Claims
- 1. A process for the oxidative dehydrogenation of organic compounds in the presence of an oxygen containing gas, a metal ferrite catalyst, and at least a promoting amount of sulfur.
- 2. The process according to claim 1 wherein the metal has an ionic radius approximately between 0.5 and 1.1 A.
- 3. The process according to claim 1 wherein the metal is selected from the group consisting of Mg, Zn, Ni, Co, Mn, Cu, Cd, Ca, Ba, Sr, Al, Cr, Ti, V, Mo, W, Na, Li, K, Sn, Pb, Sb, Bi, Ga, Ce, La, the other rare earths and mixtures thereof.
- 4. The process according to claim 3 wherein the metal is selected from the group consisting of Mg, Ca, Sr, Ba, Mn, Cr, Co, Ni, Zn, Cd, and mixtures thereof.
- 5. The process according to claim 4 wherein the metal is Mg or Mn.
- 6. The process according to claim 4 wherein the metal is comprised of at least two components.
- 7. The process according to claim 6 wherein one of the components is Cr.
- 8. The process according to claim 7 wherein the second metal component is a metal selected from Periodic Table Groups IIA, IIB, III, and VII.
- 9. The process according to claim 1 wherein said organic compounds are hydrocarbons.
- 10. The process according to claim 9 wherein butene is oxidatively dehydrogenated.
- 11. The process for the oxidative dehydrogenation of organic compounds according to claim 1 wherein the sulfur is incorporated in the metal ferrite catalyst in a ratio of 0.001 to 0.5 atom of sulfur per atom of iron in said catalyst prior to the contact of said catalyst with the organic compounds.
- 12. The process according to claim 11 wherein the metal has an ionic radius approximately between 0.5 and 1.1 A.
- 13. The process according to claim 11 wherein the metal is selected from the group consisting of Mg, Zn, Ni, Co, Mn, Cu, Cd, Ca, Ba, Sr, Al, Cr, Ti, V, Mo, W, Na, Li, K, Sn, Pb, Sb, Bi, Ga, Ce, La, the other rare earths and mixtures thereof.
- 14. The process according to claim 13 wherein the metal is selected from the group consisting of Mg, Ca, Sr, Ba, Mn, Cr, Co, Ni, Zn, Cd, and mixtures thereof.
- 15. The process according to claim 14 wherein the metal is Mg or Mn.
- 16. The process according to claim 11 wherein the metal is comprised of at least two components.
- 17. The process according to claim 16 wherein one of the components is Cr.
- 18. The process according to claim 17 wherein the second metal component is a metal selected from Periodic Table Groups IIA, IIB, III, and VIII.
- 19. The process according to claim 11 wherein said organic compounds are hydrocarbons.
- 20. The process according to claim 19 wherein butene is oxidatively dehydrogenated.
- 21. The process for the oxidative dehydrogenation of organic compounds according to claim 1 wherein sulfur is added to the reaction in a mole ratio of sulfur to organic compounds of between 0.0003:1 and 0.5:1.
- 22. The process according to claim 21 wherein there is a ratio of gram atoms of sulfur to a mole organic compounds of between about 0.001 : 1.0 to 0.05 : 1.0.
- 23. The process according to claim 21 wherein the metal has an ionic radius approximately between 0.5 and 1.1 A.
- 24. The process according to claim 21 wherein the metal is selected from the group consisting of Mg, Zn, Ni, Co, Mn, Cu, Cd, Ca, Ba, Sr, Al, Cr, Ti, V, Mo, W, Na, Li, K, Sn, Pb, Sb, Bi, Ga, Ce, La, the oher rare earths and mixtures thereof.
- 25. The process according to claim 24 wherein the metal is selected from the group consisting of Mg, Ca, Sr, Ba, Mn, Cr, Co, Ni, Zn, Cd, and mixtures thereof.
- 26. The process according to claim 25 wherein the metal is Mg or Mn.
- 27. The process according to claim 21 wherein the metal is comprised of at least two components.
- 28. The process according to claim 27 wherein one of the components is Cr.
- 29. The process according to claim 28 wherein the second metal component is a metal selected from Periodic Table Groups IIA, IIB, III, and VIII.
- 30. The process according to claim 21 wherein said organic compounds are hydrocarbons.
- 31. The process according to claim 30 wherein butene is oxidatively dehydrogenated.
- 32. A process for the dehydrogenation of ethylbenzene to styrene comprising:
- contacting ethylbenzene and SO.sub.2 in the vapor phase under dehydrogenation conditions with a catalyst comprising:
- a ferrite of the spinel form having the formula
- A.sub.a A'.sub.b Fe.sub.c O.sub.4
- where A has a valence of plus 2 and is a metal selected from the group consisting of cobalt, nickel, zinc and magnesium; A' has a valence of plus 3 and is selected from the group consisting of chromium and lanthanum; a has a value from 0.1 to about 3; b has a value from 0 to less than 2; c has a value from greater than 0 to about 3; and a+b+c has a value of 3; or a ferrite of the perovskite form having the formula
- B.sub.d Cr.sub.e Fe.sub.f O.sub.3
- where B has a valence of plus 3 and is selected from lanthanum and yttrium; d, e and f are each values from 0.5 to 1.5 and the sum of d, e, and f is 2.
- 33. A process according to claim 32 wherein the catalyst is a ferrite of the perovskite form having the formula
- B.sub.d Cr.sub.e Fe.sub.f O.sub.3
- where B has a valence of plus 3 and is selected from lanthanum and yttrium; d, e and f are each values from 0.5 to 1.5 and the sum of d, e and f is 2.
- 34. A process according to claim 33 wherein B is lanthanum.
- 35. A process according to claim 32 wherein the catalyst is a ferrite of the spinel form having the formula
- A.sub.a A'.sub.b Fe.sub.c O.sub.4
- where A is a metal selected from the group consisting of cobalt, nickel, zinc and magnesium; A' is a metal selected from chromium and lanthanum; a has a value from 0.1 to about 3; b has a value from 0 to less than 2; c has a value from greater than 0 to about 3; and a+b+c has a value of 3.
- 36. A process according to claim 35 wherein the catalyst has the formula
- AA'.sub.x Fe.sub.y O.sub.4
- where A has a valence of plus 2 and is a metal selected from the group consisting of cobalt, nickel, zinc, and magnesium; A' is a metal having a valence of plus 3 and is selected from the group consisting of chromium and lanthanum; and x is a value from 0 to 1.5; y is a value from 0.5 to 2 and x plus y has a value equal to 2.
- 37. A process according to claim 36 wherein A is selected from zinc and magnesium; A' is chromium; x has a value from 0 to 1, y has a value from 1 to 2, and the sum of the values of x and y is 2.
- 38. A process according to claim 37 wherein the catalyst is ZnCrFeO.sub.4.
- 39. A process according to claim 37 wherein the catalyst is MgCrFeO.sub.4.
- 40. A process according to claim 35 wherein the dehydrogenation conditions include a temperature from 300.degree. to 700.degree.C.
- 41. A process according to claim 32 wherein a diluent gas is also present.
- 42. A cyclic process for the dehydrogenation of ethylbenzene to produce styrene which comprises:
- 1. contacting ethylbenzene with SO.sub.2 in the vapor phase under dehydrogenation conditions with a catalyst comprising:
- a ferrite of the spinel form having the formula
- A.sub.a A'.sub.b Fe.sub.c O.sub.4
- where A has a valence of plus 2 and is a metal selected from the group consisting of cobalt, nickel, zinc and magnesium; A' is a metal having a valence of plus 3 and is selected from the group consisting of chromium and lanthanum; a has a value from 0.1 to about 3; b has a value from 0 to less than 2; c has a value from greater than 0 to about 3; and a+b+c has a value of 3; or a ferrite of the perovskite form having the formula
- B.sub.d Cr.sub.e Fe.sub.f O.sub.3
- where B has a valence of plus 3 and is selected from lanthanum and yttrium; d, e and f are each values from 0.5 to 1.5 and the sum of d, e and f is 2;
- 2. regenerating said ferrite catalyst with a gas containing free molecular oxygen;
- 3. contacting ethylbenzene and SO.sub.2 in the vapor phase under dehydrogenation conditions with said regenerated ferrite catalyst to obtain substantially the same yields of styrene as were obtained initially.
- 43. A proces according to claim 42 wherein the dehydrogenation conditions include a temperature from 300.degree. to 700.degree.C, a liquid hourly space velocity of ethylbenzene from 0.15 to about 5.
- 44. A process according to claim 43 wherein the surface area of the catalyst is less than 10 m..sup.2 /gram.
- 45. A process according to claim 44 wherein a diluent gas is also present.
- 46. A process for the dehydrogenation of ethylbenzene to styrene comprising:
- contacting ethylbenzene and SO.sub.2 in the vapor phase under dehydrogenation conditions with a catalyst comprising:
- a ferrite having two elements other than iron and oxygen with said elements being selected from the group consisting of (1) (a) a member selected from the group consisting of cobalt, nickel, zinc and magnesium together with (b) a metal selected from the group consisting of chromium and lanthanum or (2) a member selected from the group consisting of (a) lanthanum and yttrium together with (b) chromium.
- 47. A process according to claim 46 wherein (1) (b) is chromium and (2) (a) is lanthanum.
- 48. A process according to claim 41 wherein the molar ratio of diluent to ethylbenzene is from 3 to 35; the SO.sub.2 to ethylbenzene ratio is from 0.0003 : 1.0 to 0.50 : 1.0 calculated as gram atoms of sulfur; and the liquid hourly space velocity of the ethylbenzene is from 0.1 to 10.
- 49. A process according to claim 46 wherein the said SO.sub.2 is fed incrementally to said process.
- 50. A process for the dehydrogenation of ethylbenzene to styrene comprising:
- contacting ethylbenzene and SO.sub.2 in the vapor phase under dehydrogenation conditions with a catalyst comprising:
- a ferrite selected from the group consisting of magnesium chromium ferrite, zinc chromium ferrite, lanthanum chromiun ferrite, nickel chromium ferrite and cobalt chromium ferrite.
- 51. The process of claim 50 wherein the catalyst comprises lanthanum chromium ferrite.
- 52. The process of claim 50 wherein the catalyst comprises nickel chromium ferrite.
Parent Case Info
This application is a division of Ser. No. 859,565, filed Sept. 19, 1969 now U.S. Pat. No. 3,666,687.
US Referenced Citations (7)
Divisions (1)
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Number |
Date |
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Parent |
859565 |
Sep 1969 |
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