Patent EA-002444-B1 (EA)
Title: Catalytic membrane reactor with two component three-dimensional catalysis
Inventor: SCHWARTZ MICHAEL
IPC: B01J35/00
Filed: 1998-10-29
Abstract: 1. A catalytic membrane reactor which comprises: an oxidation zone and a reduction zone separated by a gas-impermeable membrane which has an oxidation surface in contact with the oxidation zone and a reduction surface in contact with the reduction zone; an adherent catalyst layer on the oxidation surface of the membrane; and  a three-dimensional catalyst in the oxidation zone wherein the membrane is a single-phase mixed ionic and electronic conducting ceramic of the formula: A2-xA'B2-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 metals of the lanthanide series and 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 and y are, independently of each other, numbers greater than or equal to zero and less than or equal to 2; and z is a number that renders the ceramic material charge neutral and the catalyst layer and the three-dimensional catalyst promote an oxidation reaction. 2. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst promote a partial oxidation of a hydrocarbon. 3. The catalytic membrane reactor of claim 1 wherein the membrane ceramic has the formula: XaRe1-aZbZ'1-bOc where X is Ca, Sr, Ba or mixtures thereof, Re is a rare earth or lanthanide metal, including Yttrium, or mixtures thereof; Z is Al, Ga, In or mixtures thereof; Z'is Cr, Mn, Fe, or Co or mixtures thereof; 0 is <= a <= 1, 0 is <= b <= 1 and c is a number, dependent upon the oxidation states of the other components, and the values of a and b, that render the composition charge neutral. 4. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer is a mixed ionic and electronic conducting ceramic having the formula: M/XaRe1-aZbZ'1-bOc where X is Ca, Sr, Ba or mixtures thereof, Re is a rare earth or lanthanide metal, including Yttrium, or mixtures therof; Z is Al, Ga, In or mixtures thereof; Z' is Cr, Mn, Fe, or Co, or mixtures thereof; 0 is <= a <= 1 and 0 is <= b <= 1 and  c is a number, dependent upon the oxidation states of the other components, and the values of a and b, that renders the composition charge neutral; M is a metal selected from Ni, Pt, Pd, Rh, Ir, Ag, Cr, V, Mo, W or mixtures thereof wherein the weight percent of metal to mixed conducting catalyst ranges from about 1 wt% to about 50 wt%. 5. The catalytic membrane reactor of claim 1 further comprising an oxygen reduction catalyst layer on the reduction surface of the membrane. 6. The catalytic membrane reactor of claim 5 wherein the oxygen reduction catalyst is LaaSr1-aCoO3-x, where a is a number such that 0 <= a <= 1 and x is a number such that the compound is charge neutral. 7. The catalytic membrane reactor of claim 5 wherein the oxygen reduction catalyst is a metal selected from Ag, Pt or Pd. 8. The catalytic membrane reactor of claim 5 wherein the oxygen reduction catalyst is a catalyst of the formula: ACo1-xMxO3-δ, where A is Ca, Sr, Ba or combinations thereof, x is a number less than 1 and δ is a number that renders the catalyst charge neutral; M is a metal ion with empty metal eg orbitals and filled metal t2g orbitals. 9. The catalytic membrane reactor of claim 1 wherein the membrane ceramic has the formula: A2-xLaxB2-yFeyO5+z where A is an alkaline earth metal ion or mixture of alkaline earth metal ions, B is metal ion or mixture of metal ions where the metal is selected from the group consisting of the 3d transition metals, or the group 13 metals; x and y, independently of one another, are numbers greater than or equal to zero and less than or equal to 2, and z is a number that renders the ceramic charge neutral. 10. The catalytic membrane reactor of claim 1 wherein the three-dimensional catalyst is a packed-bed catalyst. 11. The catalytic membrane reactor of claim 1 wherein the three-dimensional catalyst is a metal supported on an inert oxide or supported on a mixed ionic and electronic conducting oxide. 12. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst are selected from catalysts that promote the partial oxidation of methane or higher hydrocarbons to CO and hydrogen. 13. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst are selected from catalysts that promote the partial oxidation of hydrocarbons to oxygenated species. 14. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst are selected from catalysts that promote the partial oxidation of hydrocarbons to epoxides. 15. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst are selected from catalysts that promote the oxidative dehydrogenation of alkanes. 16. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer and the three-dimensional catalyst are selected from catalysts that promote the oxidative coupling of methane or higher hydrocarbons. 17. The catalytic membrane reactor of claim 1 wherein the adherent catalyst layer protects the membrane from decomposition. 18. A catalytic reactor membrane having an oxidation surface and a reduction surface with an adherent catalyst layer on the oxidation surface wherein the membrane comprises a ceramic of the formula: 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 metals of the lanthanide series and 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 and y are, independently of each other, numbers greater than or equal to zero and less than or equal to 2; and z is a number that renders the ceramic material charge neutral. 19. The catalytic reactor membrane of claim 18 wherein the adherent catalyst layer is a mixed ionic and electronic conducting ceramic of the formula: XaRe1-aZbZ'1-bOc where X is Ca, Sr or Ba, or mixtures thereof Re is a rare earth or lanthanide metal, including yttrium, or mixtures thereof; Z is Al, Ga or In or mixtures thereof and Z' is Cr, Mn, Fe or Co or mixtures thereof, with a and b numbers such that 0 <= a <= 1 and 0 <= b <= 1 and c is a number, dependent upon the oxidation states of the other components, and the values of a and b, that renders the composition charge neutral. 20. The catalytic reactor membrane of claim 18 wherein the adherent catalyst layer is a mixed ionic and electronic conducting material of the formula: M/XaRe1-aZbZ'1-bOc where X is Ca, Sr or Ba, or mixtures thereof, Re is a rare earth or lanthanide metal, including yttrium, or mixtures thereof; Z is Al, Ga or In or mixtures thereof and Z' is Cr, Mn, Fe, Co, Cr, V, Mo, W or mixtures thereof, with a and b numbers such that 0 <= a <= 1 and 0 <= b <= 1 and c is a number, dependent upon the oxidation states of the other components, and the values of a and b, that renders the composition charge neutral; and M is a metal selected from Ni, Pt, Pd, Rh, Ir, Ag or mixtures therof and wherein the weight percent of metal to mixed conducting material ranges from about 1wt% to about 50wt%. 21. The catalytic reactor membrane of claim 18 wherein the adherent catalyst layer prevents decomposition of the membrane. 22. A catalytic membrane reactor of claim 1 for the production of synthesis gas by oxidation of a methane-containing gas wherein the adherent catalyst layer is a ceramic exhibiting both ionic and electronic conduction and the three-dimensional catalyst comprises a first row transition metal ion in a weakly basic matrix. 23. The catalytic membrane reaction of claim 5 wherein the oxygen reduction catalyst is a metal selected from the group Pd, LaaSr1-aCoO3-x, where a is a number such that 0 <= a <= 1 and x is a number such that the compound is charge neutral. 24. The catalytic membrane reactor of claim 23 wherein the oxygen reduction catalyst is Pd (5wt%) on La0,8Sr0,2CoO3-x the adherent catalyst layer is Ni (20wr%) on La0,8Sr0,2NmO3 and the three dimensional catalyst is Ni (5wt%) on alumina. 25. A method for oxidizing a reactant gas which comprises the steps of: (a) providing a catalytic membrane reactor of claim 1; (b) introducing a reactant gas into the oxidation zone of the reactor; (c) introducing an oxygen-containing gas into the reduction zone of the reactor; and (d) heating the oxygen ion-conducting, gas-impermeable membrane separating the oxidation zone and the reduction zone to effect reduction of the oxygen-containing gas and transport of oxygen ions to the oxidation zone and effect oxidation of the reactant gas. 26. A method for oxidizing a reactant gas and reducing an oxygen-containing gas which comprises the steps of: (a) providing a gas-impermeable, oxygen ion-conducting membrane of the formula: 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 metals of the lanthanide series and 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 con