Patent EA-000659-B1 (EA)
Title: Solid state membrane, catalytic membrane reactor (variants) and process using same therefor
Inventor: SCHWARTZ MICHAEL
IPC: C01B3/38
Filed: 1996-09-13
Abstract: 1. A solid-state membrane for use in a catalytic membrane reactor, which comprises: a reduction surface which in operation in a catalytic membrane reactor contacts an oxygen-containing gas and an oxidation surface which in operation in a catalytic membrane reactor contacts a reactant gas, a partial vacuum or an oxygen-depleted gas, wherein said membrane is fabricated from a mixed metal oxide material having a brownmillerite structure and having the general stoichiometry A2-XA' XB2-YB' YO5+Z where: A is an alkaline earth metal ion or mixture of alkaline earth metal ions; A' is a metal ion or mixture of metal ions where the metal is selected from the group consisting of the lanthanide series or is yttrium; B is a metal ion or mixture of metal ions wherein the metal is selected from the group consisting of 3d transition metals, and the group 13 metals; B' is a metal ion or mixture of metal ions where the metal is selected from the group consisting of the 3d transition metals, the group 13 metals, the lanthanides and yttrium; x is a number greater than 0 and less than 2, y is a number greater than 0 and less than or equal to 2, and z is a number greater than zero and less than one that renders the compound charge neutral. 2. The membrane of Claim 1 wherein in said mixed metal oxide x is a number greater than 0 and less than or equal to about 1 and y is a number greater than or equal to 1 and less than or equal to 2. 3. The membrane of Claim 1 wherein the B metal is selected from the group consisting of group 13 metals and mixtures thereof and the B' metal is selected from the group of 3d transition metals or mixtures thereof. 4. The membrane of Claim 3 wherein the B metal is selected from the group of Ai, Ga and In. 5. The membrane of Claim 4 wherein the B metal is Ga. 6. The membrane of Claim 1 wherein the B metal is selected from the group Co, Ti, V, Cr, Mn, Ni and Fe. 7. The membrane of Claim 6 wherein the B metal is Cr, Mn or Fe. 8. The membrane of Claim 7 wherein the B metal is Fe. 9. The membrane of Claim 1 wherein the A metal is Sr, Ba, or Ca. 10. The membrane of Claim 9 wherein A is Sr. 11. The membrane of Claim 1 wherein the A' metal is La or Y. 12. The membrane of Claim 11 wherein the A' metal is La. 13. The membrane of Claim 1 wherein the brownmillerite mixed metal oxide has the stoichiometry A2-XLaXB2-YFeyO5+z, where A is Sr, Ba or Ca and B is Al, Ga or In. 14. The membrane of Claim 13 wherein x is 0.2 to 0.8 and y is 1.0 to 1.8. 15. The membrane of Claim 14 wherein A is Sr and B is Ga. 16. The membrane of Claim l wherein the brownmillerite mixed metal oxide has the stoichiometry: Sr2-xLaxGa2-yCyO5+z, where C is a 3d transition metal ion selected from the group Co, Ti, V, Cr, Mn, Ni, or Fe. 17. The membrane of Claim 16 wherein c is a metal ion selected from the group Cr, Mn and Fe. 18. The membrane of Claim 17 having the general stoichiometry: Sr2-xLaxGa2-yCyO5+z. 19. The membrane of Claim 15 wherein the brownmillerite material is selected from the group of mixed metal oxides consisting essentially of Sri1.7La0.3GaFeO5.15, Sr1.8La0.2GaFeO5.1, Sr1.6La0.4GaFeO5.2, Sri1.4La0.6GaFeO5.3, Sri1.6La0.4Ga0.2Fe1.8O5.2, Sri1.6La0.4Ga0.4Fe1.6O5.2, Sri1.6La0.4Ga0.6Fe1.4O5.2, Sri1.6La0.4Ga0.8Fe1.2O5.2, Sri1.7La0.3Ga0.2Fe1.8O5.15, Sri1.7La0.3Ga0.4Fe1.6O5.15, Sri1.7La0.3Ga0.6Fe1.4O5.15, Sri1.7La0.3Ga0.8Fe1.2O5.15, Sri1.8La0.2Ga0.4Fe1.6O5.1, Sri1.8La0.2Ga0.6Fe1.4O5.1, Sri1.8La0.2Ga0.8Fe1.2O5.1, and Sri1.8La0.2Ga0.2Fe1.8O5.1. 20. The membrane of Claim 1 wherein in said brownmillerite material z is a number greater than zero and less than or equal to 0.4. 21. The membrane of Claim 1 wherein in said brownmillerite material z is a number greater than zero and less than or equal to 0.3. 22. The membrane of Claim 1 further comprising a catalyst on the reduction or oxidation surfaces or on both the oxidation and reduction surfaces of the membrane. 23. The membrane of Claim 22 comprising a catalyst on the oxidation surface of the membrane selected from the group consisting of Ni, Pd, Pt, Rh. Ir. Os, Fe, Mn, and Co, and alloys thereof, wherein these metals are incorporated as clusters into metal oxide ceramics selected from the group consisting of CeO2, Bi2C3, ZrO2, CaB1-x, B'xO3, SrxB'xO3 and Ba1-3B'xO3, where B is Ce, Tb, or Pr, B' is a 3+ lanthanide ion and 0< x< 0.2. 24. The membrane of Claim 22 comprising a catalyst on the oxidation surface of the membrane having the composition A1-xA'xB1-yB'yO3 where A is a lanthanide metal ion or a yttrium ion, A' is an alkali or an alkaline earth ion, B is a first row transition metal ion, B' is Ce, Cu, Ag, Au, Pt, Pd, or Mi, 0 < x < 0.8 and 0 < y < 0.3. 25. The membrane of Claim 22 comprising a catalyst on the reduction surface of the membrane selected from the group consisting of Ag, SrCo1-xMxO3 or BaCo1-xMxO3 where M is Fe, Co or Ni and 0 < x < 0.5. 26. The membrane of Claim 22 for use in a catalytic membrane reactor for reduction of NOx, which comprises: a reduction surface which in operation in said catalytic membrane reactor contacts NOx and an oxidation surface which in operation in a catalytic membrane reactor contacts H2 light hydrocarbons, CO or a partial vacuum, and a catalyst on the oxidation surface of said membrane selected from the group consisting of Ag, Ni, SrCo1-xMxO3 or BaCo1-xMxO3 where M is Fe, Co or Ni and 0 < x < 0.5. 27. The membrane of Claim 22 for use in a catalytic membrane reactor for reduction of SOx which comprises: a reduction surface which in operation in said catalytic membrane reactor contacts SOx and an oxidation surface which in operation in said catalytic membrane reactor contacts Ha, light hydrocarbons, CO or a partial vacuum; a catalyst on the reduction surface of the membrane selected from the group consisting of ABS3, where A is a lanthanide or yttrium ion, and B is Fe, Co, Ni or Cu, AB2S4, where A is a 2+ first row transition metal ion and B is a 3+ first row transition metal ion; and Chevrel phases A2Mo6S8, where A is Fe, Co, Ni, Cu or Zn; and a catalyst on the oxidation surface of the membrane selected from the group consisting of Ag, Ni, SrCo1-xMxO3, or BaCo1-xMxO3, where M is Fe, Co or Ni and o < x < 0.5. 28. A membrane according to Claim 22 which comprises: a reduction surface in contact with oxygen, air or a gas mixture containing 0; and an oxidation surface in contact with H2S, a catalyst on the oxidation surface of said membrane selected from the group consisting of AB2S4 where A is a 2+ Group VIII ion and B is a 3+ Group VIII ion; and WS2, and a catalyst on the reduction surface of said membrane selected from the group Ag, SrCo1-xMxO3, or BaCo1-xMxO3, where M is Fe, Co or Ni and 0 < x < 0.5. 29. A membrane according to Claim 22 for use in the catalytic separation of oxygen from a mixture with other gases which comprises: an oxidation surface which in operation is in contact with a gas containing oxygen and a reduction surface in contact with an oxygen-depleted gas, inert gas or partial vacuum; and a catalyst on the reduction surface of the membrane selected from the group consisting of Ag, SrCo1-xMxO3, or BaCo1-xMxO3, where M is Fe, Co or Ni and 0 < x < 0.5. 30. A membrane according to Claim 29 which comprises a catalyst on the oxidation surface of said membrane selected from the group consisting of AM1-xM'xO3 where A is Sr or Ba, M is Co or Ru and M' is Fe, Co, Mi or Ag and 0<x<0.5; A2M2O5, where A is Ca or Sr and M is Fe or Mn; Pb2Ru2Q7; AB2O4, where A is a 2+ ion of Ni, Co, Fe, or Cu and B is a 3+ ion of Co, Fe, or Ni; and A1-xA'xMnO3, where A is a lanthanide metal ion or yttrium ion and A' is an alkaline earth metal ion. 31. The membrane of Claim 22 which comprises a catalyst on the oxidation surface of the membrane wherein the catalyst is Ni supported on α-Al2O3. 32. The membrane of Claim 22 which comprises a catalyst on the oxidation surface of the membrane wherein the catalyst is Ni supported on La0.8Sr0.2MnO3-x. 33. A catalytic membrane reactor for reacting an oxygen-containing gas with a reactant gas which comprises: a membrane as in Claim 1, a reactor cell having a reduction zone and an oxidation zone separated by said membrane; a first entrance port for introduction of said oxygen-containing gas into said reduction zone; a second entrance port for introduction of said reactant gas into said oxidation zone; an exit port for gases exiting the reactor; and a passage between said entrance ports and said exit port for movement of one or more gases through the reactor. 34. A catalytic membrane reactor for reacting an oxygen-containing gas with a reactant gas which comprises: a reduction zone; a plurality of reactor cells each having a membrane as in Claim 1 and each having an oxidation zone separated from said reduction zone by said membrane; a shell which contains the reactor cells; an entrance port in said shell for introduction of said oxygen-containing gas into said reduction zone and an exit port in said shell for removal of reacted gas from said reduction zone; and a means for introduction of said reactant gas into said oxidation zones and a means for removal of reacted gas from said oxidation zones; said reactor cells positioned within the shell so that the shell, the reactor cells and the membranes of the reactor cells together form the reduction zone which is separated from the oxidation zones of said reactors by said membranes. 35. A catalytic membrane reactor for separating oxygen from an oxygen-containing gas, which comprises a reactor cell having a reduction zone and an oxidation zone separated by a membrane as in Claim 1. 36. A catalytic membrane reactor for separating oxygen from a mixture of gases containing oxygen, which comprises: a reduction zone; a plurality of reactor cells each having a membrane as in Claim 1 and each having an oxidation zone separated from said reduction zone by said membrane; a shell which contains the reactor cells; an entrance port in said shell for introduction of said mixture of g