Gas permeable membranes and methods of using thereof
Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membrane can comprise a support layer; and a selective polymer layer disposed on the support layer. The selective polymer layer can comprise a selective polymer matrix (e.g., hydrophilic polymer, an amine-containing polymer, a low molecular weight amino compound, a CO 2 -philic ether, or a combination thereof), and graphene oxide dispersed within the selective polymer matrix. The membranes can be used to separate carbon dioxide for hydrogen. Also provided are methods of purifying syngas using the membranes described herein.
1. A membrane comprising:
a support layer; and
a selective polymer layer disposed on the support layer, the selective polymer layer comprising a selective polymer matrix and graphene oxide dispersed within the selective polymer matrix wherein the selective polymer matrix comprises a hydrophilic polymer, amine-containing polymer, a CO 2 -philic ether, and a low molecular weight amino compound; and
wherein the low molecular weight amino compound has a molecular weight of less than 1,000 Da.
2. The membrane of claim 1 , wherein the amine-containing polymer is selected from the group consisting of polyvinylamine, polyallylamine, polyethyleneimine, poly-N-isopropylallylamine, poly-N-tert-butylallylamine, poly-N-1,2-dimethylpropylallylamine, poly-N-methylallylamine, poly-N,N-dimethylallylamine, poly-2-vinylpiperidine, poly-4-vinylpiperidine, polyaminostyrene, chitosan, copolymers, and blends thereof.
3. The membrane of claim 1 , wherein the low molecular weight amino compound comprises a salt of a primary amine or a salt of a secondary amine.
4. The membrane of claim 1 , wherein the low molecular weight amino compound comprises a salt defined by a general formula below
wherein R 1 , R 2 , R 3 , and R 4 are hydrogen or hydrocarbon groups having from 1 to 4 carbon atoms, n is an integer ranging from 0 to 4, and A m+ is a cation having a valence of 1 to 3, and m is an integer equal to the valence of the cation.
5. The membrane of claim 1 , wherein the low molecular weight amino compound comprises a salt selected from the group consisting of aminoisobutyric acid-potassium salt, aminoisobutyric acid-lithium salt, aminoisobutyric acid-piperazine salt, glycine-potassium salt, glycine-lithium salt, glycine-piperazine salt, dimethylglycine-potassium salt, dimethylglycine-lithium salt, dimethylglycine-piperazine salt, piperadine-2-carboxlic acid-potassium salt, piperadine-2-carboxlic acid-lithium salt, piperadine-2-carboxlic acid-piperazine salt, piperadine-4-carboxlic acid-potassium salt, piperadine-4-carboxlic acid-lithium salt, piperadine-4-carboxlic acid-piperazine salt, piperadine-3-carboxlic acid-potassium salt, piperadine-3-carboxlic acid-lithium salt, piperadine-3-carboxlic acid-piperazine salt, and blends thereof.
6. The membrane of claim 1 , wherein the low molecular weight amino compound comprises an amino acid salt.
7. The membrane of claim 6 , wherein the amino acid salt is defined by the formula below
wherein, independently for each occurrence in the amino acid, each of R 1 , R 2 , R 3 , and R 4 is selected from one of the following
or R 1 and R 3 , together with the atoms to which they are attached, form a five-membered heterocycle defined by the structure below when n is 1, or a six-membered heterocycle defined by the structure below when n is 2.
8. The membrane of claim 6 , wherein the amino acid salt comprises a glycinate salt, a sarcosinate salt, or an aminoisobutyrate salt.
9. The membrane of claim 1 , wherein the hydrophilic polymer comprises a polymer selected from the group consisting of polyvinylalcohol, polyvinylacetate, polyethylene oxide, polyvinylpyrrolidone, polyacrylamine, a polyamine polysiloxane, copolymers thereof, and blends thereof.
10. The membrane of claim 1 , wherein the CO 2 -philic ether is chosen from an alcohol ether, a polyalkylene alcohol ether, a polyalkylene glycol, a poly(oxyalkylene)glycol, a poly(oxyalkylene)glycol ether, an ethoxylated phenol, and combinations thereof.
11. The membrane of claim 1 , wherein the selective polymer matrix further comprises a cross-linking agent selected from the group consisting of formaldehyde, glutaraldehyde, maleic anhydride, glyoxal, divinylsulfone, toluenediisocyanate, trimethylol melamine, terephthalatealdehyde, epichlorohydrin, vinyl acrylate, and combinations thereof.
12. The membrane of claim 1 , wherein the graphene oxide has a carbon to oxygen ratio of from 3 to 20.
13. The membrane of claim 1 , wherein the graphene oxide has a carbon to oxygen ratio of from 1 to 3.
14. The membrane of claim 1 , wherein the selective polymer layer comprises from 0.01% to 5% by weight graphene oxide, based on the total dry weight of the selective polymer layer.
15. The membrane of claim 1 , wherein the graphene oxide is nanoporous.
16. The membrane of claim 1 , wherein the support layer comprises a gas permeable polymer chosen from polyamides, polyimides, polypyrrolones, polyesters, sulfone-based polymers, nitrile-based polymers, polymeric organosilicones, fluorinated polymers, polyolefins, copolymers thereof, and blends thereof.
17. The membrane of claim 1 , wherein the selective polymer matrix has a CO 2 :H 2 selectivity of from 50 to 500 at 107° C. and 31.7 bar feed pressure.
18. A method for separating a first gas from a feed gas stream, the method comprising contacting a membrane defined by claim 1 with the feed gas stream comprising the first gas under conditions effective to afford transmembrane permeation of the first gas.
19. The membrane of claim 9 , wherein the hydrophilic polymer comprises polyallylamine, polyvinyl amine, polyethylenimine, a copolymer thereof, or a blend thereof.