Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing

A method for production of synthesis gas by reaction of an oxygen-containing gas with a hydrocarbon which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas impermeable mixed phase ceramic reactor membrane having a reduction surface and an oxidation surface and comprising:
• about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase or phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′)ByB′y′B″2−(y+y′)O5+z
• where A is an element from the f block lanthanide elements;
• A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) heating said reactor cell to d temperature of from about 300° C. to about 1200° C.;
• (c) passing an oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing a hydrocarbon gas in contact with the reduction surface of said membrane to effect the production of synthesis gas.

A method for effecting the decomposition of H2S which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas-impermeable ceramic membrane having a reduction surface and an oxidation surface and comprising:
• about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase or phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has tie formula:
• AxA′x′A″2−(x+x′)ByB′y′B″2−(y+y′)O5+z
• where A is an element from the u-block lanthanide elements;
• A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z vales to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) heating said reactor cell to a temperature of from about 300° C. to about 1200° C.;
• (c) passing an oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing H2S in contact with die oxidation surface of said membrane of said heated reactor in said oxidation zone to effect the production of sulfur and H2O.

A method for production of ethylene by reaction of an oxygen-containing gas with a ethane which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas-impermeable ceramic membrane having a reduction surface and an oxidation surface and comprising:
• about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase dr phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′)ByB′y′B″2−(y+y′)O5+z
• where A is an element from the f block lanthanide elements;
• A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) beating said reactor cell to a temperature of from about 300° C. to about 1200° C.;
• (c) passing an oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing a ethane gas in contact with the reduction surface of said membrane to effect the production of ethylene.

A method for separating and producing high purity oxygen by reaction of an oxygen-containing gas with a reactant gas which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas-impermeable ceramic membrane having a reduction surface and an oxidation surface and comprising;
• about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase or phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′) ByB′y′B″2−(y+y′) O5+z
• where A is an element from the f block lanthanide elements;
• A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) heating said reactor cell to a temperature of from about 300° C. to about 1200° C.;
• (c) passing an oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing a reactant gas in contact with the reduction surface of said membrane to effect the oxidation of said reactant gas.

A method for coupling two or more hydrocarbons which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas-impermeable ceramic membrane having a reduction surface and an oxidation surface and comprising about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase or phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′)BYB′y′B″2−(y+y′)O5+z
• where A is an element from the f block lanthanide elements, A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) heating said reactor cell to a temperature of from about 300° C. to about 1200° C.;
• (c) passing an oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing said two or more hydrocarbons in contact with the reduction surface of said membrane to effect the oxidative coupling of said two or more hydrocarbons.

A method for reduction of an oxygen containing gas which comprises the steps of:

• (a) providing a catalytic membrane reactor cell comprising an oxidation zone and a reduction zone separated by a gas-impermeable ceramic membrane having a reduction surface and an oxidation surface and comprising about 80% by weight or more of a mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of one or more structurally distinct second phases which impart mechanical strength to the membrane, wherein said second phase or phases is formed from one or more of the same metal elements as the first phase;
• wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′)BYB′y′B″2−(y+y′)O5+z
• where A is an element from the f block lanthanide elements, A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials;
• (b) heating said reactor cell to a temperature of from about 300° C. to about 1200° C.;
• (c) passing said oxygen-containing gas in contact with the reduction surface of said membrane of said heated reactor in said reduction zone;
• and
• (d) passing a reactant gas in contact wit the oxidation surface of said membrane of said heated reactor in said oxidation zone to effect oxidation of said reactant gas.

A method for making a mixed phase ceramic material which comprises a mixed ionic and electronic conducting metal oxide and at least one second phase which comprises the steps of:

• a. combining metal precursors of the mixed ionic and electronic conducting metal oxide to obtain a combination of metal ions in which the relative amounts of metal ions are off-stoichiometric for at least one metal ion with respect to the formula of the mixed ionic and electronic conducting metal oxide;
• b. milling the combined metal precursors to obtain a homogeneous mixture;
• c. calcining the homogeneous mixture to obtain the mixed ionic and electronic conducting metal oxide in combination with a second phase containing at least one metal ion of the metal ions of the mixed ionic and electronic conducting metal oxide to form a homogeneous powder mix;
• d. reducing the particle size of the powder mix, if necessary, to less than about 2 microns;
• and
• e. repeating steps c and d until reaction is complete, wherein the mixed ionic and electronic conducting first phase has the formula:
• AxA′x′A″2−(x+x′)ByB′y′B″2−(y+y′)O5+z
• where A is an element from the f block lanthanide elements;
• A′ is an element selected from the Group 2 elements;
• A″ is an element from the f block lanthanide or Group 2 elements;
• B is an element selected from Al, Ga, In or mixtures thereof;
• B′ and B″ are different elements and are selected independently from the group of elements consisting of Mg, and the d-block transition elements;
• 0<x<2, 0<x′<2, 0<y<2, 0<y′<2 where x+x′≦2 and y+y′≦2, and z varies to maintain electroneutrality, and wherein the mixed phase ceramic material comprises about 80% by weight or more of the mixed ionic and electronic conducting first phase and from about 0.1 to about 20% by weight of the one or more structurally distinct second phases;
• and wherein the second phase or phases is formed from one or more of the same metal elements as the first phase;
• and wherein said membrane being made by forming the first and second phase or phases simultaneously by mixing an off-stoichiometric ratio of the first-phase materials.