METAL-CONTAINING MOR-TYPE ZEOLITES FOR CAPTURE OF CARBON DIOXIDE FROM LOW-CO2 CONTENT SOURCES AND METHODS OF USING THE SAME
20230234038 · 2023-07-27
Inventors
Cpc classification
B01D2259/40083
PERFORMING OPERATIONS; TRANSPORTING
B01J29/005
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/40
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J29/85
PERFORMING OPERATIONS; TRANSPORTING
B01D2253/1085
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J29/85
PERFORMING OPERATIONS; TRANSPORTING
B01J29/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present disclosure is directed to metal ion-containing zeolitic compositions having MOR topology that are useful for scavenging CO.sub.2 from low-CO.sub.2-content feed streams, including air, and method of making and using the same.
Claims
1. A metal ion-doped crystalline microporous aluminosilicate composition comprising: a three-dimensional aluminosilicate framework having Mordenite topology comprising 12-MR channels and 8-MR side pockets; wherein the crystalline microporous aluminosilicate contains 2.5 to 9 metal ions per unit cell, wherein the ratio of metal ions to aluminum within the unit cell is from 0.3 to 1.4; and wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs carbon dioxide when exposed to a gaseous mixture comprising CO.sub.2.
2. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the gaseous mixture further comprises oxygen.
3. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the gaseous mixture further comprises air.
4. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the composition has a Si:Al atomic ratio in a range of from 4:1 to 13:1.
5. The metal ion-doped crystalline microporous aluminosilicate composition of claim 4, wherein the composition has a Si:Al atomic ratio in a range of from 6:1 to 13:1.
6. The metal ion-doped crystalline microporous aluminosilicate composition of claim 4, wherein the composition has a Si:Al atomic ratio in a range of from 4:1 to 6:1.
7. The metal ion-doped crystalline microporous aluminosilicate composition of claim 4, wherein the composition has a Si:Al atomic ratio in a range of from 4:1 to 5.9:1.
8. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ions are positioned within the voids or channels of the three-dimensional aluminosilicate framework.
9. The composition according to claim 1, wherein the metal ions are alkali metal cations.
10.-15. (canceled)
16. The composition according to claim 1, wherein the crystalline microporous aluminosilicate contains 6 to 9 metal ions per unit cell.
17. The composition according to claim 1, wherein the crystalline microporous aluminosilicate contains 2.5 to 5 metal ions in the 8-MR side-pocket per unit cell.
18. The composition according to claim 1, wherein the metal ions are alkaline earth metal cations.
19.-23. (canceled)
24. The composition according to claim 1, wherein the crystalline microporous aluminosilicate contains 3 to 4.5 metal ions per unit cell.
25. The composition according to claim 1, wherein the crystalline microporous aluminosilicate contains 1.2 to 2.5 metal ions in the 8-MR side-pocket per unit cell.
26.-33. (canceled)
34. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs at least 0.9 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
35. (canceled)
36. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs at least 1.1 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
37. (canceled)
38. (canceled)
39. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs at least 1.4 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
40. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs at least 2.0 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of −11° C.
41.-45. (canceled)
46. The metal ion-doped crystalline microporous aluminosilicate composition of claim 1, wherein passage of a gaseous mixture having (a) a total pressure in a range of from 50 kPa to 350 kPa, and (b) a CO.sub.2 content in a range of from 350 to 1000 ppm, through a tube containing a fixed bed of the metal ion-doped crystalline microporous aluminosilicate composition, results in complete breakthrough of CO.sub.2 after adsorption of an amount of CO.sub.2 (on a mmol/g basis) that is 1.5-2 times greater than the amount of CO.sub.2 adsorbed by an equal weight of zeolite 13X before complete saturation of CO.sub.2 occurs under the same conditions.
47.-56. (canceled)
57. A method of capturing carbon dioxide from a gaseous source mixture that comprises carbon dioxide, the method comprising contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate of claim 1 such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate.
58. (canceled)
59. The method of claim 57, wherein the gaseous mixture further comprises air.
60.-66. (canceled)
67. The method of claim 57, wherein contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than 50° C.
68.-76. (canceled)
77. The method of claim 57, wherein the gaseous source mixture has (a) a total pressure in a range of from 50 kPa to 350 kPa, and (b) a CO.sub.2 content in a range of from 350 to 1000 ppm.
78.-80. (canceled)
81. The method of claim 77, wherein the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 425 ppm.
82. The method of claim 77, wherein the gaseous source mixture has a total pressure in a range of from 50 kPa to 300 kPa.
83.-87. (canceled)
88. A method of capturing carbon dioxide from a humid gaseous source mixture that comprises water and carbon dioxide, wherein the method comprises contacting the gaseous source mixture first with a desiccant, then with the metal ion-doped crystalline microporous aluminosilicate of claim 1, such that such that water in the gaseous source mixture is adsorbed by the desiccant and carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate.
89. The method of claim 88, wherein the desiccant is SAPO-34 or ALPO-34.
90.-94. (canceled)
95. The method of claim 88, wherein the desiccant is regenerated by passing a gas through the desiccant at a temperature of 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
96. (canceled)
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The file of this patent or application contains at least one drawing/photograph executed in color. Copies of this patent or patent application publication with color drawing(s)/photograph(s) will be provided by the Office upon request and payment of the necessary fee.
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DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0066] In the present disclosure the singular forms “a,” “an,” and “the” include the plural reference, and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise. Thus, for example, a reference to “a material” is a reference to at least one of such materials and equivalents thereof known to those skilled in the art, and so forth.
[0067] When a value is expressed as an approximation by use of the descriptor “about,” it will be understood that the particular value forms another embodiment. In general, use of the term “about” indicates approximations that can vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the specific context in which it is used, based on its function. The person skilled in the art will be able to interpret this as a matter of routine. In some cases, the number of significant figures used for a particular value may be one non-limiting method of determining the extent of the word “about.” In other cases, the gradations used in a series of values may be used to determine the intended range available to the term “about” for each value. Where present, all ranges are inclusive and combinable. That is, references to values stated in ranges include every value within that range. For example, a range defined as from 400 to 450 ppm includes 400 ppm and 450 ppm as independent embodiments.
[0068] It is to be appreciated that certain features of the invention which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless obviously incompatible or specifically excluded, each individual embodiment is deemed to be combinable with any other embodiment(s) and such a combination is considered to be another embodiment. Conversely, various features of the invention that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step may also be considered an independent embodiment in itself, combinable with others.
[0069] The transitional terms “comprising,” “consisting essentially of” and “consisting” are intended to connote their generally in accepted meanings in the patent vernacular; that is, (i) “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; (ii) “consisting of” excludes any element, step, or ingredient not specified in the claim; and (iii) “consisting essentially of” limits the scope of a claim to the specified materials or steps “and those that do not materially affect the basic and novel characteristic(s)” of the claimed invention. Embodiments described in terms of the phrase “comprising” (or its equivalents), also provide, as embodiments, those which are independently described in terms of “consisting of” and “consisting essentially of” For those embodiments provided in terms of “consisting essentially of,” the basic and novel characteristic(s) is the facile operability of the methods or compositions/systems to provide the aluminosilicate compositions at meaningful yields (or the ability of the systems using only those ingredients listed. Other components or steps may be included, as long as these additional components or steps do not materially affect the basic and novel characteristic(s) of the claimed invention.
[0070] When a list is presented, unless stated otherwise, it is to be understood that each individual element of that list, and every combination of that list, is a separate embodiment. For example, a list of embodiments presented as “A, B, or C” is to be interpreted as including the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,” or “A, B, or C,” as separate embodiments, as well as C1-3.
[0071] Throughout this specification, words are to be afforded their normal meaning, as would be understood by those skilled in the relevant art. However, to avoid misunderstanding, the meanings of certain terms will be specifically defined or clarified.
[0072] The terms “method(s)” and “process(es)” are considered interchangeable within this disclosure.
[0073] The terms “separating” or “separated” carry their ordinary meaning as would be understood by the skilled artisan, insofar as they connote physically partitioning or isolating of one material from another or the selective capture of one component from a broader mixture. For example, in the case where the terms are used in the context of gas processing, the terms “separating” or “separated” connote a partitioning of the gases by adsorption or by permeation based on size or physical or chemical properties, as would be understood by those skilled in the art.
[0074] In the context of CO.sub.2 content in a gaseous source mixture, the terms “low concentration” or “low-CO.sub.2-content” refers to embodiments where the CO.sub.2 content of is in a range of from 100 ppm to 1000 ppm, or more preferably in an amount approximating the content of CO.sub.2 in our atmosphere (i.e., ca. 400 ppm), but also the higher levels found in, e.g., buildings of process streams. In some specific embodiments, the CO.sub.2 content in a gaseous source mixture may range from 300 to 350 ppm, 350 to 400 ppm, 400 to 450 ppm, 450 to 500 ppm, 500 to 600 ppm, 600 to 700 ppm, 700 to 800 ppm, 800 to 900 ppm, 900 to 1000 ppm, or the CO.sub.2 content may be defined in terms of any of the foregoing values or two or more of the foregoing ranges. The term “gaseous source mixture” or the like refers to the gas from which the CO.sub.2 is being extracted, typically air or, in the case of testing, helium, optionally in the presence of argon present as an internal standard. The gaseous source mixture is typically present at ambient atmospheric pressure (i.e., 101 kPa) or within 10% or 20% of that pressure, though higher pressures (i.e., up to 350 kPa) or lower pressures (i.e., down to 50 kPa) may also be considered in the present context.
[0075] The term “microporous,” according to IUPAC notation refers to a material having pore diameters of less than 2 nm. Similarly, the term “macroporous” refers to materials having pore diameters of greater than 50 nm. And the term “mesoporous” refers to materials whose pore sizes are intermediate between microporous and macroporous. Within the context of the present disclosure, the material properties and applications depend on the properties of the framework such as pore size and dimensionality, cage dimensions and material composition.
[0076] “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally heated” refers to both embodiments where the material is and is not heated. Similarly, the term “optionally present” refers to both embodiments where the component is and is not present. Each of these embodiments (is and is not heated or is and is not present) represents individual and independent embodiments.
[0077] As used herein, the term “crystalline microporous solids” or “crystalline microporous aluminosilicate” are crystalline structures having very regular pore structures of molecular dimensions, i.e., under 2 nm. The maximum size of the species that can enter the pores of a crystalline microporous solid is controlled by the dimensions of the openings. These materials are sometimes referred to as “molecular sieves,” having very regular pore structures of molecular dimensions, i.e., under 2 nm. The term “molecular sieve” refers to the ability of the material to selectively sort molecules based primarily on a size exclusion process. The maximum size of the species that can enter the pores of a crystalline microporous solid is controlled by the dimensions of the openings. These are conventionally defined by the ring size of the aperture, where, for example, the term “8-MR” or “8-membered ring” refers to a closed loop that is typically built from eight tetrahedrally coordinated silicon (or aluminum) atoms and 8 oxygen atoms. These rings are not necessarily symmetrical, due to a variety of effects including strain induced by the bonding between units that are needed to produce the overall structure, or coordination of some of the oxygen atoms of the rings to cations within the structure. As used herein, in the context of the invention, the term “8-MR” or 8-MR zeolite” refers only to those aluminosilicate crystalline materials, or optionally substituted derivatives, having frameworks comprising 8-membered rings as the largest ring for entrance of molecules into the intracrystalline void space. Exemplary structures can be identified in Baerlocher, et al., Atlas of Zeolite Framework Types, Sixth Revised Edition (2007), this reference being incorporated by reference herein for this teaching.
[0078] The term “metal ion-doped” is intended to confer the same meaning as “metal ion-containing” in the context of the metal ions set forth elsewhere herein.
[0079] The term “silicate” refers to any composition including silicate (or silicon oxide) within its framework. It is a general term encompassing, for example, pure-silica (i.e., absent other detectable metal oxides within the framework), aluminosilicate, borosilicate, ferrosilicate, germanosilicate, stannosilicate, titanosilicate, or zincosilicate structures. The term “aluminosilicate” refers to any composition including both silicon and aluminum oxides within its framework. The term “zeolite” refers to an aluminosilicate composition that is a member of this family. For this reason, the terms “metal ion-doped zeolitic composition(s)” and “metal ion-doped crystalline microporous aluminosilicate composition(s)” are considered equivalent and are used interchangeably herein. Such aluminosilicates may be “pure-aluminosilicates (i.e., absent other detectable metal oxides within the framework) or optionally substituted (i.e., containing other metal oxides within the lattice framework). When described as “optionally substituted,” the respective framework may contain boron, gallium, germanium, hafnium, iron, tin, titanium, indium, vanadium, zinc, zirconium, or other atoms substituted for one or more of the atoms not already contained in the parent lattice or framework.
[0080] In some cases herein, the term “metal ion-doped crystalline microporous aluminosilicate compositions” are referred to as “zeolitic compositions” or “metal-doped zeolitic compositions,” and the like.
[0081] The present disclosure is directed to new compositions of matter useful for extracting carbon dioxide (CO.sub.2) from feed streams, especially feed streams containing low levels of CO.sub.2, including air. Such new compositions comprise metal-containing zeolites, including those zeolites having the framework characteristics set forth herein, and preferably those compositions where the metal is an alkali or alkaline earth metal and the zeolites have MOR topologies. The disclosure is also directed to methods of making and using these compositions, including configurations useful for using these compositions to extract the CO.sub.2 from gaseous feed streams.
[0082] The present invention may be understood more readily by reference to the following description taken in connection with the accompanying Figures and Examples, all of which form a part of this disclosure. It is to be understood that this invention is not limited to the specific products, methods, conditions, or parameters described or shown herein, and that the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting of any claimed invention. Similarly, unless specifically otherwise stated, any description as to a possible mechanism or mode of action or reason for improvement is meant to be illustrative only, and the invention herein is not to be constrained by the correctness or incorrectness of any such suggested mechanism or mode of action or reason for improvement. For example, though the some of the present disclosure comments on the placement of the metal ions in the zeolitic framework, the present inventions are not constrained by the correctness or incorrectness of these comments as to the placement. Throughout this text, it is recognized that the descriptions refer to compositions and methods of using said compositions. That is, where the disclosure describes or claims a feature or embodiment associated with a composition or a method of making or using a composition, it is appreciated that such a description or claim is intended to extend these features or embodiment to embodiments in each of these contexts (i.e., compositions, methods of making, and methods of using).
Compositions
[0083] In some aspects, the disclosure is directed to metal ion-doped crystalline microporous aluminosilicate composition comprising: a three-dimensional aluminosilicate framework having Mordenite (or MOR-type) topology comprising 12-MR channels and 8-MR side pockets; wherein the crystalline microporous aluminosilicate contains 2.5 to 9 metal ions per unit cell, wherein the ratio of metal ions to aluminum within the unit cell is from 0.3 to 1.4; and wherein the metal ion-doped crystalline microporous aluminosilicate composition adsorbs carbon dioxide when exposed to a gaseous mixture comprising CO.sub.2.
[0084] In some aspects, the gaseous mixture comprising CO.sub.2 further comprises oxygen.
[0085] In some aspects, the gaseous mixture comprising CO.sub.2 further comprises nitrogen.
[0086] In some aspects, the gaseous mixture comprising CO.sub.2 further comprises air.
[0087] In some aspects, the gaseous mixture comprising CO.sub.2 further comprises oxygen and air.
[0088] As used herein, “air” refers to a gaseous mixture which comprises carbon dioxide, and nitrogen. In some embodiments, “air” further comprises oxygen, i.e., air comprises carbon dioxide, oxygen, and nitrogen. In some embodiments, air refers to atmospheric air. In other embodiments, air refers to the gaseous effluent from a process.
[0089] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a Si:Al atomic ratio in a range of from 4:1 to 13:1, such as, for example, one of 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2:1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11:1, 11.1:1, 11.2:1, 11.3:1, 11.4:1, 11.5:1, 11.6:1, 11.7:1, 11.8:1, 11.9:1, 12:1, 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1, or 13:1.
[0090] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a Si:Al atomic ratio in a range of from 6:1 to 13:1, such as, for example, one of 6:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7:1, 7.1:1, 7.2:1, 7.3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10:1, 10.1:1, 10.2:1, 10.3:1, 10.4:1, 10.5:1, 10.6:1, 10.7:1, 10.8:1, 10.9:1, 11:1, 11.1:1, 11.2:1, 11.3:1, 11.4:1, 11.5:1, 11.6:1, 11.7:1, 11.8:1, 11.9:1, 12:1, 12.1:1, 12.2:1, 12.3:1, 12.4:1, 12.5:1, 12.6:1, 12.7:1, 12.8:1, 12.9:1, or 13:1.
[0091] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a Si:Al atomic ratio in a range of from 4:1 to 6:1, such as, for example, one of 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, or 6:1.
[0092] In yet other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a Si:Al atomic ratio in a range of from 4:1 to 5.9:1, such as, for example, one of 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, or 5.9:1.
[0093] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain metal ions. In this aspect, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain 2.5 to 9 metal ions per unit cell, such as, for example, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, or 9 metal ions per unit cell.
[0094] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain 6 to 9 metal ions per unit cell, such as, for example, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, or 9 metal ions per unit cell.
[0095] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain 3 to 4.5 metal ions per unit cell, such as, for example, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4, or 4.5 metal ions per unit cell.
[0096] In some aspects, the ratio of metal ions to aluminum within the unit cell is from 0.3 to 1.4, such as, for example, one of 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, or 1.4.
[0097] In some embodiments, the metal ions are positioned within the voids or channels of the three-dimensional aluminosilicate framework.
[0098] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain 2.5 to 5 metal ions, such as for example, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4:1, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5 metal ions, in the 8-MR side-pocket per unit cell.
[0099] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure contain 1.2 to 2.5 metal ions, such as, for example, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5 metal ions, in the 8-MR side-pocket per unit cell.
[0100] In some embodiments, the metal ions are alkali metal cations.
[0101] In some embodiments, the alkali metal cations are Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, or Cs.sup.+.
[0102] In some embodiments, the alkali metal cations are Li.sup.+.
[0103] In some embodiments, the alkali metal cations are Na.sup.+.
[0104] In some embodiments, the alkali metal cations are K.sup.+.
[0105] In some embodiments, the alkali metal cations are Rb.sup.+.
[0106] In some embodiments, the alkali metal cations are Cs.sup.+.
[0107] In other embodiments, the metal ions are alkaline earth metal cations.
[0108] In some embodiments, the alkali earth metal cations are Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, or Ba.sup.2+.
[0109] In some embodiments, the alkali earth metal cations are Mg.sup.2+.
[0110] In some embodiments, the alkali earth metal cations are Ca.sup.2+.
[0111] In some embodiments, the alkali earth metal cations are Sr.sup.2+.
[0112] In some embodiments, the alkali earth metal cations are Ba.sup.2+.
[0113] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure are characterized by specific performance characteristics. Thus, in some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure are characterized by the carbon dioxide adsorption capacity. In some aspects, the carbon dioxide adsorption capacity is measured in mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition under specified conditions of pressure and temperature. Methods for measuring the mmol of carbon dioxide adsorbed per gram of composition under specified conditions of pressure and temperature are known by those of skill in the art, and include those methods set forth herein. The capacity is often measured by volumetric based approaches, e.g., isotherms or fixed-bed column breakthrough experiments, or by gravimetric based methods using instruments with microbalance, e.g., thermogravimetric analysis.
[0114] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb at least 0.1 mmol; or at least 0.2 mmol; or at least 0.3 mmol; or at least 0.4 mmol; or at least 0.5 mmol; or at least 0.6 mmol; or at least 0.7 mmol; or at least 0.8 mmol; or at least 0.9 mmol; or at least 1 mmol; or at least 1.1 mmol; or at least 1.2 mmol; or at least 1.3 mmol; or at least 1.4 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0115] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb at least 2.0 mmol of carbon dioxide per gram of metal ion-doped crystalline microporous aluminosilicate composition when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of −11° C.
[0116] In other aspects, the carbon dioxide adsorption capacity is measured in molecules of adsorbed carbon dioxide per unit cell of metal ion-doped crystalline microporous aluminosilicate composition under specified conditions of pressure and temperature. Methods for measuring the number of molecules of carbon dioxide adsorbed per unit cell of composition under specified conditions of pressure and temperature are known by those of skill in the art, and include those methods set forth herein. The number of carbon dioxide molecules adsorbed per unit cell was calculated using the molar weight of unit cell based on compositions measured by elemental analysis, e.g., EDX, and the carbon dioxide capacity measured by volumetric or gravimetric methods.
[0117] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 0.3 to 4.4 molecules, such as, for example, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, or 4.4, molecules molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0118] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 0.3 to 3.5 molecules, such as, for example, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, or 3.5, molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0119] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 0.3 to 2.4 molecules, such as, for example, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, or 2.4, molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0120] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 2.5 to 3.4 molecules, such as, for example, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, or 3.5, molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0121] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 3.5 to 4.4 molecules, such as, for example, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, or 4.4, molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of 25° C.
[0122] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure adsorb from 5.8 to 6.2 molecules, such as, for example, 5.8, 5.9, 6, 6.1, or 6.2, molecules of CO.sub.2 per unit cell when exposed to CO.sub.2 at a pressure of 0.0004 bar and a temperature of −11° C.
[0123] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions are those wherein passage of a gaseous mixture having (a) a total pressure in a range of from 50 kPa to 350 kPa, and (b) a CO.sub.2 content in a range of from 350 to 1000 ppm, through a tube containing a fixed bed of the metal ion-doped crystalline microporous aluminosilicate composition results in complete breakthrough of CO.sub.2 after adsorption of an amount of CO.sub.2 (on a mmol/g basis) that is 1.5-2 times greater than the amount of CO.sub.2 adsorbed by an equal weight of zeolite 13X before complete saturation of CO.sub.2 occurs under the same conditions.
[0124] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions are those wherein passage of a gaseous mixture having (a) a total pressure in a range of from 50 kPa to 350 kPa, and (b) a CO.sub.2 content in a range of from 350 to 1000 ppm, through a tube containing powders of the metal ion-doped crystalline microporous aluminosilicate composition results in equilibrium of CO.sub.2 after adsorption of an amount of CO.sub.2 (on a mmol/g basis) that is 1.5-2 times greater than the amount of CO.sub.2 adsorbed by an equal weight of zeolite 13X before complete equilibrium of CO.sub.2 occurs under the same conditions.
[0125] In some aspects, the gaseous mixture has a total pressure in a range of from 50 kPa to 350 kPa, such as, for example, 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.
[0126] In other aspects, the gaseous mixture has a CO.sub.2 content in a range of from 350 to 1000 ppm, such as, for example, 350 ppm, 375 ppm, 400 ppm, 425 ppm, 450 ppm, 475 ppm, 500 ppm, 525 ppm, 550 ppm, 575 ppm, 600 ppm, 625 ppm, 650 ppm, 675 ppm, 700 ppm, 725 ppm, 750 ppm, 775 ppm, 800 ppm, 825 ppm, 850 ppm, 875 ppm, 900 ppm, 925 ppm, 950 ppm, 975 ppm, or 1000 ppm.
[0127] In some aspects, passage of the gaseous mixture through the fixed bed of the metal ion-doped crystalline microporous aluminosilicate composition results in complete breakthrough of CO.sub.2 after adsorption of an amount of CO.sub.2 (on a mmol/g basis) that is 1.5-2, such as, for example, 1.5 times, 1.6 times, 1.7 times, 1.8 time, 1.9 times, or 2, times greater than the amount of CO.sub.2 adsorbed by an equal weight of zeolite 13X before complete saturation of CO.sub.2 occurs under the same conditions. As used herein, “complete breakthrough” means that the amount or concentration of CO.sub.2 exiting the fixed bed of the metal ion-doped crystalline microporous aluminosilicate composition is the same as the amount or concentration of CO.sub.2 entering the fixed bed. Methods for measuring “complete breakthrough” are known by those of skill in the art, and include those methods set forth herein.
[0128] In some embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/He at a flow rate of 20 mL.Math.min.sup.−1 at 30° C.
[0129] In other embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/20% He/balance N.sub.2 at a flow rate of 20 mL.Math.min.sup.−1 at 30° C.
[0130] In yet other embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/20% O.sub.2/balance N.sub.2, at a flow rate of 20 mL.Math.min.sup.−1 at 30° C.
[0131] In some embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/He at a flow rate of 20 mL.Math.min.sup.−1 at −11° C.
[0132] In other embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/20% He/balance N.sub.2 at a flow rate of 20 mL.Math.min.sup.−1 at −11° C.
[0133] In yet other embodiments, the gaseous mixture is 400 ppm CO.sub.2/1% Ar/20% O.sub.2/balance N.sub.2, at a flow rate of 20 mL.Math.min.sup.−1 at −11° C.
[0134] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure which have adsorbed carbon dioxide, have the adsorbed carbon dioxide desorbed at a temperature of less than 150° C. In such embodiments, the carbon dioxide may be desorbed by heating the metal ion-doped crystalline microporous aluminosilicate compositions while passing a stream of inert gas through the composition.
[0135] In other embodiments of the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure, the adsorbed carbon dioxide is desorbed at a temperature of less than 125° C.
[0136] In other embodiments of the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure, the adsorbed carbon dioxide is desorbed at a temperature of less than 100° C.
[0137] In other embodiments of the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure, the adsorbed carbon dioxide is desorbed at a temperature of less than 75° C.
[0138] In other embodiments of the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure, the adsorbed carbon dioxide is desorbed at a temperature of less than 60° C.
[0139] In other embodiments of the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure, the adsorbed carbon dioxide is desorbed at a temperature of less than 50° C.
[0140] In some aspects, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure are those wherein the metal ion-doped crystalline microporous aluminosilicate composition has a selectivity for CO.sub.2 over N.sub.2. As used herein, “selectivity” means that the metal ion-doped crystalline microporous aluminosilicate composition adsorbs one species of molecule in preference to another species of molecule. Selectivity is expressed as a ratio of one molecule to another molecule against the ratio of the molar fraction of one molecule to another molecule. The CO.sub.2/N.sub.2 selectivity is defined as
where qi and pi denote the capacity and partial pressure, respectively, of component i.
[0141] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a selectivity for CO.sub.2 over N.sub.2 of at least 4000:1.
[0142] In other embodiments, the metal ion-doped crystalline microporous aluminosilicate compositions of the disclosure have a selectivity for CO.sub.2 over N.sub.2 of at least 3000:1.
Methods of Use
[0143] In some aspects, the disclosure is directed to methods of capturing carbon dioxide from a gaseous source mixture that comprises carbon dioxide, wherein the methods comprise contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate as described in the disclosure such that carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate.
[0144] In some embodiments, the gaseous mixture further comprises oxygen.
[0145] In other embodiments, the gaseous mixture further comprises nitrogen.
[0146] In other embodiments, the gaseous mixture further comprises air.
[0147] In some aspects, the methods of the disclosure further comprise desorbing the adsorbed carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate.
[0148] In some embodiments of the methods of the disclosure, the contacting of the metal ion-doped crystalline microporous aluminosilicate compositions with the gaseous source mixture is done in the absence of, or without the use of, an added desiccant.
[0149] In other embodiments of the methods of the disclosure, the contacting of the metal ion-doped crystalline microporous aluminosilicate with the gaseous source mixture is done in the presence of, or with the use of, an added desiccant.
[0150] In some embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate comprises passing the gaseous source mixture through a fixed-bed of adsorbent comprising the metal ion-doped crystalline microporous aluminosilicate.
[0151] In some embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than 50° C.
[0152] In some embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than 30° C.
[0153] In other embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than 10° C.
[0154] In some embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than 0° C.
[0155] In other embodiments of the methods of the disclosure, contacting the gaseous source mixture with the metal ion-doped crystalline microporous aluminosilicate occurs at a temperature of less than −10° C.
[0156] In some embodiments of the methods of the disclosure, desorbing the carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate occurs at a temperature less than 150° C.
[0157] In other embodiments of the methods of the disclosure, desorbing the carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate occurs at a temperature less than 125° C.
[0158] In other embodiments of the methods of the disclosure, desorbing the carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate occurs at a temperature less than 100° C.
[0159] In other embodiments of the methods of the disclosure, desorbing the carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate occurs at a temperature less than 75° C.
[0160] In other embodiments of the methods of the disclosure, desorbing the carbon dioxide from the carbon-dioxide laden metal ion-doped crystalline microporous aluminosilicate occurs at a temperature less than 60° C.
[0161] In some aspects of the methods of the disclosure, the gaseous source mixture has (a) a total pressure in a range of from 50 kPa to 350 kPa, and (b) a CO.sub.2 content in a range of from 350 to 1000 ppm.
[0162] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 350 kPa, such as, for example, 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.
[0163] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 350 kPa, such as, for example, 50 kPa, 75 kPa, 100 kPa, 125 kPa, 150 kPa, 175 kPa, 200 kPa, 225 kPa, 250 kPa, 275 kPa, 300 kPa, 325 kPa, or 350 kPa.
[0164] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 300 kPa.
[0165] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 250 kPa.
[0166] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 200 kPa.
[0167] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 150 kPa.
[0168] In some embodiments of the disclosed methods, the gaseous source mixture has a total pressure in a range of from 50 kPa to 125 kPa.
[0169] The method of any one of claims 74 to 83, wherein the gaseous source mixture has a total pressure in a range of from 50 kPa to 100 kPa.
[0170] In some aspects of the methods of the disclosure, the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 1000 ppm, such as, for example, 350 ppm, 375 ppm, 400 ppm, 425 ppm, 450 ppm, 475 ppm, 500 ppm, 525 ppm, 550 ppm, 575 ppm, 600 ppm, 625 ppm, 650 ppm, 675 ppm, 700 ppm, 725 ppm, 750 ppm, 775 ppm, 800 ppm, 825 ppm, 850 ppm, 875 ppm, 900 ppm, 925 ppm, 950 ppm, 975 ppm, or 1000 ppm.
[0171] In some embodiments of the disclosed methods, the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 750 ppm.
[0172] In some embodiments of the disclosed methods, the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 600 ppm.
[0173] In some embodiments of the disclosed methods, the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 500 ppm.
[0174] In some embodiments of the disclosed methods, the gaseous source mixture has a CO.sub.2 content in a range of from 350 to 425 ppm.
[0175] In some embodiments of the methods of the disclosure, the gaseous source mixture is humid, i.e., contains water vapor.
[0176] In some embodiments, the gaseous source mixture contains 30,000 ppm or less of water, such as, for example, 30,000 ppm or less, 20,000 ppm or less, 17,500 ppm or less, 15,000 ppm or less, 12,500 ppm or less, 10,000 ppm or less, 7500 ppm or less, 5000 ppm or less, or 2500 ppm or less.
[0177] In some embodiments, the gaseous source mixture contains 2500 ppm or less water.
[0178] In some embodiments of the methods of the disclosure, the humid gaseous source mixture passes through a desiccant before passing through the metal ion-doped crystalline microporous aluminosilicate. Without intending to be bound by theory, it is believed that the desiccant removes water from the gaseous source mixture. Water in the gaseous source mixture can reduce the CO.sub.2 adsorption capacity of the metal ion-doped crystalline microporous aluminosilicate; thus, by removing the water in the gaseous source mixture, the CO.sub.2 adsorption capacity of the metal ion-doped crystalline microporous aluminosilicate is maximized. Moreover, the temperature required to desorb water from the metal ion-doped crystalline microporous aluminosilicates of the disclosure is significantly higher than the temperature required to desorp CO.sub.2 from the metal ion-doped crystalline microporous aluminosilicate.
[0179] In some embodiments, the desiccant is selected by matching the temperature at which water is desorbed from the desiccant to the temperature at which CO.sub.2 is desorbed from the metal ion-doped crystalline microporous aluminosilicate. Selecting the desiccant in this manner allows regeneration of both the desiccant and the metal ion-doped crystalline microporous aluminosilicate simultaneously, and at the same temperature.
[0180] In some embodiments, the desiccant desorbs water at a temperature of 150° C. or less, such as, for example, 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0181] In some embodiments, the desiccant desorbs water at a temperature of 120° C. or less.
[0182] In some embodiments, the desiccant desorbs water at a temperature of 110° C. or less.
[0183] In some embodiments, the desiccant desorbs water at a temperature of 100° C. or less.
[0184] In some aspects, the disclosure is directed to methods of capturing carbon dioxide from a humid gaseous source mixture that comprises water and carbon dioxide, wherein the methods comprise contacting the gaseous source mixture first with a desiccant, the with the metal ion-doped crystalline microporous aluminosilicate as described in the disclosure, such that such that water in the gaseous source mixture is adsorbed by the desiccant and carbon dioxide in the gaseous source mixture is adsorbed by the metal ion-doped crystalline microporous aluminosilicate.
[0185] In some embodiments, the desiccant is SAPO-34.
[0186] In other embodiments, the desiccant is ALPO-34.
[0187] In some embodiments, the humid gaseous source mixture is contacted with the desiccant at a temperature of 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less, 70° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 30° C. or less, 20° C. or less, 10° C. or less, 0° C. or less, −10° C. or less, or −20° C. or less.
[0188] In some embodiments, the humid gaseous source mixture is contacted with the desiccant at a temperature of 30° C. or less.
[0189] In other embodiments, the humid gaseous source mixture is contacted with the desiccant at a temperature of 10° C. or less.
[0190] In other embodiments, the humid gaseous source mixture is contacted with the desiccant at a temperature of 0° C. or less.
[0191] In other embodiments, the humid gaseous source mixture is contacted with the desiccant at a temperature of −10° C. or less.
[0192] In some embodiments, after the humid gaseous source mixture is contacted with the desiccant, it is contacted with the metal ion-doped crystalline microporous aluminosilicate at a temperature of 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less, 70° C. or less, 60° C. or less, 50° C. or less, 40° C. or less, 30° C. or less, 20° C. or less, 10° C. or less, 0° C. or less, −10° C. or less, or −20° C. or less.
[0193] In some embodiments, after the humid gaseous source mixture is contacted with the desiccant, it is contacted with the metal ion-doped crystalline microporous aluminosilicate at a temperature of 30° C. or less.
[0194] In some embodiments, after the humid gaseous source mixture is contacted with the desiccant, it is contacted with the metal ion-doped crystalline microporous aluminosilicate at a temperature of 10° C. or less.
[0195] In some embodiments, after the humid gaseous source mixture is contacted with the desiccant, it is contacted with the metal ion-doped crystalline microporous aluminosilicate at a temperature of 0° C. or less.
[0196] In some embodiments, after the humid gaseous source mixture is contacted with the desiccant, it is contacted with the metal ion-doped crystalline microporous aluminosilicate at a temperature of −10° C. or less.
[0197] In some embodiments, the desiccant and the metal ion-doped crystalline microporous aluminosilicate are arranged in sequential layers in a single vessel (such as, for example, a column). In these embodiments, the humid gaseous source mixture passes first through the desiccant layer and then through the metal ion-doped crystalline microporous aluminosilicate layer.
[0198] In other embodiments, the desiccant and the metal ion-doped crystalline microporous aluminosilicate are contained in separate vessels. In these embodiments, the humid gaseous source mixture passes first through the desiccant in a first vessel, and then through the metal ion-doped crystalline microporous aluminosilicate in a second vessel.
[0199] In some embodiments, the methods of capturing carbon dioxide from a humid gaseous source mixture using a desiccant and metal ion-doped crystalline microporous aluminosilicate further comprise regenerating the desiccant and the metal ion-doped crystalline microporous aluminosilicate by passing a gas through the metal ion-doped crystalline microporous aluminosilicate and through the desiccant at a temperature of 150° C. or less, such as, for example, 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0200] In some embodiments, regenerating the desiccant and metal ion-doped crystalline microporous aluminosilicate by passing a gas through the metal ion-doped crystalline microporous aluminosilicate and through the desiccant is conducted at a temperature of 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0201] In some embodiments, regenerating the metal ion-doped crystalline microporous aluminosilicate and the desiccant by passing a gas through the desiccant and metal ion-doped crystalline microporous aluminosilicate is conducted at a temperature of 100° C. or less.
[0202] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion-doped crystalline microporous aluminosilicate and through the desiccant at a temperature of 150° C. or less, such as, for example, 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0203] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion-doped crystalline microporous aluminosilicate at a temperature of 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0204] In some embodiments, the metal ion-doped crystalline microporous aluminosilicate is regenerated by passing a gas through the metal ion-doped crystalline microporous aluminosilicate at a temperature of 100° C. or less.
[0205] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 150° C. or less, such as, for example, 150° C. or less, 140° C. or less, 130° C. or less, 120° C. or less, 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0206] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 110° C. or less, 100° C. or less, 90° C. or less, or 80° C. or less.
[0207] In some embodiments, the desiccant is regenerated by passing a gas through the desiccant at a temperature of 100° C. or less.
[0208] In some embodiments, regeneration of the desiccant and the metal ion-doped crystalline microporous aluminosilicate, water desorbed from the desiccant during regeneration is not passed through the metal ion-doped crystalline microporous aluminosilicate.
[0209] In some embodiments, the regeneration gas is an inert gas such as, nitrogen, argon, helium, or mixtures thereof. In other embodiments, the regeneration gas is air.
[0210] In embodiments in which the desiccant and the metal ion-doped crystalline microporous aluminosilicate are contained in separate vessels, water may be collected for beneficial use from the regeneration gas after regenerating the desiccant.
[0211] In some aspects, the disclosure is directed to a multi-unit system comprising two or more parallel adsorption units, wherein each unit comprises a bed of desiccant and a bed of a metal ion-doped crystalline microporous aluminosilicate. In these aspects, humid gaseous source mixture is passed through a first adsorption unit, passing first through the desiccant bed and then through the metal ion-doped crystalline microporous aluminosilicate bed. The effluent from that first adsorption unit is then passed through a second, parallel adsorption unit in the opposite orientation (i.e., the effluent from the first adsorption unit is passed first through the metal ion-doped crystalline microporous aluminosilicate bed of the second unit and then through the desiccant bed of the second adsorption unit.
[0212] In some embodiments, the adsorption and desorption processes are conducted at the same temperature.
[0213] In other embodiments, the adsorption and desorption processes are conducted at the different temperatures.
[0214] In some embodiments, the adsorption process is conducted at about 30° C. or less.
[0215] In some embodiments, the desorption process is conducted at about 150° C. or less.
[0216] In some embodiments, the desorption process is conducted at about 100° C.
EXAMPLES
[0217] Synthesis of Materials
[0218] MOR-type zeolites were synthesized from mixtures with or without organic structure directing agents. Large MOR crystals (ca. 40 μm) were synthesized for the single-crystal X-ray diffraction (XRD) analysis. The synthesis procedures for MOR-type as well as MAZ-, *BEA-, MFI-, MEL-type zeolites are given below.
[0219] MOR-type zeolites. MOR-type zeolites with Si/Al=6.5 (CBV10A, Zeolyst) were used as received. MOR-type zeolites with Si/Al=5 were synthesized by modifying the recipe reported in M. Wang, et al., Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether. Chin. J. Catal. 37, 1530-1537 (2016) using different OSDAs. Typically, sodium hydroxide (50 wt % aqueous solution, Sigma-Aldrich), silica (Ludox-40, Sigma-Aldrich), sodium aluminate and water were mixed in a Teflon liner. After 30 min stirring, the OSDA (pyrrolidine, piperidine, azepane, piperazine, DABCO, 4-Methylpiperidine) was added, and the mixture was stirred for 60 min. Then ca. 5 wt % (silica based) seeds (CBV10A) were added before charging into Teflon lined Parr autoclaves. The molar composition of the synthesize gel was: 1 Sift: 0.067 Al.sub.2O.sub.3: 0.23 OSDA:0.75 Na.sub.2O: 11 H.sub.2O. The autoclaves were loaded into a preheated static convection oven at 170° C. for 3 days.
[0220] The procedure for the synthesis of OSDA-free MOR with Si/Al=4 zeolites followed J. Zhu, et al., Ultrafast, OSDA-free synthesis of mordenite zeolite. CrystEngComm 19, 632-640 (2017). Silica, sodium aluminate, sodium hydroxide and water were mixed and stirred for 30 min. Then ca. 5 wt % (silica based) seeds (CBV10A) were added before charging into Teflon-lined Parr autoclaves. The molar composition of the synthesize gel was: 1 Sift: 0.1 Al.sub.2O.sub.3: 0.2 Na.sub.2O: 26 H.sub.2O. The autoclaves were loaded into a preheated rotatory convection oven at 170° C. for 7 days.
[0221] Large MOR-type zeolite crystals were synthesized following L. Zhang, A. N. C. van Laak, P. E. de Jongh, K. P. de Jong, Synthesis of large mordenite crystals with different aspect ratios. Microporous Mesoporous Mater. 126, 115-124 (2009). Silica (Ludox-40, Sigma-Aldrich), sodium aluminate, sodium hydroxide (50 wt % aqueous solution, Sigma-Aldrich) and water were mixed and stirred for 30 min. Then ca. 5 wt % (silica based) seeds (CBV10A, Zeolyst) were added before charging into Teflon-lined Parr autoclaves. The molar composition of the synthesize gel was: 1 SiO.sub.2: 0.052 Al.sub.2O.sub.3: 0.23 Na.sub.2O: 3.42 H.sub.2O. The autoclaves were loaded into a preheated rotatory convection oven at 170° C. for 7 days.
[0222] Omega-1 (MAZ). Omega-1 zeolites were synthesized following A. J. Perrotta, C. Kibby, B. R. Mitchell, E. R. Tucci, The synthesis, characterization, and catalytic activity of omega and ZSM-4 zeolites. J. Catal. 55, 240-249 (1978). The OSDA (TMAOH, Sigma-Aldrich) was first mixed with water. Then sodium hydroxide and sodium aluminate were added. To the solution silica (Ludox-40, Sigma-Aldrich) was added and stirred for 30 min. The molar composition of the resulting solution was: 10 SiO.sub.2: 1.0 Al.sub.2O.sub.3: 1.6 TMAOH: 3.2 Na.sub.2O: 160 H.sub.2O. The solution was charged into a polypropylene bottle and heated to 95° C. for 10 days.
[0223] *BEA. *BEA-type zeolites were synthesized following S.-T. Yang, J. Kim, W.-S. Ahn, CO.sub.2 adsorption over ion-exchanged zeolite beta with alkali and alkaline earth metal ions. Microporous Mesoporous Mater. 135, 90-94 (2010). Sodium aluminate, the OSDA (TEAOH, Sigma-Aldrich) and water were mixed. Then silica (Carbosil M5) was added and stirred for 120 min. The molar composition of the resulting gel was: 1 SiO.sub.2: 0.1 Al.sub.2O.sub.3: 1.0 TEAOH: 0.1 Na.sub.2O: 6.2 H.sub.2O. The thick gel was charged into Teflon-lined Parr autoclaves and put in a preheated static convection oven at 170° C. for 3 days. MEL(ZSM-11). ZSM-11 zeolites with Si/Al=15 were synthesized following L. Zhang, et al., Differences between ZSM-5 and ZSM-11 zeolite catalysts in 1-hexene aromatization and isomerization. Fuel Process. Technol. 91, 449-455 (2010). Silica (TEOS) and the OSDA (TBABr) were mixed. Then aluminum sulfate and sodium hydroxide were added and stirred for 60 min to obtain a solution. The molar composition of the resulting solution was: 1 SiO.sub.2: 0.025 Al.sub.2O.sub.3: 0.18 TBABr: 0.14 Na.sub.2O: 42.35 H.sub.2O. The solution was charged into Teflon-lined Parr autoclaves and put in a rotatory convection oven at 150° C. for 3 days.
[0224] MFI, FER and LTL. FER-type (CP914C, NH.sub.4-form) with Si/Al=10 and MFI-type (CBV2314, NH.sub.4-form ZSM-5) with Si/Al=12 zeolites were obtained from Zeolyst. LTL-type zeolite (HSZ500, K-form) with Si/Al=3 was obtained from Tosoh. The LTL-type zeolite was converted to NH.sub.4-form by ion exchange with 1M NH.sub.4NO.sub.3 for three times (72 h in total) at 80° C.
[0225] Calcination of zeolites. After the synthesis was completed, the resulting solids were washed three times with distilled water. The materials synthesized with OSDAs were further washed by acetone. To remove the OSDAs from zeolites, the obtained solids were then dried at 80° C. before calcining in a flow air furnace at 580° C. for 8 h, with a ramp rate of 1.0° C./min. Crystallinity of the materials was examined using lab-based X-ray diffraction (XRD).
[0226] Aqueous-phase Ion-Exchange of Zeolites. Na-type zeolites were prepared by ion exchange of calcined or as received zeolites with 1M aqueous NaNO.sub.3 solution. Typically, 600 mg of zeolites were added to 30 mL of salt solutions, which were then stirred at 80° C. for 24 h. The exchanged crystals were dried at 100° C. in ambient air in a free convention oven overnight. A similar ion exchange procedure was used to prepare samples for the preparation of MOR-type zeolites with varying Na.sup.+ loading. The MOR6 zeolites (CBV10A, Zeolyst, 4 # in Table 1) were first fully converted to ammonium form after two times (48 h in total) ion exchange using 1 M NH.sub.4NO.sub.3 aqueous solution at 80° C. Depending on the targeting Na exchange level, 30 mL of 0.002 M to 5 M aqueous NaNO.sub.3 solution were used as the precursor. The materials were recovered by centrifugation and washed 6 times with copious amount of distilled water. The exchanged crystals were dried at 100° C. overnight. The Na- and H-density were measured using energy-dispersive X-ray spectroscopy (EDS) and solid state .sup.1H nuclear magnetic resonance (NMR) spectroscopy, respectively.
[0227] Pyridine-modification of zeolites. A previously reported method was followed for pyridine modification of the MOR-type zeolites, denoted as py-MOR. Briefly, Na-MOR was dehydrated at 170° C. under vacuum (0.1 mbar) overnight. The sample was cooled to room temperature and flushed with ultra-high purity Ar before dosing pyridine into MOR zeolites with an amount of ca. 0.5 mL pyridine/mg zeolites. The py-MOR zeolites were heated to 300° C. and kept for 19 h to remove the water and excess pyridine prior to the CO.sub.2 adsorption measurements at 30° C. in the dynamic column fixed bed system.
[0228] Characterizations
[0229] The crystallinity, morphology, chemical compositions, and porosity of zeolites were analyzed by powder XRD, scanning electron microscope, electron dispersive spectroscopy, and N.sub.2 physisorption, respectively. The distribution and density of Bronsted acid sites were analyzed using Fourier transform infrared spectroscopy (FTIR) and 1H solid state magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, respectively. The coordination environment of Al species in MOR-type zeolites was examined using .sup.27Al NMR spectroscopy. The locations of Na.sup.+ cations in the MOR-type zeolites were characterized using X-ray crystallography, i.e. single crystal XRD analysis. The detailed methods are given below.
[0230] X-ray diffraction. The crystallinity of the materials was examined using powder X-ray diffraction (XRD). The XRD patterns were collected using a Rigaku Miniflex II desktop instrument with a Cu radiation source, Kα=1.5418 Å.
[0231] Scanning electron microscopy. The morphology of the materials was measured using scanning electron microscopy (SEM, ZEISS 1550 VP FESEM). The SEM was equipped with an Oxford X-Max SDD. Energy dispersive X-ray spectroscopy (EDS) used for determining the element contents of each sample.
[0232] Solid-state, magic-angle spinning nuclear magnetic resonance. Solid-state, magic-angle spinning nuclear magnetic resonance (MAS NMR) spectra were obtained on a Bruker AVANCE 500 MHz (11.2 T) spectrometer using a 4 mm zirconia rotor with a Kel-F cap. .sup.1H MAS NMR spectroscopy was measured to quantify the residue H-density of Na.sup.+ exchanged MOR-type zeolites as a function of Na.sup.+ loading. NH.sub.4-form materials were used to avoid the dealumination through ion exchange and dehydration. The samples were loaded in the rotor and dehydrated under vacuum (10-2 Torr) at 400° C. for 12 h in a Schlenk manifold. The spectra were acquired at 500.1 MHz with a 90° pulse length of 4 μs and a spinning rate of 12 kHz, and then were deconvoluted using DMFit software. The number of framework NH4 site (mmol/g) was measured by referencing the signal intensities to hexamethyl benzene and normalizing by the sample mass, followed by dividing by 4, that is the number of protons per NH.sub.4+. The residual NH.sub.4 site density of Na-exchanged MOR zeolites was then quantified with the same procedure as a function of Na loading. To examine the state of aluminum in Na-exchanged MOR zeolites, the .sup.27Al MAS NMR spectra were also recorded on the same samples without undergoing dehydration at 130.2 MHz with a 10″ pulse length of 0.5 μs, a cycle delay time of 0.5 s, and a spin rate of 12 kHz.
[0233] Fourier transform infrared spectroscopy. Fourier transform infrared (FTIR) spectra were collected on zeolite samples using a Nexus 470 FTIR spectrometer equipped with a deuterated, L-alanine doped triglycine sulfate (DTGS) detector. Catalyst samples (ca. 10-12 mg) were pressed into a self-supporting wafer (ca. 1.2 cm in diameter) and placed in a custom-built FTIR cell. The wafers were treated in flowing dry air at 723 K for 120 min, and then cooled to RT for CO.sub.2 adsorption under flowing dry air for 30 min. Spectra were collected with a resolution of 4 cm-1 and averaged over 64 scans.
[0234] Single-crystal X-ray diffraction. Single-crystal X-ray diffraction was performed at 100 K on a Bruker D8Venture CCD diffractometer using Cu Kα radiation (λ=1.5406 Å). Crystal was mounted on Mitegen MicroMount. A multi-scan absorption correction was applied to the collected reflections. The structure was solved with the ShelXS structure solution program using Direct Methods and refined with the ShelXL refinement package using Least Squares minimization. All non-hydrogen atoms were refined anisotropically. The figures were exported using Olex2.
[0235] Adsorption performance testing. The adsorption performance of zeolites for CO.sub.2 was tested using both single component static adsorption and dynamic column breakthrough methods. For the single component experiments, UHP-grade (99.999% purity) carbon dioxide was used for all adsorption measurements. CO.sub.2 isotherms were measured on a Quantachrome Autosorb iQ adsorption. For each measurement, ca. 100 mg adsorbent was placed in a sample holder that was immersed into a liquid bath connected to a recirculating chiller with a precise temperature controller. Prior to adsorption measurements, all samples were outgassed at 60° C. for 0.5 h, followed by holds of 0.5 h at 120° C. and 6 h at 350° C. with all the ramp rates of 1.0° C./min. The zeolite performance for CO.sub.2 adsorption was also tested using fixed bed column breakthrough experiments. (30) Typically, ca. 500 mg of materials were placed in a quartz tubing (6.74 mm I.D.) to form a fixed bed. First, the adsorbent bed was purged under a 20 mL/min-1 flow of 5% Ar/He gas at 550° C. for 24 h before a breakthrough experiment to completely remove the water and CO.sub.2.
[0236] Upon cooling to 30° C., the gas flow was switched to the desired gas mixture (ca. 400 ppm CO.sub.2/400 ppm Ar (internal standard)/He or 400 ppm CO.sub.2/1Ar % (internal standard)/20% O.sub.2/N.sub.2) at a flow rate of 20 mL/min. The outlet composition was continuously monitored using a Ametek Dymaxion Dycor mass spectrometer until a complete breakthrough was achieved. After each breakthrough experiment, the packed column bed was regenerated at 550° C. for 2 h, or 100° C. or 60° C. for 240 min with a constant 5% Ar/He flow (20 mL/min) to test the recyclability of the materials. The CO.sub.2/N.sub.2 selectivity is defined as
[0237] where qi and pi denote the capacity and partial pressure of component i.
[0238] CO.sub.2 adsorption kinetics. The adsorption kinetics of MOR-type zeolites for CO.sub.2 adsorption was examined using TGA (Perkin Elmer STA6000). Typically, ca. 35-50 mg zeolites were loaded into an alumina sample pan. The loaded sample was activated at 600° C. for 20 h with a 70 mL/min He flow. After the temperature was cooled to 30° C., the gas was switched to a 70 mL/min 400 ppm CO.sub.2/He flow. Desorption was performed with a ramp rate of 10° C./min to 600° C. with a 70 mL/min He flow. The weight of the sample was recorded as a function of time on stream.
[0239] Isosteric heat of adsorption. The isotherms measured at different temperatures were first fitted using the Langmuir-Freundlich (LF) isotherm model:
where “a” is the saturation uptake (mmol/g), “b” is the corresponding adsorption equilibrium constant showing the affinity coefficient, “n” is the deviation from the ideal homogeneous surface, “p” is the equilibrium pressure.
[0240] The heat of adsorption was calculated from the Clausius-Clapeyron equation:
where “p” is the pressure (bar), “ΔH” is the changing in enthalpy (kJ/mol), “R” is the universal gas constant (8.314 J/K/mol), and “T” is the temperature (K). The function can be simplified to:
for the calculation of AH (isosteric heat of adsorption).
Results
[0241] MOR-type zeolites for capture of low concentration CO.sub.2. The MOR-type zeolite framework (
[0242] Na.sup.+ cations are active sites for the adsorption of CO.sub.2 in zeolites, and their distributions in the two channels of the MOR framework locations can be determined by deconvoluting the OH stretching region of the Fourier transform infrared spectra (FTIR,
TABLE-US-00001 TABLE S1 Physicochemical properties of MOR-type zeolite samples. Sample code Sample source Adsorbent Si/Al ratio.sup.a Na/Al 1 Commercial Na-HSZ620 7.36 0.93 2 Na-HSZ640 9.19 0.67 3 Na-HSZ660 12.79 0.83 4 CBV10A 5.81 1.03 5 OSDA-directed synthesis 5.30 0.91 6 5.67 0.95 7 5.04 0.89 8 5.35 0.86 9 5.37 0.83 10 5.51 0.82 11 5.10 0.81 12 5.72 0.90 13 4.89 0.98 14 OSDA-free synthesis 4.38 0.75 15 9.46 1.03 16 13.47 0.94 .sup.aElemental analysis was performed using EDS.
[0243] The equilibrium capacities were obtained from CO.sub.2 isotherms (
TABLE-US-00002 TABLE S2 The capacities of MOR-type zeolites for 400 ppm CO.sub.2 as well as the number of Na.sup.+ cations in the 8MR side-pocket for each MOR unit cell. CO.sub.2 capacity Na.sup.+ in 8MR side- Sample code (mmol/g).sup.a pocket per unit cell.sup.b 1 0.49 2.62 4 0.77 3.94 5 0.88 4.53 6 0.91 4.19 7 1.15 4.70 8 0.98 4.79 9 0.85 4.02 10 0.85 3.86 11 0.90 3.83 12 0.89 4.24 13 1.00 4.66 Note: .sup.aThe CO.sub.2 capacity obtained at 0.0004 bar from the isotherms measured at 30° C. .sup.bThe number of Na.sup.+ cations in the 8MR side-pocket for each MOR unit cell was calculated from the FTIR results in the OH stretching region and the elemental analysis from EDS.
[0244] The capacity of MOR (7 #) is also about 2-fold of the recently developed Zn-CHA adsorbent. D. Fu, Y. Park, M. E. Davis, Zinc containing small-pore zeolites for capture of low concentration carbon dioxide. Angew. Chem. Int. Ed. 61, e202112916 (2022). We successfully synthesized an OSDA-free MOR-type zeolite (14 #) with slightly increased Al content (Si/Al=4) that gave a capacity of 1.14 mmol/g (
[0245] Adsorption sites in MOR-type zeolites. Studies were performed to identify the active sites responsible for the adsorption of low concentration CO.sub.2 in MOR-type zeolites. MOR-type (4 #) zeolites were modified with pyridine, denoted as py-MOR, to selectively block the adsorption sites in the 12-MR channel as well as the intersection between the 12-MR channel and 8-MR side-pocket (
[0246] To better understand the structural features and the active adsorption sites that provide the adsorption performance of MOR-type zeolites, a series of Na-MOR-type samples (
TABLE-US-00003 TABLE S3 CO.sub.2 adsorption results from the MOR-type (4# in NH.sub.4.sup.+ form) zeolites as a function of Na.sup.+ loadings. Sample Capacity (mmol/g) code Samples 400 ppm 1 bar CO.sub.2/U.C. 17 H-MOR7 0.02 2.92 0.06 18 0.002Na 0.03 2.82 0.09 19 0.005Na 0.04 2.90 0.12 20 0.01Na 0.05 2.89 0.15 21 0.05Na 0.09 2.93 0.27 22 0.1Na 0.16 3.07 0.46 23 0.2Na 0.33 3.26 0.97 24 0.5Na 0.49 3.38 1.47 25 1Na 0.62 3.36 1.84 26 2Na 0.60 3.33 1.81 27 3Na 0.65 3.30 1.98 28 4Na 0.68 3.48 2.20 29 5Na 0.75 3.30 2.26
TABLE-US-00004 TABLE S4 Proton densities and Na.sup.+ distributions in the MOR-type (4# in NH.sub.4.sup.+ form) zeolites as a function of Na.sup.+ loadings. Sample code Proton density.sup.a Na/U.C..sup.b Na @ 8MR.sup.c Na @ 12 MR.sup.c 17 5.82 0.00 0.00 0.00 18 5.64 0.18 0.17 0.01 19 5.21 0.60 0.55 0.05 20 4.94 0.87 0.84 0.03 21 4.30 1.50 1.47 0.03 22 3.91 1.89 1.72 0.18 23 3.30 2.50 2.18 0.32 24 1.97 3.83 2.43 1.40 25 1.76 4.04 2.66 1.37 26 1.24 4.56 3.04 1.52 27 1.18 4.62 2.99 1.62 28 1.00 4.80 2.97 1.83 29 0.88 4.92 3.16 1.76 Note: .sup.aThe values were obtained from 1H NMR. .sup.bThe values were calculated based on the proton density from 1H NMR. .sup.cThe values were calculated based on the proton density from 1H NMR and the deconvolution of FTIR spectra of corresponding samples.
[0247] As shown in
TABLE-US-00005 TABLE S5 Assignments of IR Bands of CO.sub.2 in Na-form zeolites. Wavenumbers/cm.sup.−1 Vibration Mode Physical Meaning ref 656 v.sub.2 Deformation mode (9) 1382 v.sub.1 Symmetric stretching (9) 1365 and 1700 pair Carbonate-like (10) 1425 and 1485 pair Carbonate-like (10) 2290 v.sub.3 of .sup.13CO.sub.2 Asymmetric stretching of isotope (11) .sup.13CO.sub.2 2349 v.sub.3 Asymmetric stretching of gas phase (10) CO.sub.2 in zeolites 2350-2360 v.sub.3 Asymmetric stretching of linearly (9, 10, adsorbed, end on form of CO.sub.2 12) 2360-2370 Unssigned (10) 2422 v.sub.2 + v.sub.lib Asymmetric stretching with hindered (13) rotation mode; v.sub.lib is from the Na—O intermolecular stretching 3598-3725 v.sub.3 + v.sub.1 and v.sub.3 + 2v.sub.2 (10)
[0248] With an increase of Na.sup.+ density, a shoulder at 2359 cm.sup.−1 evolved on the right side of the gas phase vibration, suggesting that CO.sub.2 molecules physiosorbed linearly. Importantly, in the second stage, an extra band attributed to the Na—O vibration was observed between 2400-2430 cm.sup.−1, indicating the strong/close interaction between the extraframework Na.sup.+ cation and the O atom of CO.sub.2 molecules. B. Bonelli, B. Onida, B. Fubini, C. O. Arean, E. Garrone, Vibrational and thermodynamic study of the adsorption of carbon dioxide on the zeolite Na-ZSM-5. Langmuir 16, 4976-4983 (2000). Single-crystal XRD analysis was performed to locate the Na.sup.+ in the MOR-type framework as a function of Na.sup.+ loading. Representative samples with Na.sup.+ densities of 0.88, 2.59, 4.38 and 5.96 Na.sup.+/U.C. were evaluated (
TABLE-US-00006 TABLE S6 Compositions of MOR-type zeolite large crystals for single- crystal X-ray diffraction measurements. Sample code Si/Al ratio Na/Al Al.sup.3+/U.C. Na.sup.+/U.C. 30 5.51 0.12 7.37 0.88 31 5.48 0.35 7.41 2.59 32 5.47 0.59 7.42 4.38 33 5.52 0.81 7.36 5.96 Note: The compositions were measured using EDS.
[0249] The structure was solved using an orthorhombic Cmcm space group with lattice parameters of a typical MOR unit cell: a) 18.094 Å, b) 20.516 Å, and c) 7.524 Å. The refinement gave a chemical formula of Na.sub.xSi40.6Al7.4O96, where x denotes the number of Na.sup.+ cations detected per MOR unit cell. The results (
TABLE-US-00007 TABLE S7 Single crystal X-ray structure data and refinement conditions for MOR (30#). Oxygen position Na number Occupancy (%) O31 0.88 44 O33 O44 O42
TABLE-US-00008 TABLE S8 Single crystal X-ray structure data and refinement conditions for MOR (31#). Oxygen position Na number Occupancy (%) O31 1.39 70 O32 1.22 61 O44 O42
TABLE-US-00009 TABLE S9 Single crystal X-ray structure data and refinement conditions for MOR (32#). Oxygen position Na number Occupancy (%) O31 2 100 O33 2 100 O44 0.4 O42
TABLE-US-00010 TABLE S10 Single crystal X-ray structure data and refinement conditions for MOR (33#). Oxygen position Na number Occupancy (%) O31 2.01 100 O33 2.01 100 O44 0.75 N.A. O42 1.12 N.A.
[0250] Specifically, the O atom site in the 8-MR side-pocket connecting to T1 is the only position occupied at stage I (sample A), while Na.sup.+ cations started siting in the O33 site connecting to T4 at stage II with 61% occupancy observed for sample B. As the CO.sub.2 capacity sharply increases at stage II, it can be concluded that O33 site is responsible for the adsorption of low concentration CO.sub.2. Similarly, Corma et al. demonstrated that the O33 site is active for the selective carbonylation of DME as it stabilizes the adsorbed methoxy species. M. Boronat, C. Martinez-Sanchez, D. Law, A. Corma, Enzyme-like Specificity in Zeolites: A unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO. J. Am. Chem. Soc. 130, 16316-16323 (2008). Interestingly, the CO.sub.2 capacity continues to increase after the O33 site is fully occupied, as shown in sample C. The material possessed partial occupancy of the O44 site connecting to T4 that is located in the intersection of 8-MR side-pocket and 12-MR channel. These data suggest that the O44 site also contributes to the adsorption of low concentration CO.sub.2, corroborating the results from py-MOR (
[0251] Confinement effects facilitate low concentration CO.sub.2 adsorption. Zeolites with different topologies were investigated to determine the relationship between the size of the zeolite pores space and the adsorption behavior for capturing low concentration CO.sub.2 (
TABLE-US-00011 TABLE S11 Physicochemical properties of the zeolite samples. Micropore Adsorbent Framework Si/Al ratio.sup.a Na/Al.sup.a volume (cm.sup.3/g) 34 FAU 1.22 0.82 0.28 35 LTL 2.79 0.84 0.17 36 MAZ 3.15 0.78 0.05 37 BEA 4.31 0.93 0.21 4 MOR 5.81 1.03 0.17 38 FER 10 0.98 — 39 MFI 9.84 1.00 0.14 40 MEL 15.49 0.98 0.12 .sup.aElemental analysis was performed using EDS.
TABLE-US-00012 TABLE S12 Capacity of zeolites with different framework topologies as measured by isotherms at 25° C. 400 ppm Ads. 1 bar Sample Frame- Capacity Efficiency Capacity code work Samples (mmol/g) (CO.sub.2/Na.sup.+) (mmol/g) 34 FAU FAU1 (13X) 0.41 0.06 5.64 35 LTL LTL3 0.02 0.01 2.39 36 MAZ MAZ3 (Omega-1) 0.65 0.22 4.06 37 BEA BEA5 0.23 0.08 3.13 4 MOR MOR6 0.77 0.32 3.32 14 MOR4 1.13 0.49 3.57 (OSDA free) 38 FER FER10 (ZSM-35) 0.11 0.08 2.12 39 MFI MFI12 (ZSM-5) 0.57 0.38 2.78 40 MEL MEL15 (ZSM-11) 0.17 0.17 2.39
[0252] The window of the 8-MR channel in LTL-type zeolite has an elliptical structure of 2.3×5.2 Å.sup.2 that is too small to allow CO.sub.2 molecules to enter. LTL-type zeolites with a Si/Al of 3 showed almost no uptake for 400 ppm CO.sub.2 (
[0253] However, there is a relationship between the adsorption efficiency (CO.sub.2/Na.sup.+) and the size of the confined space (see definition in
[0254] MOR-type zeolites for DAC. Real time breakthrough experiments were performed with the commercially available MOR-type zeolites (4 #) using simulated air with a gas mixture of 400 ppm CO.sub.2/1% Ar/20% O.sub.2/N.sub.2 at 30° C., with Ar as the internal standard for quantitative analysis. A CO.sub.2 capacity of 0.72 mmol/g was obtained with a breakthrough time of 1839 min/g (800 min for 435 mg dry material) under a flow of 20 mL/min. This value is slightly lower than the 0.77 mmol/g obtained from the 400 ppm CO.sub.2/He under the same conditions, which may be attributed to the weak competitive adsorption between CO.sub.2 and N.sub.2. The preferential adsorption of CO.sub.2 also led to a higher CO.sub.2/N.sub.2 selectivity (
[0255] Summary MOR-type zeolites are promising physisorbents for the capture of low concentration CO.sub.2, e.g., DAC. The Na.sup.+ located at the O33 site in the 8-MR side-pocket of the MOR framework is responsible for the capture of most of the 1.15 mmol CO.sub.2/g zeolites under low concentration conditions, and the value is among the highest obtained for physisorbents with a low isosteric heat of adsorption of ca. 30 kJ/mol. The size of the confined space in the zeolite is critical to achieve high performance for the adsorption of low concentration CO.sub.2. MOR-type zeolites show the greatest effects from confinement. They also adsorb CO.sub.2 with negligible impact from the presence of N.sub.2 and O.sub.2, the latter can cause the time-dependent degradation of amine-based adsorbents. Additionally, the capacity of the MOR-type zeolite can be further increased to over 2 mmol CO.sub.2/g zeolite at sub-ambient temperatures, outperforming amine-based adsorbents under those conditions as the latter shows a decline in capacity with the decrease in temperature.
[0256] MOR-Type Zeolites for DAC from Humid Gaseous Source Mixture.
[0257] Simulated air containing 2500 ppm H.sub.2O was passed through a column of MOR zeolite at 30° C. The MOR zeolite exhibited a CO.sub.2 capacity of 0.94 mmol/gram of zeolite. Regeneration of the zeolite at 200° C. returned the zeolite to a CO.sub.2 capacity of only 0.73 mmol/gram. Regeneration of the zeolite at 300° C. returned the zeolite to a CO.sub.2 capacity of only 0.93 mmol/gram. Thus, in the absence of a desiccant, a regeneration temperature of 300° C. is needed to maintain CO.sub.2 capacity.
[0258] Simulated air containing 2500 ppm H.sub.2O was passed through a column of SAPO-34 and then a column of MOR zeolite at 30° C. The MOR zeolite exhibited a CO.sub.2 capacity of 0.94 mmol/gram of zeolite. Regeneration of the zeolite at 100° C. returned the zeolite to a CO.sub.2 capacity of 0.93 mmol/gram in a first cycle, and then 0.94 mmol/gram in a second cycle. Thus, when SAPO-34 is used as a desiccant to pre-treat the source gas mixture, a regeneration temperature of only 100° C. is needed to maintain the CO.sub.2 capacity of MOR7. The results of this study are shown in Figure. 52.
[0259] MOR-type zeolites for DAC from Humid Gaseous Source Mixture at low temperatures.
[0260] For multi-layer bed experiments, SAPO-34 (Mitsubishi Plastic Inc.) was loaded in the upstream of CO.sub.2 adsorbent bed and the two materials were separated with quartz wool. The ratio between SAPO-34 and CO.sub.2 adsorbent was determined by the duration of water breakthrough with SAPO-34 and the duration of CO.sub.2 saturation with adsorbent. Typically, 300 mg SAPO-34 and 250 mg MOR-type zeolites were used for simulated air with 2500 ppm H.sub.2O. 350 mg SAPO-34 and 150 mg MOR-type zeolites with Si/Al=7 (MOR7, CBV10A) were used for simulated air with 20000 ppm H.sub.2O. The adsorption measurements were performed at 30 or −10° C. with a 60 mL/min flow of simulated air. A reversed flow of 5% Ar/He gas was used for regeneration at corresponding temperatures.
[0261] The effect of temperature of the ability of SAPO-34 desiccant to maintain the CO.sub.2 capacity of MOR7 at low temperatures was also demonstrated. Simulated air containing 2500 ppm H.sub.2O was passed through a column of SAPO-34 and then a column of MOR zeolite at −10° C., and at 30° C. The CO.sub.2 capacity of MOR was the same as the CO.sub.2 capacity observed with dry air at the same temperatures. The results of this experiment are shown in
[0262] Multicycle adsorption-desorption of two parallel adsorption units with dual-layer beds.
[0263] A two-bed system was designed and employed for the multi-cycle experiments with two parallel SAPO-34+MOR units. Typically, one unit (Unit A) is running for CO.sub.2 adsorption at 30° C. with simulated, humid air, while another unit (Unit B) is running for regeneration at 100° C. with the exhaust gas from Unit A. The adsorption measurements were performed at 30° C. with a ca. 64 mL/min flow of simulated air. A reversed flow of 5% Ar/He gas was used for regeneration at corresponding temperatures.
[0264] Adsorption-desorption in a DAC system having two parallel adsorption units was demonstrated through 15 adsorption-desorption cycles. Each adsorption unit had a dual layer bed comprising a layer of SAPO-34 upstream of a layer of MOR. Adsorption was demonstrated using simulated air at containing 2500 ppm water at 30° C. Desorption was achieved by passing the effluent gas from an adsorption unit through the unit undergoing desorption at 100° C. These results demonstrated that running two parallel units can efficiently capture CO.sub.2 from humid air (2500 ppm H.sub.2O) with adsorption and desorption at 30 and 100° C., respectively. The results of this experiment are shown in