Enhanced dual phase membranes for separating carbon from carbon-containing feed gases and separation methods using the same
Dual phase membranes include a porous support providing a solid phase having a matrix of connected pores, and a liquefiable ion transport phase within the pores of the porous support. The ion transport phase is formed of at least one alkali metal hydroxide, and at least one oxide ion transport agent providing a source of ions selected from the group consisting of borate ions, nitrate ions, phosphate ions, vanadate ions, niobate ions or sulfate ions. The at least one alkali metal hydroxide may be selected from the group consisting of NaOH, KOH, LiOH, RbOH, CsOH and mixtures thereof. The oxide ion transport agent is preferably present in the ion transport phase in an amount between about 1 to about 30 molar %. Substantially lower operational temperatures may be realized when the membrane is used to separate CO2 from a feed gas.
1 . A dual phase separation membrane having an operational temperature within a range of 100° C. to 500° C., wherein the membrane comprises:
a porous support providing a solid phase having a matrix of connected pores; and
a liquefiable ion transport phase which is molten at the operational temperature within the pores of the porous support, wherein the ion transport phase comprises:
(i) at least one alkali metal hydroxide, and
(ii) at least one oxide ion transport agent providing a source of ions selected from the group consisting of alkali and alkaline earth metal salts of vanadate present in the ion transport phase in an amount between 1 to 30 molar %.
2 . The dual phase membrane according to claim 1 , wherein the at least one alkali metal hydroxide is selected from the group consisting of NaOH, KOH, LiOH, RbOH, CsOH and mixtures thereof.
3 . The dual phase membrane according to claim 1 , wherein the ion transport phase further comprises a melt temperature depression component in a molar amount sufficient to depress operational temperatures of the membrane to about 100° C. or above.
4 . The dual phase membrane according to claim 3 , wherein the melt temperature depression component comprises at least one alkali earth metal hydroxide, at least one alkali metal nitrate and/or at least one alkali earth metal nitrate.
5 . The dual phase membrane according to claim 4 , wherein the melt temperature depression component comprises at least one compound selected from the group consisting of Be(OH) 2 , Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , LiNO 3 , NaNO 3 , KNO 3 , RbNO 3 , CsNO 3 , Be(NO 3 ) 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , Sr(NO 3 ) 2 , Ba(NO 3 ) 2 and mixtures thereof.
6 . The dual phase membrane according to claim 1 , wherein the membrane has an operational temperature within a range of about 125° C. to about 300° C.
7 . The dual phase membrane according to claim 1 , wherein the porous support is comprised of a metal or ceramic material.
8 . The dual phase membrane according to claim 7 , wherein the porous support is comprised of at least one material selected from the group consisting of nickel-chromium based alloys, stainless steels, zirconium oxides, cerium oxides, magnesium oxides, aluminum oxides, lanthanum oxides, samarium oxides, gadolinium oxides, iron oxides, calcium carbonates, silicon oxides and silicon carbides.
9 . The dual phase membrane according to claim 1 , wherein the pores have an average pore size of about 10 nm up to about 1 mm.
10 . A process to separate a gaseous species from a feed gas, the process comprising:
(a) contacting a surface of the dual phase membrane according to claim 1 with a feed gas containing a gaseous species to be separated therefrom at the operational temperature within a range of 100° C. to 500° C. sufficient to render the ion transport phase molten; and
(b) allowing the gaseous species to be transported through the molten ion transport phase to an opposite surface of the membrane.
11 . The process according to claim 10 , wherein the feed gas comprises a concentration of CO 2 .
12 . The process according to claim 10 , which further comprises contacting the opposite surface of the membrane with a sweep gas.
13 . The process according to claim 12 , wherein the sweep gas is steam.
14 . The process according to claim 13 , wherein the steam sweep gas results in a CO 2 concentration in the steam sweep gas exiting the membrane that is greater than a concentration of CO 2 in the feed gas.
15 . The process according to claim 10 , wherein the at least one alkali metal hydroxide is selected from the group consisting of NaOH, KOH, LiOH, RbOH, CsOH and mixtures thereof.
16 . The process according to claim 10 , wherein steps (a) and (b) are practiced at an operational temperature within a range of about 125° C. to about 300° C.
17 . The process according to claim 10 , wherein the ion transport phase further comprises a melt temperature depression component in a molar amount sufficient to depress operational temperatures of the membrane to about 100° C. or above.
18 . The process according to claim 17 , wherein the melt temperature depression component comprises at least one alkali earth metal hydroxide, at least one alkali metal nitrate and/or at least one alkali earth metal nitrate.
19 . The process according to claim 18 , wherein the melt temperature depression component comprises at least one compound selected from the group consisting of Be(OH) 2 , Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , LiNO 3 , NaNO 3 , KNO 3 , RbNO 3 , CsNO 3 , Be(NO 3 ) 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , Sr(NO 3 ) 2 , Ba(NO 3 ) 2 and mixtures thereof.
20 . A dual phase separation membrane comprising:
a porous support providing a solid phase having a matrix of connected pores; and
a liquefiable ion transport phase within the pores of the porous support, wherein the ion transport phase comprises:
(i) at least one alkali metal hydroxide,
(ii) at least one oxide ion transport agent providing a source of ions selected from the group consisting of borates, nitrates, phosphates, vanadates, niobates, and sulfates, and
(iii) a melt temperature depression component in a molar amount sufficient to depress operational temperatures of the membrane to about 100° C. or above, wherein the melt temperature depression component comprises at least one alkali earth metal hydroxide, at least one alkali metal nitrate and/or at least one alkali earth metal nitrate.
21 . The dual phase membrane according to claim 20 , wherein the melt temperature depression component comprises at least one compound selected from the group consisting of Be(OH) 2 , Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , LiNO 3 , NaNO 3 , KNO 3 , RbNO 3 , CsNO 3 , Be(NO 3 ) 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , Sr(NO 3 ) 2 , Ba(NO 3 ) 2 and mixtures thereof.
22 . The dual phase membrane according to claim 20 , wherein the membrane has an operational temperature within a range of about 100° C. to about 500° C.
23 . The dual phase membrane according to claim 20 , wherein the oxide ion transport agent is present in the ion transport phase in an amount between about 1 to about 30 molar %.
24 . A process to separate carbon from a feed gas, the process comprising:
(a) contacting a surface of the dual phase membrane according to claim 20 with a feed gas containing a gaseous species to be separated therefrom at an operational temperature within a range of 100° C. to 500° C. sufficient to render the ion transport phase molten; and
(b) allowing the gaseous species to be transported through the molten ion transport phase to an opposite surface of the membrane.
25 . The process according to claim 24 , wherein the feed gas comprises a concentration of CO 2 .
26 . The process according to claim 24 , which further comprises contacting the opposite surface of the membrane with a sweep gas.
27 . The process according to claim 26 , wherein the sweep gas is steam.
28 . The process according to claim 27 , wherein the steam sweep gas results in a CO 2 concentration in the steam sweep gas exiting the membrane that is greater than a concentration of CO 2 in the feed gas.