solution before the latter reaches a pH above about 8; and 4. drying and calcining said coprecipitate.
References Cited (Backward Citations)
US1830705A
Cited
US2151329A
Cited
US2409690A
Cited
US2697078A
Cited
US2898306A
Cited
US3147227A
Cited
US3320182A
Cited
US3361535A
Cited
US3625665A
Cited
US3642460A
Cited
US3709669A
Cited
US3872030A
Cited
US3928000A
Cited
US3958957A
Cited
US3988263A
Cited
US3999961A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-12-26 | 1981-06-27 | 1981-12-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-12-26 | 1985-06-27 | 1985-12-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-12-26 | 1989-06-27 | 1989-12-27 | $7700.00 | Window Closed / Lapsed |