CN110650789A - High flux permeable reverse osmosis membrane and method of making same - Google Patents

High flux permeable reverse osmosis membrane and method of making same Download PDF

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CN110650789A
CN110650789A CN201780090691.0A CN201780090691A CN110650789A CN 110650789 A CN110650789 A CN 110650789A CN 201780090691 A CN201780090691 A CN 201780090691A CN 110650789 A CN110650789 A CN 110650789A
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membrane
microporous membrane
reverse osmosis
polyfunctional
water
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邱长泉
吕愉斌
刘敏玲
刘朝军
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Honeywell International Inc
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Honeywell International Inc
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    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • 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
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2325/00—Details relating to properties of membranes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
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    • 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
    • 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
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides

Abstract

A high permeability Reverse Osmosis (RO) membrane having a polyamide layer with embedded graphene oxide particles and a method of making the same are disclosed.

Description

High flux permeable reverse osmosis membrane and method of making same
Background
Cleaning drinking water is important for human health, as uncleaned water may contain bacteria, viruses and heavy metals that are harmful to humans. However, due to the growth of the population and the development of industry, a large amount of waste or contaminated water is being produced, which deteriorates the environment and threatens the health of people.
In many countries, the quality of drinking water provided by governments is compromised and citizens need to rely on additional filtration technology. RO (reverse osmosis) technology has dominated many water treatment applications because of its unique advantages in removing salts and contaminants from almost all water.
Therefore, it is important to develop ultra-low pressure RO membranes for residential water purification that can be competitive with, or even superior to, commercial RO membranes.
Generally, a successful ultra-low pressure RO membrane for use in a residential/commercial water purifier should meet such requirements of water flux of 3.6-7.0LMH @1bar and rejection of greater than 95%. Although many existing ultra low pressure RO membrane products are made using thin but selective PA (polyamide) layers, there is still a need to develop ultra low pressure RO membranes that can meet or exceed the above water flux parameters.
Disclosure of Invention
In one embodiment, the present invention provides a reverse osmosis membrane. The reverse osmosis membrane includes a microporous membrane having a polyamide material thereon, the polyamide material comprising graphene oxide, and the reverse osmosis membrane has 6.0 to 8.0L/m2Water flux per hour per bar (LMH per bar).
Surprisingly and advantageously, some embodiments of the membranes of the present invention have particularly high water flux and rejection rates due to the presence of graphene oxide in the polyamide material. It has been surprisingly found that some embodiments of reverse osmosis membranes prepared according to the methods described herein are capable of achieving greater water flux than some of the best commercially available reverse osmosis membranes.
Drawings
The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present invention.
Fig. 1 is an SEM (scanning electron microscope) image of a cross-section of a porous UF (ultra-fine) membrane substrate according to various embodiments.
Fig. 2 is an SEM image of a surface of an RO membrane according to various embodiments.
Fig. 3 is a chemical structure of Graphene Oxide (GO) according to various embodiments.
Fig. 4 is a structure of a conventional RO membrane with a GO embedded RO membrane according to various embodiments.
Detailed Description
Reference will now be made in detail to specific embodiments of the disclosed subject matter, examples of which are illustrated in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims of the disclosed subject matter.
Throughout this document, numerical values expressed as ranges are to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the ranges, but also all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" should be interpreted as including not only about 0.1% to about 5%, but also including individual values (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. Unless otherwise indicated, the phrase "about X to Y" has the same meaning as "about X to about Y". Likewise, unless otherwise indicated, the statement "about X, Y, or about Z" has the same meaning as "about X, about Y, or about Z".
In this document, the terms "a", "an" or "the" are used to include one or more than one unless the context clearly indicates otherwise. The term "or" is used to refer to a non-exclusive "or" unless otherwise indicated. The statement "at least one of a and B" or "at least one of a or B" has the same meaning as "A, B or a and B". Also, it is to be understood that the phraseology or terminology employed herein, and not otherwise specified, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid in reading the document and is not to be construed as limiting, and information related to section headings can occur within or outside of that particular section.
In the methods described herein, acts may be performed in any order, unless otherwise indicated herein, without departing from the principles of the invention. Further, unless explicit claim language mentions that the specified actions occur separately, they can occur simultaneously. For example, the claimed act of practicing X and the claimed act of practicing Y can be performed simultaneously within a single operation, and the resulting method will fall within the literal scope of the claimed method.
As used herein, the term "about" can allow for a degree of fluctuation in a value or range, such as within 10%, within 5%, or within 1% of a specified value or specified range limit, and includes the exact specified value or range.
The term "substantially" as used herein refers to a majority or majority, such as at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more, or 100%. As used herein, the term "substantially free" can mean completely free or containing trace amounts such that the amount of material present does not affect the material properties of the material comprising the composition such that the composition is from about 0 wt% to about 5 wt%, or from about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.5 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.01 wt%, or about 0.001 wt% or less of the material. The term "substantially free" can mean having a trace amount such that the composition is from about 0 wt% to about 5 wt%, or from about 0 wt% to about 1 wt%, or about 5 wt% or less, or less than, equal to, or greater than about 4.5 wt%, 4 wt%, 3.5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.5 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.01 wt%, or about 0.001 wt% or less, or about 0 wt% of the material.
As used herein, the term "amine" refers to a compound having, for example, the formula N (group)3Wherein each group can independently be H or non-H, such as alkyl, aryl, and the like. The amine may comprise R-NH2Such as alkyl amines, aryl amines, alkyl aryl amines; r2NH, where each R is independently selected, such as dialkylamines, diarylamines, arylalkylamines, heterocyclylamines, or the like; and R3N, where each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like. The term "amine" also includes ammonium ions as used herein.
As used herein, the term "amino group" refers to the form-NH2、-NHR、-NR2、-NR3 +Wherein each R is independently selected and is in the protonated form, -NR, as described above3 +Except that this cannot be protonated. Thus, any compound substituted with an amino group can be considered an amine. An "amino group" within the meaning of this document may be a primary, secondary, tertiary or quaternary amino group. "alkylamino" groups include monoalkylamino, dialkylamino, and trialkylamino groups.
As used herein, the term "solvent" refers to a liquid that can dissolve a solid, liquid, or gas. Non-limiting examples of solvents are siloxanes, organic compounds, water, alcohols, ionic liquids, and supercritical fluids.
As used herein, the term "substituted" used in conjunction with a molecule or organic group as defined herein refers to a state in which one or more hydrogen atoms contained therein are replaced with one or more non-hydrogen atoms. As used herein, the term "functional group" or "substituent" refers to a group that can be or be substituted on a molecule or organic group. Examples of substituents or functional groups include, but are not limited to, halogens (e.g., F, Cl, Br, and I); groups (such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo (carbonyl groups)) Groups, oxygen atoms in carboxyl groups (including carboxylic acids, carboxylates, and carboxylates)); a sulfur atom in a group (such as a thiol group, an alkylsulfide group, and an arylsulfide group, a sulfoxide group, a sulfone group, a sulfonyl group, and a sulfonamide group); nitrogen atoms in groups such as amines, hydroxylamines, nitriles, nitro groups, N-oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non-limiting examples of substituents that may be bonded to a substituted carbon (or other) atom include: F. cl, Br, I, OR, OC (O) N (R)2、CN、NO、NO2、ONO2Azido group, CF3、OCF3R, O (oxo), S (thiocarbonyl), C (O), S (O), methylenedioxy, ethylenedioxy, N (R)2、SR、SOR、SO2R、SO2N(R)2、SO3R、C(O)R、C(O)C(O)R、C(O)CH2C(O)R、C(S)R、C(O)OR、OC(O)R、C(O)N(R)2、OC(O)N(R)2、C(S)N(R)2、(CH2)0-2N(R)C(O)R、(CH2)0-2N(R)N(R)2、N(R)N(R)C(O)R、N(R)N(R)C(O)OR、N(R)N(R)CON(R)2、N(R)SO2R、N(R)SO2N(R)2、N(R)C(O)OR、N(R)C(O)R、N(R)C(S)R、N(R)C(O)N(R)2、N(R)C(S)N(R)2、N(COR)COR、N(OR)R、C(＝NH)N(R)2C (o) n (or) R, and C (═ NOR) R, where R can be hydrogen or a carbon-based moiety; for example, R may be hydrogen, (C)1-C100) Hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or where two R groups bonded to a nitrogen atom or adjacent nitrogen atoms may form a heterocyclic group together with one or more nitrogen atoms.
As used herein, the term "aryl" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms in the ring. Thus, aryl groups include, but are not limited to, phenyl, azulenyl, heptenyl, biphenyl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, naphthonaphthyl, naphthyl,
Figure BDA0002269187790000041
Phenyl, biphenylene, anthracenyl and naphthyl groups. In some embodiments, the aryl group comprises from about 6 to about 14 carbons in the ring portion of the group. The aryl group may be unsubstituted or substituted, as defined herein. Representative substituted aryl groups may be mono-or multiply substituted, such as, but not limited to, phenyl groups substituted at any one or more of the 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or naphthyl groups substituted at any one or more of the 2-to 8-positions thereof.
As used herein, the term "alkyl" refers to straight and branched chain alkyl and cycloalkyl groups having from 1 to 40 carbon atoms, from 1 to about 20 carbon atoms, from 1 to 12 carbons, or in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those having 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, isopentyl, and 2, 2-dimethylpropyl groups. As used herein, the term "alkyl" includes n-alkyl, iso-alkyl, and trans-iso-alkyl groups as well as other branched forms of alkyl groups. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxyl, cyano, carboxyl, nitro, thio, alkoxy, and halogen groups.
As used herein, the term "aromatic" refers to a cyclic aromatic hydrocarbon group that does not contain heteroatoms in the ring. Thus, the aromatic group may include phenyl, azulenyl, heptenyl, biphenyl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, naphthonaphthyl, naphthyl,
Figure BDA0002269187790000051
Phenyl, biphenylene, anthracenyl and naphthyl groups. In some embodiments, the aromatic group comprises from about 6 to about 14 carbons in the ring portion of the group. As defined herein, an aromatic group can be unsubstituted or substituted. Representative substituted aromatic groups may be mono-or multiply substituted, such as but not limited to 2-, 3-, 4-, on the phenyl ring,A phenyl group substituted in any one or more of the 5-or 6-positions, or a naphthyl group substituted in any one or more of the 2-to 8-positions thereof.
As used herein, the term "contact angle" refers to a measure of the wettability of a surface by a liquid. Contact angle thetaCIs given by the Young's formula, where γSG—γSl—γLG cosθC0, and γSG、γSLAnd gammaLGRespectively solid-vapor, solid-liquid, and liquid-vapor interfacial energies. The contact angle can be measured, for example, by profiling a liquid drop (e.g., water) on a collection surface (e.g., a membrane) and measuring the angle between the liquid-solid and liquid-vapor interfaces. Contact angle goniometers may be used for such measurements.
As used herein, the term "rejection" refers to the ratio of the concentration of solutes (such as metal salts) in the permeate (water that passes through the membrane) to the concentration of solutes in the retentate (water that does not pass through the membrane), expressed as a percentage. The formula R can be used as 100% × (1- (C)p/Cr) Calculating rejection ratio, where R is rejection ratio, CpIs the concentration of solute in the permeate, and CrIs the concentration of solute in the retentate.
As used herein, "LMH/bar" units are normalized flux units, where flux is in L/m2Pressure measurement per hour unit/1 bar.
Reverse osmosis membrane。
In one embodiment, a reverse osmosis membrane is provided. The reverse osmosis membrane includes a microporous membrane having a polyamide material thereon, the polyamide material comprising graphene oxide, and the reverse osmosis membrane has 6.0 to 8.0L/m2Water flux per hour per bar (LMH per bar). In some embodiments, the reverse osmosis membrane has a water flux of about 6.25 LMH/bar to about 8.0 LMH/bar, about 6.5 LMH/bar to about 8.0 LMH/bar, 6.75 LMH/bar to about 8.0 LMH/bar, 7.0 LMH/bar to about 8.0 LMH/bar, 7.25 LMH/bar to about 8.0 LMH/bar, 7.5 LMH/bar to about 8.0 LMH/bar, or about 7.5 LMH/bar to about 8.0 LMH/bar. In some embodiments, the reverse osmosis membrane has less than, equal to, or greater than about 7.1 LMH/bar, about 7.2 LMH/bar, about 7.3 LMH/bar, about 7.4 LMH/bar,A water flux of about 7.5 LMH/bar, about 7.6 LMH/bar, about 7.7 LMH/bar, about 7.8 LMH/bar, about 7.9 LMH/bar, or about 8.0 LMH/bar, or any range between any of these values.
In one embodiment, the microporous membrane has a thickness of about 30 μm to about 80 μm, a contact angle of about 60 degrees to about 90 degrees, and about 160L/m2Hour/bar to about 350L/m2Water flux per hour per bar (LMH per bar).
In one embodiment, the rejection rate of the reverse osmosis membrane is at least 95%. In some embodiments, the rejection rate of the reverse osmosis membrane is at least about 95.25%, 95.5%, 95.75%, 96.0%, 96.25%, 96.5%, 96.75%, 97.0%, 97.25%, 97.5%, 97.75%, 98.0%, 98.25%, 98.5%, 98.75%, 99.0%, 99.25%, 99.5%, or about 99.75%, or any range between any of these values.
In one embodiment, a method of making a reverse osmosis membrane includes reacting a polyfunctional acid chloride composition with a polyfunctional amine composition comprising graphene oxide on a microporous membrane to form a polyamide material on the microporous membrane. In some embodiments, the reverse osmosis membranes described herein are suitable for use in residential or commercial water filtration facilities. In some embodiments, the reverse osmosis membrane is suitable for home use by a consumer.
Multifunctional amine composition。
The polyfunctional amine can be any molecule having two or more amine functional groups. In some embodiments, the amine functional group can be a primary or secondary amine. In one embodiment, the polyfunctional amine may comprise primary and secondary amines. In one embodiment, the polyfunctional amine may be an aromatic diamine or triamine. Examples of the aromatic diamine may include substituted or unsubstituted 1, 2-diaminobenzene, 1, 3-diaminobenzene, and 1, 4-diaminobenzene. Examples of the aromatic triamine may include 1,2, 3-triaminobenzene and 1,3, 5-triaminobenzene. In one embodiment, the polyfunctional amine is 1, 3-diaminobenzene (m-phenylenediamine, MPD). The aromatic diamine may be further substituted with one or more groups such as, but not limited to, C1-4Alkyl, halogen (F, Cl or Br), nitrile (CN) and Nitro (NO)2)。
In another embodiment, the polyfunctional amine is present in an amount of about 0.01% to about 10% by weight of the polyfunctional amine composition. In another embodiment, the polyfunctional amine is present in an amount of about 0.01% to about 5%, about 0.01% to about 4%, about 0.01% to about 3%, about 0.01% to about 2%, about 0.01% to about 1.5%, about 0.01% to about 1%, about 0.05% to about 5%, about 0.05% to about 4%, about 0.05% to about 3%, about 0.05% to about 2%, about 0.05% to about 1.5%, about 0.05% to about 1%, 0.1% to about 5%, about 0.1% to about 4%, about 0.1% to about 3%, about 0.1% to about 2%, about 0.1% to about 1.5%, or about 0.1% to about 1% by weight of the polyfunctional amine composition. In some embodiments, the polyfunctional amine is present in an amount of about 0.5% to 1.5% by weight of the polyfunctional amine composition. In some embodiments, the polyfunctional amine is present in an amount less than, equal to, or greater than about 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or about 1.0 wt%. In some embodiments, metaphenylene diamine is present in an amount of about 0.5% by weight.
In one embodiment, the polyfunctional amine composition comprises water and at least one water-soluble organic solvent. In some embodiments, the water soluble organic solvent is also miscible with water. In some embodiments, the water soluble organic solvent is a polar aprotic solvent. Examples of water-soluble organic solvents include, but are not limited to, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), acetonitrile (MeCN), and Tetrahydrofuran (THF). In some embodiments, the ratio of water soluble organic solvent to water in the polyfunctional amine composition is about 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, or 90: 10. In some embodiments, the ratio of water soluble organic solvent to water in the polyfunctional amine composition is 1:99, 2:98, 3:97, 4:96, 5:95, 6:94, 7:93, 8:92, or 9: 91. In some embodiments, the ratio of water soluble organic solvent to water in the polyfunctional amine composition is 1.5:98.5, 2.5:97.5, 3.5:96.5, 4.5:95.5, or 5.5: 94.5. In one embodiment, the ratio of DMSO to water is 10: 90. In one embodiment, the ratio of DMF to water is 2.5: 97.5. In one embodiment, the ratio of NMP to water is 2.5: 97.5.
Multifunctional acid chloride compositions。
The polyfunctional acid chloride can be any molecule having two or more acid chloride functional groups. In some embodiments, the polyfunctional acid chloride comprises two acid chloride functional groups or three acid chloride functional groups. In one embodiment, the polyfunctional acid chloride is a polyfunctional aromatic acid chloride. Examples of polyfunctional aromatic acid chlorides include, but are not limited to, 1, 2-benzenedicarbonyl dichloride, 1, 3-benzenedicarbonyl dichloride, 1, 4-benzenedicarbonyl dichloride, or 1,3, 5-benzenetricarbonyl trichloride. In one embodiment, the polyfunctional acid chloride is 1,3, 5-benzenetricarbonyl trichloride (trimesoyl chloride, TMC).
In one embodiment, the polyfunctional acid chloride is present in an amount of about 0.001% to about 5% by weight of the polyfunctional acid chloride composition. In some embodiments, the polyfunctional acid chloride is present in an amount of about 0.001% to about 4%, about 0.001% to about 3%, about 0.001% to about 2%, about 0.001% to about 1%, about 0.01% to about 5%, about 0.01% to about 4%, about 0.01% to about 3%, about 0.01% to about 2%, about 0.01% to about 1%, about 0.01% to about 0.9%, about 0.01% to about 0.8%, about 0.01% to about 0.7%, about 0.01% to about 0.6%, about 0.01% to about 0.5%, about 0.01% to about 0.4%, about 0.01% to about 0.3%, about 0.01% to about 0.2%, about 0.01% to about 0.05%, about 0.05% to about 0.05%, by weight of the polyfunctional acid chloride composition, From about 0.05 wt% to about 0.8 wt%, from about 0.05 wt% to about 0.7 wt%, from about 0.05 wt% to about 0.6 wt%, from about 0.05 wt% to about 0.5 wt%, from about 0.05 wt% to about 0.4 wt%, from about 0.05 wt% to about 0.3 wt%, from about 0.05 wt% to about 0.2 wt%, or from about 0.05 wt% to about 0.1 wt%. In some embodiments, the polyfunctional acid chloride is present in an amount of about 0.01%, 0.02%, 0.3%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1% by weight of the polyfunctional acid chloride composition. In one embodiment, trimesoyl chloride is present in an amount of about 0.08% by weight of the polyfunctional acid chloride composition.
In one embodiment, the acid chloride composition comprises at least one organic solvent. In one embodiment, the acid chloride composition comprises at least one organic solvent and at least one ketone co-solvent. In some embodiments, the at least one organic solvent is a non-polar solvent. In some embodiments, the at least one organic solvent may be, but is not limited to, paraffin, pentane, hexane, heptane, octane, nonane, or decane, isomers thereof, and/or mixtures thereof. In one embodiment, the at least one organic solvent is paraffin, hexane, decane, or mixtures thereof. In another embodiment, the at least one organic solvent is hexane. In some embodiments, the at least one organic solvent may comprise petroleum ether or mineral oil.
The ketone co-solvent is any suitable ketone dissolved in at least one organic solvent. Examples of ketones include, but are not limited to, acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone, cyclohexanone, or mixtures thereof. In one embodiment, the at least one ketone co-solvent is acetone, butanone, or a mixture thereof. In one embodiment, the ketone co-solvent is present in an amount from about 0.1% to about 10% by weight of the polyfunctional acid chloride composition. In some embodiments, the ketone co-solvent is present in an amount from about 0.1% to about 8%, from about 0.1% to about 6%, from about 0.1% to about 4%, from about 0.1% to about 8%, from about 0.1% to about 2%, or from about 0.1% to about 1% by weight of the polyfunctional acid chloride composition. In some embodiments, the ketone co-solvent is present in an amount of about 0.5 wt.%, about 1 wt.%, about 1.5 wt.%, about 2 wt.%, about 2.5 wt.%, or about 3 wt.% of the polyfunctional acid chloride composition. In one embodiment, the ketone co-solvent is acetone. In one embodiment, the ketone co-solvent is about 2% by weight of the multifunctional acid chloride composition.
Method of forming polyamide material and reverse osmosis membrane。
In one embodiment, the reaction comprises an interfacial polymerization process.
In one embodiment, an interfacial polymerization process comprises contacting a surface of a microporous membrane with a polyfunctional amine composition to form a coated microporous membrane, and contacting the coated microporous membrane with a polyfunctional acid chloride composition. In some embodiments, the interfacial polymerization process is conducted at a solid/liquid interface, where the solid phase may comprise a microporous membrane coated with a polyfunctional amine composition, and the liquid phase may comprise a polyfunctional acid chloride composition.
In one embodiment, the method comprises contacting a surface of the microporous membrane with the polyfunctional amine composition by immersing the microporous membrane in the polyfunctional amine composition. In another embodiment, excess polyfunctional amine composition is removed from the surface of the microporous membrane.
Microporous films may be used as substrates for polyamide materials. In some embodiments, the polyamide material is thin relative to the microporous membrane. In some embodiments, the polyamide material has a thickness of about 0.01 μm to about 1 μm. In some embodiments, the polyamide material may have a thickness of about 0.05 μm to 0.9 μm, 0.1 μm to 0.8 μm, 0.15 μm to 0.5 μm, 0.2 μm to 0.4 μm, 0.25 μm to 0.3 μm, or any range or subrange therebetween. The interfacial polymerization process may include impregnating a portion of the microporous membrane (including the surface of the microporous membrane) into the polyfunctional amine composition. The portion of the microporous membrane immersed in the polyfunctional amine composition may remain immersed in the polyfunctional amine composition for 10 seconds to 5 minutes. In some embodiments, the microporous membrane is dipped into the polyfunctional amine composition for about 2 minutes. After removing the microporous membrane from the polyfunctional amine composition, excess polyfunctional amine composition may be removed from the surface of the microporous membrane.
In some embodiments, after the microporous membrane has been impregnated into the polyfunctional amine composition, the microporous membrane is impregnated into the polyfunctional acid chloride composition for 10 seconds to 5 minutes to form the reverse osmosis membrane. In some embodiments, the microporous membrane, after having been impregnated into the polyfunctional amine composition, is impregnated into the polyfunctional acid chloride composition for about 1 minute. In some embodiments, the interfacial polymerization process occurs while the microporous membrane is impregnated into the polyfunctional acid chloride composition. After removing the microporous membrane from the polyfunctional acid chloride composition forming the reverse osmosis membrane, the reverse osmosis membrane may be washed with deionized water.
In one embodiment, the microporous membrane comprises a polysulfone membrane.
Polysulfone membranes can be made of polysulfone (PSf) materials as described herein, such as PSf-1 or PSf-2. Exemplary PSf materials include, but are not limited to, those manufactured by Solvay
Figure BDA0002269187790000101
PSU Resins P-1700, P-1720, P-3500 LCD, GF-110, GF-120, and GF-130. In some embodiments, the microporous membrane is an ultra-fine (UF) membrane.
Methods for making microporous membranes from PSf materials are generally known to those skilled in the art. In one exemplary method, a solution comprising about 10 wt% to about 30 wt% PSf, about 0.5 wt% to 5 wt% polyethylene glycol (PEG), and about 70 wt% to about 90 wt% NMP is formed and cast onto a suitable material such as polyethylene terephthalate (PET). In some embodiments, the PEG has a molecular weight of less than 2,000. In some embodiments, the PGE has a molecular weight of about 300 to about 2000. In some embodiments, the PEG has a molecular weight of 300 or 600. In some embodiments, the PET material has a thickness of about 5 μm to about 300 μm. Casting may be performed with a casting knife such as Elcometer 3700. In one embodiment, the microporous membrane is formed by casting a polysulfone/polyethylene glycol/N-methyl-2-pyrrolidone (PSf/PEG/NMP) solution onto a polyethylene terephthalate (PET) material. In one embodiment, a solution comprising 20 wt% PSf, 2 wt% PEG, and 78 wt% NMP was cast onto PET material. In some embodiments, the polysulfone membrane has a thickness of about 5 μm to 100 μm. In some embodiments, the polysulfone membrane has a pore size of about 1nm to about 15 nm. In some embodiments, the polysulfone membrane has a pore size of about 5nm to about 12nm, or about 7nm to about 10 nm.
Graphene oxide composition。
In one embodiment, the graphene oxide is Graphene Oxide (GO). The chemical structure of graphene oxide is shown in fig. 3.
In one embodiment, the graphene oxide is present in an amount from about 0.1 mg/kg to about 100 mg/kg of the polyfunctional amine composition. In some embodiments, the graphene oxide forms a dispersion in the polyfunctional amine composition. In some embodiments, the graphene oxide particles in the dispersion have an average particle size (largest dimension of the graphene oxide particles) of about 100nm to 2000 nm.
In one embodiment, the graphene oxide is embedded in the polyamide material. In one embodiment, the graphene oxide is embedded in the pores of the polyamide material. In some embodiments, the graphene oxide is not reacted with a multifunctional amine or a multifunctional acid chloride. Without being bound by theory, it is believed that graphene oxide is embedded in the structure of the polyamide material and loosens the polyamide material than a polyamide material without graphene oxide. The looser material allows water to flow more easily, resulting in higher measured water flux values in RO membranes comprising a polyamide layer with embedded GO particles. In some embodiments, the enhancement of water flux through the RO membrane may be caused primarily by the loosening of the polyamide material structure. Fig. 4 illustrates the structure of a conventional RO membrane with an RO membrane with embedded GO according to some embodiments.
In one embodiment, a method of preparing a reverse osmosis membrane comprises impregnating a microporous membrane in a polyfunctional amine composition comprising about 0.01% to about 10% by weight of a polyfunctional amine, water, at least one water-soluble organic solvent, and about 0.1mg to about 100mg of graphene oxide per kilogram of the polyfunctional amine composition, and contacting the coated microporous membrane with a polyfunctional acid chloride composition comprising about 0.001% to about 1% by weight of a polyfunctional acid chloride, at least one organic solvent, and at least one ketone co-solvent.
In one embodiment, a method of purifying water using a reverse osmosis membrane is provided. The method includes filtering water through a reverse osmosis membrane to form purified water.
Examples
Various embodiments of the present invention may be better understood by reference to the following examples, which are provided as illustrations. The present invention is not limited to the examples given herein.
First a porous PSf or PES (polyethersulfone) membrane substrate was chosen, depending on the most desirable features in the RO membrane. Polyamide selective PA layers were fabricated on PSf or PES membranes during interfacial polymerization of polyfunctional amines with polyfunctional acid chlorides as described above by adding Graphene Oxide (GO) to the aqueous phase. The properties of the finished RO membrane were characterized, including pure water flux, contact angle, thickness, etc.
Example 1: manufacture of PSf/PES Membrane。
A 20/2/78 weight percent PSf/PEG/NMP solution was cast onto a section of 100 μm thick PET fabric using a casting knife and exposed to air for a period of 30 seconds before submersion in water at room temperature (25 ℃) to form a PSf porous UF membrane substrate with a membrane thickness of 35-50 μm. The pure water flux of the PSf film thus formed was 200L/m2Per hour (LMH) @1bar, contact angles of 70 ° -80 ° were obtained (table 1), and a cross-sectional SEM image of the PSf film can be seen in fig. 1.
Table 1: characteristics of the PSf UF Membrane substrate。
Sample (I) Thickness (μm) Average pore diameter (nm) Contact angle (degree) Pure water flux (LMH @1 bar)
PSf-1 35 9.88 75±1.08 210
PSf-2 45 11.5 82±1.15 188
The PSf films were immersed in 0.4-1.5 wt% aqueous solutions of 1, 3-phenylenediamine (MPD) for 2 minutes, with or without different ratios of DMSO/water in the polyfunctional amine composition, using various ratios of graphene oxide/water (mg/g) (e.g., 4/1000, 10/1000, 40/1000), as described in table 2. After removing excess solution from the surface of the PSf film, the PSf film was contacted with a multifunctional acid chloride composition comprising 0.04-0.2 wt% 1,3, 5-benzene tricarbonyl Trichloride (TMC) solution and comprising various amounts of ketone co-solvent for 1 minute (table 2). After removal of the PSf membrane from the polyfunctional acid chloride composition, the membrane was washed with DI water and a thin film ultra low pressure RO membrane was obtained. The SEM image of the surface of the RO membrane is shown in fig. 2. The RO membrane is stored in water for later use. In some embodiments, the RO membrane is subjected to a further curing step, which may include a thermal curing step.
Example 2: effect of graphene oxide on RO Membrane Water flux。
The effect of interfacial polymerization conditions on RO performance, such as amine monomer and reactive acid chloride monomer species, monomer concentration, contact time, co-solvent ratio, and therefore solvent species, GO concentration, and water soluble organic solvent species, water soluble organic species concentration in the aqueous phase, and the like. Using the process disclosed herein, RO membranes were obtained with a water flux of 7.7 LMH/bar and a rejection percentage of greater than 95%, which was higher than TW30-1812-50(Dow Filmtech) membranes and XLE-440(DOW) RO membranes used for residential RO purification.
Table 2: performance of thin film composite RO Membrane。
Figure BDA0002269187790000121
Figure BDA0002269187790000131
Test conditions for water flux determination: 500ppm NaCl, 25 ℃, 50psi water pressure. The water flux and rejection results for TW30-1812-50 and XLE-440 membranes were obtained from the manufacturer's catalog.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the invention. Thus, it should be understood that although the present invention has been specifically disclosed by particular embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of embodiments of this invention.
Exemplary embodiments：
The following exemplary embodiments are provided, the numbering of which should not be construed as designating the importance of the rank:
embodiment 1 provides a reverse osmosis membrane comprising:
a microporous membrane comprising a polyamide material thereon, the polyamide material comprising graphene oxide, wherein the reverse osmosis membrane has about 6.0L/m2A water flux of between/hour/bar (LMH/bar) and about 8.0 LMH/bar.
Embodiment 2 provides the reverse osmosis membrane of embodiment 1, wherein the microporous membrane has: a thickness of about 30 μm to about 80 μm, a contact angle of about 60 degrees to about 90 degrees, and a water flux of about 160 LMH/bar to about 350 LMH/bar.
Embodiment 3 provides a reverse osmosis membrane according to any one of embodiments 1-2, wherein the rejection rate of the reverse osmosis membrane is at least 95%.
Embodiment 4 provides a method of making a reverse osmosis membrane according to any one of embodiments 1-3 comprising:
reacting a polyfunctional acid chloride composition with a polyfunctional amine composition comprising graphene oxide on a microporous membrane to form a polyamide material on the microporous membrane.
Embodiment 5 provides the method of embodiment 4, wherein the polyfunctional amine composition comprises water and at least one water-soluble organic solvent.
Embodiment 6 provides the method of any one of embodiments 4-5, wherein the multifunctional acid chloride composition comprises at least one organic solvent and at least one ketone co-solvent.
Embodiment 7 provides the method of any one of embodiments 4-6, wherein the at least one ketone co-solvent is acetone, butanone, or a mixture thereof.
Embodiment 8 provides the method of any one of embodiments 4-7, wherein the at least one organic solvent is paraffin, hexane, decane, or mixtures thereof.
Embodiment 9 provides the method of any one of embodiments 4-8, wherein the reacting comprises an interfacial polymerization process.
Embodiment 10 provides the method of any one of embodiments 4-9, wherein the interfacial polymerization process comprises:
contacting a surface of the microporous membrane with the polyfunctional amine composition to form a coated microporous membrane, and
contacting the coated microporous membrane with the polyfunctional acid chloride composition.
Embodiment 11 provides the method of any of embodiments 4-10, wherein contacting the surface of the microporous membrane with the polyfunctional amine composition comprises:
immersing the microporous membrane in the polyfunctional amine composition.
Embodiment 12 provides the method of any of embodiments 4-11, wherein the polyfunctional amine comprises from about 0.01% to about 10% by weight of the polyfunctional amine composition.
Embodiment 13 provides the method of any one of embodiments 4-12 wherein the polyfunctional amine is m-phenylenediamine (MPD).
Embodiment 14 provides the method of any of embodiments 4-13, wherein the polyfunctional acid chloride composition comprises from about 0.001% to about 5% by weight polyfunctional acid chloride.
Embodiment 15 provides the method of any one of embodiments 4-14, wherein the multifunctional acid chloride is trimesoyl chloride (TMC).
Embodiment 16 provides the method of any one of embodiments 4-15, wherein the microporous membrane comprises polysulfone.
Embodiment 17 provides the method of any one of embodiments 4-16, wherein the microporous membrane is formed by casting a polysulfone/polyethylene glycol/N-methyl-2-pyrrolidone (PSf/PEG/NMP) solution onto a polyethylene terephthalate (PET) material.
Embodiment 18 provides the method of any one of embodiments 4-17, wherein the graphene oxide is graphene oxide.
Embodiment 19 provides the method of any one of embodiments 4-18, wherein the graphene oxide is present in an amount of about 0.1mg per kilogram to about 100mg per kilogram of the polyfunctional amine composition.
Embodiment 20 provides the method of any one of embodiments 4-19, wherein the graphene oxide is embedded in the polyamide material.
Embodiment 21 provides a method of making a reverse osmosis membrane according to any one of embodiments 1-3 comprising:
impregnating a microporous membrane in a polyfunctional amine composition comprising about 0.01 to about 10 weight percent polyfunctional amine, water, at least one water-soluble organic solvent, and about 0.1 to about 100mg of graphene oxide per kilogram polyfunctional amine composition, and
contacting the coated microporous membrane with a polyfunctional acid chloride composition comprising about 0.001% to about 1% by weight of a polyfunctional acid chloride, at least one organic solvent, and at least one ketone co-solvent.
Embodiment 22 provides a method of purifying water using a reverse osmosis membrane according to any one of embodiments 1-3, comprising: the water is filtered through a reverse osmosis membrane to form purified water.

Claims (10)

1. A reverse osmosis membrane comprising:
a microporous membrane comprising a polyamide material thereon, the polyamide material comprising graphene oxide, wherein the reverse osmosis membrane has about 6.0/m2A water flux of between/hour/bar (LMH/bar) and about 8.0 LMH/bar.
2. The reverse osmosis membrane of claim 1, wherein the microporous membrane has:
a thickness of about 30 μm to about 80 μm,
a contact angle of about 60 degrees to about 90 degrees, an
A water flux of about 160 LMH/bar to about 350 LMH/bar.
3. A method of making a reverse osmosis membrane according to claim 1 comprising:
reacting a polyfunctional acid chloride composition with a polyfunctional amine composition comprising and graphene oxide on a microporous membrane to form a polyamide material on the microporous membrane.
4. The method of claim 3, wherein the reaction comprises an interfacial polymerization process.
5. The method of claim 4, wherein the interfacial polymerization process comprises:
contacting a surface of the microporous membrane with the polyfunctional amine composition to form a coated microporous membrane, and
contacting the coated microporous membrane with the polyfunctional acid chloride composition.
6. The method of claim 3, wherein the polyfunctional amine is m-phenylenediamine (MPD).
7. The method of claim 3, wherein the multifunctional acid chloride is trimesoyl chloride (TMC).
8. The method of claim 3, wherein the microporous membrane comprises polysulfone.
9. The method of claim 3, wherein the graphene oxide is graphene oxide.
10. A method of making a reverse osmosis membrane according to claim 1 comprising:
impregnating a microporous membrane in a polyfunctional amine composition comprising about 0.01 to about 10 weight percent polyfunctional amine, water, at least one water-soluble organic solvent, and about 0.1 to about 100mg of graphene oxide per kilogram polyfunctional amine composition, and
contacting the coated microporous membrane with a polyfunctional acid chloride composition comprising about 0.001% to about 1% by weight of a polyfunctional acid chloride, at least one organic solvent, and at least one ketone co-solvent.
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