WO2020257348A1 - Membrane résistante au chlore, à composé d'oxyde de graphène réticulé avec de la séricine, et son procédé de fabrication - Google Patents

Membrane résistante au chlore, à composé d'oxyde de graphène réticulé avec de la séricine, et son procédé de fabrication Download PDF

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Publication number
WO2020257348A1
WO2020257348A1 PCT/US2020/038232 US2020038232W WO2020257348A1 WO 2020257348 A1 WO2020257348 A1 WO 2020257348A1 US 2020038232 W US2020038232 W US 2020038232W WO 2020257348 A1 WO2020257348 A1 WO 2020257348A1
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Prior art keywords
selectively permeable
graphene oxide
permeable membrane
membrane element
protective coating
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PCT/US2020/038232
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English (en)
Inventor
Shijun Zheng
Weiping Lin
Tissa Sajoto
Isamu KITAHARA
Ozair Siddiqui
Wan-Yun Hsieh
Bita BAGGE
Peng Wang
Takashi Kondo
Yuji YAMASHIRO
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Nitto Denko Corporation
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Publication of WO2020257348A1 publication Critical patent/WO2020257348A1/fr

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    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • 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
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
    • B01D69/144—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers" containing embedded or bound biomolecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration

Definitions

  • Reverse osmosis membranes have been used for the generation of potable water from saline water.
  • TFC thin-film composite
  • a thin aromatic polyamide selective layer on top of a microporous substrate, typically a polysulfone membrane on a non-woven polyester.
  • these membranes can provide excellent salt rejection and high-water flux, the reverse osmosis processes in which they are used lack desired energy efficiency.
  • Reverse osmosis membranes can also be compromised by fouling resulting from algae growth, which may cause a decrease of water flux and higher energy consumption.
  • One current response to fouling resulting from algae growth has been to incorporate chlorine or chloramine into the aqueous feed solution in order to suppress the growth of biological species on the reverse osmosis membrane surface.
  • chlorine and chloramine even if used at low levels, may be detrimental to the reverse osmosis membrane structure and cause a decrease in salt rejection and water flux.
  • a selectively permeable membrane element includes a membrane or porous support, and a protective coating including a crosslinked mixture of a graphene oxide compound and a crosslinker including sericin.
  • the protective coating is disposed on a surface of the membrane or porous support and is effective for protecting the membrane or porous support from chlorine degradation.
  • a desalination method includes applying to a selectively permeable membrane element a saline solution including at least one salt and water in a manner effective for providing a portion of the solution that passes through the selectively permeable membrane element with a lower salt content.
  • the selectively permeable membrane element includes a membrane or porous support, and a protective coating including a crosslinked mixture of a graphene oxide compound and a crosslinker including sericin.
  • the protective coating is disposed on a surface of the membrane or porous support and is effective for protecting the membrane or porous support from chlorine degradation.
  • a method of making a selectively permeable membrane element includes the steps of (1) mixing a graphene oxide compound and sericin; (2) applying the resulting mixture on a membrane or porous support to form a protective coating on said membrane or said porous support; and (3) curing the selectively permeable membrane element to facilitate crosslinking within the mixture.
  • FIG. 1 is a schematic illustration of a protective coated selectively permeable membrane element.
  • FIG. 2 is a schematic illustration of one non-limiting process for making a selectively permeable membrane element.
  • FIG. 3 is a schematic illustration of a test cell in which a selectively permeable membrane element may be placed for mechanical strength and salt rejection testing.
  • the present disclosure generally relates to a selectively permeable membrane element. More particularly, but not exclusively, the present disclosure relates to a selectively permeable membrane element which includes a protective coating which is effective for protecting the membrane element from chlorine degradation.
  • the protective coating may be disposed on a surface of a membrane or porous support, and it may include a crosslinked mixture of a graphene oxide compound and a sericin.
  • Certain graphene materials have properties which may be desirable for various applications. Among these is a 2-dimentional sheet-like structure having nanometer scale thickness and high mechanical strength.
  • Graphene oxide which may be prepared from the exfoliative oxidation of graphite, can be mass produced at a low cost.
  • Graphene oxide is unique in that it contains oxygen groups on its surface that can readily react with various nucleophiles to create a more functionalized surface.
  • the oxygen groups of graphene oxide are generally hydroxyl groups, carboxyl groups, or epoxide groups which can react with a variety of molecules including but not limited to amines, amides, alcohols, carboxylic acids and sulfonic acids.
  • graphene oxide membranes Unlike traditional membranes, where water is transported through the pores of the material, in graphene oxide membranes the transportation of water can be between the interlayer spaces.
  • the capillary effect of graphene oxide may result in long water slip lengths that offer fast water transportation rates.
  • the selectivity and water flux of a graphene oxide membrane may be tuned by manipulating the interlayer distance of the graphene sheets. In some cases, this manipulation may be accomplished by crosslinking.
  • the surface of graphene oxide contains a large number of carbon-carbon double bonds, which can chemically react with and absorb chlorine and chloramine.
  • the present disclosure relates to a selectively permeable membrane element which includes a hydrophilic composite material with resistance to chlorine fouling, low organic compound permeability, and desired mechanical and chemical stability and which may be useful in a reverse osmosis membrane.
  • the composite material is highly hydrophilic and provides high mechanical and chemical stability.
  • the selectively permeable membrane elements disclosed herein may be suitable for purifying drinking water, or for waste water treatment, amongst other possibilities.
  • Some selectively permeable membrane elements described herein are graphene oxide-based membrane elements having a high- water flux along with resistance to detrimental effects to the membrane structure caused by chlorine and chloramine (hereinafter referred to as "chlorine fouling", which may result in improved efficiency of the reverse osmosis membranes and improved water recovery/separation efficiency.
  • a graphene oxide-based membrane element may include one or more filtering layers, where at least one layer may include a composite protective coating which includes a graphene oxide compound crosslinked with a hydrophilic biopolymer.
  • the hydrophilic biopolymer may be the silk protein sericin.
  • the protective coating may be formed by reacting a graphene oxide compound with a crosslinker including sericin. It is believed that crosslinking a graphene oxide compound with sericin may protect the membrane elements from chlorine fouling.
  • the membrane elements described herein may be prepared using water as a solvent, reducing environmental impact and increasing cost effectiveness of the related manufacturing process.
  • a selectively permeable membrane element described herein may be suitable for the desalination of seawater or purification of unprocessed fluids.
  • One or more of the selectively permeable membrane elements may be useful for solute removal from an unprocessed fluid, for example in waste water treatment.
  • one or more of the selectively permeable membrane elements may be suitable for fluid streams exposed to chlorinated solutions.
  • the selectively permeable membrane elements disclosed herein can be useful in preventing chlorine fouling.
  • the selectively permeable membrane elements described herein may be useful in the removal of water/water vapor from an unprocessed fluid.
  • the selectively permeable membrane elements disclosed herein may have a high rate of water flux.
  • the selectively permeable membrane elements disclosed herein may have a high level of salt rejection.
  • one or more of the selectively permeable membrane elements described herein may include a protective coating, and the protective coating may chemically absorb chlorine and resist chlorine degradation.
  • a selectively permeable membrane element may include a porous support and a protective coating
  • the protective coating may include a crosslinked graphene oxide compound.
  • the crosslinked graphene oxide compound may be formed by reacting a mixture of a graphene oxide compound and a sericin crosslinker.
  • the protective coating mixture may be disposed on a surface of the membrane or porous support, and the protective coating may protect the membrane or porous support from chlorine fouling.
  • a selectively permeable membrane element 100 includes a membrane or porous support 120 and a protective coating 110 is coated or disposed onto the membrane or porous support 120.
  • the membrane or porous support 120 may be a polymer.
  • the polymer may be polyethylene, polypropylene, polysulfone, polyether sulfone, polyvinylidene fluoride, polyamide, polyimide, and/or mixtures thereof, just to provide a few examples.
  • the polymer may be polysulfone.
  • the membrane or porous support may include a polyamide.
  • the polyamide may include a selective membrane.
  • the polyamide may include ESPA.
  • the membrane or porous support may be a reverse osmosis membrane.
  • the membrane or porous support may include hollow fibers.
  • the hollow fibers may, for example, be cast or extruded.
  • the hollow fibers may be made according to a variety of techniques, including for example those described in United States Patent Numbers 4,900,626 and 6,805,730 and United States Patent Application Publication No. 2015/0165389.
  • the membrane or porous support may include a surface for fluid communication or contact with a chlorine solution (e.g., the protective coating).
  • a protective coating can be disposed upon the membrane or porous support's surface, which is in fluid communication with a chlorine solution.
  • the protective coating may include a crosslinked graphene oxide compound in some forms.
  • the crosslinked graphene oxide compound may be formed by reacting a mixture of a graphene oxide compound with a hydrophilic biopolymer crosslinker.
  • the hydrophilic biopolymer may include sericin.
  • the crosslinked graphene oxide compound can be formed by reacting a mixture of a graphene oxide compound with a crosslinker including sericin.
  • the protective coating may include an optionally substituted graphene oxide compound and a sericin crosslinker in fluid communication.
  • the protective coating including an optionally substituted graphene oxide material and a sericin crosslinker can be disposed on a surface of the membrane or porous support.
  • the graphene oxide compound and the sericin crosslinker are crosslinked.
  • the fluid passing through the selectively permeable membrane element travels through all of the components regardless of whether they are in physical communication or order of arrangement.
  • the protective coating includes a graphene oxide compound.
  • the graphene oxide compound may include graphene oxide, a reduced graphene oxide, a functionalized graphene oxide, or combinations thereof.
  • the graphene oxide compound may be an optionally substituted graphene oxide.
  • the optionally substituted graphene oxide may be arranged amongst the crosslinker material in such a manner as to create an exfoliated nanocomposite, an intercalated nanocomposite, or a phase-separated micro-composite.
  • a phase-separated micro-composite phase may occur when, although mixed, the optionally substituted graphene oxide exists as a separate and distinct phase apart from the crosslinker.
  • An intercalated nanocomposite may occur when the crosslinker compounds begin to intermingle amongst or between the graphene platelets, but the graphene material may not be distributed throughout the crosslinker.
  • an exfoliated nanocomposite phase the individual graphene platelets may be distributed within or throughout the crosslinker.
  • An exfoliated nanocomposite phase may be achieved by chemically exfoliating the graphene material by a modified Hummer's method, a process known to persons skill in the art.
  • the majority of the graphene material may be staggered to create an exfoliated nanocomposite as a dominant material phase.
  • a graphene oxide may include any graphene having hydroxyl substituents and saturated carbon atoms.
  • a modified graphene may include a functionalized graphene base.
  • more than about 90%, about 80-90%, about 70-80%, about 60-70%, about 50-60%, about 40-50%, about 30-40%, about 20-30%, or about 10-20%, or any other percentage in a range bounded by these values, of the optionally substituted graphene oxide may be functionalized.
  • the majority of optionally substituted graphene oxide may be functionalized.
  • substantially all the optionally substituted graphene oxide may be functionalized.
  • the functionalized graphene oxide may include a graphene base and functional compound.
  • a graphene base may be "functionalized," becoming functionalized graphene when there are one or more types of functional groups present.
  • the graphene oxide compound may be functionalized as a result of synthesis reactions, such as in graphene oxide where epoxide- based functional groups are formed.
  • the graphene oxide compound may be selected from reduced graphene oxide and/or graphene oxide.
  • the graphene oxide compound may be graphene oxide, reduced-graphene oxide, functionalized graphene oxide, functionalized reduced-graphene oxide or combinations thereof.
  • the optionally substituted graphene oxide may be in the form of sheets, planes or flakes.
  • the graphene material may have a surface area of between about 100 m 2 /grn to about 5000 m 2 /grn.
  • the graphene material may have a surface area of about 100-200 m 2 /gm, about 200-300 m 2 /gm, about 300-400 m 2 /gm, about 400-500 m 2 /gm, about 500-600 m 2 /gm, about 600-700 m 2 /gm, about 700-800 m 2 /gm, about 800-900 m 2 /gm, about 900-1000 m 2 /gm, about 1000-2000 m 2 /gm, about 2000-3000 m 2 /gm, about 3000-4000 m 2 /gm, or about 4000-5000 m 2 /gm, or any surface area in a range bounded by these surface areas.
  • the graphene oxide may be in the form of platelets having one or more dimensions in the nanometer to micron range.
  • the platelets may have dimensions in the x, y and/or z dimension.
  • the platelets may have: an average x dimension between about 0.05 pm to about 50 pm, about 0.05-0.1 pm, about 0.1- 0.2 pm, about 0.2-0.3 pm, about 0.3-0.4 pm, about 0.4-0.5 pm, about 0.5-0.6 pm, about 0.6- 0.7 pm, about 0.7-0.8 pm, about 0.8-0.9 pm, about 0.9-1 pm, about 1-2 pm, about 2-5 pm, about 5-10 pm, about 10-20 pm, about 20-30 pm, about 30-40 pm, about 40-50 pm, about 0.05-1 pm, or any value in a range bounded by any of these lengths; an average y dimension between about 0.05 pm to about 50 pm, about 0.05-0.1 pm, about 0.1-0.2 pm, about 0.2-0.3 pm, about 0.3-0.4 pm, about
  • the platelets include an average size of about 0.05 miti to about 50 miti, about 0.05-0.1 miti, about 0.1-0.2 miti, about 0.2-0.3 miti, about 0.3- 0.4 miti, about 0.4-0.5 miti, about 0.5-0.6 miti, about 0.6-0.7 miti, about 0.7-0.8 miti, about 0.8- 0.9 miti, about 0.9-1 miti, about 1-2 miti, about 2-5 miti, about 5-10 miti, about 10-20 miti, about 20-30 miti, about 30-40 miti, about 40-50 miti, about 0.05-1 miti, or any size in a range bounded by any of these values.
  • the optionally substituted graphene oxide may be unsubstituted. In some embodiments, the optionally substituted graphene oxide may comprise a non-functionalized graphene base. In some embodiments, the graphene material may comprise a functionalized graphene base prepared by any suitable method.
  • the mass percentage of the graphene oxide base relative to the total composition of the protective coating can be between about 1 wt% and about 95 wt%. In some embodiments, the mass percentage of the graphene oxide base relative to the total composition of the graphene material containing layer can be about 1-2 wt%, about 2-5 wt%, about 5-10 wt%, about 10-20 wt%, about 20-30 wt%, about 30-40 wt%, about 40-50 wt%, about 50-60 wt%, about 60-70 wt%, about 70-80 wt%, about 80-90 wt%, or about 90- 95 wt%.
  • the sericin crosslinker contains a combination of polar side groups, such as hydroxyl groups and amine groups. Sericin comprises 18 different amino acids, and about 32% of the amino acids are serine. The sericin chain contains numerous free amino and free hydroxyl nucleophilic pendent groups which may covalently crosslink with graphene oxide.
  • the crosslinked graphene oxide-sericin protective layer may have chlorine-reactive sites such as amide linkages (-CON H-), free hydroxyl groups (-OH), and free amine groups (-N H2). These reactive functional groups may act as chlorine-sensitive or chlorine-reactive sites on the graphene oxide-sericin protective layer and therefore operate as sacrificial sites for chlorine reactivity, allowing for the extended durability of the polyamide layer.
  • Graphene oxide may also have a high aspect ratio which provides a large available gas/water diffusion surface over that of other materials and has the ability to decrease the effective pore diameter of any substrate supporting material to minimize contaminant infusion while retaining flux rates.
  • the epoxy or hydroxyl groups of graphene oxide may increase the hydrophilicity of the materials, and thus contribute to the increase in water vapor permeability and selectivity of the membrane.
  • a compound or chemical structure such as graphene oxide
  • optionally substituted it includes a compound or chemical structure that has no substituents (i.e., unsubstituted), or has one or more substituents (i.e., substituted).
  • substituted 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 about 15-50 g/mol, about 15-100 g/mol, about 15-150 g/mol, about 15-200 g/mol, about 15-300 g/mol, or about 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: about 0-30, about 0-20, about 0-10 or about 0-5 carbon atoms: and about 0-30, about 0-20, about 0-10 or about 0-5 heteroatoms, wherein each heteroatom may independently be: N, O, S, Si, F, Cl, Br, or I: provided that the substituent includes one C, N, O, S, Si, F, Cl, 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, a I kylthio, 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,
  • molecular weight may be 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 the molecule, even though it may not be a complete molecule.
  • fluid means any substance that continually deforms, or flows, under an applied shear stress, such as gases, liquids, and/or plasmas.
  • fluid communication means that the individual components, membranes, or layers, referred to as being in fluid communication are arranged such that a fluid passing through the membrane travels through all the identified components regardless of whether they are in physical communication or order of arrangement.
  • chlorine resistant refers to the permeable membrane having a substantially similar or reduced membrane activity loss when exposed to chlorine, chloramine or hypochlorites in the fluid medium.
  • the protective coating may further include at least one additional crosslinker.
  • the at least one additional crosslinker may be calcium chloride (CaCh), potassium tetraborate (K2B4O7, or KBO), poly(ethylene glycol) diglycidyl ether (PEG-DE), and/or combinations thereof.
  • the mass ratio of a graphene oxide compound to sericin in the protective coating may be from about 1:100 to about 15:1.
  • the weight ratio of optionally substituted graphene oxide to optionally substituted crosslinker may be from about 1:100 to about 15:1 (e.g. 15 mg graphene oxide and 1 mg sericin), about 1:90, about 1:80, about 1:70, about 1:60, about 1:50, about 1:40, about 1:30, about 1:20, about 1:10, about 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 10:1, about 15:1, or any ratio in a range bounded by any of these values.
  • the weight ratio of optionally substituted graphene oxide to optionally substituted crosslinker may be about 1:11, about 1:2.3, about 1:1.45, about 1:1, about 1.04:1; about 1.58:1, or about 2.5:1.
  • the sericin can be about 15-95 wt%, about 20-30 wt%, about 30-40 wt%, about 40-50 wt%, about 50-60 wt%, about 60-70 wt%, about 70-80 wt%, about 80-90 wt%, about 90-95 wt%, or any weight percentage in a range bounded by any of these values, of the total weight percentage of the protective coating.
  • the ranges may encompass about 28 wt%, about 38 wt%, about 48 wt%, about 50 wt%, about 58 wt%, about 68 wt%, about 78 wt%, or about 88 wt%.
  • the graphene oxide may be about 5-75 wt%, about 5-15 wt%, about 15-25 wt%, about 25-35 wt%, about 35-45 wt%, about 45-55 wt% about 55-65 wt%, about 65-75 wt%, or any weight percentage in a range bounded by any of these values, of the total weight of the protective coating.
  • the ranges may encompass about 8 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, or about 70 wt%.
  • the additional crosslinker may include calcium chloride (CaCh).
  • the calcium chloride may be about 0-10 wt%, about 0-1 wt%, about 1-8 wt%, about 1-10 wt%, about 1-2 wt%, about 2-3 wt%, about 3-4 wt%, about 4-5 wt%, about 5-6 wt%, about 6-7 wt%, about 7-8 wt%, about 8-9 wt%, about 9-10 wt%, about 1-3 wt%, about 3-5 wt%, or any weight percentage in a range bounded by any of these values, of the total weight of the protective coating.
  • the ranges may encompass one or more of the following weight percentages: about 2 wt% and about 4 wt%.
  • the additional crosslinker may include potassium tetraborate (K2B4O7).
  • the potassium tetraborate can be about 0-10 wt%, about 0-1 wt%, about 1-8 wt%, about 1-10 wt%, about 1-2 wt%, about 2-3 wt%, about 3-4 wt%, about 4-5 wt%, about 5-6 wt%, about 6-7 wt%, about 7-8 wt%, about 8-9 wt%, about 9-10 wt%, about 1-3 wt%, about 3-5 wt%, or any weight percentage in a range bounded by any of these values, of the total weight percentage of the protective coating.
  • the ranges may encompass one or more of the following weight percentages: about 2 wt% and about 4 wt%.
  • the additional crosslinker may include poly(ethylene glycol) diglycidyl ether (PEG-DE).
  • PEG-DE poly(ethylene glycol) diglycidyl ether
  • the PEG-DE can be about 0-10 wt%, about 0-1 wt%, about 1-8 wt%, about 1-10 wt%, about 1-2 wt%, about 2-3 wt%, about 3-4 wt%, about 4-5 wt%, about 5-6 wt%, about 6-7 wt%, about 7-8 wt%, about 8-9 wt%, about 9-10 wt%, about 1-3 wt%, about 3-5 wt%, or any weight percentage in a range bounded by any of these values, of the total weight percentage of the protective coating.
  • the ranges may encompass one or more of the following weight percentages: about 2 wt% and about 4 wt%.
  • a selectively permeable membrane element e.g., selectively permeable membrane element 100 in FIG. 1, include a membrane or porous support and a protective coating.
  • the selectively permeable membrane element may include a membrane or porous support, e.g., membrane or porous support 120, and a protective coating, e.g., protective coating 110.
  • the selectively permeable membrane may comprise a protective coating, and the protective coating can protect the components of the membrane or porous support from chlorinated environments and/or solutions.
  • the protective coating may include graphene oxide cross-linked with sericin. In some embodiments, the protective coating may be disposed on the surface of the membrane or porous support. The surface of the element can be exposed to, or in fluid communication with, a solution containing chlorine, hypochlorites, or other chlorine oxides.
  • the membrane or porous support may include any of the previously described copolymers.
  • the selectively permeable membrane element may include a separate salt rejection layer of a membrane construct. In some embodiments, the membrane or porous support may contain polyamide.
  • a selectively permeable membrane element may be permeable to water while being impermeable to gas, solute, or liquid material from passing therethrough.
  • the selectively permeable membrane element may provide a durable desalination system that can be selectively permeable to water, and less permeable to salts.
  • the selectively permeable membrane element may provide a durable reverse osmosis system that may effectively filter or desalinate saline/polluted water or feed fluids.
  • the selectively permeable membrane element with a protective coating may provide any or all of the above-mentioned functions.
  • the selectively permeable membrane element with a protective coating can provide substantially similar flux and/or salt rejection during or after contact with a chlorinated solution.
  • a protective coating including a graphene oxide/sericin mixture can also include at least one additional crosslinker.
  • the at least one additional crosslinker may be CaCh, K2B4O7, PEG-DE and/or a combination thereof.
  • the weight ratio of the additional crosslinker to graphene oxide can be from about 1:35 (e.g., 1 mg of additional crosslinker to 35 mg of graphene oxide) to about 1:2, about 1:35 to about 1:30, about 1:30 to about 1:25, about 1:25 to about 1:20, about 1:20 to about 1:15, about 1:15 to about 1:10, about 1:10 to about 1:5, about 1:5 to about 1:2, or about 1:2, about 1:15, about 1:20, about 1:25, about 1:30, about 1:35, or any weight ratio in a range bounded by any of these values.
  • 1:35 e.g., 1 mg of additional crosslinker to 35 mg of graphene oxide
  • the additional crosslinker may be about 0.5-6 wt%, about 1-5 wt%, about 2-4 wt%, about 0.5-1 wt%, about 1-2 wt%, about 2-3 wt%, about 3-4 wt%, about 4-5 wt%, or about 5-6 wt% of the total weight of the protective coating, or any wt% in a range bounded by any of these values. In some forms the ranges may encompass one or more of the following weight percentages: about 2 wt%, about 3 wt%, about 4 wt% and about 5 wt%.
  • the protective coating may have a thickness ranging from about 5-2500 nm, about 50- 2500 nm, about 500-1000 nm, about 1000-1500 nm, about 1500-2000 nm, about 2000-2500 nm, about 10-1000 nm, about 50-900 nm, about 50-800 nm, about 50-700 nm, about 50-600 nm, about 50-500 nm, about 50-400 nm, about 50-300 nm, about 100-200 nm, about 200- 300 nm, about 300-400 nm, about 400-500 nm, about 500-600 nm, about 600-700 nm, about 700-800 nm, about 800-900 nm, about 900-1000 nm, 1000-1100 nm, about 1100-1200 nm, about 1200-1300 nm, about 1300-1400 nm, about 1400-1500 nm, about 1500-1600 nm, about 1600-1700 nm,
  • the ranges may encompass the following thicknesses: about 600 nm, about 1300-1400 nm, about 1500-1600 nm, about 1700-1800 nm, about 1800-1900 nm, about 2100-2200 nm and about 2200-2300 nm.
  • the selectively permeable membrane element can provide a flux of about greater than at least 5 gallons per square feet per day (GFD), at least about 5-10 GFD, at least about 10-20 GFD, at least about 20-30 GFD, at least about 30-40 GFD, at least about 40-50 GFD, at least about 50-60 GFD, at least about 60-70 GFD, or at least about 5.0 GFD, or any flux in a range bounded by any of these values.
  • GFD gallons per square feet per day
  • the selectively permeable membrane element can provide a resistance to chlorine deterioration.
  • the selectively permeable membrane may maintain at least 75%, 75-80%, 80-85%, 85-90%, 90-95% 95-100%, or at least 100% of the original flux rate over a period of time, e.g., of at least about 100 hours, about 100-200 hours, about 200-300 hours, about 300-400 hours, about 400-500 hours, about 500- 600 hours, about 600-700 hours, about 700-800 hours, about 800-900 hours, about 900-1000 hours, about 1000-1200 hours, about 12-00-1400 hours, about 1400-1600 hours, about 1600- 1800 hours, about 1800-2000 hours, about 2000-4000 hours, about 4000-6000 hours, about 6000-8000 hours, about 8000-10000 hours, or at least about 10,000 hours, or any time period in a range bounded by any of these time periods.
  • the selectively permeable membrane may maintain at least about 75%, about 75-80%, about 80-85%, about 85-90%, about 90-95%, about 95-100%, or at least about 100% of the original flux rate after being in contact with an amount of chlorine exposure, e.g., of at least about 100 ppm-h, about 100-200 ppm-h, about 200-300 ppm-h, about 300-400 ppm-h, about 400-500 ppm-h, about 500-600 ppm-h, about 600-700 ppm-h, about 700-800 ppm-h, about 800-900 ppm-h, about 900-1000 ppm-h, about 1000-1200 ppm-h, about 1200-1400 ppm-h, about 1400-1600 ppm-h, about 1600-1800 ppm-h, about 1800-2000 ppm-h, about 2000-4000 ppm-h, about 4000-6000 ppm-h, about 6000-8000 ppm-h
  • the selectively permeable membrane may maintain at least about 75%, about 75-80%, about 80-85%, about 85-90%, about 90-95%, or about 95-100%, or at least about 80% of the original salt rejection rate after being in contact with an amount of chlorine exposure, e.g., of at least about 100 ppm-h, about 100-200 ppm-h, about 200-300 ppm-h, about 300-400 ppm-h, about 400-500 ppm-h, about 500-600 ppm-h, about 600-700 ppm-h, about 700-800 ppm-h, about 800-900 ppm-h, about 900-1000 ppm-h, about 1000- 1200 ppm-h, about 1200-1400 ppm-h, about 1400-1600 ppm-h, about 1600-1800 ppm-h, about 1800-2000 ppm-h, about 2000-4000 ppm-h, about 4000-6000 ppm-h, about 6000-8000
  • a method for preparation of the aforedescribed selectively permeable membrane element includes applying a protective coating (which may include one material or a mixture of materials) to a membrane or porous support by any suitable coating method, and then exposing the resulting membrane to a temperature of about 70 °C to about 120 °C for about 30 seconds to about 15 minutes.
  • a protective coating which may include one material or a mixture of materials
  • a selectively permeable membrane element described herein may be used in an arrangement where it is disposed between or separates a fluidly communicated first fluid reservoir and a second fluid reservoir.
  • the first reservoir may contain an unprocessed fluid, e.g., a feed fluid or solution, upstream and/or at the membrane.
  • the feed fluid or solution may include chlorine, hypochlorites, or other chlorine oxides.
  • the second reservoir may contain a processed fluid downstream and/or at the membrane.
  • the selectively permeable membrane element can allow passing of water therethrough while retaining the solute or contaminant fluid material.
  • the selectively permeable membrane element may allow filtering to selectively remove solute and/or suspended contaminants from feed fluid.
  • the selectively permeable membrane element may provide a desired flow rate.
  • the selectively permeable membrane element may provide a desired flux rate.
  • the selectively permeable membrane element can provide the desired flow rate and/or flux rate over a desired period of time, e.g., as described elsewhere herein.
  • the selectively permeable membrane element can maintain the desired salt rejection rate over a desired period of time, e.g., as described elsewhere herein.
  • the selectively permeable membrane element may comprise ultrafiltration material.
  • the selectively permeable membrane element may comprise additional crosslinkers described herein.
  • a method of desalinating water includes applying a saline water that includes one or more salts and water to a selectively permeable membrane element described herein.
  • the saline water is applied to the selectively permeable membrane element so that some of the water passes through the element, while at least some of the salt does not pass through the element, to yield water with a lower salt content.
  • step (1) further includes the addition of an additional crosslinker comprising calcium chloride (CaCh), potassium tetraborate (K2B4O7), poly(ethylene glycol) diglycidyl ether (PEG-DE), or a combination thereof.
  • the desired thickness may be, for example, between about 100 nm and about 2500 nm.
  • the curing may be performed at a temperature of 70 °C to 120 °C for 30 seconds to 15 minutes.
  • the protective coating mixture may be blade coated on a permeable substrate to create a thin film between about 100 nm to about 2500 nm, e.g., and may then cast on a substrate to form a partial element.
  • the mixture may be disposed upon the substrate— which may be permeable, or porous— by spray coating, dip coating, spin coating and/or other methods for deposition of the mixture on a substrate known to those skilled in the art.
  • the casting may be done by co extrusion, film deposition, blade coating or any other suitable method for deposition of a film on a substrate.
  • the mixture is cast onto a substrate by blade coating (or tape casting) by using a doctor blade and dried to form a partial element.
  • the thickness of the resulting cast tape may be adjusted by changing the gap between the doctor blade and the moving substrate.
  • the gap between the doctor blade and the moving substrate is in the range of about 0.002 mm to about 1.0 mm, although other variations are contemplated.
  • the gap between the doctor blade and the moving substrate is preferably between about 0.20 mm to about 0.50 mm.
  • the gap between the doctor blade and the moving substrate is about 10 mil.
  • the speed of the moving substrate may have a rate in the range of about 30 cm/min to about 600 cm/min. By adjusting the moving substrate speed and the gap between the blade and moving substrate, the thickness of the resulting protective coating layer may be expected to be between about 400 nm and about 2500 nm although other variations are possible.
  • Graphene Oxide Solution Preparation Graphene oxide (GO) was prepared from graphite using a modified Hummers method. Graphite flake (2.0 g MilliporeSigma, 100 mesh) was oxidized in a mixture of NaN03 (2.0 g), KMn04 (10 g) and concentrated 98% H2SO4 (96 mL) at 50 °C for 15 hrs. The resulting pasty mixture was poured into ice (400 g) followed by the addition of 30% hydrogen peroxide (20 mL). The solution was then stirred for two (2) hours to reduce manganese dioxide, then filtered through filter paper and washed with Dl water.
  • the solid was collected and dispersed in Dl water by stirring followed by centrifugation at 6,300 rpm for 40 minutes. Following the centrifugation, the aqueous layer was decanted. The remaining solid was dispersed in Dl water and the washing step was repeated four (4) more times. The purified GO was then dispersed in Dl water under sonication (20 W) for 2.5 hours, resulting in a 0.4 % GO dispersion.
  • Example 1.1.2 GO-Sericin coating preparations:
  • Composition GO/Sericin 50/50 (Tl): In a vial, 7.62 mL of GO solution (0.4 % in water), 0.61 mL of sericin solution (5 % in water), and 0.04 mL water were added, and the resulting solution was stirred for 15 minutes. Once mixed, the solution was poured on to a ESPA2+ substrate (Hydranautics, Oceanside, CA, USA) which was mounted on a coating station under vacuum and coated onto the substrate with a 10 mil spacer. The coated sample was then allowed to dry under vacuum for at least 20 minutes and finally baked inside an oven at 110 °C for 8 minutes.
  • ESPA2+ substrate Hydranautics, Oceanside, CA, USA
  • Composition GO/Sericin/KBO 50/48/2 (T2): In a vial, 7.82 mL of GO solution (0.4 % in water), 0.6 mL of sericin solution (5 % in water), and 0.062 mL KBO solution (2 % in water) were added, and the resulting solution was stirred for 15 minutes. Once mixed, the solution was poured on to an ESPA2+ substrate (Hydranautics, Oceanside, CA, USA) which was mounted on a coating station under vacuum and coated onto the substrate with a 10 mil spacer. The coated sample was then allowed to dry under vacuum for at least 20 minutes and finally baked inside an oven at 110 °C for 8 minutes.
  • ESPA2+ substrate Hydranautics, Oceanside, CA, USA
  • Composition GO/Sericin/CaCl2 50/48/2 (T3-A): In a vial, 7.82 mL of GO solution (0.4 % in water), 0.6 mL of sericin solution (5 % in water), and 0.062 mL CaCh solution (2 % in water) were added, and the resulting solution was stirred for 15 minutes. Once mixed, the solution was poured on to an ESPA2+ substrate (Hydranautics, Oceanside, CA, USA) which was mounted on a coating station under vacuum and coated onto the substrate with a 10 mil spacer. The coated sample was then allowed to dry under vacuum for at least 20 minutes and finally baked inside an oven at 110 °C for 8 minutes.
  • ESPA2+ substrate Hydranautics, Oceanside, CA, USA
  • Composition GO/Sericin/PEG-DE 50/48/2 (T4-C): In a vial, 7.82 mL of GO solution (0.4 % in water), 0.6 mL of sericin solution (5 % in water), and 0.062 mL PEG-DE solution (2 % in water) were added, and the resulting solution was stirred for 15 minutes. Once mixed, the solution was poured on to an ESPA2+ substrate (Hydranautics, Oceanside, CA, USA) which was mounted on a coating station under vacuum and coated onto the substrate with a 10 mil spacer. The coated sample was then allowed to dry under vacuum for at least 20 minutes and finally baked inside an oven at 110 °C for 8 minutes.
  • ESPA2+ substrate Hydranautics, Oceanside, CA, USA
  • the membranes were tested by placing them into a laboratory apparatus similar to the one shown in FIG 3. Once secured in the test apparatus, the membrane was exposed to the unprocessed fluid at a gauge pressure of 50 PSI. The water flux through the membrane was recorded at different time intervals to see the flux over time. The initial water flux was recorded, shown in Table 1. From the data collected, it was shown that the graphene oxide-sericin based membrane can withstand reverse osmosis pressures while providing sufficient flux.
  • a selectively permeable membrane element comprising:
  • a protective coating including a crosslinked mixture of a graphene oxide compound and a crosslinker including a sericin; wherein the protective coating is disposed on a surface of the membrane or porous support and is effective for protecting the membrane or porous support from chlorine degradation.
  • Embodiment 2 The selectively permeable membrane element of embodiment 1, wherein the graphene oxide compound includes a graphene oxide, a reduced graphene oxide, a functionalized graphene oxide, or a combination thereof.
  • Embodiment 3 The selectively permeable membrane element of embodiment 1 or 2, wherein the graphene oxide compound is graphene oxide.
  • Embodiment 4 The selectively permeable membrane element of any one of embodiments 1-3, further comprising at least one additional crosslinker.
  • Embodiment s The selectively permeable membrane element of embodiment 4, wherein the additional crosslinker comprises calcium chloride, potassium tetraborate, poly(ethylene glycol) diglycidyl ether (PEG-DE), or a combination thereof.
  • the additional crosslinker comprises calcium chloride, potassium tetraborate, poly(ethylene glycol) diglycidyl ether (PEG-DE), or a combination thereof.
  • Embodiment 6 The selectively permeable membrane element of embodiment 4 or 5, wherein the additional crosslinker comprises calcium chloride.
  • Embodiment ? The selectively permeable membrane element of any one of embodiments 4-6 wherein the additional crosslinker comprises potassium tetraborate.
  • Embodiment s The selectively permeable membrane element of any one of embodiments 4-7, wherein the additional crosslinker comprises poly(ethylene glycol) diglycidyl ether (PEG-DE).
  • PEG-DE poly(ethylene glycol) diglycidyl ether
  • Embodiment s The selectively permeable membrane element of any one of embodiments 4-8, wherein the additional crosslinker is present in an amount of about 1-8 wt% of the total weight of the protective coating.
  • Embodiment 10 The selectively permeable membrane element of any one of embodiments 1-9, wherein the weight ratio of graphene oxide to the crosslinker is about 1:100 to about 15:1.
  • Embodiment 11 The selectively permeable membrane element of any one of embodiments 1-10 7 wherein the weight ratio of graphene oxide to the crosslinker is about 1:11 to about 2.5:1.
  • Embodiment 12 The selectively permeable membrane element of any one embodiments 1-11, wherein the graphene oxide comprises platelets having a size between about 50 nm to about 1,000 nm.
  • Embodiment 13 The selectively permeable membrane element of any one of embodiments 1-12, wherein the protective coating comprises a thickness of about 400 nm to about 2,500 nm.
  • Embodiment 14 A desalination method, comprising applying to the selectively permeable membrane element of any one of embodiments 1-13 a saline solution including at least one salt and water in a manner effective for providing a portion of the solution that passes through the selectively permeable membrane element with a lower salt content.
  • Embodiment 15 A method of making a selectively permeable membrane element, comprising the steps of:
  • Embodiment 16 The method of embodiment 15, wherein the curing is performed at a temperature of 70 °C to 120 °C for 30 seconds to 15 minutes.
  • Embodiment 17 The method of embodiment 15, further comprising repeating step (2) as necessary to achieve a desired thickness of the protective coating.
  • Embodiment 18 The method of embodiment 17, wherein the desired thickness is between about 100 nm and about 2500 nm.
  • Embodiment 19 The method of embodiment 15, wherein step (1) further comprises mixing at least one of calcium chloride (CaCh), potassium tetraborate (K2B4O7), poly(ethylene glycol)diglycidyl ether (PEG-DE), or a combination thereof with the graphene oxide compound and sericin.
  • CaCh calcium chloride
  • K2B4O7 potassium tetraborate
  • PEG-DE poly(ethylene glycol)diglycidyl ether

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Abstract

Selon un mode de réalisation, l'invention concerne une membrane à perméabilité sélective pouvant être protégée de la dégradation due à une exposition à des oxydants à base de chlore. Certains modes de réalisation comprennent des éléments membrane à perméabilité sélective comportant un revêtement protecteur comprenant de l'oxyde de graphène et de la séricine, qui sont perméables à l'eau mais imperméables aux solutés. Selon un mode de réalisation, l'oxyde de graphène et la séricine sont réticulés, et le revêtement protecteur peut comprendre au moins un autre composé de réticulation.
PCT/US2020/038232 2019-06-20 2020-06-17 Membrane résistante au chlore, à composé d'oxyde de graphène réticulé avec de la séricine, et son procédé de fabrication WO2020257348A1 (fr)

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