POLYMER REINFORCEMENT ON DOUBLE AMINE COATED SORBENT
20250205681 ยท 2025-06-26
Inventors
- Jeremy Aaron Willman (Redwood City, CA, US)
- Chaokun Gong (Sunnyvale, CA, US)
- Amanda Marie Rampertab (Santa Clara, CA, US)
- Jacques Gagne (Los Gatos, CA, US)
Cpc classification
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
B01J20/262
PERFORMING OPERATIONS; TRANSPORTING
International classification
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
B01J20/26
PERFORMING OPERATIONS; TRANSPORTING
B01J20/32
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Disclosed herein are methods, and compositions produced using the methods, including introducing porous substrate particles and a first reagent comprising a polymer to a solvent to provide a plurality of coated particles; and introducing a second reagent comprising a polymeric amine and a third reagent comprising a silane moiety and an amine moiety to the coated particles, thereby providing a plurality of functionalized, coated particles.
Claims
1. A method, comprising: forming a plurality of coated particles by introducing (i) at least a portion of a plurality of porous substrate particles and (ii) a first reagent, comprising a polymer, to a solvent; and forming a plurality of functionalized coated particles by introducing (i) a second reagent comprising a polymeric amine and (ii) a third reagent, comprising a silane-functionalized amine or an amino-functionalized silane (aminosilane), to at least a portion of the plurality of coated particles.
2. A method comprising: forming a plurality of functionalized particles by introducing (i) a second reagent, comprising a polymeric amine, and (ii) a third reagent, comprising a silane-functionalized amine or an amino-functionalized silane, to a portion of a plurality of porous substrate particles; and forming a plurality of functionalized coated particles by introducing a first reagent, comprising a polymer, to at least a portion of the plurality of functionalized particles.
3. The method of claim 1, wherein introducing the second reagent and the third reagent comprises mixing the second reagent and the third reagent in a different solvent to form a mixture and spraying the mixture on the coated particles.
4. The method of claim 1, wherein the first reagent comprises polyvinyl alcohol.
5. The method of claim 1, wherein the plurality of porous substrate particles is introduced to the solvent at a ratio in a range from 1.5 to 4:1 wt/wt of solvent to the plurality of porous substrate particles.
6. The method of claim 1, wherein the first reagent is introduced to the solvent at a ratio in a range of up to 20% wt/wt of the first reagent to the plurality of porous substrate particles.
7. The method of claim 3, wherein a ratio of the third reagent to the different solvent, while mixing the second reagent and the third reagent in the different solvent, is between 20% and 80% wt/wt of the third reagent to the plurality of porous substrate particles.
8. The method of claim 1, wherein the silane-functionalized amine or amino-functionalized silane is an alkoxysilane, a methoxysilane, a silanetriol, an alkoxysilanol, a chlorosilane, a hydrosilane, an ethoxysilane, or a mixture thereof.
9. The method of claim 8, wherein the silane-functionalized amine or amino-functionalized silane is 3-aminopropyl) trimethoxysilane, (3-aminopropyl)triethoxysilane, [3-(2-aminoethylamino)propyl]trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl silanetriol, N1-(3-trimethoxysilylpropyl) diethylenetriamine, 3-aminopropylsilanetriol, N-(2Aminoethyl)-3-aminopropylsilanetriol, tris(ethylmethylamino) chlorosilane, tris(dimethylamino) chlorosilane, an amino silane oligomer, or a mixture thereof.
10. The method of claim 1, wherein the polymeric amine of the second reagent is linear or branched, and wherein the polymeric amine of the second reagent is selected from a group comprising polyethylenimine (PEI), polypropylenimine, tetraethylenepentamine (TEPA), triethylenetetramine (TETA), diethanolamine, or a mixture thereof.
11.-12. (canceled)
13. The method of claim 1, further comprising, before introducing the second reagent and the third reagent: drying the plurality of coated particles, under vacuum, until a hydration threshold of less than 5% wt/wt of water to coated substrate is reached.
14. The method of claim 1, further comprising introducing a fourth reagent comprising an antioxidant at a weight ratio of 5% to the plurality of porous substrate particles, wherein the antioxidant is 2,2-thiodiethanol, 2-hydroxyethyl disulfide, 3,3-dithiodipropionic acid, or a mixture thereof.
15. (canceled)
16. The method of claim 1, wherein the plurality of porous substrate particles are amorphous silica particles.
17. The method of claim 1, wherein the plurality of porous substrate particles are alumina particles, calcium silicate particles, sodium alumino silicate particles, borosilicate particles, amorphous zirconium silicate particles, porous ziriconia (ZrO.sub.2) particles, calcium aluminate particles, amorphous magnesium silicate particles, zeolite particles, potassium alumino silicate particles, or amorphous lithium sulfate particles.
18. The method of claim 1, wherein the plurality of coated particles have (i) a distribution of pore sizes from 10 nanometers to 200 nanometers and (ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.
19. The method of claim 1, wherein the plurality of coated particles have (i) a distribution of pore sizes from 50 Angstroms to 300 Angstroms and (ii) a distribution of sieve diameters from 0.4 millimeters to 4 millimeters.
20.-28. (canceled)
29. A composition comprising: a plurality of porous substrate particles modified according to the method of claim 1.
30.-33. (canceled)
34. The composition of claim 29, wherein the composition has an abrasion resistance of less than 1% w/w loss according to an ASTM D4058-96 test.
35. The composition of claim 29, wherein the composition has a crush strength of at least 1.5 MPa.
36.-39. (canceled)
40. A method, comprising using the functionalized particles of claim 1 to remove atmospheric CO.sub.2 from air by direct air capture.
41.-70. (canceled)
Description
DESCRIPTION OF DRAWINGS
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[0039] In the figures, like references indicate like elements.
DETAILED DESCRIPTION
[0040] In some embodiments, amorphous silica is used as a porous sorbent substrate for functionalization to achieve carbon capture. Without being limited to any one theory of operation, in some embodiments, sorbent substrates with amine functionalization, e.g., one or more amine-containing groups covalently bonded on surfaces, achieve reversible capture of carbon dioxide from gaseous mixtures (e.g., the atmosphere).
[0041] As used herein, the term moiety is used to describe characteristic parts of organic molecules. For example, an amine moiety is a molecule, compound, or portion of a compound containing an amine group (e.g., NR.sup.N1R.sup.N2, as described herein), whereas a silane moiety is a molecule, compound, or portion of a compound containing a silane group (e.g., SiR.sup.S1R.sup.S2R.sup.S3, as described herein). In one non-limiting instance, an amine moiety includes an aminoalkyl group (e.g., -Ak-NR.sup.N1R.sup.N2, as described herein), as may be present in an aminosilane compound or a polymeric amine compound. The term moiety is used to describe both larger molecules containing the group, or may be used to describe the group itself.
[0042] As used herein, interact is used to describe covalent or non-covalent interactions between chemicals, such as by way of physical adsorption or ionic interactions.
[0043] By acyl or alkanoyl, as used interchangeably herein, is meant an aliphatic or alkyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In particular embodiments, the alkanoyl is C(O)-Ak, in which Ak is an aliphatic or alkyl group, as defined herein. In some embodiments, an unsubstituted alkanoyl is a C.sub.2-7 alkanoyl group. Exemplary alkanoyl groups include acetyl.
[0044] By acyloxy or alkanoyloxy, as used interchangeably herein, is meant an acyl or alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group. In particular embodiments, the alkanoyloxy is OC(O)-Ak, in which Ak is an aliphatic or alkyl group, as defined herein. In some embodiments, an unsubstituted alkanoyloxy is a C.sub.2-7 alkanoyloxy group. Exemplary alkanoyloxy groups include acetoxy.
[0045] By acyl halide is meant C(O)X, where X is a halogen, such as Br, F, I, or Cl.
[0046] By aliphatic is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C.sub.1-50), such as one to 25 carbon atoms (C.sub.1-25), or one to ten carbon atoms (C.sub.1-10), and which includes alkanes (or alkyl, e.g., as described herein), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. In some embodiments, such a hydrocarbon is unsubstituted or substituted with one or more groups, such as groups described herein for an alkyl group.
[0047] By aliphatic-aryl is meant an aryl group that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled through an aliphatic group, as defined herein. In some embodiments, the aliphatic-aryl group is -L-R, in which L is an aliphatic group, as defined herein, and R is an aryl group, as defined herein.
[0048] By aliphatic-heteroaryl is meant a heteroaryl group that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled through an aliphatic group, as defined herein. In some embodiments, the aliphatic-heteroaryl group is -L-R, in which L is an aliphatic group, as defined herein, and R is a heteroaryl group, as defined herein.
[0049] By alkenyl is meant an optionally substituted C.sub.2-24 alkyl group having one or more double bonds. The alkenyl group can be cyclic (e.g., C.sub.3-24 cycloalkenyl) or acyclic. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include allyl and vinyl. In some embodiments, the unsubstituted alkenyl group is a C.sub.2-6, C.sub.2-8, C.sub.2-10, C.sub.2-12, C.sub.2-16, C.sub.2-18, C.sub.2-20, C.sub.2-24, C.sub.3-8, C.sub.3-10, C.sub.3-12, C.sub.3-16, C.sub.3-18, C.sub.3-20, or C.sub.3-24 alkenyl group. Non-limiting examples of alkenyl groups include vinyl or ethenyl (CHCH.sub.2), 1-propenyl (CHCHCH.sub.3), allyl or 2-propenyl (CH.sub.2CHCH.sub.2), 1-butenyl (CHCHCH.sub.2CH.sub.3), 2-butenyl (CH.sub.2CHCHCH.sub.3), 3-butenyl (CH.sub.2CH.sub.2CHCH.sub.2), 2-butenylidene (CHCHCHCH.sub.3), and the like.
[0050] By alkenylene is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C.sub.2-24 alkyl group having one or more double bonds. The alkenylene group can be cyclic (e.g., C.sub.3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of alkenylene include-CHCH or CHCHCH.sub.2.
[0051] By alkoxy is meant-OR, where R is an optionally substituted aliphatic or alkyl group, as described herein. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of unsubstituted alkoxy include C.sub.1-3, C.sub.1-6, C.sub.1-12, C.sub.1-16, C.sub.1-18, C.sub.1-20, or C.sub.1-24 alkoxy groups.
[0052] By alkoxyalkyl is meant an alkyl group, as defined herein, which is substituted with an alkoxy group, as defined herein. Non-limiting examples of unsubstituted alkoxyalkyl groups include between 2 to 12 carbons (C.sub.2-12 alkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.g., C.sub.1-6 alkoxy-C.sub.1-6 alkyl). In some embodiments, the alkoxyalkyl group is -L-OR, in which L is an alkylene group, as defined herein, and R is an alkyl group, as defined herein.
[0053] By alkyl and the prefix alk is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (i-Pr), cyclopropyl, n-butyl (n-Bu), isobutyl (i-Bu), s-butyl (s-Bu), t-butyl (tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. In some embodiments, the alkyl group is cyclic (e.g., C.sub.3-24 cycloalkyl) or acyclic. In some embodiments, the alkyl group is branched or unbranched. In some embodiments, the alkyl group is also substituted or unsubstituted. For example, in some embodiments, the alkyl group is substituted with one or more alkenyl, alkoxy, alkynyl, amino, aryl, carboxyaldehyde (e.g., C(O)H), carboxyl (e.g., CO.sub.2H), cyano (e.g., CN), halo, nitro (e.g., NO.sub.2), oxo (e.g., O), and the like. In some embodiments, the alkyl group is substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C.sub.1-6 alkoxy (e.g., OR, in which R is C.sub.1-6 alkyl); (2) C.sub.1-6 alkylsulfinyl (e.g., S(O)R, in which R is C.sub.1-6 alkyl); (3) C.sub.1-6 alkylsulfonyl (e.g., SO.sub.2R, in which R is C.sub.1-6 alkyl); (4) amine (e.g., C(O)NR.sup.1R.sup.2 or NHCOR.sup.1, where each of R.sup.1 and R.sup.2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R.sup.1 and R.sup.2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein); (5) aryl (e.g., C.sub.4-18 aryl); (6) arylalkoxy (e.g., O-L-R, in which L is C.sub.1-6 alkylene and R is C.sub.4-18 aryl); (7) aryloyl (e.g., C(O)R, in which R is C.sub.4-18 aryl); (8) azido (e.g., N.sub.3); (9) cyano (e.g., CN); (10) aldehyde (e.g., C(O)H); (11) C.sub.3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., OR, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., C(O)R, in which R is heterocyclyl, as defined herein); (16) hydroxy (e.g., OH); (17) N-protected amino; (18) nitro (e.g., NO.sub.2); (19) oxo (e.g., O); (20) C.sub.1-6 thioalkoxy (e.g., SR, in which R is alkyl); (21) thiol (e.g., SH); (22) CO.sub.2R.sup.1, where R.sup.1 is selected from the group consisting of (a) hydrogen, (b) C.sub.1-6 alkyl, (c) C.sub.4-18 aryl, and (d) C.sub.1-6 alkyl-C.sub.4-18 aryl (e.g., -L-R, in which L is C.sub.1-6 alkylene and R is C.sub.4-18 aryl); (23) C(O)NR.sup.1R.sup.2, where each of R.sup.1 and R.sup.2 is, independently, selected from the group consisting of (a) hydrogen, (b) C.sub.1-6 alkyl, (c) C.sub.4-18 aryl, and (d) C.sub.1-6 alkyl-C.sub.4-18 aryl (e.g., -L-R, in which L is C.sub.1-6 alkylene and R is C.sub.4-18 aryl); (24) SO.sub.2R.sup.1, where R.sup.1 is selected from the group consisting of (a) C.sub.1-6 alkyl, (b) C.sub.4-18 aryl, and (c) C.sub.1-6 alkyl-C.sub.4-18 aryl (e.g., -L-R, in which Lis C.sub.1-6 alkylene and R is C.sub.4-18 aryl); (25) SO.sub.2NR.sup.1R.sub.2, where each of R.sup.1 and R.sup.2 is, independently, selected from the group consisting of (a) hydrogen, (b) C.sub.1-6 alkyl, (c) C.sub.4-18 aryl, and (d) C.sub.1-6 alkyl-C.sub.4-18 aryl (e.g., -L-R, in which L is C.sub.1-6 alkylene and R is C.sub.4-18 aryl); and (26) NR.sup.1R.sup.2, where each of R.sup.1 and R.sup.2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C.sub.1-6 alkyl, (d) C.sub.2-6 alkenyl, (e) C.sub.2-6 alkynyl, (f) C.sub.4-18 aryl, (g) C.sub.1-6 alkyl-C.sub.4-18 aryl (e.g., -L-R, in which L is C.sub.1-6 alkylene and R is C.sub.4-18 aryl), (h) C.sub.3-8 cycloalkyl, and (i) C.sub.1-6 alkyl-C.sub.3-8 cycloalkyl (e.g., -L-R, in which Lis C.sub.1-6 alkylene and R is C.sub.3-8 cycloalkyl), where in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group.
[0054] In some embodiments, the alkyl group is a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C.sub.1-3, C.sub.1-4, C.sub.1-6, C.sub.1-8, C.sub.1-10, C.sub.1-12, C.sub.1-16, C.sub.1-18, C.sub.1-20, C.sub.1-24, C.sub.2-6, C.sub.2-8, C.sub.2-10, C.sub.2-12, C.sub.2-16, C.sub.2-18, C.sub.2-20, C.sub.2-24, C.sub.3-8, C.sub.3-10, C.sub.3-12, C.sub.3-16, C.sub.3-18, C.sub.3-20, or C.sub.3-24 alkyl group. Unless stated otherwise specifically in the specification, an alkyl group is optionally substituted by one or more of substituents that are independently heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, OR.sup.a, SR.sup.a, OC(O)R.sup.a, N(R.sup.a).sub.2, C(O)R.sup.a, C(O)OR.sup.a, OC(O)N(R.sup.a).sub.2, C(O)N(R.sup.a).sub.2, N(R.sup.a)C(O)OR.sup.a, N(R.sup.a)C(O)R.sup.a, N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, N(R.sup.a)S(O).sub.tR.sup.a (where tis 1 or 2), S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tOR.sup.a (where t is 1 or 2), S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2 where each R.sup.a is independently hydrogen, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
[0055] By alkylene is meant a multivalent (e.g., bivalent) form of an aliphatic or alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C.sub.1-3, C.sub.1-4, C.sub.1-6, C.sub.1-12, C.sub.1-16, C.sub.1-18, C.sub.1-20, C.sub.1-24, C.sub.2-3, C.sub.2-6, C.sub.2-12, C.sub.2-16, C.sub.2-18, C.sub.2-20, or C.sub.2-24 alkylene group. In some embodiments, the alkylene group is branched or unbranched. The alkylene group is also substituted or unsubstituted. For example, in some embodiments, the alkylene group is substituted with one or more substitution groups, as described herein for alkyl.
[0056] The term alkoxy refers to the group-O-alkyl, including from 1 to 24 carbon atoms of a straight, branched, cyclic configuration and combinations thereof attached to the parent structure through an oxygen. Exemplary alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, butoxy, cyclohexyloxy, and trihaloalkoxy, such as trifluoromethoxy, etc. In some embodiments, the alkoxy group is substituted or unsubstituted. For example, in some embodiments, the alkoxy group is substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C.sub.1-3, C.sub.1-6, C.sub.1-12, C.sub.1-16, C.sub.1-18, C.sub.1-20, or C.sub.1-24 alkoxy groups.
[0057] The term substituted alkoxy refers to alkoxy wherein the alkyl constituent is substituted (e.g., O-(substituted alkyl)). Unless stated otherwise specifically in the specification, the alkyl moiety of an alkoxy group is optionally substituted by one or more substituents the independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, OR.sup.a, SR.sup.a, OC(O)R.sup.a, N(R.sup.a).sub.2, C(O)R.sup.a, C(O)OR.sup.a, OC(O)N(R.sup.a).sub.2, C(O)N(R.sup.a).sub.2, N(R.sup.a)C(O)OR.sup.a, N(R.sup.a)C(O)R.sup.a, N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a) N(R.sup.a).sub.2, N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tOR.sup.a (where t is 1 or 2), S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
[0058] The term alkylsilyl, as used herein, refers to SiR.sup.1R.sup.2R.sup.3 group, wherein R.sup.1 is an optionally substituted alkyl, and wherein each of R.sup.2 and R.sup.3 is independently selected from H and an optionally substituted alkyl. Alkylsilyls include mono, bis, and tris alkylsilyls. Examples of alkylsilyls include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, ethylsilyl, and the like.
[0059] By alkylsulfinyl is meant an alkyl group, as defined herein, attached to the parent molecular group through an S(O) group. In some embodiments, the unsubstituted alkylsulfinyl group is a C.sub.1-6 or C.sub.1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is S(O)R, in which R is an alkyl group, as defined herein.
[0060] By alkylsulfinylalkyl is meant an alkyl group, as defined herein, substituted by an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is a C.sub.2-12 or C.sub.2-24 alkylsulfinylalkyl group (e.g., C.sub.1-6 alkylsulfinyl-C.sub.1-6 alkyl or C.sub.1-12 alkylsulfinyl-C.sub.1-12 alkyl). In other embodiments, the alkylsulfinylalkyl group is -L-S(O)R, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.
[0061] By alkylsulfonyl is meant an alkyl group, as defined herein, attached to the parent molecular group through an SO.sub.2 group. In some embodiments, the unsubstituted alkylsulfonyl group is a C.sub.1-6 or C.sub.1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is SO.sub.2R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted C.sub.1-12 alkyl, haloalkyl, or perfluoroalkyl).
[0062] By alkylsulfonylalkyl is meant an alkyl group, as defined herein, substituted by an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is a C.sub.2-12 or C.sub.2-24 alkylsulfonylalkyl group (e.g., C.sub.1-6 alkylsulfonyl-C.sub.1-6 alkyl or C.sub.1-12 alkylsulfonyl-C.sub.1-12 alkyl). In other embodiments, the alkylsulfonylalkyl group is -L-SO.sub.2R, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.
[0063] By alkynyl is meant an optionally substituted C.sub.2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkynyl groups include C.sub.2-8 alkynyl, C.sub.2-6 alkynyl, C.sub.2-5 alkynyl, C.sub.2-4 alkynyl, or C.sub.2-3 alkynyl. Non-limiting examples of alkynyl groups include ethynyl (CCH), 1-propynyl (CCCH.sub.3), 2-propynyl or propargyl (CH.sub.2CCH), 1-butynyl (CCCH.sub.2CH.sub.3), 2-butynyl (CH.sub.2CCCH.sub.3), 3-butynyl (CH.sub.2CH.sub.2CCH), and the like. In some embodiments, the unsubstituted alkynyl group is a C.sub.2-6, C.sub.2-8, C.sub.2-10, C.sub.2-12, C.sub.2-16, C.sub.2-18, C.sub.2-20, C.sub.2-24, C.sub.3-8, C.sub.3-10, C.sub.3-12, C.sub.3-16, C.sub.3-18, C.sub.3-20, or C.sub.3-24 alkynyl group.
[0064] By alkynylene is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C.sub.2-24 alkyl group having one or more triple bonds. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting examples of alkynylene groups include CC or CCCH.sub.2.
[0065] By amido is meant C(O)NR.sup.1R.sup.2 or NHCOR.sup.1, where each of R.sup.1 and R.sup.2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or where R.sup.1 and R.sup.2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein.
[0066] By amino or amino is meant a N(R.sup.a).sub.2 radical group, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl, unless stated otherwise specifically in the specification. When a N(R.sup.a).sub.2 group has two R.sup.a substituents other than hydrogen, they can be combined with the nitrogen atom to form a 4-, 5-, 6- or 7-membered ring. For example, N(R.sup.a).sub.2 is intended to include, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl. Unless stated otherwise specifically in the specification, an amino group is optionally substituted by one or more substituents which independently are: alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, OR.sup.a, SR.sup.a, OC(O)R.sup.a, N(R.sup.a).sub.2, C(O)R.sup.a, C(O)OR.sup.a, OC(O)N(R.sup.a).sub.2, C(O)N(R.sup.a).sub.2, N(R.sup.a)C(O)OR.sup.a, N(R.sup.a)C(O)R.sup.a, N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a) N(R.sup.a).sub.2, N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tOR.sup.a (where t is 1 or 2), S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or PO.sub.3(R.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
[0067] The term substituted amino also refers to N-oxides of the groups NHR.sup.a, and NR.sup.aR.sup.a each as described above. N-oxides can be prepared by treatment of the corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid.
[0068] By aminoalkyl is meant an aliphatic or alkyl group, as described herein, substituted with one, two, three, or more amine groups. In some embodiments, the aminoalkyl includes internal amine groups or terminal amine groups. In some embodiments, the aminoalkyl group is further substituted. For example, in some embodiments, the aminoalkyl group is substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted aminoalkyl groups include C.sub.1-3, C.sub.1-6, C.sub.1-12, C.sub.1-16, C.sub.1-18, C.sub.1-20, or C.sub.1-24 aminoalkyl groups. In some embodiments, the aminoalkyl group is -L-NR.sup.1R.sub.2, in which L is an aliphatic or alkylene group, as defined herein, and each of R.sup.1 and R.sup.2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R.sup.1 and R.sup.2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR.sup.1R.sub.2) (R.sub.3)R.sup.4, in which L is a covalent bond, an aliphatic group, or an alkylene group, as defined herein; each of R.sup.1 and R.sup.2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof; or R.sup.1 and R.sup.2, taken together with the nitrogen atom to which each are attached, can form a heterocyclyl group, as defined herein; and each of R.sup.3 and R.sup.4 is, independently, H or alkyl, as defined herein.
[0069] By aminoaryl is meant an aromatic or aryl group, as defined herein, substituted by an amino group, as defined herein.
[0070] By aromatic is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized -electron system. Typically, the number of out of plane -electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system.
[0071] By aryl is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C.sub.5-15), such as five to ten carbon atoms (C.sub.5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. In some embodiments, aryl groups are substituted with one or more groups other than hydrogen, such as alkyl, as well as any substitution groups described herein for alkyl. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. In particular embodiments, an unsubstituted aryl group is a C.sub.4-18, C.sub.4-14, C.sub.4-12, C.sub.4-10, C.sub.6-18, C.sub.6-14, C.sub.6-12, or C.sub.6-10 aryl group. Aryl groups can have any suitable number of carbon ring atoms and any suitable number of rings. Aryl groups can include any suitable number of carbon ring atoms, such as C.sub.6, C.sub.7, C.sub.8, C.sub.9, C.sub.10, C.sub.11, C.sub.12, C.sub.13, C.sub.14, C.sub.15 or C.sub.16, as well as C.sub.6-12, C.sub.6-10, or C.sub.6-14. Bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals. Bivalent radicals derived from univalent polycyclic hydrocarbon radicals whose names end in -yl by removal of one hydrogen atom from the carbon atom with the free valence are named by adding -idene to the name of the corresponding univalent radical, e.g., a naphthyl group with two points of attachment is termed naphthylidene. Whenever it appears herein, a numerical range such as 6 to 10 (e.g., C.sub.6-C.sub.10 aromatic or C.sub.6-C.sub.10 aryl) refers to each integer in the given range; e.g., 6 to 10 ring atoms means that the aryl group may consist of 6 ring atoms, 7 ring atoms, etc., up to and including 10 ring atoms. Aryl groups can be monocyclic, fused (i.e., rings which share adjacent pairs of ring atoms) to form bicyclic (e.g., benzocyclohexyl) or tricyclic groups or polycyclic groups, or linked by a bond to form a biaryl group. Representative aryl groups include phenyl, naphthyl and biphenyl. Other aryl groups include benzyl, having a methylene linking group. Unless stated otherwise specifically in the specification, an aryl moiety is optionally substituted by one or more substituents which are independently alkyl, heteroalkyl, acylsulfonamido, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, hydroxamate, aryl, arylalkyl, heteroaryl, heteroarylalkyl, hydroxy, halo, cyano, trifluoromethyl, trifluoromethoxy, nitro, trimethylsilanyl, OR.sup.a, SR.sup.a, S(O).sub.tR.sup.a (where t is 1 or 2), OC(O)R.sup.a, N(R.sup.a).sub.2, C(O)R.sup.a, C(O)OR.sup.a, OC(O)N(R.sup.a).sub.2, C(O)N(R.sup.a).sub.2, N(R.sup.a)C(O)OR.sup.a, N(R.sup.a)C(O)R.sup.a, N(R.sup.a)C(O)N(R.sup.a).sub.2, N(R.sup.a)C(NR.sup.a)N(R.sup.a).sub.2, N(R.sup.a)S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tR.sup.a (where t is 1 or 2), S(O).sub.tOR.sup.a (where t is 1 or 2), S(O).sub.tN(R.sup.a).sub.2 (where t is 1 or 2), or PO(OR.sup.a).sub.2, where each R.sup.a is independently hydrogen, alkyl, fluoroalkyl, carbocyclyl, carbocyclylalkyl, aryl, aralkyl, heterocycloalkyl, heterocycloalkylalkyl, heteroaryl or heteroarylalkyl.
[0072] By arylene is meant a multivalent (e.g., bivalent) form of an aromatic or aryl group, as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is a C.sub.4-18, C.sub.4-14, C.sub.4-12, C.sub.4-10, C.sub.6-18, C.sub.6-14, C.sub.6-12, or C.sub.6-10 arylene group. In some embodiments, the arylene group is branched or unbranched. In some embodiments, the arylene group is further substituted or unsubstituted. For example, In some embodiments, the arylene group is substituted with one or more substitution groups, as described herein for alkyl or aryl.
[0073] By aryloxy is meant-OR, where R is an optionally substituted aromatic or aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C.sub.4-18 or C.sub.6-18 aryloxy group.
[0074] By carbonyl is meant a C(O) group.
[0075] By arylalkoxy is meant an alkyl-aryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is O-L-R, in which L is an alkylene group, as defined herein, and R is an aryl group, as defined herein.
[0076] By aryloxycarbonyl is meant an aryloxy group, as defined herein, that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is a C.sub.5-19 aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is C(O)OR, in which R is an aryl group, as defined herein.
[0077] By aryloyl is meant an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is a C.sub.7-11 aryloyl or C.sub.5-19 aryloyl group. In other embodiments, the aryloyl group is C(O)R, in which R is an aryl group, as defined herein.
[0078] By (aryl) (alkyl) ene is meant a bivalent form including an arylene group, as described herein, attached to an alkylene or a heteroalkylene group, as described herein. In some embodiments, the (aryl) (alkyl) ene group is -L-Ar- or -L-Ar-L- or Ar-L-, in which Ar is an aromatic or arylene group and each L is, independently, an optionally substituted aliphatic, alkylene group, heteroaliphatic, or heteroalkylene group.
[0079] By borono is meant a B(OH).sub.2 group.
[0080] By carbonyl is meant a C(O) group, which can also be represented as >CO, or a CO group.
[0081] By carboxyl or carboxylic acid is meant a CO.sub.2H group or a compound including such a group, including deprotonated and protonated forms thereof.
[0082] By carboxyalkyl is meant an alkyl group, as defined herein, substituted by one or more carboxyl groups, as defined herein.
[0083] By carboxyaryl is meant an aryl group, as defined herein, substituted by one or more carboxyl groups, as defined herein.
[0084] By cyclic anhydride is meant a 3-, 4-, 5-, 6- or 7-membered ring (e.g., a 5-, 6- or 7-membered ring), unless otherwise specified, having a C(O)OC(O) group within the ring. The term cyclic anhydride also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring. Exemplary cyclic anhydride groups include a radical formed from succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, isochroman-1,3-dione, oxepanedione, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, naphthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, etc., by removing one or more hydrogen. Other exemplary cyclic anhydride groups include dioxotetrahydrofuranyl, dioxodihydroisobenzofuranyl, etc. The cyclic anhydride group can also be substituted or unsubstituted. For example, the cyclic anhydride group can be substituted with one or more groups including those described herein for heterocyclyl.
[0085] By cycloaliphatic is meant an aliphatic group, as defined herein, that is cyclic.
[0086] By cycloalkoxy is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is OR, in which R is a cycloalkyl group, as defined herein.
[0087] By cycloalkylalkoxy is meant an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is O-L-R, in which L is an alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.
[0088] By cycloalkyl is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl.
[0089] By cycloheteroaliphatic is meant a heteroaliphatic group, as defined herein, that is cyclic.
[0090] By disulfide is meant SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.
[0091] By formyl is meant a C(O)H group.
[0092] By halo is meant F, Cl, Br, or I.
[0093] By haloaliphatic is meant an aliphatic group, as defined herein, substituted with one or more halo.
[0094] By haloalkyl is meant an alkyl group, as defined herein, substituted with one or more halo.
[0095] By haloalkenyl is meant an alkenyl group, as defined herein, substituted with one or more halo.
[0096] By haloalkynyl is meant an alkynyl group, as defined herein, substituted with one or more halo.
[0097] By haloalkylene is meant an alkylene group, as defined herein, substituted with one or more halo.
[0098] By halocarbonyl is meant a C(O)X group, in which X is halo, as defined herein.
[0099] By haloheteroaliphatic is meant a heteroaliphatic, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.
[0100] By heteroaliphatic is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to boron, halo, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and, if applicable, oxidized forms thereof within the group.
[0101] By heteroalkyl is meant an aliphatic or alkyl group, as defined herein, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of boron, halo, nitrogen (e.g., as present in imino), oxygen, phosphorus, selenium, silicon, sulfur, and, if applicable, oxidized forms thereof).
[0102] By heteroalkylene is meant a multivalent (e.g., bivalent) form of a heteroaliphatic or heteroalkyl group, as described herein. The heteroalkylene group can be substituted or unsubstituted. For example, in some embodiments, the heteroalkylene group is substituted with one or more substitution groups, as described herein for alkyl.
[0103] By heteroalkenylene is meant a multivalent (e.g., bivalent) form of a heteroalkenyl group, which is an optionally substituted heteroalkyl group having one or more double bonds. The heteroalkenylene group can be cyclic or acyclic. The heteroalkenylene group can be substituted or unsubstituted. For example, the heteroalkenylene group can be substituted with one or more substitution groups, as described herein for alkyl.
[0104] By heteroalkynylene is meant a multivalent (e.g., bivalent) form of a heteroalkynyl group, which is an optionally substituted heteroalkyl group having one or more triple bonds. The heteroalkynylene group can be cyclic or acyclic. The heteroalkynylene group can be substituted or unsubstituted. For example, the heteroalkynylene group can be substituted with one or more substitution groups, as described herein for alkyl.
[0105] By heteroaromatic is meant an aromatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and oxidized forms thereof within the group.
[0106] By heteroaryl is meant an aryl group including at least one heteroatom to six heteroatoms, such as one to four heteroatoms, which can be selected from, but not limited to, boron, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, and oxidized forms thereof within the ring. In some embodiments, such heteroaryl groups have a single ring or multiple condensed rings, where the condensed rings may or may not be aromatic or may contain a heteroatom, provided that the point of attachment is through an atom of the aromatic heteroaryl group. In some embodiments, heteroaryl groups are substituted with one or more groups other than hydrogen, such as alkyl, as well as any substitution groups described herein for alkyl. An exemplary heteroaryl includes a subset of heterocyclyl groups, as defined herein, which are aromatic, e.g., they contain 4n+2 pi electrons within the mono- or multicyclic ring system.
[0107] By heteroarylene is meant a multivalent (e.g., bivalent) form of a heteroaromatic or heteroaryl group, as described herein. Exemplary heteroarylene groups include pyridinylene and the like. In some embodiments, the heteroarylene group is a C.sub.4-18, C.sub.4-14, C.sub.4-12, C.sub.4-10, C.sub.6-18, C.sub.6-14, C.sub.6-12, or C.sub.6-10 heteroarylene group. In some embodiments, the heteroarylene group is branched or unbranched. In some embodiments, the heteroarylene group is further substituted or unsubstituted. For example, in some embodiments, the heteroarylene group is substituted with one or more substitution groups, as described herein for alkyl or aryl.
[0108] By heterocyclyl is meant a 3-, 4-, 5-, 6- or 7-membered ring (e.g., a 5-, 6- or 7-membered ring), unless otherwise specified, containing one, two, three, or four noncarbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, selenium, silicon, or sulfur). The 3-membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term heterocyclyl also includes bicyclic, tricyclic, tetracyclic, or other multicyclic groups. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., -carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxooxolanyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxolanyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and/or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for alkyl.
[0109] By heterocyclyloxy is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is OR, in which R is a heterocyclyl group, as defined herein.
[0110] By heterocyclyloyl is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is C(O)R, in which R is a heterocyclyl group, as defined herein.
[0111] By hydroxyl is meant OH.
[0112] By hydroxyalkyl is meant an alkyl group, as defined herein, substituted by one to three hydroxy groups, with the proviso that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl, and the like.
[0113] By hydroxyaryl is meant an aryl group, as defined herein, substituted by one to three hydroxy groups, with the proviso that no more than one hydroxy group may be attached to a single carbon atom of the aryl group and is exemplified by hydroxyphenyl, dihydroxyphenyl, and the like.
[0114] By imido is meant a NR group, where R is selected from H, aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl, as defined herein, or any combination thereof.
[0115] By imino is meant NR, in which R can be H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, or aryl.
[0116] By isocyanato is meant a NCO griyo.
[0117] By nitro is meant an NO.sub.2 group.
[0118] By nitroalkyl is meant an alkyl group, as defined herein, substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, in which L is an alkylene group, as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO) (R.sup.1)R.sup.2, in which L is a covalent bond or an alkylene group, as defined herein, and each of R.sup.1 and R.sup.2 is, independently, H or alkyl, as defined herein.
[0119] By oxiranyl is meant a
##STR00001##
group or a
##STR00002##
group, in which one or more hydrogen atoms can be optionally substituted with another functional group (e.g., halo, alkyl, or any described herein as a substituent for alkyl).
[0120] By oxy is meant O.
[0121] By phosphono or phosphonic acid is meant a P(O)(OH).sub.2 group or a compound including such a group, including deprotonated and protonated forms thereof.
[0122] By perfluoroalkyl is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Non-limiting examples of perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is (CF.sub.2).sub.nCF.sub.3, in which n is an integer from 0 to 20, 1 to 20, 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, and ranges therebetween.
[0123] By perfluoroalkoxy is meant an alkoxy group, as defined herein, having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is OR, in which R is a perfluoroalkyl group, as defined herein.
[0124] By salt is meant an ionic form of a compound or structure (e.g., any formulas, compounds, or compositions described herein), which includes a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge S. M. et al., Pharmaceutical salts, J. Pharm. Sci. 1977 January; 66 (1): 1-19; and in Handbook of Pharmaceutical Salts: Properties, Selection, and Use, Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention or separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting the acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium, quaternary ammonium, and amine cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).
[0125] By silane is meant SiR.sup.S1R.sup.S2R.sup.S3 or a compound having such a group, where each of R.sup.31, R.sup.S2, and R.sup.S3 is, independently, H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkyl, aromatic, aryl, amine, or others described herein; or R.sup.S1 and R.sup.S2, taken together with the silicon atom to which each are attached, form a heterocyclyl group.
[0126] By silyl ether is meant a functional group including a silicon atom covalently bound to an alkoxy group, as defined herein. In some embodiments, the silyl ether is SiOR or SiOR, in which R is an alkyl group, as defined herein.
[0127] By sulfinyl is meant an S(O) group.
[0128] By sulfo or sulfonic acid is meant an S(O).sub.2OH group or a compound including such a group, including deprotonated and protonated forms thereof.
[0129] By sulfonyl or sulfonate is meant an S(O).sub.2 group or a SO.sub.2R, where R is selected from hydrogen, aliphatic, alkyl, heteroaliphatic, heteroalkyl, haloaliphatic, haloheteroaliphatic, aromatic, aryl, as defined herein, or any combination thereof.
[0130] By thio is meant S.
[0131] By thioalkoxy is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Non-limiting examples of unsubstituted thioalkoxy groups include C.sub.1-6 thioalkoxy. In some embodiments, the thioalkoxy group is SR, in which R is an aliphatic or alkyl group, as defined herein.
[0132] By thioalkoxyalkyl is meant an alkyl group, as defined herein, which is substituted with a thioalkoxy group, as defined herein. Non-limiting examples of unsubstituted thioalkoxyalkyl groups include between 2 to 12 carbons (C.sub.2-12 thioalkoxyalkyl), as well as those having an alkyl group with 1 to 6 carbons and a thioalkoxy group with 1 to 6 carbons (i.e., C.sub.1-6 thioalkoxy-C.sub.1-6 alkyl). In some embodiments, the thioalkoxyalkyl group is -L-SR, in which L is alkylene, as defined herein, and R is an alkyl group, as defined herein.
Example Embodiments for Coated, Functionalized Materials
[0133] Disclosed herein is a functionalized material having a protective polymer coating for reversibly capturing (e.g., adsorbing) carbon dioxide (CO.sub.2) and a method of producing such protected sorbents. In general, in some embodiments, functionalized material (e.g., the sorbent) are beads or powder over which gaseous mixtures including CO.sub.2 are flowed. Without being limited to any one theory of operation, in some embodiments, gas exiting the layer of functionalized material has a lower concentration of CO.sub.2 than the entering gas. During carbon capture adsorption and desorption processes, the functionalized material experiences mechanical attrition through handling, use, and transport through the capture and regeneration processes. Advantageously, providing a protective polymer coating on the functionalized material sorbents decreases friability and attrition of the sorbents, leading to longer product life and reduced production of fines.
[0134]
[0135] One example of the substrate particle 102 is composed of amorphous silica, e.g., non-crystalline silica. In some embodiments, other examples of compounds that provide the substrate particle 102 are porous alumina, calcium silicate, and sodium alumino silicate. In some embodiments, other examples of compounds that provide the substrate particle 102 are amorphous borosilicate, amorphous zirconium silicate, porous ziriconia (ZrO.sub.2), calcium aluminate, amorphous magnesium silicate, zeolites, potassium alumino silicate, and amorphous lithium sulfate.
[0136] The depicted porous substrate particle 102 is substantially spherical, though, in some embodiments, the overall structure of the porous substrate particle 102 is any shape suitable for production, including having porous structures such as hexagonal tubes (e.g., MCM-41). In some embodiments, the porous substrate particle 102 is bead-shaped, though this is not limiting. In some embodiments, the porous substrate particle 102 is irregular-shaped.
[0137] In some embodiments the porous substrate particles have pore sizes from 10 nanometers to 200 nanometers. In other words, referring to
[0138] In some embodiments the porous substrate particles have a distribution of sieve diameters between 0.4 millimeters and 4 millimeters. In some such embodiments, at least fifty percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, at least sixty percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, at least seventy percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, at least eighty percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, at least ninety percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, at least 95 percent of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters. In some such embodiments, all of the porous substrate particles have a sieve diameter that is between 0.4 millimeters and 4 millimeters.
[0139] In some embodiments the porous substrate particles have pore sizes from 50 Angstroms to 300 Angstroms. In other words, referring to
[0140] In some embodiments, the polymer coating disposed on the surface 103 is a polymer, or mixture of polymers, which alters the mechanical characteristics of the porous substrate particle 102. One example of the polymer that makes up the polymer coating is polyvinyl alcohol (PVA), a water-soluble synthetic polymer having the formula [CH.sub.2CH(OH)].sub.n, where n is a positive integer. PVA is readily available from commercial sources and has low toxicity for safe handling during application.
[0141] Additional non-limiting examples of polymers which provide the coating contemplated for use in the present disclosure include pebax, polyether block amide (PEBA), polysulfones, polyethersulfones, polyethers, polyamides, ethylcellulose, polyethylene glycol, cellulose acetate, polyurethanes, polystyrenes, polyesters, polyolefins, polyacrylamides, polyacrylates, and combinations, copolymers, and/or block copolymers of those listed herein.
[0142] In some embodiments, the polymer coating is disposed on the porous substrate particle 102 to achieve desirable outcomes for the total coated particle 100 under mechanical stresses, such as abrasion. In some embodiments, the polymer coating decreases the attrition of the coated particle 100 according to one or more standardized testing requirements. Briefly, attrition is the propensity of a product to produce fines in the course of transportation, handling, and use. In some embodiments, the polymer coating reduces the attrition such that an attrition loss of the particles 100 is 1% or less (e.g., 0.9% or less, 0.8% or less) as measured by ASTM D4058-96 or comparable standards by which attrition, friability, or attrition loss, is quantified. In some embodiments, the coated particle 100 is characterized by mechanical properties including compressive strength. In some embodiments, the functionalized material is durable, e.g., having a 50% strain crush strength of at least 1.5 megapascals (MPa) (e.g., at least 2 MPa, at least 3 MPa), e.g., have a 50% strain crush strength in a range from 1.5 to 3.5 MPa.
[0143] In some embodiments, the coated particle 100 reversibly adsorbs CO.sub.2 over a number of cycles, e.g., a number of adsorption and desorption steps. Higher cycle counts achieve longer product lifetimes when used in CO.sub.2 capture application. In some implementations, the coated particle 100 reversibly adsorbs CO.sub.2 over 100 cycles (e.g., over 500 cycles, over 1000 cycles, over 2000 cycles, over 3000 cycles). Here and throughout the specification, reference to a measurable value such as an amount, a temporal duration, and the like, the recitation of the value encompasses the precise value, approximately the value, and within 10% of the value. For example, here 100 cycles includes precisely 100 cycles, approximately 100 cycles, and within 10% of 100 cycles.
[0144] In some embodiments, CO.sub.2 adsorbed to the coated particle 100 is released (e.g., desorbed) under some conditions. As one example, in some embodiments, reducing the gas pressure surrounding the coated particle 100 desorbs captured CO.sub.2. This facilitates recapture of the adsorbed CO.sub.2 in a secondary environment. In some implementations, the coated particle 100 is exposed to a reduced gas pressure of less than 5 psi (e.g., less than 3 psi, less than 1.5 psi, less than 1 psi, or less than 0.1 psi).
[0145] As a second example, in some embodiments, increasing the temperature of the coated particle 100 destabilizes the bond between the amine moiety and the CO.sub.2, thereby desorbing the CO.sub.2 from the coated particle 100. In some implementations, the coated particle 100 desorbs CO.sub.2 at temperatures above 40 C. (e.g., above 50 C., above 60 C., above 70 C., above 80 C., or above 90 C.). Increasing the temperature and decreasing gas pressure concurrently can increase the rate at which the CO.sub.2 desorbs from the coated particle 100.
Substrate Particles.
[0146] In some embodiments, the sieve diameter of the porous substrate particle is a measure of central tendency determined over the sieve diameter of a plurality of porous substrate particles. As used herein, the term sieve diameter is the smallest mesh size through which a particle can pass. As used herein, the term measure of central tendency refers to a central or representative value for a distribution of values. Non-limiting examples of measures of central tendency include a mean, arithmetic mean, weighted mean, midrange, midhinge, trimean, geometric mean, geometric median, Winsorized mean, median, and mode of the distribution of values. For instance, in some embodiments, the sieve diameter of the porous substrate particles is an average sieve diameter of a plurality of porous substrate particles used for generating the functionalized material.
[0147] In some embodiments, the plurality of porous substrate particles comprises a distribution of sieve diameters.
[0148] In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is at least 0.2 millimeters (mm), at least 0.3 mm, at least 0.4 mm, at least 0.5 mm, at least 0.6 mm, at least 0.7 mm, at least 1 mm, at least 1.5 mm, at least 2 mm, at least 2.5 mm, at least 3 mm, at least 3.5 mm, at least 4 mm, or at least 5 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is no more than 10 mm, no more than 5 mm, no more than 4 mm, no more than 3.5 mm, no more than 3 mm, no more than 2.5 mm, no more than 2 mm, no more than 1.5 mm, no more than 1 mm, no more than 0.5 mm, or no more than 0.3 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is from 0.2 mm to 1 mm, from 0.5 mm to 2 mm, from 1 mm to 4 mm, from 0.4 mm to 4 mm, from 3 mm to 5 mm, or from 4 mm to 10 mm. In some embodiments, the sieve diameter, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles falls within another range starting no lower than 0.2 mm and ending no higher than 10 mm.
[0149] In some embodiments, the sieve diameter of the porous substrate particle 102 varies based on the application and/or the source. In some embodiments, the porous substrate particle 102 has an average sieve diameter in the range from 0.25 mm to 4.0 mm (e.g., 0.25 mm to 1.5 mm, 0.5 mm to 1.5 mm, 0.5 mm to 1.0 mm, 1.0 mm to 2.0 mm, 1.5 to 2.0 mm, 0.5 mm to 4.0 mm, 1.0 mm to 4.0 mm, or 2.0 mm to 4.0 mm). In some embodiments, the porous substrate particle 102 has a distribution of sieve diameters having an average (e.g., mean) diameter ranging from 1 mm to 1.2 mm. In some embodiments, the distribution of sieve diameters for the plurality of porous substrate particles comprises sieve diameters of from 0.2 mm to 1 mm, from 0.5 mm to 2 mm, from 1 mm to 4 mm, from 0.4 mm to 4 mm, from 3 mm to 5 mm, from 0.2 mm to 5 mm, from 1 mm to 8 mm, from 0.3 mm to 5 mm, from 0.2 mm to 10 mm, or from 4 mm to 10 mm. In some embodiments, the distribution of sieve diameters for the plurality of porous substrate particles falls within another range starting no lower than 0.2 mm and ending no higher than 10 mm.
[0150] The width of the distribution around the average sieve diameter affects adsorption performance of the porous substrate particle 102. In some implementations, the width of the distribution is in a range from 100 m to 500 m around the average (e.g., from 100 m to 400 m, or 200 m to 300 m). In some embodiments, the width of the distribution is at least 25 m, at least 50 m, at least 100 m, at least 200 m, at least 300 m, at least 400 m, at least 500 m, at least 800 m, at least 1 mm, at least 2 mm, or at least 3 mm. In some embodiments, the width of the distribution is no more than 5 mm, no more than 3 mm, no more than 2 mm, no more than 1 mm, no more than 500 m, no more than 200 m, or no more than 100 m. In some embodiments, the width of the distribution is from 25 m to 200 m, from 100 m to 500 m, from 100 m to 1 mm, from 500 m to 2 mm, from 1 mm to 3 mm, or from 2 mm to 5 mm. In some embodiments, the width of the distribution falls within another range starting no lower than 2 m and ending no higher than 10 mm.
[0151] Without being limited to any one theory of operation, in general, larger particles take longer to saturate with CO.sub.2 since the CO.sub.2 has further to travel to reach the interior, e.g., higher overall absorptive surface area, and therefore have slower adsorption/desorption kinetics than smaller particles. Advantageously, in some embodiments, larger particles last longer under attrition conditions, e.g., regular handling or movement, as they have a higher breakdown capacity before the particles are converted completely to fines (<0.5 mm) than smaller particles. Larger particles utilize higher coating materials in some manufacturing methods (e.g., spray on coating) to achieve complete coating as the larger particles have larger interiors that are further from the surfaces compared to smaller particles.
[0152] In some embodiments, the width of the distribution is alternatively described using D90, D50, or D10 values. These values signify a percentage of the total distribution of the material diameters in the sample is contained, up to and including the value. For example, a D90 of 500 m indicates 90% of the sample (e.g., the plurality of porous particles) within a sample has a size of 500 m or smaller. In some embodiments, the coated particle 100 has a D10 value of 30 m or a D90 value of 150 m. In some examples, the coated particle 100 has a D10 value of 100 m or a D90 value of 500 m, a D10 value of 150 m or a D90 value of 400 m, a D10 value of 200 m or a D90 value of 300 m.
[0153] In some embodiments, the plurality of porous substrate particles comprises a D90 for any of the sieve diameters disclosed herein, and/or any of the measures of central tendency or distributions thereof. For instance, in some embodiments, the plurality of porous substrate particles comprises a D90 of 2 mm, indicating that 90% of the porous substrate particles have a sieve diameter of 2 mm or smaller. In some embodiments, the plurality of porous substrate particles comprises a D50 for any of the diameters disclosed herein, and/or any of the measures of central tendency or distributions thereof. In some embodiments, the plurality of porous substrate particles comprises a D10 for any of the sieve diameters disclosed herein, and/or any of the measures of central tendency or distributions thereof.
[0154] In general and without wishing to be bound by theory, smaller particle 100 size advantageously facilitates better mechanical resistance to attrition, decreased friability, and enables higher CO.sub.2 capture capacity. In some embodiments, smaller porous substrate particle 102 results in higher inter-particle volumes that enables higher gas flow capacity and faster adsorption as gas diffusion paths are shorter in the coated particle 100 as a whole. Further, smaller porous substrate particle 102 size enables relatively higher total coated particle 100 surface area leading to higher amine coating concentrations. Smaller porous substrate particle 102 size, e.g., average sieve diameter, reduces the adsorption process energy cost for a fluidization process.
[0155] In some embodiments, the pore size of the porous substrate particle is a measure of central tendency determined over the pore size found in a plurality of porous substrate particles. For instance, in some embodiments, the pore size of the porous substrate particles is an average pore size over the pores found in a plurality of porous substrate particles used for generating the functionalized material. In some embodiments, the plurality of porous substrate particles comprises a distribution of pore sizes.
[0156] In some embodiments, the pore size for the porous substrate particle, or the plurality of porous substrate particles, is measured as a diameter of a pore, pore volume, and/or surface area for the porous substrate particle, including but not limited to a Brunauer, Emmett and Teller (BET) surface area. Generally, BET surface area refers to a technique for determining the surface area of particles. Samples are introduced to a probe gas that physically adsorbs to the surface of the sample. The volume of probe gas adsorbed is measured to determine the quantity of gas required to cover the surface of the sample. The BET theory is then applied to the adsorption data to generate a specific surface area, reported in units of area per mass of sample (m.sup.2/g). See, for example, BET Specific Surface Area, available on the Internet at particletechlabs.com/analytical-testing/bet-specific-surface-area.
[0157] In some embodiments, the pore size of the pores 104 is in a range from 60 angstroms () to 700 (e.g., 80 to 300 , 100 to 200 , 150 to 250 , 60 to 300 , 100 to 700 , 200 to 700 , 300 to 700 , 500 to 700 , 100 to 500 , or 300 to 500 ). In some implementation, the pores 104 have an average pore size or a mean pore size from about 60 Angstroms to 400 Angstroms. In some implementations, the diameter of the pores 104 is greater than 90 (e.g., greater than 100 , greater than 120 , greater than 150 ). Larger pore sizes of the pores 104 increases adsorption and desorption rates and facilitates higher filling of the pores 104 with amine moieties without pore-clogging which can reduce adsorption and desorption efficiency.
[0158] In some embodiments, the pore size, or the measure of central tendency (e.g., mean) thereof, for the pores in the plurality of porous substrate particles is at least 10 , at least 20 , at least 40 , at least 50 , at least 60 , at least 80 , at least 100 , at least 200 , at least 300 , at least 400 , at least 500 , at least 800 , at least 1000 , at least 1500 , at least 2000 , or at least 3000 . In some embodiments, the pore size, or the measure of central tendency (e.g., mean) thereof, for the pores in the plurality of porous substrate particles is no more than 5000 , no more than 3000 , no more than 2000 , no more than 1000 , no more than 800 , no more than 500 , no more than 200 , no more than 100 , no more than 60 , or no more than 20 . In some embodiments, the pore size, or the measure of central tendency (e.g., mean) thereof, for the pores in the plurality of porous substrate particles is from 10 to 200 , from 60 to 1000 , from 100 to 800 , from 200 to 2000 , or from 500 to 5000 . In some embodiments, the pore size, or the measure of central tendency (e.g., mean) thereof, for the pores in the plurality of porous substrate particles falls within another range starting no lower than 10 and ending no higher than 5000 .
[0159] In some embodiments, the pore size, or the measure of central tendency (e.g., mean) thereof, for the pores in the plurality of porous substrate particles is from 10 nanometers (nm) to 200 nm (100 to 2000 ), from 1 nm to 200 nm (10 to 2000 ), and/or from 30 nm to 80 nm (300 to 800 ).
[0160] In some embodiments, the pores 104 extend into the central volume of the porous substrate particle 102 and form interconnected channels. In some embodiments, the pores 104 create a volume within the porous substrate particle 102 in which gases may flow and create additional surface area for functionalization. In some embodiments, the volume of the pores 104 is greater than 0.5 mL/g, and preferentially greater than 0.8 mL/g (e.g., greater than 1 mL/g, greater than 1.2 mL/g, greater than 1.5 mL/g, or greater than 1.8 mL/g). In some embodiments, advantageously, increased total volume of the pores 104 increases the adsorption potential of the coated particle 100. In some embodiments, the pores 104 have an irregularly round cross-sectional shape, or a hexagonal cross-sectional shape, though this is not limiting.
[0161] In some embodiments, the pore volume, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is at least 0.1 mL/g, at least 0.2 mL/g, at least 0.5 mL/g, at least 0.1 mL/g, at least 1 mL/g, at least 1.2 mL/g, at least 1.5 mL/g, at least 2 mL/g, at least 2.5 mL/g, at least 3 mL/g, at least 3.5 mL/g, at least 4 mL/g, at least 4.5 mL/g, at least 5 mL/g, or at least 8 mL/g. In some embodiments, the pore volume, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is no more than 10 mL/g, no more than 5 mL/g, no more than 3 mL/g, no more than 2 mL/g, no more than 1.5 mL/g, no more than 1 mL/g, no more than 0.5 mL/g, no more than 0.3 mL/g, or no more than 0.2 mL/g. In some embodiments, the pore volume, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles is from 0.1 mL/g to 0.8 mL/g, from 0.5 mL/g to 1.5 mL/g, from 0.8 mL/g to 3 mL/g, from 1 mL/g to 4 mL/g, from 3 mL/g to 10 mL/g, from 0.5 mL/g to 5 mL/g, or from 0.1 mL/g to 10 mL/g. In some embodiments, the pore volume, or the measure of central tendency (e.g., mean) thereof, for the plurality of porous substrate particles falls within another range starting no lower than 0.1 mL/g and ending no higher than 10 mL/g.
[0162] In some embodiments, the surface area of the porous substrate particle is total surface area. In some embodiments, the total surface area of the porous substrate particle 102 includes the surface 103 and the surface area within the pores 104. In some embodiments, the total surface area is greater than 100 m.sup.2 per dry gram (m.sup.2/g) of porous substrate particle 102, and in some implementations, the total surface area is greater than 300 m.sup.2/g (e.g., greater than 200 m.sup.2/g, greater than 400 m.sup.2/g, greater than 500 m.sup.2/g, or greater than 700 m.sup.2/g). Advantageously, in some embodiments, higher total surface area increases the available area for functionalization, and increases the adsorption potential of the coated particle 100. In some embodiments, the surface area of a porous substrate particle is a BET surface area.
[0163] In some embodiments, the surface area of the porous substrate particle comprises at least 10 m.sup.2/g, at least 50 m.sup.2/g, at least 100 m.sup.2/g, at least 200 m.sup.2/g, at least 300 m.sup.2/g, at least 400 m.sup.2/g, at least 500 m.sup.2/g, at least 600 m.sup.2/g, at least 700 m.sup.2/g, at least 1000 m.sup.2/g, or at least 2000 m.sup.2/g. In some embodiments, the surface area of the porous substrate particle comprises no more than 5000 m.sup.2/g, no more than 2000 m.sup.2/g, no more than 1000 m.sup.2/g, no more than 500 m.sup.2/g, no more than 200 m.sup.2/g, no more than 100 m.sup.2/g, or no more than 50 m.sup.2-/g. In some embodiments, the surface area of the porous substrate particle comprises from 10 m.sup.2/g to 200 m.sup.2/g, from 50 m.sup.2/g to 500 m.sup.2/g, from 100 m.sup.2/g to 1000 m.sup.2/g, from 200 m.sup.2/g to 800 m.sup.2/g, from 500 m.sup.2/g to 2000 m.sup.2/g, or from 1000 m.sup.2/g to 5000 m.sup.2/g. In some embodiments, the surface area of the porous substrate particle falls within another range starting no lower than from 10 m.sup.2/g and ending no higher than from 5000 m.sup.2/g.
Surface Modifications.
[0164] In some embodiments, the surface 103 of the coated particle 100 is functionalized by a CO.sub.2 absorbing compound 106 including an aminosilane (silane-functionalized amine or an amino-functionalized silane) 108 and a polymeric amine 110. In some embodiments, together the aminosilane 108 and a polymeric amine 110 form a network and provide the stable CO.sub.2 absorbing function. In some embodiments, the aminosilane 108 includes at least one silane group (e.g., one, two, three, or more silane groups) and at least one amine group. In some embodiments, the aminosilane 108 is covalently bonded to the exterior surface of the porous substrate particle 102 and within the pores 104. In some embodiments, the aminosilane 108 includes one to three or more silane groups, e.g., silane group 208. In some implementations, the silane group is a methoxysilane, triethoxysilane, and the like), a dialkoxysilanol group (e.g., Si(OR).sub.2OH, in which each R is independently alkyl), a hydrosilane group (e.g., SiH.sub.3), a dialkylsilane (e.g., -SiR.sup.S1R.sup.S2R.sup.S3, in which each of R.sup.S1 and R.sup.S2 is independently alkyl, and R.sup.S3 is a reactive group or a leaving group, such as any described herein; and in which a non-limiting example of dialkylsilane is dialkylalkoxysilane or dialkylhalosilane), a monoalkylsilane group (e.g., -SiR.sup.S1R.sup.S2R.sup.S3, in which R.sup.S1 is alkyl, and each of R.sup.S2 and R.sup.S3 is independently a leaving group or a reactive group, such as any described herein; and in which a non-limiting example of monoalkysilane is alkyldialkoxysilane or alkyldihalosilane), a trihalosilane group (e.g., SiZ.sub.3, in which each Z is independently halo, such as trichlorosilane), or a silanetriol group (e.g., Si(OH).sub.3), as well as others described herein. Without being limited to any one theory of operation, higher numbers (e.g., three or more) of silane moieties in the aminosilane 108 increase the covalent bond stability with the porous substrate particle 102 as higher numbers of siloxane bonds between the silane moieties and the porous substrate particle 102 surfaces increase. In the case of more than three silane groups, this refers to a molecule such as, but not limited to, bis(3-trimethoxysilylpropyl)amine. Additionally, a silane moiety can form up to 3 siloxane bonds (SiOSi) to the porous substrate surface which increases stability. The number of siloxane bonds that can be formed by the silane moiety depends on the composition of the groups (X.sup.1-X.sup.3) capable of forming siloxane bonds (e.g., OMe, OEt, Cl, OH, or a combination of any of these).
[0165] In some embodiments, the aminosilane compound has any useful structure. In one non-limiting example, the aminosilane includes a structure having formula (I):
[R.sup.A].sub.aSi[X].sub.4-a(I),
where each R.sup.A is, independently, an amine moiety comprising at least one amine group, each X is, independently, a side group, a reactive group, or a leaving group, and a is an integer from 1 to 4.
[0166] In some embodiments, the amine moiety (e.g., R.sup.A) includes one or more amine groups. In one instance, the amine group is NR.sup.N1R.sup.N2 or NR.sup.N1, in which each of R.sup.N1 and R.sup.N2 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxyl (e.g., OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted alkoxy (e.g., OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., OSiR.sub.3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., OSi[OR].sub.3, in which each R is independently an optionally substituted alkyl). In some embodiments, each of R.sup.N1, R.sup.N2, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.
[0167] In some embodiments, the amine moiety (e.g., R.sup.A) includes one, two, three, or more amine groups. In other embodiments, the amine moiety includes a terminal amine group (e.g., as NR.sup.N1R.sup.N2) and/or an internal amine group (e.g. as NR.sup.N1).
[0168] Non-limiting examples of amine moieties (e.g., R.sup.A) include NR.sup.N1R.sup.N2, -L-NR.sup.N1R.sup.N2, NR.sup.N3-L-NR.sup.N1R.sup.N2, -L.sup.2-NR.sup.N3-L.sup.1-NR.sup.N1R.sup.N2, -L.sup.3-NR.sup.N4-L.sup.2-NR.sup.N3-L.sup.1-NR.sup.N1R.sup.N2, L.sup.2-SiR.sup.S1R.sup.S2-L.sup.1-NR.sup.N1R.sup.N2, and -L.sup.3-SiR.sup.S1R.sup.S2-L.sup.2-NR.sup.N3-L.sup.1-NR.sup.N1R.sup.N2 in which each of R.sup.N1, R.sup.N2, R.sup.S1, and R.sup.S2 are any described herein; in which each of R.sup.N3 and R.sup.N4 are any described herein for R.sup.N1 and R.sup.N2; and in which each L, L.sup.1, L.sup.2, or L.sup.3 is independently a linker. Non-limiting examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, each of R.sup.N1, R.sup.N2, R.sup.N3, R.sup.N4, R.sup.S1, and R.sup.S2 is, independently, H, optionally substituted aliphatic, or optionally substituted alkyl. Other examples of R.sup.N1, R.sup.N2, and R.sup.N3 are described herein.
[0169] In some embodiments, the aminosilane includes a reactive group, a leaving group, or another group (e.g., X). Non-limiting examples of such groups include H, halo (e.g., F, Cl, Br, or I), hydroxyl (e.g., OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted alkoxy (e.g., OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., OR, in which R is an optionally substituted aryl), or optionally substituted alkanoyloxy. In some embodiments, X is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.
[0170] In one non-limiting example, the aminosilane includes a structure having formula Ia:
R.sup.A1SiX.sup.1X.sup.2X.sub.3(Ia),
where R.sup.A1 is an amine moiety comprising at least one amine group; and each of X.sup.1, X.sup.2, and X.sup.3 is, independently, a side group, a reactive group, or a leaving group. Each of R.sup.A1, X.sup.1, X.sup.2, and X.sup.3 is any described herein for R.sup.A and X. An example of formula IA is shown in
[0171] In another non-limiting example, the aminosilane includes a structure having formula Ib, Ic, Id, or Ie:
R.sup.A1-L.sup.1-SiX.sup.1X.sup.2X.sup.3(Ib),
R.sup.N1R.sup.N2N-L.sup.1-SiX.sup.1X.sup.2X.sup.3(Ic),
R.sup.A1-L.sup.1-R.sup.A2-L.sup.2-SiX.sup.1X.sup.2X.sup.3(Id), or
R.sup.N1R.sup.N2N-L.sup.1-N(R.sup.N3)-L.sup.2-SiX.sup.1X.sup.2X.sup.3(Ie),
where Nis nitrogen, each R.sup.A1 or R.sup.A2 is, independently, an amine moiety comprising at least one amine group, each of R.sup.N1, R.sup.N2, and R.sup.N3 is any described herein, each of X.sup.1, X.sup.2, and X.sup.3 is, independently, a side group, a reactive group, or a leaving group, and each of L.sup.1 and L.sup.2 is a linker. In some embodiments, each of R.sup.A1, R.sup.A2, X.sup.1, X.sup.2, X.sup.3, L.sup.1, and L.sup.2 is any described herein for R.sup.A, X, and L, respectively. In some embodiments, each of X.sup.1, X.sup.2, and X.sup.3 is, independently, H, halo, optionally substituted alkyl (e.g., optionally substituted C.sub.1-3 alkyl), or optionally substituted alkoxy (e.g., optionally substituted C.sub.1-3 alkoxy). In other embodiments, each of X.sup.1, X.sup.2, and X.sup.3 is, independently, optionally substituted alkoxy (e.g., optionally substituted C.sub.1-3 alkoxy). In yet other embodiments, L is optionally substituted alkylene (e.g., optionally substituted C.sub.1-12, C.sub.1-10, C.sub.1-8, or C.sub.1-6 alkylene).
[0172] In yet another non-limiting example, the aminosilane includes a structure having formula If:
R.sup.A1R.sup.A2R.sup.A3SiX.sup.1(If),
where each R.sup.A1, R.sup.A2, or R.sup.A3 is, independently, an amine moiety comprising at least one amine group; and X.sup.1 is a side group, a reactive group, or a leaving group. In some embodiments, each of R.sup.A1, R.sup.A2, R.sup.A3, and X.sup.1 is any described herein for R.sup.A and X, respectively.
[0173] In some embodiments, the aminosilane includes a structure of formula II:
[R.sup.B].sub.bN[Y].sub.3-b(II),
where N is nitrogen, each R.sup.B is, independently, a silane moiety comprising at least one silane group, each Y is, independently, H, optionally substituted alkyl, or optionally substituted aryl; and b is an integer from 1 to 3. In some embodiments, each Y is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.
[0174] In some embodiments, the silane moiety (e.g., R.sup.B) includes one or more silane groups. In one instance, the silane group is SiR.sup.S1R.sup.S2R.sup.S3 or SiR.sup.S1R.sup.S2, in which each of R.sup.S1, R.sup.S2, and R.sup.S3 is, independently, hydrogen (H), halo (e.g., F, Cl, Br, or I), hydroxyl (e.g., OH), optionally substituted alkyl, optionally substituted aminoalkyl, optionally substituted alkoxy (e.g., OR, in which R is an optionally substituted alkyl), optionally substituted aryl, optionally substituted aryloxy (e.g., OR, in which R is an optionally substituted aryl), trialkylsilyloxy (e.g., OSiR.sub.3, in which each R is independently an optionally substituted alkyl), or trialkoxylsilyloxy (e.g., OSi[OR].sub.3, in which each R is independently an optionally substituted alkyl). In some embodiments, each of R.sup.S1, R.sup.S2, R.sup.S3, and R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic.
[0175] In some embodiments, the silane moiety (e.g., R.sup.B) includes one, two, three, or more silane groups. In some embodiments, the silane moiety includes a terminal silane group (e.g., as SiR.sup.S1R.sup.S2R.sup.S3) and an internal silane group (e.g. as SiR.sup.S1R.sup.S2).
[0176] Non-limiting examples of silane moieties (e.g., R.sup.B) include SiR.sup.S1R.sup.S2R.sup.S3, Si(OR.sup.S1)(R.sup.S2)(R.sup.S3), Si(OR.sup.S1)(OR.sup.S2)(R.sup.S3), Si(OR.sup.S1)(OR.sup.S2)(OR.sup.S3), -L-SiR.sup.S1R.sup.S2R.sup.S3, -L-Si(OR.sup.S1)(R.sup.S2)(R.sup.S3), -L-Si(OR.sup.S1)(OR.sup.S2)(R.sup.S3), -L-Si(OR.sup.S1)(OR.sup.S2) (OR.sup.S3), SiR.sup.S4R.sup.S5-LSiR.sup.S1R.sup.S2R.sup.S3, and SiR.sup.S1R.sup.S2NR.sup.N1R.sup.N2, in which each of R.sup.S1, R.sup.S2, R.sup.S3, R.sup.N1, and R.sup.N2 is any described herein, in which each of R.sup.S4 and R.sup.S5 can be any described herein for R.sup.S1, R.sup.S2, and R.sup.S3, and in which L is a linker. Examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene. In some non-limiting embodiments, each of R.sup.S1, R.sup.S2, R.sup.S3, R.sup.S4, R.sup.S5, R.sup.N1, and R.sup.N2 is, independently, H, optionally substituted aliphatic, or optionally substituted alkyl.
[0177] In one non-limiting example, the aminosilane includes a structure having formula IIa:
R.sup.B1NY.sup.1Y.sup.2(IIa),
where Nis nitrogen, R.sup.B1 is a silane moiety comprising at least one silane group; and each of Y.sup.1 and Y.sup.2 is any described herein for Y, and R.sup.B1 is any described herein for R.sup.B.
[0178] In another non-limiting example, the aminosilane includes a structure having formula IIb, IIc, or IId:
R.sup.B1R.sup.B2NY.sup.1(IIb),
[R.sup.S1R.sup.S2R.sup.S3Si-L.sup.1-]NY.sup.1Y.sup.2(IIc), or
[R.sup.S1R.sup.S2R.sup.S3Si-L.sup.1-]NY.sup.1[-L.sup.2-SiR.sup.S1R.sup.S2R.sup.S3](IId),
where N is nitrogen, each R.sup.B1 or R.sup.B2 is, independently, a silane moiety comprising at least one silane group, each of Y.sup.1 and Y.sup.2 is, independently, a side group, a reactive group, or a leaving group, each of R.sup.S1, R.sup.S2, and R.sup.S3 is any described herein; and each of L.sup.1 and L.sup.2 is a linker. Each of R.sup.B1, R.sup.B2, Y.sup.1, Y.sup.2, L.sup.1, and L.sup.2 is any described herein for R.sup.B, Y, and L, respectively.
[0179]
[0180] In some embodiments, an aminosilane 206 used as aminosilane 108 has any combination of these functional groups, e.g., amine group 210 and silane groups 208 (e.g., X.sup.1-X.sup.3), and has at least one amine group 210 and at least one group silane group 208 (e.g., OMe, OEt, Cl, OH, or others described herein) capable of forming a siloxane bond (e.g., an SiO or SiOSi linkage).
[0181] As non-limiting examples,
[0182] In some embodiments, the aminosilane 108 has the structure of formula IIIa:
##STR00003##
[0183] In formula IIIa, Q is (CP.sub.2).sub.n where n is 2, 3, 4, or 5, and each P is independently a hydrogen, hydroxy, or halogen. In one embodiment, each P is halogen and n is 3:CH.sub.2CH.sub.2CH.sub.2 (e.g., compounds 1402, 1404, 1406, 1408, 1410, 1412, 1414, 1422, 1424, and 1426 of
[0184] In formula IIIa, each R.sub.1, R.sub.2, and R.sub.3 is independently hydrogen, alkyl, a substituted alkyl, an alkylene, or a substituted alkylene. In some embodiments, each R.sub.1, R.sub.2, and R.sub.3 is CH.sub.3, CH.sub.2CH.sub.3, or CH.sub.2CH.sub.2CH.sub.3. In one embodiment, each R.sub.1, R.sub.2, and R.sub.3 is hydrogen (e.g., compounds 1408, 1412 and 1414 of
[0185] In formula IIIa, each R.sub.4 and R.sub.5 is independently hydrogen, a substituted alkane, a substituted alkylene, an aryl, or a substituted aryl.
[0186] In some embodiments R.sub.4 and R.sub.5 are each methyl (e.g., compound 1428 of
[0187] In one embodiment one of R.sub.4 and R.sub.5 is (CH.sub.2).sub.mNH(R.sub.5), where m is 1, 2, 3, 4 or 5, and R.sub.5 is hydrogen or a substituted alkane, while the other of R.sub.4 and R.sub.5 is hydrogen.
[0188] In one embodiment R.sub.4 is (CH.sub.2).sub.mNH(R.sub.6), where m is 1, 2, 3, 4 or 5, and R.sub.6 is hydrogen or a substituted alkane, and R.sub.4 is hydrogen. In some such embodiments, m is 2 and R.sub.6 is hydrogen:CH.sub.2CH.sub.2NH.sub.2 (e.g., compounds 1406 and 1408 of
[0189] In some embodiments, the aminosilane 108 has the structure of formula IIIb:
##STR00004##
[0190] In formula IIIb, Q is (CP.sub.2).sub.n where n is 2, 3, 4, or 5, and each P is independently a hydrogen, hydroxy, or halogen. In one embodiment, each P is halogen and n is 3:CH.sub.2CH.sub.2CH.sub.2 (e.g., compounds 1402, 1404, 1406, 1408, 1410, 1412, 1414, 1420, 1422, 1424, and 1426 of
[0191] In formula IIIb, each R.sub.1, R.sub.2, and R.sub.3 is independently hydrogen, alkyl, a substituted alkyl, an alkylene, a substituted alkylene, an alkoxy, or a substituted alkoxy. In some embodiments, R.sub.1 and R.sub.2 are each OCH.sub.2CH.sub.3, and R.sub.3 is CH3 (e.g., compound 1420 of
[0192] In formula IIIa, each R.sub.4 and R.sub.5 is independently hydrogen, a substituted alkane, a substituted alkylene, an aryl, or a substituted aryl.
[0193] In some embodiments R.sub.4 and R.sub.5 are each methyl (e.g., compound 1428 of
[0194] In some embodiments R.sub.4 and R.sub.5 are each hydrogen (e.g., compound 1420 of
[0195] In some embodiments, one of R.sub.4 and R.sub.5 is (CH.sub.2).sub.mNH(R.sub.5), where m is 1, 2, 3, 4 or 5, and R.sub.5 is hydrogen or a substituted alkane, while the other of R.sub.4 and R.sub.5 is hydrogen.
[0196] In some embodiments, R.sub.4 is (CH.sub.2).sub.mNH(R.sub.6), where m is 1, 2, 3, 4 or 5, and R.sub.6 is hydrogen or a substituted alkane, and R.sub.5 is hydrogen. In some such embodiments, m is 2 and R.sub.6 is hydrogen:CH.sub.2CH.sub.2NH.sub.2 (e.g., compounds 1406 and 1408 of
[0197] In some embodiments, the aminosilane 108 has the structure of formula IV:
##STR00005##
[0198] In formula IV, each R.sub.1, R.sub.2, R.sup.3, R.sub.4, R.sub.5, and R.sub.6 is independently hydrogen, alkyl, a substituted alkyl, an alkylene, or a substituted alkylene. In one embodiment, each R.sup.1, R.sup.2, R.sup.3, R.sub.4, R.sub.5, and R.sub.6 is CH.sub.3 (e.g., compound 1418 of
[0199] In some embodiments, the amine moieties of the aminosilane 108 interact with one or more of the X.sup.1-X.sup.3 sites of neighboring aminosilanes 108 or interact with polymeric amines 110. In some embodiments, the amine moiety is or includes an amine group such as the amine groups of
[0200] Optionally, in some embodiments, a further linker is present between the amine moiety and the silane moiety of the aminosilane compound.
[0201] In some implementations, the aminosilanes (silane-functionalized amines or amino-functionalized silanes) 108 include (3-aminopropyl) trimethoxysilane (compound 1402 in
[0202] In some embodiments, the amine moieties of the aminosilane 108 and polymeric amine compound interact with silanol groups (or other groups) of the aminosilane 108 through hydrogen bonding and ionic interactions to form a network over the porous substrate surface. In some examples, the polymeric amine 110 is a polymeric/oligomeric amine such as polyethylenimine (PEI), poly(propylenimine) (PPI), or other large molecule amine mixture (e.g., Amix 1000, as produced by BASF, Ludwigshafen, DE). In some embodiments, the polymeric amine 110 is a small molecule containing amine moieties, such as tetraethylenepentamine (TEPA), triethylenetetramine (TETA), ethanolamine, diethylenetriamine, piperazine, pentaethylenehexamine, or tetramethylethylenediamine.
[0203] In some embodiments, the polymeric amine has any useful structure. In one non-limiting example, the polymeric amine includes a structure having formula V:
(R.sup.A-L).sub.n-(V).
where each R.sup.A is, independently, an amine moiety comprising at least one amine group; each L is, independently, a linker; and n is an integer greater than 1 (e.g., from 1-1000, 1-100, 1-50, 1-20, 1-10, 5-1000, 5-100, 5-50, 5-20, 5-10, as well as ranges therebetween). In some embodiments, R.sup.A and L are any described herein. In some embodiments, R.sup.A is or includes-NH, NR.sup.N1, N(-L-NR.sup.N1R.sup.N2), N(-L.sup.2-NR.sup.N3-L.sup.1-NR.sup.N1R.sup.N2), N[-L.sup.2-N(-L.sup.1NR.sup.N1R.sup.N2).sub.2], NH.sub.2, or NR.sup.N1R.sup.N2, in which each of R.sup.N1 and R.sup.N2 is any described herein; in some embodiments, each of R.sup.N3 is any described herein for R.sup.N1 and R.sup.N2; and in which each L, L.sup.1, or L.sup.2 is independently a linker. Examples of linkers include, e.g., a covalent bond, an atom (e.g., carbonyl, oxy, thio, imino, and the like), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, or optionally substituted heteroarylene.
[0204]
[0205]
Adsorption and Desorption.
[0206] In some embodiments, when exposed to a gaseous mixture including CO.sub.2, the amine compound reacts with the CO.sub.2 to bond the CO.sub.2 to the functional groups. This thereby functionally adsorbs the CO.sub.2 to the porous substrate particle 102 through the compound 106 bonded to the porous substrate particle 102 surface. Without wishing to be bound by theory, the total surface area, volume of the pores 104, and number of amine groups within the amine compound and silane compound determine the adsorption capacity of the coated particle 100. In some embodiments, the adsorption capacity (e.g., uptake) of the functionalized material is in a range from 0.1 to 2.5 mol CO.sub.2/kg of functionalized material (e.g., from 0.1 to 2 mol CO.sub.2/kg, 0.1 to 1.8 mol CO.sub.2/kg, 0.1 to 1.5 mol CO.sub.2/kg, 0.1 to 1.2 mol CO.sub.2/kg, 0.1 to 1.0 mol CO.sub.2/kg, 0.1 to 0.5 mol CO.sub.2/kg, 0.2 to 2 mol CO.sub.2/kg, 0.2 to 1.0 mol CO.sub.2/kg, 0.2 to 0.8 mol CO.sub.2/kg, 0.5 to 2.5 mol CO.sub.2/kg, 0.5 to 2.2 mol CO.sub.2/kg, 0.5 to 2 mol CO.sub.2/kg, 0.5 to 1.8 mol CO.sub.2/kg, 0.5 to 1.5 mol CO.sub.2/kg, 0.5 to 0.8 mol CO.sub.2/kg, 0.8 to 2.5 mol CO.sub.2/kg, 0.8 to 2.2 mol CO.sub.2/kg, 0.8 to 2 mol CO.sub.2/kg, 0.8 to 1.8 mol CO.sub.2/kg, 0.8 to 1.5 mol CO.sub.2/kg, 1 to 2 mol CO.sub.2/kg, 1 to 1.4 mol CO.sub.2/kg, 1 to 1.5 mol CO.sub.2/kg, 1.2 to 2.0 mol CO.sub.2/kg, 1.2 to 1.8 mol CO.sub.2/kg, 1.5 to 2.5 mol CO.sub.2/kg, 1.5 to 2 mol CO.sub.2/kg, or 2 to 2.5 mol CO.sub.2/kg). In some embodiments, the range is greater than 0.5, 1, 1.5, 2, or 2.5 mol CO.sub.2/kg. In some implementations, the functionalized material achieves CO.sub.2 adsorption capacity up to 1 mol CO.sub.2/kg or up to 2 mol CO.sub.2/kg at 420 ppm CO.sub.2 in ambient air conditions.
[0207] In some embodiments, the functionalized material adsorbs CO.sub.2 per dry kilogram in a range from 0.5 mol to 2.5 mol. In some embodiments, the functionalized material adsorbs at least 0.1, at least 0.2, at least 0.5, at least 0.8, at least 1, at least 1.5, at least 2, at least 2.5, or at least 3 mol CO.sub.2/kg. In some embodiments, the functionalized material adsorbs no more than 5, no more than 3, no more than 2.5, no more than 2, no more than 1.5, no more than 1, no more than 0.5, or no more than 0.2 mol CO.sub.2/kg. In some embodiments, the functionalized material adsorption falls within another range starting no lower than 0.1 mol CO.sub.2/kg and ending no higher than 5 mol CO.sub.2/kg.
[0208] In environmental conditions, the atmosphere includes a concentration of water vapor (e.g., humidity). The coated particle 100 captures CO.sub.2 from atmospheric conditions in a range of relative humidity levels. For example, the coated particle 100 captures CO.sub.2 from atmospheric conditions in a range from 0% to 100% relative humidity (RH), such as for example 5% to 95% RH (e.g., 15% to 50% RH, 25% to 40% RH, or 10% to 60% RH, 5% to 90% RH, 10% to 90% RH, or 20% to 80% RH). In some implementations, the coated particle 100 captures CO.sub.2 from atmospheric conditions having greater than 60% RH, greater than 75% RH, greater than 90% RH, or greater than 95% RH.
[0209] In some embodiments, the present disclosure provides a composition (e.g., a functionalized material) comprising porous substrate particles modified according to any of the methods and/or embodiments disclosed herein. In some embodiments, the functionalized material is reactive to carbon dioxide. In some embodiments, the functionalized material comprises a polymeric amine that is reactive to carbon dioxide.
[0210] In some embodiments, the functionalized material desorbs in a temperature range between about 65 C. to 90 C. In some embodiments, the functionalized material desorbs at a temperature of at least 40, at least 50, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, or at least 95 C. In some embodiments, the functionalized material desorbs at a temperature of no more than 100, no more than 90, no more than 80, no more than 70, no more than 60, or no more than 50 C. In some embodiments, the functionalized material desorbs at a temperature from 40 C. and 80 C., from 60 C. to 90 C., from 65 C. to 95 C., or from 80 C. to 100 C. In some embodiments, the functionalized material desorbs at a temperature that falls within another range starting no lower than 40 C. and ending no higher than 100 C.
[0211] In some embodiments, the functionalized material has an abrasion resistance determined using an attrition and/or abrasion test. Non-limiting examples of attrition and/or abrasion tests include the American Society for Testing and Materials (ASTM) D4058-96 test and the L.A. abrasion test. In some embodiments, the functionalized material has an abrasion resistance of less than 1% weight per weight (w/w) loss according to an ASTM D4058-96 test.
[0212] In some embodiments, the functionalized material has an abrasion resistance of at least 0.01%, at least 0.05%, at least 0.1%, or at least 0.5% w/w loss. In some embodiments, the functionalized material has an abrasion resistance of no more than 10%, no more than 5%, no more than 3%, no more than 2%, no more than 1%, no more than 0.5%, or no more than 0.1% w/w loss. In some embodiments, the functionalized material has an abrasion resistance of from 0.01% to 0.1%, from 0.01% to 1%, from 0.1% to 1%, from 0.5% to 2%, or from 1% to 10% w/w loss. In some embodiments, the functionalized material has an abrasion resistance that falls within another range starting no lower than 0.01% w/w loss and ending no higher than 10% w/w loss.
[0213] In some embodiments, the functionalized material has a crush strength of at least 1.5 (megapascal) MPa. In some embodiments, the functionalized material has a crush strength of at least 0.1, at least 0.5, at least 1, at least 1.5, at least 2, at least 2.5, at least 3, or at least 5 MPa. In some embodiments, the functionalized material has a crush strength of no more than 10, no more than 5, no more than 3, no more than 2, no more than 1.5, or no more than 1 MPa. In some embodiments, the functionalized material has a crush strength of from 0.1 to 1 MPa, from 0.5 to 2 MPa, from 1 to 4 MPa, from 1.5 to 5 MPa, or from 4 to 10 MPa. In some embodiments, the functionalized material has a crush strength falling within another range starting no lower than 0.1 MPa and ending no higher than 10 MPa.
Additional Additives.
[0214] In some implementations, the coated particle 100 includes antioxidant additives which prevent the degradation of the amine polymeric amines 110 by atmospheric oxygen and extends the cycling lifetime of the coated particle 100. For example, in some embodiments, the antioxidant additives are organic sulfur-containing compounds, such as 2,2-thiodiethanol, 2-hydroxyethyl disulfide, and 3,3-dithiodipropionic acid. In another example, the antioxidant additives are hindered amine light stabilizers (HALS). In some embodiments, the amount of antioxidant additives in the coated particle 100 is 5% wt/wt to porous substrate (e.g., 3% wt/wt, 4% wt/wt, 6% wt/wt, or 8% wt/wt). The term wt/wt is in reference to a ratio of the weight of a first component to a second component. For example, 1 g of a first substance and 10 g of a second substance defines a 10% wt/wt ratio of the first substance to the second substance.
[0215] In some embodiments, the amount of antioxidant additives is at least 1% wt/wt, at least 2% wt/wt, at least 3% wt/wt, at least 4% wt/wt, at least 5% wt/wt, at least 6% wt/wt, at least 7% wt/wt, at least 8% wt/wt, at least 9% wt/wt, at least 10% wt/wt, or at least 15% wt/wt. In some embodiments, the amount of antioxidant additives is no more than 20% wt/wt, no more than 15% wt/wt, no more than 10% wt/wt, no more than 8% wt/wt, no more than 5% wt/wt, or no more than 3% wt/wt. In some embodiments, the amount of antioxidant additives is from 1% to 5% wt/wt, from 2% to 10% wt/wt, from 3% to 15% wt/wt, or from 5% to 20% wt/wt. In some embodiments, the amount of antioxidant additives falls within another range starting no lower than 1% wt/wt and ending no higher than 20% wt/wt.
[0216] In some embodiments, the antioxidant additives are added during steps 304, 306, or 308 of the following synthesis procedure or afterward through dissolving in methanol and then soaking the porous substrate in the additive/methanol mixture for 1 hr.
[0217] In some implementations, the functionalized particles 100 include, or are functionalized with, other hydrophobic compounds including hydrophobic silanes or hydrophobic polymer coatings. In some embodiments, for the hydrophobic silane, it is a silane molecule with one or two or three alkyl chains. Alkyl chains on the silane molecule can increase the hydrophobicity of the silane molecule. When the silane molecule bonds to the porous substrate, the hydrophobicity of the coated particle 100 increases. Thus, the water adsorption capacity of the coated particle 100 could be reduced, which can be beneficial for some cases such as when using the sorbent in high humidity conditions. For the same purpose of increasing the hydrophobicity of the coated particle 100, in some embodiments, additional hydrophobic polymer coatings are used. In some embodiments, polydimethylsiloxane (PDMS), silicone oil, polyethylene, polytetrafluorethylene, and polyurethanes are possible hydrophobic polymers used to coat the outer surface of the coated particle 100 to reduce water adsorption for high humidity applications.
[0218] In some embodiments, the plurality of functionalized coated particles comprises 15% wt/wt polyvinylalcohol, 1% wt/wt etidronic acid (ETDA), 10% wt/wt polyethyleneimine (PEI), 45% wt/wt aminopropyltrimethoxysilane (DAMO), 1% hindered amine light stabilizer, and 1% wt/wt terephthalaldehyde (TALD).
[0219] In some embodiments, the plurality of functionalized coated particles comprises between 5% wt/wt and 25% wt/wt polyvinylalcohol, between 0.3% wt/wt and 2% wt/wt etidronic acid (ETDA), between 3% wt/wt and 20% wt/wt polyethyleneimine (PEI), between 25% wt/wt and 60% wt/wt aminopropyltrimethoxysilane (DAMO), between 0.5% wt/wt and 2% hindered amine light stabilizer, and between 0.5% wt/wt and 2% wt/wt terephthalaldehyde (TALD).
[0220] In some embodiments, the plurality of functionalized coated particles comprises: between 1% wt/wt and 15% wt/wt polyvinylpyrrolidone (PVP), between 0.3% wt/wt and 2% wt/wt etidronic acid (ETDA), between 3% wt/wt and 20% wt/wt polyethyleneimine (PEI), between 25% wt/wt and 60% wt/wt aminopropyltrimethoxysilane (DAMO), between 0.5% wt/wt and 2% hindered amine light stabilizer, and between 0.5% wt/wt and 2% wt/wt terephthalaldehyde (TALD).
[0221] In some embodiments, the plurality of functionalized coated particles comprises: between 1% wt/wt and 15% wt/wt cellulose acetate (CA), between 0.3% wt/wt and 2% wt/wt etidronic acid (ETDA), between 3% wt/wt and 20% wt/wt polyethyleneimine (PEI), between 25% wt/wt and 60% wt/wt aminopropyltrimethoxysilane (DAMO), between 0.5% wt/wt and 2% hindered amine light stabilizer, and between 0.5% wt/wt and 2% wt/wt terephthalaldehyde (TALD).
[0222] In some embodiments, the plurality of functionalized coated particles comprises: between 1% wt/wt and 20% wt/wt polysulfone coating, between 0.3% wt/wt and 2% wt/wt etidronic acid (ETDA), between 3% wt/wt and 20% wt/wt polyethyleneimine (PEI), between 25% wt/wt and 60% wt/wt aminopropyltrimethoxysilane (DAMO), between 0.5% wt/wt and 2% hindered amine light stabilizer, and between 0.5% wt/wt and 2% wt/wt terephthalaldehyde (TALD).
[0223] In some embodiments, the plurality of functionalized coated particles comprises: between 3% wt/wt and 20% wt/wt polyethyleneimine (PEI), between 25% wt/wt and 60% wt/wt aminopropyltrimethoxysilane (DAMO), between 0.5% wt/wt and 2% hindered amine light stabilizer, and between 0.5% wt/wt and 2% wt/wt terephthalaldehyde (TALD).
[0224] In some embodiments, the hindered amine light stabilizer is Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][imino(2,2,6,6-tetramethyl-4-piperidinyl)]-1,6-hexanediylimino(2,2,6,6-tetramethyl-4-piperidinyl)]] (Chimassorb 944 FDL).
Example Embodiments for Processes
[0225] In some embodiments, the synthesis of the coated particle 100 is done under industrially applicable reaction conditions, such as liquid application to particles undergoing tumbling or mixing motion. After synthesis, the adsorbent is purified, dried, and activated before using it as a CO.sub.2 adsorbent, such as coated particle 100.
[0226] Referring to
[0227] In some embodiments, the process produces at least 10, at least 20, at least 50, at least 100, at least 500, at least 1000, at least 2000, at least 5000, at least 10,000, or at least 100,000 kg of coated particle. In some embodiments, the process produces no more than 500,000, no more than 100,000, no more than 10,000, no more than 5000, no more than 1000, no more than 500, no more than 100, or no more than 50 kg of coated particle. In some embodiments, the process produces from 10 to 500, from 100 to 1000, from 500 to 2000, from 1000 to 10,000, from 5000 to 50,000, or from 50,000 to 500,000 kg of coated particle. In some embodiments, the process produces another range of coated particle starting no lower than 10 kg and ending no higher than 500,000 kg of coated particle.
[0228] In some embodiments, the process 300 includes introducing porous substrate particles and a first reagent including a polymer to a solvent to provide a plurality of coated porous substrate particles (step 302). In some embodiments, the porous substrate particles are provided by porous substrate particle 102 of
[0229] In some embodiments, the porous substrate particles comprise any of the substrate particles disclosed above (see, for example, the section entitled Substrate particles, above). In some embodiments, the first reagent comprises any of the polymers and/or polymer coatings disclosed above (see, for example, the section entitled Surface modifications, above).
[0230] Optionally, referring to
[0231] Referring to Block 306, in some embodiments, the process 300 includes introducing a first reagent comprising a polymer into a volume of a first solvent to create a coating mixture. Referring to Block 308, in some embodiments, the process 300 further includes agitating the coating mixture for a first duration. Referring to Block 310, the process 300 further includes introducing at least a portion of a plurality of porous substrate particles into the coating mixture to create a coating suspension.
[0232] Referring to Block 302, in some embodiments, the solvent depends on the polymer to be suspended. Using the example polymer provided herein, PVA is water-soluble and therefore an example of the solvent is water. Other solvents can be selected based on the criteria of the polymer which creates the protective coating.
[0233] In some embodiments, the process 300 is a wet method, such as dip-coating, in which the volume of solvent is much larger than the volume of liquid the porous substrate particles are capable of absorbing. In some embodiments, the porous substrate particles are introduced to the solvent such that the particles are fully submerged in the solvent and at a wt/wt ratio in a range from 1.5 to 4:1 solvent to porous substrate particles. In some embodiments, the solvent to particle ratio is at least 0.5:1, at least 1:1, at least 1.5:1, at least 2:1, at least 2.5:1, at least 3:1, at least 3.5:1, or at least 4:1 wt/wt. In some embodiments, the solvent to particle ratio is no more than 5:1, no more than 4:1, no more than 3:1, no more than 2:1, or no more than 1:1 wt/wt. In some embodiments, the solvent to particle ratio falls within another range starting no lower than 0.5:1 wt/wt and ending no higher than 5:1 wt/wt.
[0234] In some embodiments of the batch method, the polymer is introduced to the solvent at a ratio sufficient that the polymer is fully dissolved in the solvent, e.g., no precipitation occurs, no precipitant is present. In some embodiments, the quantity of polymer introduced to the solvent is sufficient to coat the quantity of porous substrate particles to be coated in the process 300 to achieve the desired characteristics described herein. In the example of PVA, the polymer is introduced in a wt/wt ratio range of up to 20% of the polymer to the porous substrate particles (e.g., up to 18%, up to 12%, less than 18%, or less than 16%). In some embodiments, the polymer to particle ratio is at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, or at least 25% wt/wt. In some embodiments, the polymer to particle ratio is no more than 30%, no more than 20%, no more than 15%, no more than 10%, or no more than 5% wt/wt. In some embodiments, the polymer to particle ratio is from 1% to 10%, from 5% to 15%, from 10% to 20%, or from 15% to 30% wt/wt. In some embodiments, the polymer to particle ratio falls within another range starting no lower than 1% wt/wt and ending no higher than 30% wt/wt.
[0235] Referring Block 312, in some embodiments, the process 300 further includes agitating the coating suspension for a second duration to create a plurality of coated silica particles.
[0236] In another example, the process 300 is a spray method in which the volume of solvent is similar to the volume of liquid the porous substrate particles are capable of absorbing. In such an example, the solvent is introduced to the particles such that the particles are wetted by the solvent and at a wt/wt ratio in a range from 0.2 to 1.5:1 solvent to porous substrate particles. Higher concentrations of polymer (e.g., wt/wt %) should mean improved mechanical properties (e.g., stronger particles). Higher concentrations of polymer results in reduced CO.sub.2 uptake from the increase in nonfunctional mass of the particles because the kinetics of CO.sub.2 adsorption are decreased since the gas must diffuse through the polymer coating, or both.
[0237] In some embodiments, the solvent to particle ratio is at least 0.1:1, at least 0.2:1, at least 0.3:1, at least 0.4:1, at least 0.5:1, at least 0.7:1, at least 1:1, or at least 1.5:1 wt/wt. In some embodiments, the solvent to particle ratio is no more than 2:1, no more than 1.5:1, no more than 1:1, no more than 0.5:1, or no more than 0.2:1 wt/wt. In some embodiments, the solvent to particle ratio falls within another range starting no lower than 0.1:1 wt/wt and ending no higher than 2:1 wt/wt.
[0238] Referring to Block 314, in some embodiments, process 300 further includes recovering at least a portion of the plurality of coated silica particles by filtration or evaporation. Referring to Block 316, in some embodiments, process 300 further includes drying at least a portion of the plurality of coated silica particles until a hydration threshold is reached.
[0239] Referring to Block 304, in some embodiments, the process 300 includes introducing a second reagent comprising a polymeric amine and a third reagent comprising a silane moiety and an amine moiety to the coated porous substrate particles, thereby providing a plurality of functionalized, coated particles. Introducing the second and third reagents functionalizes the surfaces and pores of the coated particles with a silane moiety and an amine moiety, such as silane moiety 108 or amine polymeric amines 110 and generates the plurality of functionalized, coated particles for absorbing CO.sub.2.
[0240] In some embodiments, the second reagent comprises any of the surface modifications, silane moieties, and/or amine moieties disclosed elsewhere herein (see, for example, the section entitled Surface modifications, above).
[0241] In one example, functionalizing the particles includes exposing the particles to a functionalization mixture. In some embodiments, creating the functionalization mixture includes introducing a first reagent including a polymeric amine and a second reagent comprising a silane moiety and an amine functional group into a volume of a second solvent to form a functionalization mixture. In some embodiments, the second solvent is organic solvent. In some embodiments, the second solvent is selected such that the polymer used to coat the particles is not miscible in the second solvent which prevents removing the protective polymer coating from the coated particles while introducing the polymer amine and aminosilane. In some embodiments, a reagent and a compound is used interchangeably. Depending on use, in some embodiments, a reagent optionally includes one or more solvents, salts, or other compounds. In one example, the first solvent is water and the second solvent is hexane.
[0242] For instance, referring to
[0243] The first reagent, the second reagent, and the volume of second solvent are dispensed and mixed. The first reagent is a polymeric amine material, such as the polymeric amine compounds described herein. The second solvent should be dispensed to fully suspend the polymeric amine, for example, by dispensing 20 mL/g second solvent to polymeric amine material (e.g., 10 mL/g, 15 mL/g, or 25 mL/g). The polymeric amine material is added to the second solvent in a range between 5% wt/wt to 20% wt/wt of the porous substrate sorbent to be functionalized in step 304 (e.g., 6% wt/wt, 8% wt/wt, 10% wt/wt, 12% wt/wt, 14% wt/wt, 16% wt/wt, or 18% wt/wt).
[0244] In some embodiments, the polymeric amine material to porous substrate sorbent is at least 1%, at least 5%, at least 10%, at least 15%, at least 20%, or at least 25% wt/wt. In some embodiments, the polymeric amine material to porous substrate sorbent is no more than 30%, no more than 20%, no more than 15%, no more than 10%, or no more than 5% wt/wt. In some embodiments, the polymeric amine material to porous substrate sorbent is from 1% to 10%, from 5% to 15%, from 10% to 20%, or from 15% to 30% wt/wt. In some embodiments, the polymeric amine material to porous substrate sorbent falls within another range of ratios starting no lower than 1% wt/wt and ending no higher than 30% wt/wt.
[0245] The second reagent is the silane coupling material which includes the examples of aminosilanes 108 described above. The silane coupling material should be dispensed in a range between 20% wt/wt to 80% wt/wt of porous substrate sorbent to be functionalized in step 304 (e.g., 25% wt/wt, 30% wt/wt, 35% wt/wt, 45% wt/wt, 50% wt/wt, or 60% wt/wt).
[0246] In some embodiments, the proportion of silane coupling material to porous substrate sorbent is at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 70% wt/wt. In some embodiments, the proportion of silane coupling material to porous substrate sorbent is no more than 80%, no more than 70%, no more than 60%, no more than 50%, no more than 30%, no more than 20%, or no more than 15% wt/wt. In some embodiments, the proportion of silane coupling material to porous substrate sorbent is from 10% to 40%, from 15% to 55%, from 30% to 70%, or from 50% to 80% wt/wt. In some embodiments, the proportion of silane coupling material to porous substrate sorbent falls within another range of ratios starting no lower than 10% wt/wt and ending no higher than 80% wt/wt.
[0247] In some embodiments, the liquid mixture is stirred until the polymeric amine material and the silane coupling material are fully suspended in the second solvent. In some examples, mechanical stirring with a propeller, a magnetic stirrer, or sonication disperses the polymeric amine material in time in a range from 5 min to 60 min (e.g., from 10 min to 30 min, from 5 min to 30 min, from 10 min to 45 min).
[0248] In some implementations, additives are included in the functionalization mixtures to extend the operational lifetime of the particles 100. For example, the addition of Bis[3-(trimethoxysilyl) propyl]amine) (BTMSPA) to the functionalization mixture can increase the operational lifetime of the particles 100. BTMSPA is an aminosilane having two ends, in which each end has a trimethoxysilyl reactive group. The BTMSPA bonds on the porous substrate substrates with six binding points, as contrasted with the three binding points for an aminosilane with a single reactive group, such as would be present in a compound having a methoxydialkylsilyl reactive group. The increased number of binding points increases binding stability with the porous substrate. In some embodiments, the BTMSPA forms a network with other aminosilanes and polymeric amines on the surface which increases binding stability of the overall network.
[0249] In some embodiments, the additives to be included in the functionalization mixture comprise any of the additional additives disclosed elsewhere herein, for instance, in the section entitled Additional additives, above.
[0250] Optionally, in some embodiments, the functionalization mixture is agitated for a duration to allow hydrolysis of and fully dissolve the silane coupling material and polymeric amine materials. In general, the first time period is in a range from 1 minute to 10 minutes (e.g., 5 minutes).
[0251] Referring to Block 322, in some embodiments, process 300 further includes agitating the functionalization suspension to create a plurality of functionalized, coated particles. Referring to Block 324, in some embodiments, process 300 further includes recovering at least a portion of the plurality of functionalized, coated silica particles by filtration or evaporation.
[0252] In some embodiments, Blocks 302 and 304 are performed in either order, e.g., in other examples, the particles are functionalized and then coated with optional drying separating the coating/functionalization steps. For instance, in some embodiments, silica particles are introduced to the functionalization mixture to create the functionalization suspension and the functionalization suspension is agitated to provide functionalized silica particles before the functionalized silica particles are introduced into the coating mixture to provide the functionalized, coated particles.
[0253] Optionally, the process 300 includes one or more steps for drying the coated particles, the functionalized particles, or both. In some embodiments, drying the particles includes increasing the temperature, reducing the atmospheric pressure, passing an inert dry gas over the sample, passing a heated dry gas over the sample, or a combination of these. In some embodiments, drying occurs after the particles are introduced to the coating mixture, after the particles are introduced to the functionalization mixture, or both, in order to remove substantially all of the first solvent, or the second solvent entrained in or on the particles. In the case of drying the coated particles, in some embodiments, the coating is strengthened during drying.
[0254] In some embodiments, drying the functionalized silica particles comprises heating the functionalized silica particles at 120 C. for 20 minutes. In some embodiments, drying the functionalized silica particles comprises flowing an inert gas over the functionalized silica particles until a hydration threshold is reached. In some embodiments, the hydration threshold is less than 5% wt/wt of water to functionalized silica particles.
[0255] For example, in some implementations, the particles are dried in an oven at 70 C. for between 5 minutes and 20 minutes. Without being limited to any one theory of operation, in some embodiments, drying times longer than 60 minutes reduce the absorption capacity of the final product. In some embodiments, the drying time is scale- or conditions-dependent. For example, where the drying is performed under N.sub.2 or vacuum with no heat, the drying time can be longer. In examples in which batch drying is performed, even with N.sub.2 or vacuum, drying times may be longer than 60 mins, depending on the scale of the functionalized particles which are being dried. Alternatively, the particles are dried in an oven at 70 C. until a hydration threshold is reached. As non-limiting examples, the hydration threshold is a weight lost by the sample of 15% (e.g., weight lost to solvent removal), or no further weight loss @ 70 C. with inert (N.sub.2) flow through measured on thermo-gravimetric analysis (TGA). Alternatively, in some embodiments, the particles are dried in the oven until the solvent content in the material is less than 5% wt/wt.
[0256] In some embodiments, the adsorbent particles are reused through the desorption process. For example, in some embodiments, the adsorbent is reused 100 times or more (e.g., 1000 times or more, 10000 times or more). For the desorption process, in some embodiments, samples are heated to 70 C. under vacuum for 30 mins (the duration may change based on temp/vacuum level). This facilitates the CO.sub.2 captured during the adsorption process to be released which can be collected for further sequestration, described with reference to the systems for direct air capture below. An aspect of the desorption process is to maintain the adsorbent heated under a water vapor filled vacuum environment (e.g., >10% relative humidity). This reduces particles degradation.
[0257] In some embodiments, the adsorbent particles are reused at least 10, at least 50, at least 100, at least 500, at least 1000, at least 2000, at least 5000, at least 10,000, at least 50,000, or at least 100,000 times. In some embodiments, the adsorbent particles are reused no more than 110.sup.6, no more than 100,000, no more than 10,000, no more than 1000, or no more than 100 times. In some embodiments, the adsorbent particles are reused from 10 to 500, from 100 to 5000, from 500 to 10,000, from 1000 to 50,000, from 10,000 to 100,000, or from 100,000 to 110.sup.6 times. In some embodiments, the adsorbent particles are reused for a number of cycles falling with another range starting no lower than 10 cycles and ending no higher than 110.sup.6 cycles.
[0258] In some embodiments, another aspect of the present disclosure provides a method for using the functionalized material (e.g., the functionalized silica particles) to remove atmospheric CO.sub.2 from air by direct air capture.
Example Embodiments for Production Systems
[0259]
[0260]
[0261] The drive motor 408 rotates the agitator 406 such that the mixture is stirred and sheer forces are applied to the particles and functionalization mixture. The particles are mobilized within the coating liquid, and/or functionalization mixture. The vessel 402 includes a filter 412 sized to separate the solid particles and/or particles and the coating liquid/functionalization mixture during agitation, functionalization, and coating. When the discharge 410 and outlet 414 are open, the liquids are removed from the vessel 402 and discarded while the filter 412 separates the functionalized, coated particles. The filter 412 can be wire mesh, a cloth layer, or a perforated metal layer.
[0262] Some examples of the mixing system 400 include a heating mechanism integrated into the filter 412 such that, following decanting of the coating liquid/functionalization mixture in the right-most image, the separated functionalized particles can be dried within the vessel 402.
[0263]
[0264] In the left image of
[0265] In some embodiments, examples of the paddle mixer 500 and ribbon mixer 600 include heating mechanisms, such as jacketed drums 502 and 602, or forced gas venting to flow heated gas over the functionalized material particles after separating the particles from the liquid functionalization mixture. In some examples, the heated gas can be air, or an inert gas (e.g., nitrogen, N.sub.2). In some embodiments, if a heat carrier is flown through a jacket of the paddle mixer 500 or ribbon mixer 600, the heat carrier is heated oil, steam, or hot water. In some embodiments, if the heat carrier is flown inside the vessel (e.g., forced gas venting), an inert gas such as N.sub.2 is used. However, in some embodiments of forced gas venting, air is avoided to prevent oxidation.
Example Embodiments for Direct Air Capture Systems
[0266] Examples of DAC systems of CO.sub.2 using the regenerated adsorbent of the present disclosure are described with reference to
[0267] Generally, the carbon dioxide extraction system 700 operates to utilize the heated fluid 704 as thermal energy that is generated from the waste heat 702 by the thermal heat-reuse system 710. In some embodiments, the thermal energy in the heated fluid 704 is used by the carbon dioxide DAC system to separate carbon dioxide captured from the ambient airflow input 711 and supply the separated carbon dioxide as the carbon dioxide supply stream 712. In some embodiments, the heated fluid 704 is then returned via heated fluid return 713 to the thermal heat-reuse system 710 and the waste heat 702 is returned to the industrial process 705 via waste heat return 717. In some aspects, the carbon dioxide supply stream 712 is provided as an injectant into a subterranean formation during hydrocarbon production operations. In some aspects, the injected carbon dioxide is sequestered in the subterranean formation (with or without assisting in the hydrocarbon production operations).
[0268] In some embodiments, the industrial process 705 is any process that generates, as an output, thermal energy in the form of waste heat, e.g., energy, that, unless captured, that otherwise would be lost to, e.g., the ambient environment. As an example, in some embodiments, the industrial process 705 is a computer data center that, generally, houses computer systems and associated components, such as telecommunications and storage systems. In some aspects, a data center includes tens, hundreds, thousands, or even more server devices that generate heat, such as hardware processors, voltage regulators, memory modules, switches, and other devices that operate to provide a particular amount of information technology (IT) power.
[0269] Such devices, typically, utilize electrical power to operate and output heat during operation. In some embodiments, in order for such devices to operate correctly, the output heat is captured in a cooling fluid flow (e.g., air, water, refrigerant) and expelled from the data center. For instance, in some embodiments, air handling systems (e.g., fans, cooling coils) operate to capture the output heat in an airflow circulated over the heat-generating components. In some embodiments, the output heat now within the airflow is transferred to a cooling liquid, e.g., within a cooling coil. In some embodiments, the heat transferred to the cooling liquid is then typically rejected to the ambient environment as waste heat, such as through evaporative cooling systems, chiller/cooling tower systems, or otherwise. In this example, this waste heat takes the form of waste heat 702.
[0270] In some embodiments, the example thermal heat-reuse system 710 utilizes the waste heat 702 and power input 708 to provide the heated fluid 704. In some embodiments, the thermal heat reuse system 710 consists of a bank of heat pumps and a bank of heat exchangers to provide the heated fluid 704. By balancing the use of passive and active heating, power can be saved to provide the carbon dioxide DAC system with the required temperatures of heated fluid 704. Generally, the thermal heat-reuse system 710 includes one or more vapor compression cycles (heat pumps) to add thermal energy in the form of heat of compression to the waste heat 702 and transfer the sum of such energy to a fluid to generate the heated fluid 704 (e.g., a heated liquid). Generally, each heat pump and heat exchanger within the thermal heat-reuse system 710 operates to transfer thermal energy from a heat sink to a heat source, i.e., in an opposite direction of spontaneous heat transfer. In some embodiments, the one or more heat pumps of the thermal heat-reuse system 710 use the power input 706 to accomplish the work of transferring energy from the heat source to the heat sink. In some embodiments, each heat pump in the thermal heat-reuse system 710 includes the primary components of two heat exchangers (one acting as an evaporator, one acting as a condenser), an expansion device (e.g., valve or fixed orifice), and a compressor (e.g., centrifugal, screw, reciprocating, scroll, or otherwise). Each of these components are fluidly coupled within a closed-loop refrigerant circuit in the heat pump.
[0271] As is generally known, in a vapor-compression heat pump cycle, a refrigerant exits a first heat exchanger in which heat from the refrigerant is released to a first medium. In some embodiments, the refrigerant then enters a compressor in which it is compressed and a heat of compression is added thereto. In some embodiments, the refrigerant then enters a second heat exchanger in which heat from a second medium is added. In some embodiments, the refrigerant then enters an expansion device and undergoes an isenthalpic pressure drop. In some embodiments, the refrigerant completes the cycle by entering the evaporator to release the heat of compression and the heat from the second medium to the first medium.
[0272] Although the present disclosure describes a vapor-compression heat pump cycle as a heat transfer system between a source of waste heat and a carbon dioxide DAC system, other thermodynamic cycles are also contemplated for use in place of (or along with) the described vapor-compression heat pump cycle. For example, in some embodiments, one or more vapor adsorption cycles are used in place of (or along with) the described vapor compression heat pump cycle. In some embodiments, a vapor-adsorption cycle, for example, consists of a cycle of desorption-condensation-expansion-evaporation, followed by adsorption.
[0273] In some embodiments, the carbon dioxide DAC system 715, generally, operates to pass the ambient airflow input 711 (which includes gaseous carbon dioxide) over or through one or more media (e.g., filters). In some aspects, one or more fans (not shown) utilize the power input 708 to circulate the ambient airflow input 711. The media or filter, in some aspects, includes a solid adsorbent to which the atmospheric carbon dioxide in the airflow input 711 bonds. The adsorbent that is saturated with carbon dioxide may be referred to as rich adsorbent.
[0274] In the case of a solid sorbent, such as the sorbent described in the present disclosure, as the airflow input 711 passes over the solid media or filter, atmospheric carbon dioxide within the airflow input 711 bonds to the media or filter. When the media or filter is saturated with carbon dioxide, it can be heated (e.g., to 600-620 C., to 60-100 C.) to release the carbon dioxide for collection (as described below).
[0275] Using thermal energy from the heated fluid 704, in some embodiments, heat is applied to the solid or liquid adsorbent, which breaks the bonds between the carbon dioxide and the sorbent. In some embodiments, the separated carbon dioxide is provided as the carbon dioxide supply stream 712 from the carbon dioxide DAC system 715. In some embodiments, the now-lean adsorbent that is carbon dioxide free (i.e., the solid or liquid) is recycled back to capture more carbon dioxide from the ambient airflow input 711. In some embodiments, the airflow output 714, typically, contains little to no carbon dioxide.
[0276]
[0277] A natural gas plant 820 generates flue gas containing carbon dioxide and electrical power 828 that is sent to the CCS flue gas carbon dioxide scrubber system 825. In some embodiments, the scrubber system 825 separates out the carbon dioxide from the flue gas. In some embodiments, the scrubber system 825 provides waste heat 802 to a carbon dioxide direct air capture (DAC) system 815. In some embodiments, the carbon dioxide DAC system 815 also receives a power input 808 and an ambient airflow input 811. In some embodiments, the carbon dioxide DAC system 815 outputs a carbon dioxide supply stream 812 and a carbon dioxide-reduced airflow output stream 814.
[0278] Generally, the integrated system 800 operates to capture the waste heat 802, generate the heated fluid 1 that has a thermal energy that includes the waste heat 802, as well as heat of compression from the thermal heat-reuse system 810, and utilize such thermal energy in the heated fluid 1 to separate carbon dioxide captured from the ambient airflow input 811 to supply the separated carbon dioxide as the carbon dioxide supply stream 812. In some aspects, the carbon dioxide supply stream 812 is provided as an injectant into a subterranean formation during hydrocarbon production operations. In some aspects, the injected carbon dioxide is sequestered in the subterranean formation (with or without assisting in the hydrocarbon production operations).
[0279] In this implementation, the industrial process 805 is powered by the natural gas plant 820 rather than the electrical power grid since the electrical power 826 would be considered carbon negative electricity.
[0280] In some embodiments, the example thermal heat-reuse system 810 utilizes the waste heat 802 from the CCS Flue Gas CO.sub.2 Scrubber 825 and power input 806 to provide the heated fluid 1. Generally, the thermal heat-reuse system 810 includes one or more vapor-compression cycles (heat pumps) to add thermal energy in the form of heat of compression to the waste heat 802 and transfer the sum of such energy to a fluid to generate the heated fluid 1 (e.g., a heated liquid). Generally, each heat pump within the thermal heat-reuse system 810 operates to transfer thermal energy from a heat sink to a heat source, i.e., in an opposite direction of spontaneous heat transfer. In some embodiments, the one or more heat pumps of the thermal heat-reuse system 810 use the power input 806 to accomplish the work of transferring energy from the heat source to the heat sink. In some embodiments, each heat pump in the thermal heat-reuse system 810 includes the primary components of two heat exchangers (one acting as an evaporator, one acting as a condenser), an expansion device (e.g., valve or fixed orifice), and a compressor (e.g., centrifugal, screw, reciprocating, scroll, or otherwise). In some embodiments, each of these components are fluidly coupled within a closed-loop refrigerant circuit in the heat pump.
[0281] The carbon dioxide DAC system 815, generally, operates to pass the ambient airflow input 811 (which includes gaseous carbon dioxide) over or through one or more media (e.g., filters). In some aspects, one or more fans (not shown) utilize the power input 808 to circulate the ambient airflow input 811. In some embodiments, the media or filter, in some aspects, includes a solid adsorbent to which the atmospheric carbon dioxide in the airflow input 811 bonds. The adsorbent that is saturated with carbon dioxide may be referred to as rich adsorbent.
[0282] In the case of a solid sorbent, such as the sorbent described in the present disclosure, as the airflow input 811 passes over the solid media or filter, atmospheric carbon dioxide within the input 811 bonds to the media or filter. When the media or filter is saturated with carbon dioxide, it can be heated (e.g., to 100-120 C., to 60-100 C.) to release the carbon dioxide for collection (as described below).
[0283] Using thermal energy from the heated fluid 1, in some embodiments, heat is applied to the solid adsorbent, which breaks the bonds between the carbon dioxide and the sorbent. In some embodiments, the separated carbon dioxide is provided as the carbon dioxide output stream 812 from the carbon dioxide DAC system 815. In some embodiments, the now-lean adsorbent that is carbon dioxide free (i.e., the solid or liquid) is recycled back to capture more carbon dioxide from the ambient airflow input 811. In some embodiments, the airflow output 814, typically, contains little to no carbon dioxide. In some embodiments, the carbon dioxide DAC system 815 outputs carbon dioxide 812 and demineralized water 816.
[0284] As further shown in the example embodiment of
[0285] As shown in this example, in some embodiments, the power output of the power plant 820 is sized to provide a sum of the electrical power 824 to the DAC system 815 and the electrical power 828 to the scrubbing system 825 for normal operation, as well as the backup electrical power 826 to the industrial process 805 when needed (e.g., when the industrial process 805 loses or cannot use grid electrical power 817). Thus, in some aspects, when the industrial process 805 needs the backup electrical power 826, electrical power 828 and electrical power 824 are still provided to their respective users. Alternatively, in some aspects, the power output of the power plant 820 is sized to provide a sum of the electrical power 824 to the DAC system 815 and the electrical power 828 to the scrubbing system 825 for normal operation, as well as the backup electrical power 826 to the industrial process 805 when needed (e.g., when the industrial process 805 loses or cannot use grid electrical power 817), as well as one or both of power inputs 806 and 808.
[0286] Alternatively, in some aspects, the power output of the power plant 820 is sized only to provide the backup electrical power 826 to the industrial process 805 when needed (e.g., when the industrial process 805 loses or cannot use grid electrical power 817). Thus, in some embodiments during operational periods when the industrial process 805 does not need backup electrical power 826, the electrical power 828 and/or the electrical power 824 (as well as other power inputs) is provided by the power plant 820. Alternatively, in some embodiments during operational periods when the industrial process 805 does need backup electrical power 826, the electrical power 828 and/or the electrical power 824 (as well as other power inputs) is not provided by the power plant 820. For example, electrical power 822 may be routed, in such operational periods, through the switch 830 as backup electrical power 826.
[0287] In some aspects, the electrical power 826 supplied from the power plant 820 to the industrial process 805 is not backup power but instead is a primary power source for the industrial process 805. For example, in some aspects, the power plant 820 is sized to provide primary electrical power 826 to the industrial process 805, as well as, in some aspects, one or more other components shown in the integrated system 800.
[0288] As further shown in
[0289] As shown in this example implementation, the scrubbing system 825 also receives an exhaust fluid 832 (e.g., the flue gas with 100% CO.sub.2) from the power plant 820. For example, in some aspects, the power plant 820 is a natural gas power plant in which natural gas is combusted to drive electrical power generation equipment that operates to generate the electrical power shown in
[0290] In some embodiments, output from such a gas turbine (at a lower pressure than the combustion products fluid) is exhaust fluid 832 (e.g., as a flue gas). In some embodiments, a difference in pressure between the combustion products fluid and the exhaust fluid 832 drives the gas turbine to produce electrical power from the generator. As shown in this example, in some embodiments, the exhaust fluid 832 is separated by the scrubbing system 825 into multiple output streams. For example, the flue gas with 100% CO.sub.2 832 is separated into a carbon dioxide output and a flue gas stream 836 with 5% CO.sub.2. The flue gas stream 836 with 5% CO.sub.2 is sent to the DAC system 815 to remove the remaining carbon dioxide from the output airflow of the natural gas plant 820. This makes the resulting power generated from the natural gas plant carbon negative power. For example, similar to the DAC system 815, in some embodiments, outputs of a carbon dioxide supply stream 812 and a carbon dioxide-reduced airflow output stream 814 are output from the scrubbing system 825.
[0291] In some aspects, the carbon dioxide supply streams 812 are sold (e.g., for CO.sub.2-EOR, sequestration, and/or other processes). For example, in some embodiments, the carbon dioxide supply streams 812 generate revenue through emissions credits and federal tax credits. In some aspects, such revenue offset capital and/or operations costs of the DAC system 815, the power plant 820, both, or other components of the system 800.
[0292] In some embodiments, the integrated system 800 advantageously utilizes the power plant 820, which may normally be sitting idle, to produce a saleable product in the carbon dioxide fluid streams 812, which also provide environmental benefits. Additionally, in the event of a power outage at the industrial process 805, the power plant 820 would already be running, meaning the delay between the outage and providing the process 805 with power would be reduced. Further, in some embodiments, by using the thermal energy 802 from the waste heat 802 from the scrubber 825 and 834, operating costs of the DAC system 815 is significantly reduced, allowing for the carbon dioxide captured to finance the construction of the DAC system 815 as well as help subsidize the cost of the industrial process's backup power. In addition, in some embodiments, the integrated system 800 produces water from ambient humidity as the DAC system 815 pulls carbon dioxide from the air. In some embodiments, the water is sold or used, e.g., at the industrial process 805.
Additional Embodiments
[0293] Another aspect of the present disclosure provides a functionalized material, comprising a plurality of modified porous substrate particles, each modified porous substrate particle comprising: a porous particle comprising silicon dioxide or silicon oxide; a coating layer disposed on at least a portion of a surface of the porous particle, wherein the coating layer comprises a polymer; and a functionalization layer disposed on at least a portion of a surface of the porous particle, where the functionalization layer comprises a polymeric amine, a silane moiety, and an amine moiety. In some embodiments, the polymeric amine is reactive to carbon dioxide. In some embodiments, the functionalized material adsorbs CO2 per dry kilogram in a range from 0.5 mol to 2.5 mol. In some embodiments, the functionalized material desorbs in a temperature range between about 65 C. to 90 C. In some embodiments, the functionalized material adsorbs CO2 at a relative humidity in a range from 5% to 95% relative humidity. In some embodiments, the functionalized material has an abrasion resistance of less than 1% w/w loss according to an ASTM D4058-96 test. In some embodiments, the functionalized material has a crush strength of at least 1.5 MPa. In some embodiments, the functionalized material further comprises a hydrophobic compound. In some embodiments, the hydrophobic compound is a hydrophobic silane compound, or a hydrophobic polymer. In some embodiments, the hydrophobic silane compound comprises a silane molecule and one, two, or three alkyl chains. In some embodiments, the hydrophobic polymer comprises polydimethylsiloxane (PDMS), silicone oil, polyethylene, polytetrafluoroethylene, or polyurethanes.
[0294] Another aspect of the present disclosure provides a modified porous substrate particle, comprising: a porous particle comprising silicon dioxide or silicon oxide; a coating layer disposed on at least a portion of a surface of the porous particle, wherein the coating layer comprises a polymer; and a functionalization layer disposed on at least a portion of a surface of the porous particle, where the functionalization layer comprises a polymeric amine, a silane moiety, and an amine moiety.
[0295] Another aspect of the present disclosure provides a method for removing atmospheric CO.sub.2 from air, comprising: obtaining a functionalized material comprising a plurality of modified porous substrate particles, each modified porous substrate particle comprising a porous substrate particle, a coating layer comprising a polymer, disposed on at least a portion of a surface of the porous substrate particle, and a functionalization layer comprising a polymeric amine, a silane moiety, and an amine moiety, disposed on at least a portion of a surface of the porous substrate particle. In some embodiments, the method further includes using the functionalized material to remove atmospheric CO.sub.2 from air by direct air capture. In some embodiments, the polymer comprises PVA. In some embodiments, the polymeric amine is a linear or a branched polymeric amine. In some embodiments, the polymeric amine is selected from the group consisting of: Polyethylenimine (PEI), Polypropylenimine, Tetraethylenepentamine (TEPA), Triethylenetetramine (TETA), Diethanolamine, or a large molecule weight amine mixture. In some embodiments, the functionalization layer comprises an alkoxysilane, a methoxysilane, a silanetriol, an alkoxysilanol, a chlorosilane, a hydrosilane, or an ethoxysilane. In some embodiments, the functionalization layer comprises (3 Aminopropyl) trimethoxysilane, (3-Aminopropyl)triethoxysilane, [3-(2-Aminoethylamino) propyl]trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl silanetriol, N1-(3-Trimethoxysilylpropyl) diethylenetriamine, 3-Aminopropylsilanetriol, N-(2Aminoethyl)-3-aminopropylsilanetriol, tris(ethylmethylamino) chlorosilane, or tris(dimethylamino) chlorosilane, or amino silane oligomers.
[0296] While this specification contains many details, these should not be construed as limitations on the scope of what may be claimed, but rather as descriptions of features specific to particular examples. Certain features that are described in this specification in the context of separate implementations can also be combined. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple embodiments separately or in any suitable subcombination.
EXAMPLES
Example 1Silane and Polymeric Amine Functionalized Porous Substrate for Carbon Capture
[0297] Examples 1.1 to 1.3 generally relate to a functionalized porous silica and more specifically, to a functionalized porous silica for reversibly capturing carbon dioxide.
[0298] Example 1.1N1-(3-Trimethoxysilylpropyl) diethylenetriamine and PEI grafting.
[0299] In a three-necked round bottom flask, 4.85 g (80 mmol) of silica particles was added into 40 mL solvent (e.g., toluene, hexane, cyclohexane, and/or THF) at ambient temperature. The silica particles were stirred and soaked in the solvent for 2 hrs. N1-(3-trimethoxysilylpropyl) diethylenetriamine, having the chemical formula:
##STR00006##
was added into the above solution at a molar ratio in a range from 2.3 g to 4.7 g (e.g., 8 mmol to 16 mmol, e.g., a silica particle to amine material molar ratio in a range from 5:1 to 10:1). The mixture was heated and stirred at 60 C. or above (e.g., up to 90 C.). The temperature depends on the chosen solvent. The mixture was stirred for 18 hours (in some cases, the mixing continued for 24 hours). The mixture was cooled to room temperature. The functionalized silica particles were filtered from the solvent and washed twice while stirring with a 40 mL volume of solvent each time. The functionalized silica particles were dried in a vacuum oven at 50 C. for 12 hours. Alternatively, [3-(2-aminoethylamino) propyl]trimethoxysilane, having the chemical formula:
##STR00007##
was added to the solution at 2.2 g to 4.5 g (e.g., 8 mmol to 16 mmol, e.g., a silica particle to amine material molar ratio in a range from 5:1 to 10:1).
[0300] In a second round bottom flask, 30 mL of methanol or solvent mixture (e.g., cyclohexane:ethanol=2:1), 5 g of silane-treated silica from the above step, and 1.5 g polyethylenimine (PEI) or other second amine (30 wt % to silica) was added. The mixture was stirred for 1 hour. The solvent was dried from the functionalized silica through evaporation, such as on a rotovap, to recover the functionalized silica. The functionalized silica particles were dried in a vacuum oven at 50 C. for 12 hours. The second step can be performed as a large scale process such as using vacuum drying together with an amine/solvent mixture spraying process.
Example 1.2Bis[3-(trimethoxysilyl) propyl]amine grafting
[0301] Using a silane compound having two or more silane moieties (e.g., two trimethoxysilane or triethoxysilane functional groups) in the same molecule, such as for example bis[3-(trimethoxysilyl) propyl]amine, can facilitate a plurality of interactions between silane groups and silica, potentially improving binding stability of the silane bond to the silica surface.
[0302] To add bis[3-(trimethoxysilyl) propyl]amine), having the chemical formula:
##STR00008##
to the reaction, the same procedure as for [3-(2-aminoethylamino) propyl]trimethoxysilane grafting was followed.
[0303] In a three-necked round bottom flask, 4.85 g (80 mmol) of silica particles was added into 40 mL solvent (e.g., toluene, hexane, cyclohexane, and/or THF) at ambient temperature. The silica particles were stirred and soaked in the solvent for 2 hours. [3-(2-aminoethylamino) propyl] trimethoxysilane, having the chemical formula:
##STR00009##
was added into the above solution at 2.2 g to 4.5 g (e.g., 8 mmol to 16 mmol, e.g., a silica particle to amine material molar ratio in a range from 5:1 to 10:1). Bis[3-(trimethoxysilyl) propyl]amine) was added into the above solution at 0.68 g (e.g., 2 mmol, a silica particle to bisamine material ratio of 40:1). The mixture was heated and stirred at 60 C. or above (e.g., up to 90 C.). The temperature depends on the chosen solvent. The mixture was stirred for 18 hours. The mixture was cooled to room temperature. The functionalized silica particles were filtered from the solvent and washed twice while stirring with a 40 mL volume of solvent each time. The functionalized silica particles were dried in a vacuum oven at 50 C. for 12 hours.
Example 1.3Experimental Results
[0304] Functionalized silica produced using the processes described herein (e.g., in
Example 2CO.SUB.2 .Uptake Measurements for Functionalized Material
[0305] Functionalized silica produced using the processes described herein (e.g., process 300 illustrated in
[0306] In
[0307] The samples of functionalized silica were treated with an activation process before data collection. Samples were heated in a vacuum drier (e.g., vacuum heater 1328) to 70 C. for 30 minutes under vacuum (e.g., 0.3 psi) to activate the adsorbent, e.g., as the activation process. Alternatively, and as shown in
[0308] For the adsorption procedure, samples of functionalized silica in a range between 0.5 g and 10 g were placed in between two layers of glass fiber filters 1304 in the testing sample holder 1300. Compressed environmental air (e.g., input air) from gas source 1322 were continuously fed through the testing sample holder 1300 at a rate 1 to 10 standard liters per minute (slpm), thereby exposing the activated functionalized silica. The activated functionalized silica was exposed for time periods 30 to 60 minutes. The humidity of the input air was controlled to be 15% to 50% RH at 21 C. The same sample holder was then brought to vacuum by vacuum system 1330 and heated by vacuum heater 1328 to extract the carbon dioxide from the sample.
[0309] The amount of carbon dioxide extracted was measured by gas analyzer 1326. The humidity was controlled through blending of dry air and wet air with a flow meter (not shown). As an example, to produce input air having 50% RH at a flow rate of 5 slpm, dry air (e.g., <10% RH) at 2.5 slpm and wet air (e.g., >95% RH, 100% RH) was blended at 2.5 slpm each. The dry air and wet air flow control was performed using a closed loop controller.
[0310] The compressed environmental air including CO.sub.2 concentration was monitored by gas analyzers 1324 and 1326 at the input and output of the testing sample holder 1300 during the experimental time period in units of mol CO.sub.2/kg of adsorbent.
Example 3Agglomeration Trials for Functionalized Material
[0311] Shown below in Tables 1 and 2 are two trials in which fine particles were agglomerated to a baseline silica to form recycled silica particles. The CO.sub.2 uptake (mol/kg), attrition loss (wt %), crush strength (MPa), and/or bulk density (g/L) were determined.
[0312] A baseline raw silica product was used as a base for the agglomerated particles. The CO.sub.2 uptake of the baseline raw silica was determined using methods described herein to determine a normalized uptake with which to compare the agglomerated samples.
[0313] The agglomerated samples were formed as described herein using the baseline silica. The agglomerated samples of Table 1 were agglomerated using dry roller compaction under a pressure according to the specific row, e.g., either 20 kilopounds per square inch (ksi) or 30 ksi. In the Condition column, the term Milled means the baseline material was less than 100 microns in size. The term Non-milled means the baseline material was up to 500 microns.
[0314] Attrition testing was performed on the agglomerated samples. Briefly, 100 g of each sample was placed in a sieve shaker using a 20 mesh screen. The samples were agitated in the shaker for 5 minutes using a tapper. 50 g of the plus 20 mesh product was placed on the mesh 20 screen. 50 pieces of 9.5 mm ceramic beads were added to the 20 mesh screen. The samples were agitated for 5 minutes without the tapper. The weight percentage of fines found in the base pan following the agitation with the ceramic beads was determined compared to the original sample.
[0315] Following agglomeration, the samples were coated with the functionalization mixture and tested for CO.sub.2 uptake, both methods as described herein. Briefly, for the functionalization/coating process, 7.7 wt % of PEI and 36 wt % of DAMO in 160 wt % of water were added to 100 g of the silica substrate by dip coating in the PEI/DAMO/Water solution. After the dip coating, the samples were dried under vacuum at 70 C. for 24 hrs. The samples were tested with the method described in Examples 1 and 2 to determine the uptake performance.
TABLE-US-00001 TABLE 1 Uptake Trial 1 Condition Shape (mol/kg) Attrition Baseline Not from agglomeration Spherical 1.2 8.7% Silica granules BT1 Run1 Silica 150 A no-milled Flat chips 1.14 30.5% 20 ksi (70-200 um) BT1 Run2 Silica 150 A milled Flat chips 0.67 6.9% 20 ksi BT1 Run3 Silica 150 A milled Flat chips 0.53 7.7% 30 ksi BT1 Run4 Silica F1 milled Flat chips 0.64 11.3% 20 ksi
[0316] The agglomerated samples for Table 2 (below) were produced using a liquid binding mixture of PVA and water at varying wt % (PVA to water wt %) as a binder. The samples from Table 2 were agglomerated using a mixer with the liquid binding mixture.
[0317] The CO.sub.2 uptake capacity and attrition were determined using the same method as for the samples for Table 1. The agglomerated particles for Table 2 were characterized for compression strength. The bulk compression strength test utilizes a test fixture which consists of a lower crush platform and upper crusher head. The lower crush platform included a flat surface onto which samples are placed. The upper crush head included a crush head with a flat lower surface substantially parallel with the plane of surface such that force was applied evenly to particles between the crush head and surface during force application. The crush head had an outer diameter (OD) 72.6 mm and the surface was 124.5 mm in diameter. The crush platform had a diameter 125.4 mm. In another example, the crush platform had a diameter of 146 mm.
[0318] During testing, a layer of particles, e.g., the sample, was packed closely on the crush platform and roughly aligned with the center of the crush head. The particle bed diameter was about 90 mm to about 2 mm in thickness. The samples were 3-6 g dry weight depending on particle coating components. The force applied to the crush head was recorded while displacement changed. The packed particle bed was crushed to achieve 50% of its compressive strain (e.g., displacement divided by initial sample bed thickness) and the stress (MPa) (e.g., force divided by contact area) is reported as 50% strain crush strength. Samples of uncoated, and coated particles were tested. For both types of particle, at least 3 samples were tested to get the average performance for the bulk compression strength.
[0319] The bulk density was measured according to ASTM D1895 Method A. Briefly, fine granules were poured through a V shaped funnel. The material being tested were allowed to flow into a cylinder cup with a known volume of 100 mL. Testing results were averaged using more than 4 measurements.
TABLE-US-00002 TABLE 2 Crush Bulk Uptake Strength Density Trial 2 Condition Shape (mol/kg) Attrition (MPa) (g/L) Baseline Not from Spherical 1.2 12% 1.14 260 Silica agglomer- granules ation BT1 7% PVA 1.35 5-7 1.04 262 Run1 solution wt % as binder BT1 10% PVA 1.3 5-7 1.21 268 Run2 solution wt % as binder BT1 3% PVA 1.35 5-7 0.87 255 Run3 solution wt % as binder
Example 4Experimental Results of Uncoated and Coated Functionalized Material
[0320] Functionalized, coated particles produced using the process 300 described herein, and as detailed in Examples 5-10, were characterized for compression strength and attrition resistance. The bulk compression strength test utilized the test fixture 900 shown in
[0321] During testing, a thin layer of particles, e.g., the sample, was packed closely on the crush platform 902 and roughly aligned with the center of the crush head 916. The particle bed diameter was 90 mm and about 2 mm in thickness. The samples were in a range from 3-6 g dry weight depending on particle coating components. The force applied to the crush head 906 was recorded while displacement changed. The packed particle bed was crushed to achieve 50% of its compressive strain (e.g., displacement divided by initial sample bed thickness) and the stress (MPa) (e.g., force divided by contact area) was reported as 50% strain crush strength. Samples of uncoated, and coated particles were tested. For both types of particle, at least 3 samples were tested to get the average performance for the bulk compression strength.
[0322] Tables 3 and 4 presents the bulk compression strength for the samples, normalized against an uncoated substrate (Table 3; Control 1) (Table 4; Control 2). Compression strength is also known as crush strength. Samples included no coating raw porous substrate, silica coated with amine only, and silica coated with various types of polymers. The particles of each sample had average radii in a range from 1 to 1.4 mm to ensure consistent particle size distribution.
TABLE-US-00003 TABLE 3 Bulk Compression Strength Results. 50% Strain Compressive Strength Normalized % Sample (MPa) to Control Control No coating (Control 1) 1.29 100% 1 Amine coating (DAMO + PEI 1.36 105% sorbent) 2 Amine coating + 200K Mw 2.09 162% PVA (DAMO + PEI sorbent + 10 wt % 200K PVA) 3 Amine coating + 30-50K 2.05 159% Mw PVA (DAMO + PEI sorbent + 10 wt % 30-50K PVA) 4 Amine coating + 13-23K 1.73 134% Mw PVA (DAMO + PEI sorbent + 10 wt % 13-23K PVA) 5 Amine coating + cellulose 1.40 108% acetate (DAMO + PEI sorbent + 2 wt % cellulose acetate (CA)) 6 Amine coating + PVP 1.59 123% (DAMO + PEI sorbent + 2 wt % PVP) 7 Amine coating + PVA 99% 1.77 137% Hydrolyzed (DAMO + PEI sorbent + 2 wt % PVA 99% Hdrolyzed)
TABLE-US-00004 TABLE 4 Bulk Compression Strength Results. 50% Strain CO2 Compressive Stress Strength uptake Sample (MPa) Improvement % (mol/kg) No coating 1.14 100% 0 (Control 2) DAMO + PEI 1.36 119% 1.3 sorbent DAMO + PEI 2.09 183% 1.2 sorbent + 10 wt % 200K PVA DAMO + PEI 2.05 180% 1.05 sorbent + 10 wt % 30-50K PVA DAMO + PEI 1.73 152% 1.05 sorbent + 10 wt % 13-23K PVA DAMO + PEI 1.98 174% 1.04 sorbent + 10 wt % 10K PVA DAMO + PEI 1.40 122% 1.07 sorbent + 2 wt % cellulose acetate (CA) DAMO + PEI 1.59 139% 0.61 sorbent + 2 wt % PVP DAMO + PEI 1.77 155% 1.04 sorbent + 2 wt % PVA 99% Hydrolyzed DAMO + PEI 2.16 189% 0.88 sorbent + 10% Polysulfone
[0323] PVA reinforcement (Sample 2) improved the crush strength by 162% (maximum) compared to baseline raw silica. Different molecular weight PVA resulted in different reinforcement effects. Lower molecular weight PVA (Sample 4) showed less reinforcement effect compared to Sample 2, e.g., the normalized improvement was about 134%. Other polymers such as cellulose acetate, PVP also provided a reinforcement effect. Cellulose acetate reinforcement (Sample 5) provided 108% reinforcement and PVP (Sample 7) provided 137% reinforcement. A bar chart of the compression strength results comparison is shown in
[0324] Attrition and abrasion resistance was determined according to the ASTM D4058-96 (Standard Test Method for Attrition and Abrasion of Catalysts and Catalyst Carriers) testing method. The testing fixture 1100 is shown in
TABLE-US-00005 TABLE 5 Attrition Loss Results Reduction in generated Single cycle fines (%) attrition particle size particle size particle size particle size (% loss) >0.71 mm >0.1 mm >0.71 mm >0.1 mm Raw silica 1.65% 1.33% PVA coated 0.91% 0.89% 45% 33% silica test 1 PVA coated 1.05% 1.04% 36% 22% silica test 2 PVA and 0.93% 0.93% 44% 30% amine coated silica
[0325] As shown in Table 5, particles including the polymer reinforcement coating had improvement on the attrition loss resistance of between 36%-45% for particle size<0.71 mm.
Example 5Example Functionalization Mixture (Second Reagent and Third Reagent)
[0326] In one non-limiting embodiment, creating the plurality of functionalized particles includes introducing a second reagent including the polymeric amine (e.g., polyamine) polyethyleneimine (PEI) and a third reagent comprising the aminosilane aminopropyltrimethoxysilane (DAMO) having the structure:
##STR00010##
[0327] into a volume of the second solvent ethanol to form the functionalization mixture. A total of 45 g of aminopropyltrimethoxysilane (DAMO) and 10 g of polyethyleneimine PEI were charged into a 200 mL beaker and stirred till a homogenous mixture was obtained. 190 mL ethanol was charged into the DAMO-PEI mixture and stirred till a homogeneous mixture was obtained. The PEI-DAMO-ethanol solution was decanted over 100 grams of porous silica particles in a 500 ml beaker. The beaker was placed in a vacuum oven at 80 C. and 50 mbar for 12 hours till a dry product (coated particles) was obtained.
Example 6Two-Step Procedure for Sorbent Formation
[0328] This example provides a method comprising forming a plurality of coated particles by introducing at least a portion of a plurality of porous particles and a first reagent comprising a polymer to a solvent. The method further comprises forming a plurality of functionalized coated particles by introducing a second reagent comprising a polymeric amine and a third reagent comprising a silane-functionalized amine or an amino-functionalized silane (aminosilane) to at least a portion of the plurality of coated particles.
[0329] In this example the plurality of porous particles were silica particles.
[0330] In this example the polymer in the first reagent is 13K-23K MW polyvinylalcohol (PVA).
[0331] In this example the polymeric amine of the second reagent is the polyamine poly(ethyleneimine) (PEI).
[0332] In this example the silane-functionalized amine or the amino-functionalized silane (aminosilane) of the third reagent is the aminosilane aminopropyltrimethoxysilane (DAMO).
[0333] In this example the plurality of functionalized coated particles is formed in the presence of a crosslinker that is incorporated into the plurality of functionalized coated particles, where the crosslinker is the dialdehyde terephthalaldehyde (TALD.
[0334] Step 1 for a 100 g batch of coated particles.
[0335] Formation of first reagent. Slowly, 15 g of 13-23K Mw PVA was charged into 60 mL of rapidly stirring cold water in a 500 mL flask with a condenser. The mixture was heated to 70-80 C. and stirred until a homogeneous solution was obtained, approximately 30 minutes. The solution was cooled to 60-70 C. under constant stirring. Slowly, 140 mL of hot ethanol (60 C.) was charged into the flask and mixed thoroughly until a uniform solution was obtained. 1.67 g of 60% etidronic acid (ETDA) solution was charged into the warm solution (50-60 C.) and mixed thoroughly until a uniform solution was obtained.
[0336] Forming a plurality of coated particles by introducing a plurality of porous particles to a first reagent comprising a polymer. The warm PVA-ethanol-water solution was decanted over 100 g of silica in a 1 L rotary evaporation flask with mixing. The flask was placed on the rotary evaporator and set to 20 rotations per minute (rpm) until the mixture was observed to be homogenous with no dry particles. Once a uniform mixture was obtained the rotary evaporator was set to 70 C., 50 mbar, and 10 rpm. The mixture was dried until the sorbent (plurality of coated particles) contained 20-30 wt % volatiles as measured by a Mettler Toledo Halogen Moisture Analyzer HE73.
[0337] Step 2 for a 100 g (starting silica) batch.
[0338] The plurality of coated particles. The PVA-coated silica product from the first step (141 g) was left in the 1 L rotary evaporator flask.
[0339] Form the second and third reagent. 10 g of the polyamine poly(ethyleneimine) (PEI) (second reagent and 45 g of the aminosilane aminopropyltrimethoxysilane (DAMO) (third reagent) was charged into a 500 ml beaker followed by 10 mL isopropyl alcohol (IPA). The PEI, DAMO, and IPA were mixed until a uniform DAMO-PEI-IPA solution was obtained.
[0340] 1.1 g of the crosslinker terephthalaldehyde (TALD), having the chemical structure:
##STR00011##
[0341] was charged into a 250 ml beaker followed by 141 mL of hexane and 19 mL of IPA. 1 g Chimassorb 944 FDL (C944) (Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][imino(2,2,6,6-tetramethyl-4-piperidinyl)]-1,6-hexanediylimino(2,2,6,6-tetramethyl-4-piperidinyl)]]; BASF, Ludwigshafen am Rhein, 67056 Germany) was charged into the same 250 ml beaker and mixed until a uniform solution was obtained. TALD-C944-Hexane-IPA was warmed to 60 C. with mixing until a uniform solution was obtained.
[0342] The DAMO-PEI-IPA solution (second and third reagents) was warmed to 40 C. with mixing. The warm TALD-C944-hexane-IPA solution (crosslinker) was charged into the 500 ml beaker of DAMO-PEI-IPA. The temperature was maintained at 60 C. and mixed until a homogeneous solution was obtained.
[0343] Forming a plurality of functionalized coated particles by introducing the second reagent comprising the polymeric amine and the third reagent comprising a silane-functionalized amine or the amino-functionalized silane (aminosilane) to at least a portion of the plurality of coated particles. The warm PEI-DAMO-TALD-C944-Hexane-IPA solution was decanted over the 141 g of PVA-EDTA-coated silica product from step 1 (plurality of coated particles) in the 1 L rotary evaporation flask with mixing. The flask was placed on the rotary evaporator and spun at 20 rpm until the mixture was observed to be uniform. Once a uniform mixture was obtained, the rotary evaporator was set to 70 C., 50 mbar, and 10 rpm. The mixture was dried until the sorbent contained <5 wt % volatiles as measured by a Mettler Toledo Halogen Moisture Analyzer HE73.
[0344] In an embodiment, the procedure was used to obtain the sample DAMO+PEI sorbent+10 wt % 13-23K PVA described in Example 4 (Table 3 and Table 4).
[0345] In an embodiment, the polymer in the first reagent is 200K MW polyvinylalcohol (PVA), and the procedure was used to obtain the sample DAMO+PEI sorbent+10 wt % 200K PVA described in Example 4 (Table 3 and Table 4).
[0346] In an embodiment, the polymer in the first reagent is 30-50K MW polyvinylalcohol (PVA), and the procedure was used to obtain the sample DAMO+PEI sorbent+10 wt % 30-50K PVA described in Example 4 (Table 3 and Table 4).
[0347] In an embodiment, the polymer in the first reagent is 10K MW polyvinylalcohol (PVA), and the procedure was used to obtain the sample DAMO+PEI sorbent+10 wt % 10K PVA described in Example 4 (Table 3 and Table 4).
[0348] In an embodiment, the substrate particles were not introduced to the first reagent comprising the polymer, and only step 2 of the procedure was used to obtain the sample DAMO+PEI sorbent described in Example 4 (Table 3 and Table 4).
Example 7Second Procedure for Sorbent Formation
[0349] In an embodiment, the procedure included formation of the first reagent comprising adding 3 g of PVA into 60 mL of cold water, in accordance with step 1 of Example 6 above, thereby obtaining 2% by weight PVA. In an embodiment, the procedure included, after forming the second reagent and the third reagent in accordance with step 2 of Example 6 above, agitating the functionalization mixture (the second reagent and the third reagent) for a duration to allow hydrolysis of and fully dissolve the polymeric amine and the silane-functionalized amine or the amino-functionalized silane (aminosilane), thereby achieving 99% hydrolysis. In an embodiment, the procedure was used to obtain the sample DAMO+PEI sorbent+2 wt % PVA 99% Hydrolyzed described in Example 4 (Table 3 and Table 4).
Example 8 Third Procedure for Forming Coated Particles (First Reagent)
[0350] This example provides a method comprising forming a plurality of coated particles by introducing at least a portion of a plurality of porous particles and a first reagent comprising a polymer to a solvent. In an embodiment, the particles are coated with 2% by weight polyvinylpyrrolidone (PVP).
[0351] 4 g PVP was charged into 25 mL of methanol and warmed and stirred on a hotplate until a homogenous solution was obtained. The solution was decanted over 20 g of sorbent previously coated with polyamine and an aminosilane in a 100 ml beaker. The mixture was mixed until the sorbent was thoroughly wetted by the solution. The beaker was placed in a vacuum oven at 80 C. and 50 mbar for 12 hrs until a dry product was obtained.
[0352] In an embodiment, the third procedure was used to obtain the sample DAMO+PEI sorbent+2 wt % cellulose acetate (CA) described in Example 4 (Table 3 and Table 4).
Example 9Fourth Procedure for Forming Coated Particles (First Reagent)
[0353] This example provides a method comprising forming a plurality of coated particles by introducing at least a portion of a plurality of porous particles and a first reagent comprising a polymer to a solvent. In an embodiment, the particles are coated with 2% by weight cellulose acetate (CA).
[0354] 4 g CA was charged into 25 mL of THF and warmed and stirred on a hotplate until a homogenous solution was obtained. The solution was decanted over 20 g of sorbent previously coated with polyamine and an aminosilane in a 100 ml beaker. The mixture was mixed until the sorbent was thoroughly wetted by the solution. The beaker was placed in a vacuum oven at 80 C. and 50 mbar for 12 hrs until a dry product was obtained.
[0355] In an embodiment, the fourth procedure was used to obtain the sample DAMO+PEI sorbent+2 wt % PVP described in Example 4 (Table 3 and Table 4).
Example 10Fifth Procedure for Forming Coated Particles (First Reagent)
[0356] This example provides a method comprising forming a plurality of coated particles by introducing at least a portion of a plurality of porous particles and a first reagent comprising a polymer to a solvent. In an embodiment, the particles are coated with 10% by weight polysulfone.
[0357] 5 g of 35K mW polysulfone was charged and 50 mL of THF was charged into a 200 mL flask. A stir bar was added and the flask stoppered and was heated to 70 C. in a sand bath. The solution was stirred until the complete dissolution of the polymer was observed. The solution was decanted over 50 g of previously prepared silica coated with amines (PEI and DAMO 7.7/36) in a 200 mL jar. The mixture was thoroughly stirred until no dry spots were observed. The mixture was placed in a vacuum oven at 80 C. and 50 mbar for 12 hrs until a dry product was obtained.
[0358] In an embodiment, the fifth procedure was used to obtain the sample DAMO+PEI sorbent+10% Polysulfone described in Example 4 (Table 3 and Table 4).
[0359] A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other implementations are within the scope of the following claims.