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WO2018187588A1 - Élément de membrane d'oxyde de graphène sélectivement perméable au gaz - Google Patents

Élément de membrane d'oxyde de graphène sélectivement perméable au gaz Download PDF

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Publication number
WO2018187588A1
WO2018187588A1 PCT/US2018/026283 US2018026283W WO2018187588A1 WO 2018187588 A1 WO2018187588 A1 WO 2018187588A1 US 2018026283 W US2018026283 W US 2018026283W WO 2018187588 A1 WO2018187588 A1 WO 2018187588A1
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WIPO (PCT)
Prior art keywords
gas permeable
permeable membrane
membrane element
graphene oxide
gas
Prior art date
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PCT/US2018/026283
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English (en)
Inventor
Shijun Zheng
Weiping Lin
Peng Wang
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of WO2018187588A1 publication Critical patent/WO2018187588A1/fr
Priority to EP19717406.3A priority Critical patent/EP3774002A1/fr
Priority to PCT/US2019/025520 priority patent/WO2019195380A1/fr
Priority to JP2020554395A priority patent/JP7096357B2/ja
Priority to CA3097434A priority patent/CA3097434A1/fr
Priority to KR1020207032049A priority patent/KR20200140356A/ko
Priority to CN201980035684.XA priority patent/CN112203748A/zh
Priority to TW108112188A priority patent/TW202003101A/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/148—Organic/inorganic mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • B01D71/0211—Graphene or derivates thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B01D71/521—Aliphatic polyethers
    • B01D71/5211—Polyethylene glycol or polyethyleneoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides

Definitions

  • the present embodiments are related to polymeric membrane elements, such as a membrane including graphene materials with selective gas permeability.
  • This disclosure relates to a graphene oxide (GO) composition suitable for gas separation applications, such as separating C0 2 from other gas streams.
  • the GO composition may be prepared by using one or more water soluble polymers. Water can be used as a solvent in preparing these GO compositions, which makes the preparation process more environmentally friendly and more cost effective.
  • Some embodiments include a gas permeable element comprising: a porous support; and a composite coated on the support, wherein the composite comprises a diamine-functionalized graphene oxide material and a polyether block amide, wherein the diamine-functionalized graphene oxide material is distributed within the polyether block amide; and wherein the gas permeable element is selectively permeable to C0 2 gas.
  • Some embodiments include a method of making a gas permeable element described herein, comprising: curing an aqueous mixture that is coated onto a porous support. In some embodiments, curing is carried out at room temperature until dry.
  • the porous support is coated with the aqueous mixture by applying the aqueous mixture onto the porous support, and repeating as necessary to achieve a layer having a thickness of about 0.1-10 ⁇ .
  • the aqueous mixture is formed by mixing a diamine- functionalized graphene oxide material and a polyether block amide in an aqueous liquid.
  • Some embodiments include a method of preparing a diamine-functionalized graphene oxide material, comprising: mixing graphene oxide and a dimethyl alkyldiamine in an aqueous liquid, followed by heating the mixture at about 30-90 °C for about 4-24 hours, then cooling the mixture to room temperature, and quenching the mixture in an alcohol.
  • Some embodiments include a gas separation device, comprising: a wall separating a first plenum containing a first gas and second plenum containing a second gas, wherein the wall defines an aperture that allows fluid communication between both plena; and the gas permeable element described herein occluding the aperture, and wherein the device selectively allows C0 2 gas to pass between the plena.
  • FIG. 1 is a depiction of a possible embodiment of an element without a protective coating.
  • FIG. 2 is a depiction a possible embodiment of an element with a protective coating.
  • FIG. 3 is a depiction of a possible embodiment for the method of making an element.
  • FIG. 4 is a diagram depicting the experimental setup for the gas permeability testing.
  • a selectively gas permeable membrane element includes a membrane element that is selectively permeable for some gas and selectively impermeable for other gases.
  • the gas permeable element may be selectively permeable to a gas of one species or multiple species, such as C0 2 , but selectively impermeable to gas of one or more other species, such as N 2 , air, or reducing gases.
  • the selectively permeable element can be permeable to C0 2 while being relatively impermeable to N 2 .
  • a compound or a chemical structure such as graphene oxide
  • optionally substituted it includes a compound or a chemical structure that either has no substituents (i.e., unsubstituted), or has one or more substituents (i.e., substituted).
  • substituent has the broadest meaning known in the art, and includes a moiety that replaces one or more hydrogen atoms attached to a parent compound or structure.
  • a substituent may be any type of group that may be present on a structure of an organic compound, which may have a molecular weight (e.g., the sum of the atomic masses of the atoms of the substituent) of 15-50 g/mol, 15-100 g/mol, 15-150 g/mol, 15-200 g/mol, 15-300 g/mol, or 15-500 g/mol.
  • a molecular weight e.g., the sum of the atomic masses of the atoms of the substituent
  • a substituent comprises, or consists of: 0-30, 0-20, 0-10, or 0-5 carbon atoms; and 0-30, 0-20, 0-10, or 0-5 heteroatoms, wherein each heteroatom may independently be: N, O, S, P, Si, F, CI, Br, or I; provided that the substituent includes one C, N, O, S, P, Si, F, CI, Br, or I atom.
  • substituents include, but are not limited to, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, hydroxy, alkoxy, aryloxy, acyl, acyloxy, alkylcarboxylate, thiol, alkylthio, cyano, halo, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxyl, trihalomethanesulfonyl, trihalome
  • the term “molecular weight” is used with respect to a moiety or part of a molecule to indicate the sum of the atomic masses of the atoms in the moiety or part of a molecule, even though it may not be a complete molecule.
  • the term “fluid” includes any substance that continually deforms, or flows, under an applied shear stress. Such non-limiting examples of fluids include Newtonian and/or non-Newtonian fluids. In some embodiments, examples of Newtonian can be gases, liquids, and/or plasmas. In some embodiments, non- Newtonian fluids can be plastic solids (e.g., corn starch aqueous solution, toothpaste).
  • the term “fluid communication” means that a fluid can pass through a first component and travel to and through a second component or more components regardless of whether they are in physical communication or the order of arrangement.
  • the present disclosure relates to gas separation elements wherein a composite material with high mechanical and chemical stability may be used to remove undesirable gases from a primary gas stream. This element material may be suitable for purification of an unprocessed fluid stream, or removal of a gas pollutant.
  • Some selectively-permeable polymeric elements can have selective permeability to certain gas species, such as C0 2 .
  • Some selective gas permeable elements described herein can be GO-based elements having a highly selective permeability to C0 2 .
  • the GO-based elements may comprise multiple layers, wherein at least one layer comprises a GO-based composite of a graphene oxide (GO) material embedded in a polymer matrix.
  • GO graphene oxide
  • the graphene oxide can be functionalized.
  • the functionalized graphene oxide (FGO) comprises a diamine-functionalized GO.
  • the polymer can comprise a polyether block amide.
  • the selectively permeable element comprises a porous support or substrate, such as a porous support comprising a polymer or hollow fibers.
  • the composite is a GO-based composite that is disposed on the porous support.
  • the GO-composite can be in a layer form.
  • the selectively permeable element may further comprise a protective layer.
  • the protective layer can comprise a hydrophilic polymer.
  • the fluid passing through the selectively permeable element travels through all of its components regardless of whether they are in physical communication or their order of arrangement.
  • a gas permeable element 100 may be configured as depicted in Figures 1 and 2.
  • selectively permeable membrane element 100 can include porous support 120.
  • Composite 110 is coated onto porous support 120.
  • the element may further comprise a protective coating, 140.
  • the porous support or substrate may be sandwiched between two composite layers.
  • the gas permeable element selectively allows certain gas species to pass through while retaining the remaining gas species.
  • the gas upstream of the membrane element can comprise a mixture of C0 2 and another gas.
  • the other gas can comprise N 2 , air, or reducing gases.
  • the gas in the downstream of the membrane element can contain an increased molar fraction of C0 2 , as compared to the molar fractions of C0 2 in the gas in the upstream of the membrane element.
  • the element may provide a durable gas removal system that can be used to remove C0 2 from other gases such as N 2 , air, or reducing gases.
  • the element can exhibit a C0 2 permeability of about 1- 150 barrer, about 5-100 barrer, about 10-95 barrer, about 15-95 barrer, about 10-50 barrer, about 10-20 barrer, about 20-30 barrer, about 30-40 barrer, about 40-45 barrer, about 40-50 barrer, about 16.5 barrer, about 32.5 barrer, about 39.2 barrer, about 40.3 barrer, about 41.5 barrer, or any permeability in a range bounded by any of these values.
  • the element can exhibit an N 2 permeability of about 0.1-
  • an element may be selectively permeable.
  • the element can have a high selectivity of C0 2 in permeability over N 2 .
  • the selectivity of C0 2 to N 2 can be about 8-100 fold, about 20-70 fold; about 30- 65 fold, about 30-40 fold, about 40-45 fold, about 40-50 fold, 50-60 fold, about 55-65 fold, about 33.3 fold, about 39.9 fold, about 40.6 fold, about 44.3 fold, about 60.2 fold, or any selectivity in a range bounded by any of these values.
  • the elements described herein comprise a GO-based polymeric composite.
  • the GO-based composite comprises a graphene oxide material and a polymer, wherein the graphene oxide material can be distributed or dispersed in the polymer matrix.
  • the polymer can comprise a polyether block amide.
  • the graphene oxide can be functionalized.
  • the GO-based composite can be in a layer form with any suitable thickness.
  • some GO-based composite layers may have a thicknesses of about 5-2000 nm, about 5-1000 nm, about 1000-2000 nm, about 10-500 nm, about 500-1000 nm, about 50-500 nm, about 50-400 nm, about 600-1000 nm, about 600-800 nm, about 500-7000 nm, about 600-6500 nm, about 2000-3000 nm, about 6000-6500 nm, about 100 nm, about 200 nm, about 250 nm, about 300 nm, about 600 nm, about 800 nm, about 2000 nm, about 2600 nm, about 6400 nm, or any thickness in a range bounded by any of these values.
  • graphene Oxide In general, graphene-based materials have many attractive properties, such as a 2-dimensional sheet-like structure with extraordinary high mechanical strength and nanometer scale thickness. Graphene oxide (GO), an exfoliated oxidation of graphite, can be mass produced at low cost. With its high degree of oxidation, graphene oxide has high water permeability and also exhibits versatility to be chemically modified in structure to have many functional groups, such as an amino-group or a hydroxyl group or a combination thereof to form functionalized graphene oxide (FGO).
  • a graphene oxide material may be optionally substituted. In some embodiments, the optionally substituted graphene oxide may contain a graphene which has been chemically modified, or functionalized.
  • Functionalized graphene oxide includes one or more functional groups not present in graphene oxide, such as functional groups that are not OH, COOH or epoxide group directly attached to a C- atom of the graphene base.
  • functional groups that may be present in functionalized graphene include halogen, alkene, alkyne, cyano, ester, amide, or amine.
  • the graphene oxide can be functionalized by an amine.
  • the amine can be a diamine, such as an alkyldiamine.
  • the alkyldiamine can be substituted at a terminal position, or may be a terminal substituted alkyldiamine.
  • the alkyldiamine can be substituted by two methyl groups, or may be a dimethyl alkyldiamine.
  • the dimethyl alkyldiamine can comprise (2- (dimethylamino)ethyl)amine-yl with structure represented by Formula 1 below:
  • one or more functional groups can covalently attach to the graphene oxide.
  • one or more functional groups can react to an epoxide group on the surface of the graphene oxide.
  • (2- (dimethylamino)ethyl)amine-yl functionalized graphene may be depicted as the following:
  • At least about 99%, at least about 95%, at least about 90%, at least about 80%, at least about 70%, at least about 60%, at least about 50%, at least about 40%, at least about 30%, at least about 20%, at least about 10%, or at least about 5% of the graphene oxide molecules may be functionalized.
  • the functionalized graphene oxide material may provide selective permeability for gases, fluids, and/or vapors.
  • the graphene oxide material may be in the form of sheets, planes or flakes.
  • the graphene material may have a surface area of about 100-5000 m 2 /g, about 150-4000 m 2 /g, about 200-1000 m 2 /g, about 500-1000 m 2 /g, about 1000-2500 m 2 /g, about 2000-3000 m 2 /g, about 100-500 m 2 /g, about 400-500 m 2 /g, or any surface area in a range bounded by any of these values.
  • the graphene oxide material may be in the form of platelets having 1, 2, or 3 dimensions with size of each dimension independently in the nanometer to micron range.
  • the graphene material may have a platelet size in any one of the dimensions, or may have a square root of the area of the largest surface of the platelet, of about 0.05-100 ⁇ , about 0.05-50 ⁇ , about 0.1- 50 ⁇ , about 0.5-10 ⁇ , about 1-5 ⁇ , about 0.1-2 ⁇ , about 1-3 ⁇ , about 2-4 ⁇ , about 3-5 ⁇ , about 4-6 ⁇ , about 5-7 ⁇ , about 6-8 ⁇ , about 7-10 ⁇ , about 10- 15 ⁇ , about 15-20 ⁇ , about 50-100 ⁇ , about 60-80 ⁇ , about 50-60 ⁇ , about 25-50 ⁇ , or any platelet size in a range bounded by any of these values.
  • the graphene oxide material can comprise at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99% of graphene material having a molecular weight of about 5,000 Daltons (Da) to about 200,000 Da.
  • the mass percentage of the diamine relative to the total mass of the diamine-functionalized graphene oxide is about 0.1-1%; about 1-5%, about 5-10%; 10-50 wt%, about 10-30 wt%, about 20-40 wt%, about 30-50 wt%, about 15-25 wt%, about 20-30 wt%, about 25-35 wt%, about 30-40%, about 40-50%, about 50-60%, about 55-60%, or any weight percent in a range bounded by any of these values.
  • the diamine-functionalized graphene oxide has a nitrogen mass that, relative to the total mass of the diamine-functionalized graphene oxide, that is about 4-8%, about 4-5%, about 4.5-5.5%, about 5-6%, about 5-7%, about 5.9-6.4%, about 6-6.5%, about 6.1-6.6%, 6-6.2%, about 6.3-6.8%, about 5.5-6.5%, about 6-7%, about 6.5-7.5%, about 7-8%, about 6.1%, or any mass percent in a range bounded by any of these values.
  • the mass percentage of the graphene oxide material relative to the total mass or weight of the GO-based composite can be about 0.1-10 wt%, about 0.15-5 wt%, about 0.2-2.5 wt%, about 0.25-2.0 wt%, about 0.3-1.5 wt%, about 0.5-1.0 wt%, about 0.1-0.5 wt%, about 0.3-0.7 wt%, about 0.5-0.9 wt%, about 0.7-1.1 wt%, about 0.9-1.3 wt%, about 1-1.5 wt%, about 0.5 wt%, about 1 wt%, or any mass percentage in a range bonded by any of these values.
  • the GO-based composite can comprise a polymer.
  • the polymer can comprise a thermoplastic elastomer.
  • the thermoplastic elastomer can comprise a block amide of nylon and polyether, or a polyether block amide.
  • the polyether block amide can comprise a block copolymer of a polyamide with a hydroxyl- terminated polyether.
  • the thermoplastic elastomer moieties can be crosslinked, or covalently bonded, with themselves to form a polymer matrix.
  • some of the thermoplastic elastomer moieties can be crosslinked while others may be only in physical contact without crosslinking.
  • the graphene oxide material can be physically suspended within the polymer matrix.
  • the block copolymer can be obtained polycondensation of one or more polyamides and one or more polyethers.
  • the polyamide can comprise a polyamide A represented by - NH(CH 2 )x-iCO- wherein x is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 such as polyamide A6 ( -NH(CH 2 ) 5 CO-), polyamide All ( -NH(CH 2 )i 0 CO-), polyamide A12 ( -NH(CH 2 )nCO-), or a polyamide B represented by - NH(CH 2 )xNHCO(CH 2 )y- 2 CO- wherein x is 3-20, such as 3, 3-4, 4-5, 5-6, 6-7, 7-8, 8-9, 9- 10, 10-11, 11-12, 12-13, 13-14, 14-15, 15-16, 16-17, 17-18, 18-19, 19-20, or 20, and y is 3-20, such as 3, 3-4, 4-5, 5-6
  • the polyamide segment can range from about 1 polyamide to about 50 polyamides long.
  • the hydroxyl-terminated polyether can comprise a polyether of poly(tetramethylene oxide) (H-(OCH 2 -CH 2 -CH 2 -CH 2 ) z -OH)or polyethylene oxide (H-(OCH 2 -CH 2 ) z -OH), wherein z is about 1 to about 100.
  • the polyether block amide can be described by the trade names PEBAX ® (Arkema, Colombes, France) and/or VESTAMID ® E Evonik Industries, Marl, Germany), such as PEBAX MH 1657 (e.g.,
  • the molecular weight of the thermoplastic elastomer may be about 100- 1,000,000 Da, about 10,000-500,000 Da, about 10,000-50,000 Da, about 50,000- 100,000 Da, about 70,000-120,000 Da, about 80,000-130,000 Da, about 90,000- 140,000 Da, about 90,000-100,000 Da, about 95,000-100,000 Da, about 98,000 Da, or any molecular weight in a range bounded by any of these values.
  • a porous support may be any suitable material and in any suitable form upon which a layer, such as a layer of a GO-based composite, may be deposited or disposed.
  • the porous support can comprise hollow fibers or porous material.
  • Some porous supports can comprise a non-woven fabric.
  • the porous material can be a polymer.
  • the polymer may be polyamide (Nylon), polyimide (PI), polyvinylidene fluoride (PVDF), polyethylene (PE), polyethylene terephthalate (PET), polysulfone (PSF), polyether sulfone (PES), and/or mixtures thereof.
  • the porous support is PSF.
  • the porous support is PVDF.
  • Some elements may further comprise a protective coating.
  • the protective coating can be disposed on top of the selectively permeable element to protect it from the environment.
  • the protective coating may have any composition suitable for protecting the selectively permeable element from the environment.
  • Many polymers are suitable for use in a protective coating such as one or a mixture of hydrophilic polymers, e.g.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • PEG polyethylene glycol
  • PEO polyethylene oxide
  • POE polyoxyethylene
  • PAA polyacrylic acid
  • PMMA polymethacrylic acid
  • PAM polyacrylamide
  • PEI polyethylenimine
  • PES polyethersulfone
  • MC methyl cellulose
  • chitosan poly (allylamine hydrochloride) (PAH), poly (sodium 4-styrene sulfonate) (PSS), and any combinations thereof.
  • Some protective coatings can comprise PVA. VI. Gas Separation Device.
  • Some embodiments include a gas separation device.
  • the device can comprise a wall separating a first plenum containing a first gas and a second plenum containing a second gas, wherein the first gas is unprocessed and the second gas is processed.
  • the wall can define an aperture allowing fluid communication between the first gas in the first plenum and the second gas in the second plenum.
  • a selectively permeable gas element can occlude the aperture such that all fluid communication between the first and second plena must go through the selectively permeable membrane element.
  • the element can comprise any of the aforementioned selectively gas permeable elements.
  • the device may selectively allow C0 2 gas to pass between the plena.
  • Some embodiments include methods for making any one of the aforementioned selectively gas permeable elements comprising: (a) obtaining a functionalized graphene oxide material, (b) mixing the graphene oxide material and a polyether block amide in an aqueous liquid to generate a composite mixture; (c) applying the composite mixture to a porous support to achieve a coated support; and (d) curing the coated support.
  • the step of applying the mixture to a porous support can be repeated as necessary to achieve the desired thickness of the composite layer that is about 0.1-10 ⁇ .
  • the selectively gas permeable element can further comprise a protective layer. An example of one possible method of making elements is shown in Figure 3.
  • the step of obtaining a functionalized graphene oxide material can comprise generating a diamine-functionalized graphene oxide material.
  • functionalizing the graphene oxide comprises mixing the graphene oxide with an alkyldiamine and allowing them to react at certain conditions.
  • the alkyldiamine can be substituted at terminal.
  • the alkyldiamine can be substituted at terminal by two methyl groups to generate dimethyl alkyldiamine, such as N ⁇ N 1 - dimethylethane-l,2-diamine.
  • reacting the graphene oxide and the alkyldiamine can be achieved by heating the reaction mixture at an elevated temperature of about 30 °C, about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, to about 90 °C, such as about 60 °C; for a duration of about 4 hours to about 24 hours, such as about 16 hours.
  • the step of heating also comprises stirring the mixture.
  • the reaction mixture can be further cooled to room temperature followed by quenching the reaction with an alcohol, such as isopropyl alcohol.
  • Some methods can further comprise purifying the products of the reaction, which results in a functionalized graphene oxide material.
  • the step of mixing graphene oxide material and a polyether block amide in an aqueous liquid to generate a composite mixture can be accomplished by dissolving appropriate amounts of functionalized graphene oxide material and polyether block amide in water.
  • the polyether block amide can comprise any of the aforementioned block copolymers of polyamide and a hydroxyl-terminated polyether.
  • Some methods comprise mixing at least two separate aqueous liquids, e.g., a functionalized graphene oxide based liquid and a polyether block amide based liquid inappropriate mass ratios to achieve the desired results.
  • Some methods comprise creating one aqueous mixture by dissolving appropriate amounts of graphene oxide material and polyether block amide together in the same aqueous liquid.
  • applying the composite coating mixture to the porous support can be done by methods known in the art for creating a layer of desired thickness.
  • applying the coating mixture to the support or substrate can be achieved by vacuum immersing the substrate into the coating mixture first, and then drawing the solution onto the substrate by applying a negative pressure gradient across the substrate until the desired coating thickness can be achieved.
  • applying the coating mixture to the substrate can be achieved by casting, blade coating, spray coating, dip coating, die coating, or spin coating. Some methods can further comprise gently rinsing the substrate with deionized water after each application of the coating mixture to remove excess loose material.
  • the coating is done such that a composite layer of a desired thickness is created.
  • the desired thickness of the composite layer can range from about 0.1-10 ⁇ , about 0.2-8 ⁇ , about 0.5-7 ⁇ , about 0.6-6.4 ⁇ , about 0.6 ⁇ , about 0.8 ⁇ , about 2.0 ⁇ , about 2.6 ⁇ , about 4.8 ⁇ , or about 6.4 ⁇ . This process results in a fully coated substrate, or a coated support.
  • the curing of the coated support can be done at certain temperatures for certain times sufficient enough to form a dry selectively gas permeable element.
  • the coated support can be heated at a temperature of about 10-100 °C, about 20-50 °C, about 23 °C, or about room temperature. In some embodiments, the heating can be done for a duration of about 30 seconds, about 1 minute, about 15 minutes, about 30 minutes, about 1 hour, about 3 hours, about 5 hours, or until dry.
  • the coated substrate can be cured at room temperature or at 23 °C until dry.
  • the method for fabricating a selectively gas permeable element further comprises subsequently applying a protective coating on the element.
  • the applying a protective coating comprises adding a hydrophilic polymer layer.
  • applying a protective coating comprises coating the element with a polyvinyl alcohol aqueous solution. Applying a protective layer can be achieved by methods such as blade coating, spray coating, dip coating, spin coating, and etc.
  • applying a protective layer can be achieved by dip coating of the element in a protective coating solution for about 1- 10 minutes, about 1-5 minutes, about 5 minutes, or about 2 minutes.
  • the method further comprises drying the element at about 75-120 °C for about 5-15 minutes, or at about 90 °C for about 10 minutes. This process results is a selectively gas permeable element with a protective coating.
  • Embodiment 1 A gas permeable membrane element comprising:
  • the composite comprises a diamine-functionalized graphene oxide material and a polyether block amide, wherein the diamine-functionalized graphene oxide material is distributed within the polyether block amide;
  • gas permeable membrane element is selectively permeable to C0 2 gas.
  • Embodiment 2 The gas permeable membrane element of embodiment 1, wherein the porous support is a non-woven fabric.
  • Embodiment s. The gas permeable membrane element of embodiment 1 or 2, wherein the porous support comprises polyamide, polyimide, polyvinylidene fluoride, polyethylene, polyethylene terephthalate, polysulfone, or polyether sulfone.
  • Embodiment 4 The gas permeable membrane element of embodiment 1, 2, or 3, wherein the porous support is polysulfone (PSF).
  • Embodiment 5. The gas permeable membrane element of embodiment 1, 2, or 3, wherein the porous support is polyvinylidene fluoride (PVDF).
  • Embodiment 6. The gas permeable membrane element of embodiment 1, 2, 3, 4, or 5, wherein the diamine-functionalized graphene oxide comprises a graphene oxide with one or more functional groups of dimethyl alkyldiamine.
  • Embodiment 7 The gas permeable membrane element of embodiment 6, wherein the dimethyl alkyldiamine comprises 2-dimethylaminoethylamine-yl with structure represented by:
  • Embodiment s The gas permeable membrane element of embodiment 6, wherein the mass percentage of diamine-functionalized graphene oxide to the total composite is about 0.1 wt% to about 10 wt%.
  • Embodiment 9 The gas permeable membrane element of embodiment 6, wherein the mass percentage of diamine-functionalized graphene oxide to the total composite is about 0.5 wt% to about 1 wt%.
  • Embodiment 10 The gas permeable membrane element of embodiment 6, wherein the mass percentage of diamine-functionalized graphene oxide to the total composite is about 0.5 wt%.
  • Embodiment 11 The gas permeable membrane element of embodiment 6, wherein the mass percentage of diamine-functionalized graphene oxide to the total composite is about 1 wt%.
  • Embodiment 12 The gas permeable membrane element of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the polyether block amide comprises a block co-polymer of a polyamide and a hydroxyl-terminated polyether.
  • Embodiment 13 The gas permeable membrane element of embodiment 12, where the polyamide comprises a polyamide A represented by the formula: -N H(CH2)x iCO- wherein x is from 2 to 20.
  • Embodiment 14 The gas permeable membrane element of embodiment 12, where the polyamide comprises a polyamide B represented by the formula: - N H(CH2)xN HCO(CH2)y-2CO- wherein x and y are independently from 3 to 20.
  • Embodiment 15 The gas permeable membrane element of embodiment 12, where the hydroxyl-terminated polyether comprises a poly(tetramethylene oxide) represented by the formula: H-(0(CH2)4)z-OH, wherein z is from 1 to 100.
  • a poly(tetramethylene oxide) represented by the formula: H-(0(CH2)4)z-OH, wherein z is from 1 to 100.
  • Embodiment 16 The gas permeable membrane element of embodiment 12, wherein the hydroxyl-terminated polyether comprises a polyethylene oxide represented by the formula: H-(OCH2CH2)z-OH, wherein z is from 1 to 100.
  • Embodiment 17 The gas permeable membrane element of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, the composite is in a form of layer that has a thickness of about 0.1 ⁇ to about 10 ⁇ .
  • Embodiment 18 The gas permeable membrane element of embodiment 17, the composite is in a form of layer that has a thickness of about 0.6 ⁇ to about 6.4 ⁇ .
  • Embodiment 19 The gas permeable membrane element of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18, further comprising a protective coating.
  • Embodiment 20 The gas permeable membrane element of embodiment 19, wherein the protective coating is disposed on the top of the gas permeable membrane.
  • Embodiment 21 The gas permeable membrane element of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, having reduced N 2 permeability and enhanced CO2 selectivity in permeability over N2.
  • Embodiment 22 The gas permeable membrane element of embodiment 21, having reduced N2 permeability by at least 50%.
  • Embodiment 23. The gas permeable membrane element of embodiment 21, having reduced N2 permeability by about 80% or more.
  • Embodiment 24. The gas permeable membrane element of embodiment 21, having enhanced C0 2 selectivity in permeability over N 2 by at least 30-fold.
  • Embodiment 25 The gas permeable membrane element of embodiment 21, having enhanced C0 2 selectivity in permeability over N 2 by about 60-fold.
  • Embodiment 26 A gas separation device comprising: the gas permeable membrane element of embodiment 1 in fluid communication with: 1) a first plenum containing a first gas, and 2) a second plenum containing a second gas, wherein the gas permeable membrane element selectively allows C0 2 gas to pass from the first plenum to the second plenum.
  • Embodiment 27 A method of making a gas permeable element comprising:
  • porous support is coated with the aqueous mixture by applying the aqueous mixture to the porous support, and repeating as necessary to achieve a layer having a thickness of about 0.1 ⁇ to about 10 ⁇ ;
  • aqueous mixture is formed by mixing a diamine-functionalized graphene oxide material and a polyether block amide in an aqueous liquid.
  • Embodiment 28 The method of embodiment 27, wherein the diamine- functionalized graphene oxide material is obtained by mixing graphene oxide and a dimethyl alkyldiamine in an aqueous liquid followed by heating the resulting mixture at about 30 °C to about 90 °C for about 4 hours to about 24 hours, then cooling the mixture to room temperature, and finally quenching the mixture in an alcohol.
  • Embodiment 29 The method of c embodiment 28, wherein the dimethyl alkyldiamine comprises N 1 ,N 1 -dimethylethane-l,2-diamine.
  • Embodiment 30 The method of embodiment 27, wherein the polyether block amide comprises a block co-polymer of a polyamide and a hydroxyl-terminated polyether.
  • Embodiment 31 The method of embodiment 27, wherein the porous support is polysulfone (PSF) or polyvinylidene fluoride (PVDF).
  • PSF polysulfone
  • PVDF polyvinylidene fluoride
  • Embodiments of the selectively gas permeable elements described herein have improved performance as compared to other selectively permeable membranes.
  • Graphene Oxide (GO) Solution Preparation GO was prepared from graphite using the modified Hummers method. Graphite flakes (2.0 g) (Sigma Aldrich, St. Louis, MO, USA, 100 mesh) were oxidized in a mixture of 2.0 g of NaN0 3 (Aldrich), 10 g KMn0 4 of (Aldrich) and 96 mL of concentrated H 2 S0 4 (Aldrich, 98%) at 50 °C for 15 hours. The resulting paste like mixture was poured onto 400 g of ice followed by adding 30 mL of hydrogen peroxide (Aldrich, 30%).
  • the resulting solution was then stirred at room temperature for 2 hours to reduce the manganese dioxide, then filtered through a filter paper and washed with Dl water.
  • the solid was collected and then dispersed in Dl water with stirring, centrifuged at 6300 rpm for 40 minutes, and the aqueous layer was decanted. The remaining solid was then dispersed in Dl water again and the washing process was repeated 4 times.
  • the purified GO was then dispersed in Dl water under sonication (power of 10 W) for 2.5 hours to get the GO dispersion (0.4 wt%) as GO-1.
  • GO Functionalization To a GO dispersion in water (0.4 g in 100 mL) was added N 1 ,N 1 -dimethylethane-l,2-diamine (1.2 g, Aldrich). The resulting mixture was stirred at 60 °C for 16 hours and then cooled. After cooling to room temperature, the entire mixture was then poured into isopropanol (500 mL, Aldrich) to give black precipitate. The resulting precipitate was then filtered, washed with isopropanol (Aldrich), and then dried under vacuum to afford 500 mg of a solid.
  • N 1 ,N 1 -dimethylethane-l,2-diamine 1.2 g, Aldrich
  • Example 2.1.1 Preparation of a Gas Permeable Membrane.
  • Example 2.1.1.1 Preparation of Additional Gas Permeable Membranes. Additional membranes were constructed using the methods similar to Example 1.1.1 and Example 2.1.1, with the exception that parameters were varied as shown in Table 1. Specifically, individual concentrations were varied, and the knife coating was adjusted to vary the dry thickness of the membrane. Additionally for some embodiments a second-type of support, PVDF (CS Hyde Co., Lake Villa, IL USA), was used instead of PSF.
  • PVDF CS Hyde Co., Lake Villa, IL USA
  • the procedure was varied as follows. Instead of filtration, the coating solution was deposited on the membrane surface using a die caster (Taku-Die 200, Die-Gate Co., Ltd., Tokyo, Japan), which was set to create the desired coating thickness.
  • Membrane Numbering Scheme is MD-J.K.L, or CMD-J.K.L, wherein
  • Comparative Example 2.2.1 Preparation of Comparative Membranes.
  • CMD-1.1.1 A comparative gas permeable membrane (CMD-1.1.1) was created using methods similar to those used in Example 2.1.1 with the exception that a non- functionalized graphene oxide, GO-1 was used instead of functionalized graphene oxide, FGO-1, and the thickness was varied as shown in Table 1.
  • CMD-1.2.1 and CMD-1.2.2 Two additional comparative membranes, CMD-1.2.1 and CMD-1.2.2, were also created which contained the bare substrates (e.g., PSF and PVDF respectively) coated with PEBAX alone without GO or FGO.
  • Example 2.2.2 Preparation of a Membrane with a Protective Coating (Prophetic).
  • any of the membranes can be coated with protective layers.
  • a PVA solution of 2.0 wt% can be prepared by stirring 20 g of PVA (Aldrich) in 1 L of Dl water at 90 "C for 20 minutes until all the granules dissolved. The solution can then be cooled to room temperature. The selected substrates can be immersed in the solution for 10 minutes and then removed. Excess solution remaining on the membrane can then be removed by paper wipes. The resulting assembly can then be dried in an oven (DX400, Yamato Scientific) at 90 °C for 30 minutes. A membrane with a protective coating can thus be obtained.
  • Example 3.1 Performance Testing of Selected Membranes.
  • Gas Permeability Testing The selective gas permeability of GO-based membrane for C0 2 was found to be high as compared to other gases, such as N 2 . To determine the selective gas permeability an experimental setup similar to the one depicted in Figure 4 was used. First, the sample to be measured was first enclosed in a filter pressure test stand (stainless steel, 47 mm dia., XX45 047 00, Millipore, Billerica, MA USA). The test stand was set up such that it was placed in fluid communication between two vacuum cylinders (150 mL, 316L-HDF4-150, Swagelok, San Diego, CA USA) via an isolation valves.
  • a filter pressure test stand stainless steel, 47 mm dia., XX45 047 00, Millipore, Billerica, MA USA.
  • the test stand was set up such that it was placed in fluid communication between two vacuum cylinders (150 mL, 316L-HDF4
  • the upstream vacuum cylinder was in fluid communication with a gas source via a tee and isolation valve, where the gas source allows reconfiguration to different species of gases.
  • the tee further is in fluid communication to a vacuum pump via an isolation valve which allows for the evacuation the upstream cylinder before testing.
  • the downstream cylinder is in fluid communication with a vacuum pump via an isolation valve.
  • the downstream cylinder is in further fluid communication with the vacuum pump via yet another isolation valve that allows evacuation of the downstream cylinder and then isolation before testing.
  • Both upstream and downstream vacuum cylinders are instrumented to read the cylinder pressures via an upstream gauge (MG1-100-9V, SSI Technologies, Janesville, Wl USA) and a downstream gauge (DG25, Ashcroft Inc., Stratford, CT USA).
  • the tee-valve is set to vacuum and so does the isolation values to the downstream vacuum so that the residual gas in the entire test section can be evacuated. Once the residual gas is evacuated, the test section isolation valves are closed to isolate the test section. The tee-valve is then switched to the gas source of the desired gas to be tested. The downstream vacuum cylinder is then isolated from the vacuum pump to create a downstream vacuum condition. The upstream vacuum cylinder is then filled with the desired pressure of gas to be measured and then isolated from the gas source, to create an upstream pressure condition.
  • the two isolation valves on each side of the test stand are opened and the gas is allowed to pass from the upstream pressure condition through the gas membrane to the downstream vacuum condition.
  • the change in pressures as a function of time can then be used to determine the volumetric flow rate.
  • the difference in upstream vacuum cylinder was set to about 1 bar above atmospheric pressure, and downstream pressure was set to a vacuum or approximately zero bar such that the pressure differential across the membrane was about 1500 torr, or 2 bar. Similarly the test was repeated for C0 2 as the subject gas.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne des éléments perméables au gaz comprenant un composite d'oxyde de graphène fonctionnalisé distribué à l'intérieur d'un amide séquencé de polyéther, qui sont revêtus sur un support poreux, la membrane pouvant être sélectivement perméable à des gaz sélectionnés, tels que le CO2. L'invention concerne également des procédés de fabrication de tels éléments perméables au gaz, des procédés et des dispositifs d'utilisation des éléments pour éliminer des gaz tels que le CO2 à partir de flux de gaz non traités.
PCT/US2018/026283 2017-04-06 2018-04-05 Élément de membrane d'oxyde de graphène sélectivement perméable au gaz Ceased WO2018187588A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP19717406.3A EP3774002A1 (fr) 2018-04-05 2019-04-03 Membrane de matrice mélangée avec de l'oxyde de graphène et du polymère d'amide polyéther pour déshydrater du gaz
PCT/US2019/025520 WO2019195380A1 (fr) 2018-04-05 2019-04-03 Membrane de matrice mélangée avec de l'oxyde de graphène et du polymère d'amide polyéther pour déshydrater du gaz
JP2020554395A JP7096357B2 (ja) 2018-04-05 2019-04-03 ガスの脱水素化のためのグラフェンオキシドおよびポリエーテルアミドポリマーとの混合マトリックス膜
CA3097434A CA3097434A1 (fr) 2018-04-05 2019-04-03 Membrane de matrice melangee avec de l'oxyde de graphene et du polymere d'amide polyether pour deshydrater du gaz
KR1020207032049A KR20200140356A (ko) 2018-04-05 2019-04-03 가스의 탈수를 위한, 그래핀 산화물과 폴리에테르 아미드 중합체를 지닌 혼성 매트릭스 막
CN201980035684.XA CN112203748A (zh) 2018-04-05 2019-04-03 用于气体脱水的具有氧化石墨烯和聚醚酰胺聚合物的混合基质膜
TW108112188A TW202003101A (zh) 2018-04-05 2019-04-08 選擇透氣的氧化石墨烯薄膜

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