US4497971A
Expired / Lapsed
US
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Oxidative dehydrogenation and cracking of paraffins with a promoted cobalt catalyst
Assignee: Phillips Petroleum Co
•
Filing: 1983-11-16
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Granted: 1985-02-05
•
Expires: 2003-11-16
Abstract
Abstract A paraffin or mixture of paraffins having from 2 to 5 carbon atoms is oxidatively dehydrogenated in the presence of a cobalt based catalyst composition which has been calcined in the absence of oxygen. The catalyst composition comprises cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal and oxygen. The catalyst composition may also contain sulfur and/or a halogen. If the feed to the oxidative dehydrogenation process contains paraffins having more than two carbon atoms, some cracking of such paraffins will also occur at the conditions at which the oxidative dehydrogenation process is carried out.
Inventors
- 👤 Alan D. Eastman
- 👤 Jack P. Guillory
- 👤 Charles F. Cook
- 👤 James B. Kimble
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 10:23
CPC Classifications
B; B01; B01J; B01J27/00; B01J27/14; B01J27/16; B01J27/18; B01J23/00; B01J23/70; B01J23/76; B01J23/78; C; C07; C07C; C07C4/00; C07C4/02; C07C5/00; C07C5/42; C07C5/48; C07C2527/00; C07C2527/02; C07C2527/14; C07C2527/16; C07C2527/18; C07C2527/186; C07C2527/195
Claims Analysis
Total Claims: 50
Claim 1
Independent Claim
71 words
A process for the catalytic oxidative dehydrogenation of a paraffin having from 2 to 5 carbon atoms comprising the step of contacting said paraffin under suitable oxidative dehydrogenation conditions with a catalyst composition comprising cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal; and oxygen, wherein said catalyst composition is calcined in an inert atmosphere.
Claim 2
Dependent Claim
71 words
A process for the catalytic oxidative dehydrogenation of a paraffin having from 2 to 5 carbon atoms comprising the step of contacting said paraffin under suitable oxidative dehydrogenation conditions with a catalyst composition comprising cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal; and oxygen, wherein said catalyst composition is calcined in an inert atmosphere.
Claim 3
Dependent Claim
45 words
A process in accordance with claim 1 wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 450° C. to about 850° C. for a time in the range of about 1 hour to about 12 hours.
Claim 4
Dependent Claim
45 words
A process in accordance with claim 1 wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 700° C. to about 800° C. for a time in the range of about 2 hours to about 5 hours.
Claim 5
Dependent Claim
15 words
A process in accordance with claim 1 wherein said at least one promoter is zirconium.
Claim 6
Dependent Claim
99 words
A process in accordance with claim 1 wherein the atomic ratio of cobalt to said at least one promoter is in the range of about 1:1 to about 20:1, wherein the concentration of phosphorus in said catalyst composition is in the range of about 1 to about 10 weight percent calculated as the oxide and based on the weight of said catalyst composition and wherein the concentration of said at least one alkali metal is in the range of about 1 to about 10 weight percent calculated as the oxide and based on the weight of said catalyst composition.
Claim 7
Dependent Claim
95 words
A process in accordance with claim 1 wherein the atomic ratio of cobalt to said at least one promoter is in the range of about 3:1 to about 6:1, wherein the concentration of phosphorus is in the range of about 2 to about 5 weight percent calculated as the oxide and based on the weight of said catalyst composition, and wherein the concentration of said at least one alkali metal is in the range of about 2 to about 5 weight percent calculated as the oxide and based on the weight of said catalyst composition.
Claim 8
Dependent Claim
14 words
A process in accordance with claim 1 wherein said catalyst composition additionally comprises sulfur.
Claim 9
Dependent Claim
25 words
A process in accordance with claim 7 wherein said sulfur is added to said catalyst composition by utilizing cobalt sulfide to prepare said catalyst composition.
Claim 10
Dependent Claim
77 words
A process in accordance with claim 8 wherein said catalyst composition is dried in the presence of free oxygen at a temperature in the range of about 100° C. to about 180° C. for at least 5 hours and wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 450° C. to about 850° C. for a time in the range of about 1 hour to about 12 hours.
Claim 11
Dependent Claim
77 words
A process in accordance with claim 8 wherein said catalyst composition is dried in the presence of free oxygen at a temperature in the range of about 130° C. to about 150° C. for at least 5 hours and wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 700° C. to about 800° C. for a time in the range of about 2 hours to about 5 hours.
Claim 12
Dependent Claim
27 words
A process in accordance with claim 7 wherein said catalyst composition additionally comprises at least one halogen selected from the group consisting of chlorine, bromine and iodine.
Claim 13
Dependent Claim
27 words
A process in accordance with claim 11 wherein said halogen is added to said catalyst composition by using a halogen containing compound to prepare said catalyst composition.
Claim 14
Dependent Claim
40 words
A process in accordance with claim 11 wherein said halogen is added to said catalyst composition by at least periodically mixing a halogen containing compound with said paraffin prior to the step of contacting said paraffin with said catalyst composition.
Claim 15
Dependent Claim
42 words
A process in accordance with claim 13 wherein the concentration of the halogen in said paraffin is in the range of about 1 part per million to about 10 mole percent when said halogen containing compound is being mixed with said paraffin.
Claim 16
Dependent Claim
27 words
A process in accordance with claim 1 wherein said catalyst composition additionally comprises at least one halogen selected from the group consisting of chlorine, bromine and iodine.
Claim 17
Dependent Claim
27 words
A process in accordance with claim 15 wherein said halogen is added to said catalyst composition by using a halogen containing compound to prepare said catalyst composition.
Claim 18
Dependent Claim
40 words
A process in accordance with claim 15 wherein said halogen is added to said catalyst composition by at least periodically mixing a halogen containing compound with said paraffin prior to the step of contacting said paraffin with said catalyst composition.
Claim 19
Dependent Claim
42 words
A process in accordance with claim 17 wherein the concentration of the halogen in said paraffin is in the range of about 1 part per million to about 10 mole percent when said halogen containing compound is being mixed with said paraffin.
Claim 20
Dependent Claim
59 words
A process in accordance with claim 1 wherein said suitable oxidative dehydrogenation conditions comprise a temperature in the range of about 480° C. to about 815° C., a pressure in the range of about 10 to about 520 kilopascals, and a flow rate of a feedstream containing said paraffin in the range of about 100 to about 2500 GHSV.
Claim 21
Dependent Claim
56 words
A process in accordance with claim 1 wherein said suitable oxidative dehydrogenation conditions comprise a temperature in the range of about 480° C. to about 815° C., a pressure in the range of about 100 to about 200 kilopascals, and a flow rate of a feedstream containing said paraffin in the range of about 500 GHSV.
Claim 22
Dependent Claim
12 words
A process in accordance with claim 1 wherein said paraffin is ethane.
Claim 23
Dependent Claim
50 words
A process in accordance with claim 21 wherein said suitable oxidative dehydrogenation conditions comprise a temperature in the range of about 620° C. to about 705° C., a pressure in the range of about 100 to about 200 kilopascals, and a feed rate of said feedstock of about 500 GHSV.
Claim 24
Dependent Claim
58 words
A process in accordance with claim 1 wherein substantially no free oxygen is introduced with said feedstream and wherein the catalytic oxidative dehydrogenation of said paraffin is carried out in a cyclic process comprising a dehydrogenation reaction time and a regeneration time, wherein said dehydrogenation time is in the range of about 1 minute to about 30 minutes.
Claim 25
Dependent Claim
73 words
A process in accordance with claim 1 wherein free oxygen is introduced with said feed stream, wherein the catalytic oxidative dehydrogenation of said paraffin is carried out as a continuous process with a reaction time in the range of about 1 hour to about 100 hours and wherein the amount of free oxygen introduced is in the range of about 0.4 to about 0.75 moles of free oxygen per mole of said paraffin.
Claim 26
Dependent Claim
73 words
A process in accordance with claim 1 wherein free oxygen is introduced with said feed stream, wherein the catalytic oxidative dehydrogenation of said paraffin is carried out as a continuous process with a reaction time in the range of about 1 hour to about 100 hours and wherein the amount of free oxygen introduced is in the range of about 0.5 to about 0.6 moles of free oxygen per mole of said paraffin.
Claim 27
Dependent Claim
71 words
A process for the catalytic oxidative cracking of a paraffin having from 3 to 5 carbon atoms comprising the step of contacting said paraffin under suitable oxidative cracking conditions with a catalyst composition comprising cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal; and oxygen, wherein said catalyst composition is calcined in an inert atmosphere.
Claim 28
Dependent Claim
71 words
A process for the catalytic oxidative cracking of a paraffin having from 3 to 5 carbon atoms comprising the step of contacting said paraffin under suitable oxidative cracking conditions with a catalyst composition comprising cobalt; phosphorus; at least one promoter selected from the group consisting of zinc, titanium, zirconium, niobium, indium, lead and bismuth; at least one alkali metal; and oxygen, wherein said catalyst composition is calcined in an inert atmosphere.
Claim 29
Dependent Claim
45 words
A process in accordance with claim 26 wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 450° C. to about 850° C. for a time in the range of about 1 hour to about 12 hours.
Claim 30
Dependent Claim
45 words
A process in accordance with claim 26 wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 700° C. to about 800° C. for a time in the range of about 2 hours to about 5 hours.
Claim 31
Dependent Claim
15 words
A process in accordance with claim 26 wherein said at least one promoter is zirconium.
Claim 32
Dependent Claim
99 words
A process in accordance with claim 26 wherein the atomic ratio of cobalt to said at least one promoter is in the range of about 1:1 to about 20:1, wherein the concentration of phosphorus in said catalyst composition is in the range of about 1 to about 10 weight percent calculated as the oxide and based on the weight of said catalyst composition and wherein the concentration of said at least one alkali metal is in the range of about 1 to about 10 weight percent calculated as the oxide and based on the weight of said catalyst composition.
Claim 33
Dependent Claim
95 words
A process in accordance with claim 26 wherein the atomic ratio of cobalt to said at least one promoter is in the range of about 3:1 to about 6:1, wherein the concentration of phosphorus is in the range of about 2 to about 5 weight percent calculated as the oxide and based on the weight of said catalyst composition, and wherein the concentration of said at least one alkali metal is in the range of about 2 to about 5 weight percent calculated as the oxide and based on the weight of said catalyst composition.
Claim 34
Dependent Claim
14 words
A process in accordance with claim 26 wherein said catalyst composition additionally comprises sulfur.
Claim 35
Dependent Claim
25 words
A process in accordance with claim 32 wherein said sulfur is added to said catalyst composition by utilizing cobalt sulfide to prepare said catalyst composition.
Claim 36
Dependent Claim
77 words
A process in accordance with claim 33 wherein said catalyst composition is dried in the prsence of free oxygen at a temperature in the range of about 100° C. to about 180° C. for at least 5 hours and wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 450° C. to about 850° C. for a time in the range of about 1 hour to about 12 hours.
Claim 37
Dependent Claim
77 words
A process in accordance with claim 33 wherein said catalyst composition is dried in the presence of free oxygen at a temperature in the range of about 130° C. to about 150° C. for at least 5 hours and wherein said catalyst composition is calcined in a nitrogen atmosphere at a temperature in the range of about 700° C. to about 800° C. for a time in the range of about 2 hours to about 5 hours.
Claim 38
Dependent Claim
27 words
A process in accordance with claim 32 wherein said catalyst composition additionally comprises at least one halogen selected from the group consisting of chlorine, bromine and iodine.
Claim 39
Dependent Claim
27 words
A process in accordance with claim 36 wherein said halogen is added to said catalyst composition by using a halogen containing compound to prepare said catalyst composition.
Claim 40
Dependent Claim
40 words
A process in accordance with claim 36 wherein said halogen is added to said catalyst composition by at least periodically mixing a halogen containing compound with said paraffin prior to the step of contacting said paraffin with said catalyst composition.
Claim 41
Dependent Claim
42 words
A process in accordance with claim 38 wherein the concentration of the halogen in said paraffin is in the range of about 1 part per million to about 10 mole percent when said halogen containing compound is being mixed with said paraffin.
Claim 42
Dependent Claim
27 words
A process in accordance with claim 26 wherein said catalyst composition additionally comprises at least one halogen selected from the group consisting of chlorine, bromine and iodine.
Claim 43
Dependent Claim
27 words
A process in accordance with claim 40 wherein said halogen is added to said catalyst composition by using a halogen containing compound to prepare said catalyst composition.
Claim 44
Dependent Claim
40 words
A process in accordance with claim 40 wherein said halogen is added to said catalyst composition by at least periodically mixing a halogen containing compound with said paraffin prior to the step of contacting said paraffin with said catalyst composition.
Claim 45
Dependent Claim
42 words
A process in accordance with claim 42 wherein the concentration of the halogen in said paraffin is in the range of about 1 part per million to about 10 mole percent when said halogen containing compound is being mixed with said paraffin.
Claim 46
Dependent Claim
59 words
A process in accordance with claim 26 wherein said suitable oxidative cracking conditions comprise a temperature in the range of about 480° C. to about 815° C., a pressure in the range of about 10 to about 520 kilopascals, and a flow rate of a feedstream containing said paraffin in the range of about 100 to about 2500 GHSV.
Claim 47
Dependent Claim
56 words
A process in accordance with claim 26 wherein said suitable oxidative cracking conditions comprise a temperature in the range of about 480° C. to about 815° C., a pressure in the range of about 100 to about 200 kilopascals, and a flow rate of a feedstream containing said paraffin in the range of about 500 GHSV.
Claim 48
Dependent Claim
58 words
A process in accordance with claim 26 wherein substantially no free oxygen is introduced with said feedstream and wherein the catalytic oxidative cracking of said paraffin is carried out in a cyclic process comprising a cracking reaction time and a regeneration time, wherein said cracking time is in the range of about 1 minute to about 30 minutes.
Claim 49
Dependent Claim
73 words
A process in accordance with claim 26 wherein free oxygen is introduced with said feed stream, wherein the catalytic oxidative cracking of said paraffin is carried out as a continuous process with a reaction time in the range of about 1 hour to about 100 hours and wherein the amount of free oxygen introduced is in the range of about 0.4 to about 0.75 moles of free oxygen per mole of said paraffin.
Claim 50
Dependent Claim
73 words
A process in accordance with claim 26 wherein free oxygen is introduced with said feed stream, wherein the catalytic oxidative cracking of said paraffin is carried out as a continuous process with a reaction time in the range of about 1 hour to about 100 hours and wherein the amount of free oxygen introduced is in the range of about 0.5 to about 0.6 moles of free oxygen per mole of said paraffin.
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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) | 1988-02-05 | 1988-08-06 | 1989-02-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-02-05 | 1992-08-06 | 1993-02-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-02-05 | 1996-08-06 | 1997-02-05 | $7700.00 | Window Closed / Lapsed |