Claims
- 1. In an improved method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting a gas comprising dehydrogenatable hydrocarbons at oxidative dehydrogenation conditions with a solid comprising at least one oxide of at least one metal which oxides when contacted with dehydrogenatable hydrocarbons at oxidative dehydrogenation conditions are reduced and produce dehydrogenated hydrocarbons and water, the improvement which comprises conducting the contacting in the presence of a promoting amount of at least one member of the group consisting of boron and compounds thereof, said solid being substantially free of catalytically effective iron.
- 2. The method of claim 1 wherein the atomic ratio of the reducible metal oxide component (expressed as the metal) to the boron component (expressed as B) is within the range of about 0.1:1 to about 20:1.
- 3. The method of claim 1 wherein the atomic ratio of the reducible metal oxide component (expressed as the metal) to the boron component (expressed as B) is within the range of about 0.5:1 to about 5:1.
- 4. The method of claim 1 wherein the solid comprises reducible metal oxides selected from the group consisting of reducible oxides of Mn, Sn, In, Ge, Pb, Sb, Bi, Pr, Tb, Ce, Ru and mixtures thereof.
- 5. The method of claim 1 wherein the solid comprises reducible oxides of Mn.
- 6. The method of claim 1 wherein the reducible oxide and the boron promoter are associated with a support material.
- 7. The method of claim 1 wherein dehydrogenatable hydrocarbons are dehydrogenated to dehydrogenated hydrocarbon products in a cyclic manner comprising contacting the solid alternately with a gas comprising dehydrogenatable hydrocarbons and with a gaseous oxidant.
- 8. The method of claim 7 wherein the solid is contacted with a gas comprising dehydrogenatable hydrocarbons at temperatures selected within the range of about 500.degree. to about 1000.degree. C.
- 9. The method of claim 1 wherein dehydrogenatable hydrocarbons are dehydrogenated to dehydrogenated hydrocarbon products by contacting the solid concurrently with a gas comprising dehydrogenatable hydrocarbons and a gaseous oxidant.
- 10. The method of claim 9 wherein said concurrent contact is conducted at temperatures selected within range of about 500.degree. to about 1000.degree. C.
- 11. The method of claim 1 wherein the solid is a mixed oxide composition satisfying the empirical formula:
- MB.sub.b C.sub.c O.sub.x
- wherein M is selected from the group consisting of Mn, Sn, In, Ge, Pb, Sb, Bi, Pr, Tb, Ce, Ru and mixtures thereof; B is boron; and C is at least one alkaline earth metal; and wherein b is within the range of about 0.1 to about 10, c is within the range of about 0.1 to about 100, and x is the number of oxygen atoms required by the valence states of the other elements.
- 12. The method of claim 11 wherein the mixed composition comprises reducible oxides of Mn.
- 13. The method of claim 11 wherein C is Mg.
- 14. The method of claim 11 wherein C is Ca.
- 15. The method of claim 1 wherein the solid is a mixed oxide composition satisfying the empirical formula:
- MA.sub.a B.sub.b C.sub.c O.sub.x
- wherein M is selected from the group consisting of Mn, Sn, In, Ge, Pb, Sb, Bi, Pr, Tb, Ce, Ru and mixtures thereof; A is at least one alkali metal; B is boron; C is at least one alkaline earth metal; and wherein a is within the range of about 0.01 to about 10, b is within the range of about 0.1 to about 20, c is within the range of about 0.1 to about 100, and x is the number of oxygen atoms required by the valence states of the other elements.
- 16. The method of claim 15 wherein the mixed oxide composition comprises reducible oxides of Mn.
- 17. The method of claim 15 wherein A is sodium.
- 18. The method of claim 15 wherein A is lithium.
- 19. The method of claim 15 wherein C is Mg.
- 20. The method of claim 15 wherein C is Ca.
- 21. The method of claim 1 wherein C.sub.2 -C.sub.5 alkanes are dehydrogenated to form the corresponding mono-olefins.
- 22. In an improved method for dehydrogenating dehydrogenatable hydrocarbons which comprises contacting a gas comprising dehydrogenatable hydrocarbons at a temperature within the range of about 500.degree. to about 1000.degree. C. with a solid comprising at least one oxide of at least one metal which oxides when contacted with dehydrogenatable hydrocarbons are reduced and produce dehydrogenated hydrocarbons and water, the improvement which comprises conducting the contacting in the presence of:
- (a) at least one member of the group consisting of Li and compounds thereof,
- (b) at least one member selected from the group consisting of boron and compounds thereof, and
- (c) at least one member of the group consisting of alkaline earth metals and compounds thereof.
- 23. The method of claim 22 wherein the solid is a mixed oxide composition satisfying the empirical formula:
- MLi.sub.a B.sub.b C.sub.c O.sub.x
- wherein M is selected from the group consisting of Mn, Sn, In, Ge, Pb, Sb, Bi, Pr, Tb, Ce, Fe, Ru and mixtures thereof; B is boron; C is at least one alkaline earth metal; and wherein a is within the range of about 0.01 to about 10, b is within the range of about 0.1 to about 20, c is within the range of about 0.1 to about 100, and x is the number of oxygen atoms required by the valence states of the other elements.
- 24. The method of claim 23 wherein b is within the range of about 0.1 to about 10.
- 25. The method of claim 23 wherein c is within the range of about 1 to about 7.
- 26. The method of claim 23 wherein the mixed oxide composition comprises reducible oxides of Mn.
- 27. The method of claim 23 C is Mg.
- 28. The method of claim 23 C is Ca.
- 29. A method for dehydrogenating dehydrogenatable hydrocarbons to form dehydrogenated products which comprises contacting at a temperature within the range of about 500 to about 1000.degree. C. a gas comprising dehydrogenatable hydrocarbons with a mixed oxide composition containing Mn, Na, B and Mg which composition is characterized by the presence of the crystalline compound NaB.sub.2 Mg.sub.4 Mn.sub.2 O.sub.x.
- 30. The method of claim 29 wherein the mixed oxide composition is further characterized by an amount of Mn in the composition in excess of the stoichiometric amount of Mn relative to at least one of the other elements of said crystalline compound.
- 31. The method of claim 30 wherein a stoichiometric excess of Mn relative to boron is provided.
- 32. The method of claim 31 wherein the mixed oxide composition contains excess amounts of Na, Mg and Mn relative to the amounts required by the amount of boron present to satisfy the stoichiometry of said crystalline compound.
- 33. In an improved hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a solid comprising a reducible metal oxide and which is characterized by the production of hydrocarbon product, coproduct water, and a reduced metal oxide, the improvement which comprises conducting the contacting in the presence of a promoting amount of at least one member of the group consisting of boron and compounds thereof, said solid being substantially free of catalytically effective iron.
- 34. In an improved hydrocarbon conversion process which comprises contacting a hydrocarbon feedstock with a solid comprising a reducible oxide of Mn and which is characterized by the production of hydrocarbon product, coproduct water, and a reduced oxide of Mn, the improvement which comprises conducting the contacting with a mixed oxide composition containing Mn, Na, B and Mg and the mixed oxide composition is characterized by the presence of the crystalline compound NaB.sub.2 Mg.sub.4 Mn.sub.2 O.sub.x.
- 35. The method of claim 34 wherein the mixed oxide composition is further characterized by an amount of Mn in the composition in excess of the stoichiometric amount of Mn relative to at least one of the other elements of said crystalline compound.
- 36. The method of claim 35 wherein a stoichiometric excess of Mn relative to boron is provided.
- 37. The method of claim 36 wherein the mixed oxide composition contains excess amounts of Na, Mg and Mn relative to the amounts required by the amount of boron present to satisfy the stoichiometry of said crystalline compound.
Parent Case Info
This is a divisional of co-pending application Ser. No. 877,574, filed on June 23, 1986, now U.S. Pat. No. 4,777,313, which is a continuation-in-part of U.S. patent application Ser. No. 06/683,296 filed Dec. 18, 1984 (now abandoned), which in turn is a continuation-in-part of the following U.S. patent applications: (1) Ser. No. 06/522,937 filed Aug. 12, 1983 (now U.S. Pat. No. 4,499,322); (2) Ser. No. 06/522,936 filed Aug. 12, 1983; (now U.S. Pat. No. 4,495,374); (3) Ser. No. 06/600,654 filed Apr. 16, 1984 ((now U.S. Pat. No. 4,547,611), and Ser. No. 06/600,655 filed Apr. 16, 1984 (now abandoned), both of which are in turn continuations-in-part of Ser. No. 06/522,937 filed Aug. 12, 1983 and of Ser. No. 06/522,936 filed Aug. 12, 1983.
US Referenced Citations (6)
Related Publications (3)
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600654 |
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600655 |
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522936 |
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Divisions (1)
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877574 |
Jun 1986 |
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Continuation in Parts (2)
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683296 |
Dec 1984 |
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522937 |
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