Composition and process for capturing carbon dioxide
A solid sorbent composition including calcium oxide, calcium aluminate, and a mixed metal oxide characterized by a perovskite crystalline structure, for example, lanthanum aluminate. The solid sorbent finds utility in capturing carbon dioxide from a gaseous stream containing carbon dioxide, such as emissions streams produced in combustion processes or streams derived from closed environments including airplanes, spaceships, and submarines. A reversible carbon dioxide process is disclosed involving (a) contacting a carbon dioxide-containing gaseous stream with the solid sorbent composition in a carbonator to produce a solid mixture containing calcium carbonate and a gaseous product stream reduced in carbon dioxide concentration; and (b) heating the solid mixture containing calcium carbonate in a calcinator (decarbonator) to regenerate the solid sorbent composition and produce a gaseous stream enriched in carbon dioxide.
1 . A sorbent composition comprising calcium oxide, calcium aluminate, and lanthanum aluminate characterized by a perovskite crystalline structure, the sorbent composition being prepared by a process comprising:
(a) preparing a mixture of calcium oxide or a precursor thereof, calcium aluminate or a precursor thereof, and lanthanum aluminate having a perovskite crystalline structure or a precursor thereof;
(b) calcining the mixture under a dry gas to form a first calcined material;
(c) contacting the first calcined material with carbon dioxide in the presence of water vapor at a first temperature sufficient to form an at least partially carbon dioxide-saturated material;
(d) decarbonating the at least partially carbon dioxide-saturated material at a second temperature sufficient to remove the carbon dioxide and form a second calcined material;
(e) cooling the second calcined material to the first temperature; and
(f) repeating steps (c) through (e) at least once so as to yield the sorbent composition.
2 . The sorbent composition of claim 1 comprising from greater than 18 percent to less than 90 percent by weight calcium oxide (dried basis), based on the total weight of the sorbent composition.
3 . The sorbent composition of claim 1 comprising from greater than 5 percent to less than 80 percent by weight calcium aluminate, based on the total weight of the sorbent composition.
4 . The sorbent composition of claim 1 comprising from greater than 2 percent to less than 20 percent by weight mixed lanthanum aluminate, based on the total weight of the sorbent composition.
5 . The sorbent composition of claim 1 wherein the calcium aluminate is selected from the group consisting of crystalline compounds of molecular formula Ca 9 (Al 2 O 6 ) 3 , CaAl 4 O 7 , CaAl 2 O 4 , and Ca 12 Al 14 O 32 Y, wherein Y is selected from the group consisting of O 2− , N 2− , (OH − ) 2 , (F − ) 2 , (Cl − ) 2 , (H 2 O) 4 (Cl − ) 2 , (H 2 O) 4 (F − ) 2 , and (e − ) 2 where e − represents a free electron, and mixtures of the aforementioned crystalline structures.
6 . The sorbent composition of claim 1 wherein the calcium aluminate comprises a mixture of Ca 9 (Al 2 O 6 ) 3 and Ca 12 Al 14 O 33 .
7 . The sorbent composition of claim 1 wherein the mixture of step (a) is prepared in a slurry containing from 10 to 50 percent solids, further comprising a liquid diluent selected from the group consisting of water, C 1-4 alcohols, and mixtures thereof.
8 . The sorbent composition of claim 1 wherein the first calcination of step (b) is conducted under a dry gas containing less than 1 volume percent water vapor at a temperature greater than 800° C. but less than 1, 400° C.
9 . The sorbent composition of claim 1 wherein the carbonation step (c) is conducted at a temperature greater than 500° C. and less than 750° C., and optionally wherein the sorbent is exposed to a carbon-dioxide-containing stream comprising from 1 to 25 percent water vapor by volume.
10 . The sorbent composition of claim 1 wherein the decarbonation step (d) is conducted at a temperature greater than about 850° C. and less than about 1, 100° C. and under a dry sweep gas containing less than 1 volume percent water.
11 . A method of preparing a sorbent composition comprising calcium oxide, calcium aluminate and lanthanum aluminate having a perovskite crystalline structure, the method comprising:
(a) preparing a mixture comprising calcium oxide or a precursor thereof, calcium aluminate or a precursor thereof, and lanthanum aluminate having a perovskite crystalline structure or a precursor thereof;
(b) calcining the mixture under a dry gas to form a first calcined material;
(c) contacting the first calcined material with carbon dioxide in the presence of water vapor at a first temperature sufficient to form an at least partially carbon dioxide-saturated material;
(d) decarbonating the at least partially carbon dioxide-saturated material at a second temperature sufficient to remove the carbon dioxide and form a second calcined material;
(e) cooling the second calcined material to the first temperature; and
(f) repeating steps (c) through (e) at least once so as to yield the sorbent composition.
12 . The method of claim 11 wherein the precursor to calcium oxide is calcium hydroxide, calcium carbonate, calcium nitrate, or a mixture thereof.
13 . The method of claim 11 wherein the precursor to calcium aluminate is a mixture comprising calcium oxide (anhyrous or hydrated) and alumina, or hydrotalcite of molecular formula CaAl 2 (CO 3 ) 2 (OH) 4 ·3H 2 O, or hydrocalumite of molecular formula Ca 4 Al 2 (OH) 12 (Cl, OH) 2 ·4H 2 O or formula Ca 4 Al 2 (OH) 12 (CO 3 )·4H 2 O, or any mixture of the aforementioned materials.
14 . The method of claim 11 wherein the precursor to the lanthanum aluminate having the perovskite structure is a mixture of lanthanum nitrate and alumina.
15 . The method of claim 11 wherein the mixture of step (a) is prepared in a slurry containing from 10 to 50 percent solids in a liquid diluent selected from the group consisting of water, C 1-4 alcohols, and mixtures thereof.
16 . The method of claim 11 wherein the first calcination of step (b) is conducted under a dry gas containing less than 1 volume percent water vapor and at a temperature greater than 800° C. but less than 1, 400° C.
17 . The method of claim 11 wherein the carbonation step (c) is conducted at a temperature greater than 500° C. and less than 750° C. in a carbon-dioxide stream containing from 1 to 25 percent water vapor by volume.
18 . The method of claim 11 wherein the decarbonation step (d) is conducted at a temperature greater than about 850° C. and less than about 1, 100° C. under a dry gas containing less than 1 volume percent water vapor.
19 . A process of capturing carbon dioxide from a carbon dioxide-containing gaseous stream comprising contacting a gaseous feed stream comprising carbon dioxide with the solid sorbent composition of claim 1 ; the contacting occurring under carbonation process conditions sufficient to produce a solid mixture comprising calcium carbonate and a gaseous product stream comprising a reduced concentration of carbon dioxide, as compared with an initial concentration of carbon dioxide of the gaseous feed stream.
20 . A reversible process of capturing and recovering carbon dioxide from a carbon dioxide-containing gaseous stream, comprising:
(a) in a carbonation reactor, contacting a gaseous feed stream comprising carbon dioxide with the sorbent composition of claim 1 ; the contacting occurring under carbonation process conditions sufficient to produce a solid mixture comprising calcium carbonate and a gaseous product stream comprising a reduced concentration of carbon dioxide as compared with an initial carbon dioxide concentration of the gaseous feed stream; and
(b) in a calcination reactor, heating the solid mixture comprising calcium carbonate under decarbonation process conditions sufficient to regenerate the solid sorbent composition of claim 1 , thereby producing a gaseous stream enriched in carbon dioxide.