CN107970787A - A kind of reverse osmosis membrane and its preparation method and application - Google Patents
A kind of reverse osmosis membrane and its preparation method and application Download PDFInfo
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- CN107970787A CN107970787A CN201610922140.3A CN201610922140A CN107970787A CN 107970787 A CN107970787 A CN 107970787A CN 201610922140 A CN201610922140 A CN 201610922140A CN 107970787 A CN107970787 A CN 107970787A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—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
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
Abstract
The present invention relates to seperation film field, discloses a kind of reverse osmosis membrane and its preparation method and application.The reverse osmosis membrane includes supporting layer, separating layer and the anti-pollution layer stacked gradually, and the separating layer is formed by crosslinked polyamide, and the anti-pollution layer is formed by sulfonated polyethylene alcohol with amine substance by cross-linking reaction.Reverse osmosis membrane provided by the invention has stronger anti-fouling performance, and its preparation method is simple, great prospects for commercial application.
Description
Technical field
The present invention relates to seperation film field, and in particular to a kind of reverse osmosis membrane, a kind of preparation method of reverse osmosis membrane, by this
Application of the reverse osmosis membrane and the reverse osmosis membrane that method is prepared in water treatment field.
Background technology
UF membrane is a kind of separation technology for occurring and emerging rapidly after the 1960s in early 20th century.Due to
Membrane separation technique not only has the function of to separate, concentrate, purify and refine, but also there are efficient, energy-saving and environmental protection, molecular level to filter, mistake
The features such as journey is simple, easily controllable is filtered, has been widely used in food, medicine, biology, environmental protection, chemical industry, metallurgy, energy at present
The field such as source, oil, water process, electronics, bionical, generates huge economic benefit and social benefit, it has also become current separation
One of most important means in science.The core of membrane separation technique is exactly seperation film.For perforated membrane, according to membrane aperture
Size can be divided into microfiltration membranes, ultrafiltration membrane, NF membrane and reverse osmosis membrane.
Wherein, reverse osmosis membrane because with to the good separation performance of organic molecule and inorganic ion, it is safe and environment-friendly,
The advantages that easy to operate and as one of key technology of water process.So far, reverse osmosis membrane be mainly used in seawater and
The fields such as brackish water desalination, water softening, middle Water Sproading, Industrial Wastewater Treatment and ultra-pure water preparation.At present, the mainstream in market
Product is the mode for taking interfacial polymerization, and polyamide film is combined to micropore support counterdie surface.Common technical process exists
It is discussed in detail in US4277344.Such reverse osmosis membrane product not only has higher salt rejection rate, but also good with water penetration
The advantages such as good, resistance to pH scopes wide (2-12) and operating pressure are low.But fouling membrane is always to influence film properties, reduce it and make
An important factor for the service life.Fouling membrane refer in the feed liquid that is contacted with film particulate, colloidal particle or solute transportation due to film
Generation physics, chemical action are drawn because concentration polarization some solutes is exceeded its solubility and mechanism in film surface concentration
That rises adsorbs in film surface or fenestra, deposits and cause membrane aperture to diminish or block, and makes what membrane flux was decreased obviously with stalling characteristic
Irreversible change phenomenon.Absorption of the polluter in film surface and fenestra can cause flux decline and UF membrane ability to drop
Low, especially protein absorption is the main reason for causing the decline of membrane flux.The method solved at present is to prevent fouling membrane and right
Fouling membrane is post-processed.Relative to post processing, develop and reverse osmosis composite membrane material of the exploitation with anti-fouling performance is solution
The certainly most basic and most direct approach of the problem.
In order to improve the contamination resistance of polyamide composite film, do a lot of work both at home and abroad, be concentrated mainly on surface and change
Property processing, surface grafting and face coat.
The method of membrane surface modification processing is numerous, for example, U.S. Patent application US5028453 discloses using plasma
Processing, to improve the resistance tocrocking of composite membrane, but corona treatment is limited to technical conditions and cost and can not achieve at present
Large-scale production；U.S. Patent application US5151183 is disclosed carries out fluorination treatment to improve film using fluorine gas to film surface
Resistance tocrocking, while fluorine gas processing is easily broken film surface polyamide molecule chain, so as to have impact on separating property and the use of film
Service life；Mukherjee et al. (Desalination, 1996,104:Polyamide composite film 239-249) is immersed into hydrofluoric acid/silicon
It is modified in the mixed solution of fluoric acid/isopropanol/water, so that anti-pollution composite membrane be made.
Relative to surface modification treatment, the chemical reaction that surface grafting method is related to is increasingly complex, and process is also relatively numerous
It is trivial.Freger and Gilron etc. (Desalination, 2001,140:167-179) using oxidation-reduction method in polyamide table
Face grafted propylene acid and methacrylic acid, so as to reduce absorption of the pollutant in film surface.(the Journal of such as Belfer
membrane science,1998,139:175-181) it is grafted first respectively on polyamide composite film using radiation graft process
Base acrylic acid and polyethylene glycol methacrylic acid side chain, so as to improve the contamination resistance of film.In addition, Belfer etc.
(Journal of membrane science,1998,139:175-181) also acrylonitrile grafting to polyamide surface is also taken
Obtained preferable antipollution effect.
Surface coatings method, is the method for modifying for being easiest to realize industrialization production since its technique is relatively easy.In
State patent application CN1468649A and U.S. Patent application US6913694 are disclosed contains 2 in composite film surface painting last layer
The coating of the epoxide of a above epoxide group improves the stain resistance of composite membrane, but due to the limit of hydrophilic radical density
System is so that the increase rate of the composite membrane anti-fouling performance is limited.
The content of the invention
The defects of the purpose of the invention is to overcome existing reverse osmosis membrane low contamination resistance, and provide it is a kind of have compared with
The reverse osmosis membrane of good anti-fouling performance, a kind of preparation method of reverse osmosis membrane, the reverse osmosis membrane being prepared by this method and
Application of the reverse osmosis membrane in water treatment field.
To achieve these goals, the present invention provides a kind of reverse osmosis membrane, wherein, the reverse osmosis membrane includes layer successively
Folded supporting layer, separating layer and anti-pollution layer, the separating layer are formed by crosslinked polyamide, and the anti-pollution layer is gathered by sulfonation
Vinyl alcohol is formed with amine substance by cross-linking reaction.
Present invention also offers a kind of preparation method of reverse osmosis membrane, this method is included on supporting layer using crosslinked poly-
Acid amides formed separating layer, then in the separating layer by sulfonated polyethylene alcohol and amine substance progress cross-linking reaction formed it is resistance to
Pollution layer.
Present invention also offers the reverse osmosis membrane being prepared by the above method.
In addition, the application present invention also offers the reverse osmosis membrane in water treatment field.
The present inventor has found after further investigation, passes through sulfonated polyethylene alcohol and amine in polyamide separating layer
Class material carries out forming anti-pollution layer after cross-linking reaction, and the sulfonic group in sulfonated polyethylene alcohol is negatively charged, is answered with amine substance
Specific amphion is formed after conjunction, film surface is in electroneutral substantially, due to solvation of ion, this specific both sexes from
Son can form one layer of stable hydration layer by electrostatic force, and the reverse osmosis membrane so enabled to has well resistance to
Pollutant performance.In addition, the preparation method of reverse osmosis membrane provided by the invention is simple, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the infrared of polyvinyl alcohol used in preparation example 1 and the sulfonated polyethylene alcohol that is obtained by the method for preparation example 1
Spectrogram.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Reverse osmosis membrane provided by the invention includes supporting layer, separating layer and the anti-pollution layer stacked gradually, the separating layer
Formed by crosslinked polyamide, the anti-pollution layer is formed by sulfonated polyethylene alcohol with amine substance by cross-linking reaction.
There is no particular limitation for thickness of the present invention to the supporting layer, separating layer and anti-pollution layer, can be this area
Conventional selection, but in order to enable this three layers can play the role of more preferable coordinated, so as to get reverse osmosis membrane have more
Good anti-fouling performance, it is preferable that the thickness of the supporting layer is 90-150 microns, more preferably 100-120 microns；Described point
The thickness of absciss layer is 0.05-0.5 microns, more preferably 0.1-0.3 microns；The thickness of the anti-pollution layer is micro- for 0.05-0.5
Rice, is preferably 0.08-0.2 microns.
There is no particular limitation to the material of the supporting layer by the present invention, various can have certain intensity by existing
, usually can be non-sulfonated by polyester, polyacrylonitrile, Kynoar, phenolphthalein type and the material that can be used in reverse osmosis membrane is made
At least one of polyether sulphone, polyether sulfone and polysulfones are made.A kind of embodiment according to the present invention, the supporting layer
Including non-woven polyester layer of cloth and be attached in the polyester non-woven fabric layer surface by polyacrylonitrile, Kynoar, phenolphthalein
Polymeric layer made of at least one of the non-sulfonated polyether sulphone of type, polyether sulfone and polysulfones.Wherein, the non-woven polyester layer of cloth
Thickness can be 60-100 micron, the thickness of the polymeric layer can be 10-50 microns.
The reverse osmosis membrane provided according to the present invention, in the separating layer, the crosslinked polyamide can be by will be more
First amine and polynary acyl chlorides carry out interfacial polymerization and obtain.Wherein, the example of the polyamine includes but not limited to m-phenylene diamine (MPD), to benzene
At least one of diamines, o-phenylenediamine, piperazine and equal benzene triamine, from the point of view of raw material is ready availability, the polyamine is special
You Xuanwei not m-phenylene diamine (MPD).The example of the polynary acyl chlorides includes but not limited to pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and right
At least one of phthalyl chloride, from the point of view of raw material is ready availability, the polynary acyl chlorides is particularly preferably equal benzene front three
Acyl chlorides.It should be noted that in order to form crosslinked polyamide, at least one of the polyamine and polynary acyl chlorides need to contain
Have compound more than trifunctional, for example, can by ternary (more than) amine or containing ternary (more than) polyamine of amine with
Arbitrary polynary acyl chlorides carries out interfacial polymerization, can also by ternary (more than) acyl chlorides or containing ternary (more than) acyl chlorides it is polynary
Acyl chlorides carries out interfacial polymerization with arbitrary polyamine.In addition, the weight ratio between the polyamine and polynary acyl chlorides can be (1-
100):1, be preferably (5-50):1.
Interfacial polymerization between the polyamine and polynary acyl chlorides usually carries out in the presence of the solvent.The solvent can be
The existing various inertia liquid objects that polyamine and polynary acyl chlorides can be dissolved and do not acted on reactant and reaction product
Matter, its instantiation include but not limited to：Water, n-hexane, normal heptane, dodecane, Isopar E, Isopar G, Isopar H,
At least one of Isopar L and Isopar M.
There is no particular limitation for condition of the present invention to the interfacial polymerization, and it can be 40-150 to generally include polymerization temperature
DEG C, it is preferably 50-120 DEG C；Polymerization time can be 0.5-20min, be preferably 1-10min.
The reverse osmosis membrane provided according to the present invention, in the anti-pollution layer, the cross-linking reaction usually in crosslinking agent, urge
Carried out in the presence of agent and solvent.Wherein, relative to the solvent of 100 parts by weight, the dosage of the sulfonated polyethylene alcohol
It can be 0.1-50 parts by weight, be preferably 0.2-25 parts by weight, be most preferably 0.5-1.5 parts by weight；The use of the amine substance
Amount can be 0.01-50 parts by weight, be preferably 0.02-25 parts by weight, be most preferably 0.5-2 parts by weight；The use of the crosslinking agent
Amount can be 0.001-5 parts by weight, be preferably 0.01-5 parts by weight, be most preferably 0.05-1 parts by weight；The catalyst is acid
Class material and its dosage can make it that the pH value of cross-linking system is 1-5, be preferably 1-4, be most preferably 1-3.
The ion exchange capacity of the sulfonated polyethylene alcohol is preferably 0.1-3mmol/g, more preferably 0.5-2mmol/g.
In the present invention, the ion exchange capacity refers to sulfonic molal quantity in 1g sulfonated polyethylene alcohol, it can use soda acid
Titration method is measured.The sulfonated polyethylene alcohol can be commercially available, can also be public according to those skilled in the art
The various methods known are prepared.A kind of embodiment according to the present invention, the sulfonated polyethylene alcohol is according to lower section
Method is prepared：Polyvinyl alcohol is soluble in water, 0-5 DEG C is cooled to, the concentrated sulfuric acid is added dropwise under agitation, will after being added dropwise
Temperature rises to reaction 2-10h, preferably 4-8h at 30-80 DEG C, preferably 40-60 DEG C, and cooling, adding alcohol separates out product, and filtering is simultaneously
Sulfonated polyethylene alcohol is obtained after being washed through washing and/or alcohol, shown in specific reaction process such as formula (1).Wherein, relative to 100 weights
The polyvinyl alcohol of part is measured, the dosage of the concentrated sulfuric acid can be 5-100 parts by weight, be preferably 10-50 parts by weight.
According to the present invention, term " amine substance " refers to polymer or compound with amine groups, including primary amine, secondary
Amine, tertiary amine and quaternary ammonium.The amine substance preferably polymer and/or compound containing amine groups and hydroxyl, Huo Zhewei
Polymer and/or compound containing amine groups He the group that can be hydrolyzed into hydroxyl, particularly preferably contain quaternary ammonium salt base
Group and the polymer and/or compound of hydroxyl, or be the polymerization containing quaternary ammonium salt group He the group that can be hydrolyzed into hydroxyl
Thing and/or compound.It should be noted that when the amine substance is to contain amine groups and the group that can be hydrolyzed into hydroxyl
Polymer and/or during compound, before cross-linking reaction is carried out, it should first the material is hydrolyzed, to this this area skill
Art personnel can know that therefore not to repeat here.From the point of view of raw material is ready availability, the amine substance be preferably chitosan,
Chitosan quaternary ammonium salt, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane and dimethyl stearyl
At least one of [3- (trimethoxy silicon substrate) propyl group] ammonium chloride, particularly preferably chitosan quaternary ammonium salt and/or dimethyl ten
Eight alkyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride.
There is no particular limitation to the species of the crosslinking agent by the present invention, can be existing various to enable to the sulphur
Change the compound that polyvinyl alcohol and amine substance carry out cross-linking reaction, be preferably aldehyde compound, its instantiation is included but not
It is limited to：At least one of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, malonaldehyde, butanedial and glutaraldehyde, more preferably
For at least one of formaldehyde, acetaldehyde, propionic aldehyde and butyraldehyde, particularly preferably formaldehyde.
There is no particular limitation for species of the present invention to the catalyst, can be common acid, it is specific real
Example includes but not limited to：At least one of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid, are preferably sulfuric acid, hydrochloric acid and second
At least one of acid, particularly preferably hydrochloric acid.The catalyst can use in pure form, can also be with its aqueous solution
Form use.When the catalyst in the form of its aqueous solution in use, its concentration can be 0.5-1.5mol/L, be preferably
0.8-1.2mol/L。
There is no particular limitation for species of the present invention to the solvent used in the process of the cross-linking reaction, as long as can be molten
Sulfonated polyethylene alcohol, amine substance, crosslinking agent and the catalyst are solved, for example, can be water or water and methanol, second
The mixture of at least one of alcohol, acetone, glycol monoethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), particularly preferably water.
There is no particular limitation for condition of the present invention to the cross-linking reaction, for example, the condition of the cross-linking reaction is usual
Including：Reaction temperature can be 20-150 DEG C, and the reaction time can be 1min-1h；Preferably, the condition bag of the cross-linking reaction
Include：Reaction temperature is 50-120 DEG C, reaction time 2min-30min.
The preparation method of reverse osmosis membrane provided by the invention is included on supporting layer forms separation using crosslinked polyamide
Layer, then carries out cross-linking reaction by sulfonated polyethylene alcohol and amine substance in the separating layer and forms anti-pollution layer.
There is no particular limitation for thickness of the present invention to the supporting layer, separating layer and anti-pollution layer, can be this area
Conventional selection, but in order to enable this three layers can play the role of more preferable coordinated, so as to get reverse osmosis membrane have more
Excellent anti-fouling performance, it is preferable that the thickness of the supporting layer is 90-150 microns, and the thickness of the separating layer is 0.05-
0.5 micron, the thickness of the anti-pollution layer is 100-150 microns；It is highly preferred that the thickness of the supporting layer is micro- for 100-120
Rice, the thickness of the anti-pollution layer is 0.05-0.5 microns, is preferably 0.08-0.2 microns.
There is no particular limitation to the material of the supporting layer by the present invention, various can have certain intensity by existing
, usually can be non-sulfonated by polyester, polyacrylonitrile, Kynoar, phenolphthalein type and the material that can be used in reverse osmosis membrane is made
At least one of polyether sulphone, polyether sulfone and polysulfones are made.A kind of embodiment according to the present invention, the supporting layer
Including non-woven polyester layer of cloth and be attached in the polyester non-woven fabric layer surface by polyacrylonitrile, Kynoar, phenolphthalein
Polymeric layer made of at least one of the non-sulfonated polyether sulphone of type, polyether sulfone and polysulfones.Wherein, the non-woven polyester layer of cloth
Thickness can be 60-100 micron, the thickness of the polymeric layer can be 10-50 microns.
In accordance with the present invention it is preferred that the mode for forming the separating layer includes adsorbing polyamine and polynary acyl chlorides in institute
State on supporting layer, then carry out interfacial polymerization.A kind of embodiment according to the present invention, forms the mode of the separating layer
Including supporting layer is immersed in polynary amine aqueous solution and polynary solution of acid chloride successively, interfacial polymerization is then carried out.As described above, institute
State polyamine example include but not limited in m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine at least one
Kind, from the point of view of raw material is ready availability, the polyamine is particularly preferably m-phenylene diamine (MPD).The example of the polynary acyl chlorides includes
But at least one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride are not limited to, the angle ready availability from raw material
Degree considers that the polynary acyl chlorides is particularly preferably pyromellitic trimethylsilyl chloride.It should be noted that in order to form crosslinked polyamide,
At least one of the polyamine and polynary acyl chlorides need the compound more than containing trifunctional, for example, can be by ternary
(more than) amine or containing ternary (more than) polyamine of amine carries out interfacial polymerization with arbitrary polynary acyl chlorides, can also be by ternary
(more than) acyl chlorides or containing ternary (more than) the polynary acyl chlorides of acyl chlorides carries out interfacial polymerization with arbitrary polyamine.It is described polynary
Weight ratio between amine and polynary acyl chlorides can be (1-100):1, be preferably (5-50):1.The polynary amine aqueous solution and polynary acyl
The species of solvent may be the same or different in solutions of chlorine, and can be each independently water, n-hexane, normal heptane, 12
At least one of alkane, Isopar E, Isopar G, Isopar H, Isopar L and Isopar M.In addition, the polyamine
The concentration of solution can be 0.5-10 weight %, be preferably 1-5 weight %.The concentration of the polynary solution of acid chloride can be
0.025-1 weight %, are preferably 0.05-0.5 weight %.
The present invention does not have the condition for impregnating the supporting layer in polynary amine aqueous solution and in polynary solution of acid chloride
Special to limit, both usually include independently of one another：Dipping temperature can be 10-50 DEG C, be preferably 20-40 DEG C；During dipping
Between can be 5-100s, be preferably 10-60s.
There is no particular limitation for condition of the present invention to the interface polymerization reaction, and generally including polymerization temperature can be
40-150 DEG C, be preferably 50-120 DEG C；Polymerization time can be 0.5-20min, be preferably 1-10min.
In accordance with the present invention it is preferred that formed the anti-pollution layer mode include by sulfonated polyethylene alcohol, amine substance,
Crosslinking agent and catalyst, which are dissolved in solvent, is made coating liquid, then by the coating liquid coated in the separating layer, it is laggard
Row cross-linking reaction.Wherein, relative to the solvent of 100 parts by weight, the dosage of the sulfonated polyethylene alcohol can be 0.1-50 weight
Part, it is preferably 0.2-25 parts by weight, is most preferably 0.5-1.5 parts by weight；The dosage of the amine substance can be 0.01-50 weights
Part is measured, is preferably 0.02-25 parts by weight, is most preferably 0.5-2 parts by weight；The dosage of the crosslinking agent can be 0.001-5 weights
Part is measured, is preferably 0.01-5 parts by weight, is most preferably 0.05-1 parts by weight；The catalyst can be with for acid and its dosage
So that the pH value of cross-linking system is 1-5, preferably 1-4, more preferably 1-3.
Wherein, the species of the sulfonated polyethylene alcohol, amine substance, crosslinking agent and catalyst has been hereinbefore
Description, therefore not to repeat here.
There is no particular limitation for species of the present invention to solvent in the coating liquid, as long as the poly- second of the sulfonation can be dissolved
Enol, amine substance, crosslinking agent and catalyst, for example, can be water or water and methanol, ethanol, acetone, ethylene glycol
The mixture of at least one of monomethyl ether, ethylene glycol and dimethyl sulfoxide (DMSO), particularly preferably water.
There is no particular limitation for condition of the present invention to the cross-linking reaction, for example, the condition of the cross-linking reaction is usual
Including：Reaction temperature can be 20-150 DEG C, and the reaction time can be 1min-1h；Preferably, the condition bag of the cross-linking reaction
Include：Reaction temperature is 50-120 DEG C, reaction time 2min-30min.
According to the present invention, sulfonated polyethylene alcohol, amine substance, crosslinking agent and catalyst are dissolved in during solvent preferably
Carried out under conditions of stirring.The present invention is not particularly limited the condition of the stirring and the equipment of stirring, can use
Conventional mixing plant well-known to those skilled in the art carries out under appropriate stirring condition, as long as can make the poly- second of sulfonation
Enol, amine substance, crosslinking agent and catalyst are completely dissolved in solvent.In addition, in the present invention, by sulfonated polyethylene
The process that alcohol, amine substance, crosslinking agent and catalyst are dissolved in solvent carries out at normal temperatures.
Since the sulfonated polyethylene alcohol has higher molecular weight, it is difficult to be completely dissolved in a solvent, therefore, in order to
The cross-linked network structure made is more uniformly distributed, and improves the stability of the reverse osmosis membrane, described anti-under preferable case
The preparation method of permeable membrane also includes before by the coating liquid coated in separating layer, and the coating liquid is filtered.Having
During gymnastics is made, first sulfonated polyethylene alcohol, amine substance, crosslinking agent and the catalyst can be dissolved in solvent and mistake
Filter, the coating liquid uniformly clarified.In addition, the present invention is also not particularly limited for the mode of the filtering, can use
Filter method well-known to those skilled in the art and equipment carry out.
The present invention can use this to there is no particular limitation coated in the mode in the separating layer by the coating liquid
Various modes known to field technology personnel carry out, for example, spraying, blade coating, spin coating etc..
In addition, in order to enable the reverse osmosis membrane arrived is more smooth, it is preferable that the preparation side of reverse osmosis membrane provided by the invention
Method is additionally included in before forming separating layer and anti-pollution layer, and the supporting layer is fixed on a glass or on film machine.
Present invention also offers the reverse osmosis membrane being prepared by the above method.
Present invention also offers application of the above-mentioned reverse osmosis membrane in water treatment field.
The present invention will be described in detail by way of examples below.
In following embodiments and comparative example：
The stain resistance of reverse osmosis membrane is tested as follows：Reverse osmosis membrane is fitted into membrane cisterna, in 1.2MPa
After lower precompressed 0.5h, the water transit dose of reverse osmosis membrane in 1h is measured under the conditions of pressure is 1.55MPa, temperature is 25 DEG C, and lead to
Cross the following formula and water flux is calculated：Q1=J/ (At), wherein, J is water transit dose (L), Q1For water flux (L/m2H), A
For effective membrane area (m of reverse osmosis membrane2), t is the time (h).It is NaCl and bovine serum albumin(BSA) by loop test fluid exchange
(BSA) mixed aqueous solution (wherein, the concentration of NaCl is 2000ppm, and the concentration of BSA is 1000ppm), is in pressure
After 1.55MPa, temperature run 6h under the conditions of being 25 DEG C, reverse osmosis membrane is measured under the conditions of pressure is 1.55MPa, temperature is 25 DEG C
Water flux Q2；Then, after rinsing reverse osmosis membrane 0.5h with clear water, under the conditions of pressure is 1.55MPa, temperature is 25 DEG C, survey
Obtain water flux Q when circulation fluid is 2000ppmNaCl aqueous solutions3；The water flux rate of descent of reverse osmosis membrane passes through the following formula meter
Obtain：D=(Q1-Q2)/Q1× 100%；Flux recovery rate is calculated reverse osmosis membrane by the following formula after washing：H
=Q3/Q1× 100%.Wherein, water flux rate of descent is lower, flux recovery rate is higher, then shows the stain resistance of reverse osmosis membrane
Can be better.
In following embodiments and comparative example：
Polyvinyl alcohol (PVA, alcoholization degree are 95%, number-average molecular weight 95000), m-phenylene diamine (MPD), pyromellitic trimethylsilyl chloride, shell
Glycan (deacetylation degree is 90%), chitosan quaternary ammonium salt (substitution value 45%), gamma-amino propyl trimethoxy silicane, γ-
Aminopropyltriethoxywerene werene, dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group] ammonium chloride are purchased from lark prestige section
Skill Co., Ltd；Isopar E are purchased from Xi Long Chemical Co., Ltd.s；Other chemical reagent, which are purchased from Chinese medicines group chemical reagent, to be had
Limit company.
Supporting layer is made using phase inversion, is comprised the following steps that：Polysulfones (number-average molecular weight 80000) is dissolved in N, N-
In dimethylformamide, the polysulfones solution that concentration is 18 weight % is made, the standing and defoaming 120min at 25 DEG C, then, utilizes
Scraper coated in initial film is obtained on the polyester non-woven fabric that thickness is 75 microns, soaks polysulfones solution in 25 DEG C of water immediately
30min so that through inversion of phases into perforated membrane, most obtain gross thickness through repeatedly washing afterwards is the polysulfones layer on polyester non-woven fabric surface
115 microns of supporting layer.
Preparation example 1
The preparation example is used for the preparation method for illustrating sulfonated polyethylene alcohol.
2g PVA are dissolved in the beaker equipped with 30mL distilled water first, heating is allowed to be completely dissolved, then by beaker
It is put into ice-water bath, temperature is maintained at 0-5 DEG C, and the 1.0g concentrated sulfuric acids are slowly added in the case where being stirred continuously, and (concentration is 98 weights
% is measured, similarly hereinafter).Then beaker is put into 40 DEG C of water-bath, heating stirring reaction 3h, afterwards falls 100mL absolute ethyl alcohols
Enter in the mixture after reaction, there is white precipitate precipitation, centrifuge, it is straight that white precipitate is then constantly rinsed with absolute ethyl alcohol
Reach 6.0 to its pH value, products therefrom be put into baking oven, 24h is dried at 50 DEG C, obtain sulfonated polyethylene alcohol (SPVA),
It is 1.12mmol/g to measure its ion exchange capacity using acid-base titration.
Fig. 1 is the infrared spectrum of SPVA and PVA, it can be seen from the figure that the polyvinyl alcohol after sulfonation is in 1090cm-1With
1040cm-1There is sulfonic characteristic absorption peak in place, it was demonstrated that the successful preparation of SPVA.
Preparation example 2
The preparation example is used for the preparation method for illustrating sulfonated polyethylene alcohol.
Method according to preparation example 1 prepares sulfonated polyethylene alcohol, unlike, the dosage of the concentrated sulfuric acid is 0.5g, is obtained
SPVA, it is 0.53mmol/g to measure its ion exchange capacity using acid-base titration.
Preparation example 3
The preparation example is used for the preparation method for illustrating sulfonated polyethylene alcohol.
Method according to preparation example 1 prepares sulfonated polyethylene alcohol, unlike, the dosage of the concentrated sulfuric acid is 1.5g, is obtained
SPVA, it is 1.70mmol/g to measure its ion exchange capacity using acid-base titration.
Comparative example 1
The comparative example is used to illustrate reverse osmosis membrane of reference and preparation method thereof.
By the m-phenylene diamine (MPD) aqueous solution that supporting layer upper surface (polysulfones layer, similarly hereinafter) exposure concentration is 2 weight %, connect at 25 DEG C
Discharge opeing after tactile 10s；Then, supporting layer upper surface is contacted into the Isopar E containing 0.1 weight % pyromellitic trimethylsilyl chloride solution again
Solution, discharge opeing after 10s is contacted at 25 DEG C；Then, film is put into baking oven, 3min is heated at 70 DEG C, obtain reverse osmosis membrane M1,
It includes supporting layer and the polyamide separating layer being attached on one side surface of supporting layer, wherein, the thickness of supporting layer is micro- for 115
Rice, the thickness of polyamide separating layer is 0.1 micron.Water flux rate of descent after the initial water flux of reverse osmosis membrane M1 and pollution
1 is the results are shown in Table with flux recovery rate.
Comparative example 2
The comparative example is used to illustrate reverse osmosis membrane of reference and preparation method thereof.
By 1.0g polyvinyl alcohol, 1.0g dimethyl stearyls [3- (trimethoxy silicon substrate) propyl group] ammonium chloride and 0.1g
Formaldehyde is dissolved in 100g deionized waters, is then instilled the dilute hydrochloric acid of 1mol/L under agitation adjusting the pH value of solution to 1, is connect
And filtered after stirring 24h at normal temperatures, obtain clarification coating liquid；Coating liquid is coated in the reverse osmosis membrane as made from comparative example 1
Polyamide separation layer surface, then heat 10min at 100 DEG C, obtaining surface includes the reverse osmosis membrane of anti-pollution layer, its
In, the thickness of anti-pollution layer is 0.15 micron.Water flux rate of descent after the initial water flux of reverse osmosis membrane M2 and pollution
1 is the results are shown in Table with flux recovery rate.
Embodiment 1
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Sulfonated polyethylene alcohol (SPVA), the 1.0g dimethyl stearyls [3- (trimethoxies that 1.0g is obtained by preparation example 1
Base silicon substrate) propyl group] ammonium chloride and 0.1g formaldehyde is dissolved in 100g deionized waters, dilute salt of 1mol/L is then instilled under agitation
Acid filters after then stirring 24h at normal temperatures adjusting the pH value of solution to 1, obtains clarification coating liquid；Coating liquid is coated
Layer surface is separated in the polyamide of the reverse osmosis membrane as made from comparative example 1, then 10min is heated at 100 DEG C, obtains including resistance to
The reverse osmosis membrane N1 of pollution layer, which is taken out, is rinsed well with deionized water, is soaked in deionized water, wherein,
The thickness of anti-pollution layer is 0.15 micron.Water flux rate of descent and water after the initial water flux of reverse osmosis membrane N1 and pollution
Flux recovery rate the results are shown in Table 1.
Embodiment 2
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
By SPVA, 1.2g chitosan quaternary ammonium salt and 0.1g glutaraldehydes that 0.75g is obtained by preparation example 1 be dissolved in 100g go from
In sub- water, the dilute hydrochloric acid of 1mol/L is then instilled under agitation adjusting the pH value of solution to 1, is then stirred at normal temperatures
Filtered after 24h, obtain clarification coating liquid；By the coating liquid polyamide coated in the complex reverse osmosis membrane as made from comparative example 1 point
Absciss layer surface, then heats 30min at 50 DEG C, obtains the reverse osmosis membrane N2 containing anti-pollution layer, by the complex reverse osmosis membrane
Take out, rinsed well with deionized water, soaked in deionized water, wherein, the thickness of anti-pollution layer is 0.13 micron.The reverse osmosis
Water flux rate of descent and flux recovery rate after the initial water flux of permeable membrane N2 and pollution the results are shown in Table 1.
Embodiment 3
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
SPVA, 0.5g chitosan and 0.1g formaldehyde that 1.25g is obtained by preparation example 1 are dissolved in 100g deionized waters,
Then the dilute hydrochloric acid of 1mol/L is instilled under agitation adjusting the pH value of solution to 1, then stirs mistake after 24h at normal temperatures
Filter, obtains clarification coating liquid；Coating liquid is coated in the polyamide separating layer table of the complex reverse osmosis membrane as made from comparative example 1
Face, then heats 2min at 120 DEG C, obtains the reverse osmosis membrane N3 containing anti-pollution layer, which is taken out, and uses
Deionized water rinsing is clean, soaks in deionized water, wherein, the thickness of anti-pollution layer is 0.13 micron.Reverse osmosis membrane N3
Initial water flux and pollution after water flux rate of descent and flux recovery rate the results are shown in Table 1.
Embodiment 4
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, by dimethyl stearyl [3- (trimethoxy silicon
Base) propyl group] ammonium chloride using identical weight part γ aminopropyltriethoxy silane substitute, obtain reverse osmosis membrane N4.This is anti-
Water flux rate of descent and flux recovery rate after the initial water flux of permeable membrane N4 and pollution the results are shown in Table 1.
Embodiment 5
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, by dimethyl stearyl [3- (trimethoxy silicon
Base) propyl group] ammonium chloride using identical weight part gamma-amino propyl trimethoxy silicane substitute, obtain reverse osmosis membrane N5.This is anti-
Water flux rate of descent and flux recovery rate after the initial water flux of permeable membrane N5 and pollution the results are shown in Table 1.
Embodiment 6
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, dimethyl stearyl [3- (trimethoxy silicon
Base) propyl group] dosage of ammonium chloride is 0.5g, obtain reverse osmosis membrane N6.After the initial water flux of reverse osmosis membrane N6 and pollution
Water flux rate of descent and flux recovery rate the results are shown in Table 1.
Embodiment 7
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, dimethyl stearyl [3- (trimethoxy silicon
Base) propyl group] dosage of ammonium chloride is 1.5g, obtain reverse osmosis membrane N7.After the initial water flux of reverse osmosis membrane N7 and pollution
Water flux rate of descent and flux recovery rate the results are shown in Table 1.
Embodiment 8
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, the sulfonated polyethylene alcohol that will be obtained by preparation example 1
Substituted using the sulfonated polyethylene alcohol obtained by preparation example 2 of identical weight part, obtain reverse osmosis membrane N8.Reverse osmosis membrane N8's
Water flux rate of descent and flux recovery rate after initial water flux and pollution the results are shown in Table 1.
Embodiment 9
The embodiment is used to illustrate reverse osmosis membrane provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares reverse osmosis membrane, unlike, the sulfonated polyethylene alcohol that will be obtained by preparation example 1
Substituted using the sulfonated polyethylene alcohol obtained by preparation example 3 of identical weight part, obtain reverse osmosis membrane N9.Reverse osmosis membrane N9's
Water flux rate of descent and flux recovery rate after initial water flux and pollution the results are shown in Table 1.
Table 1
As can be seen from the above results, reverse osmosis membrane provided by the invention has stronger anti-fouling performance, and it is made
Preparation Method is simple, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of reverse osmosis membrane, it is characterised in that the reverse osmosis membrane includes supporting layer, separating layer and the anti-pollution stacked gradually
Layer, the separating layer are formed by crosslinked polyamide, and the anti-pollution layer passes through crosslinking by sulfonated polyethylene alcohol and amine substance
Reaction is formed.
2. reverse osmosis membrane according to claim 1, wherein, the thickness of the supporting layer is 90-150 microns, is preferably
100-120 microns；The thickness of the separating layer is 0.05-0.5 microns, is preferably 0.1-0.3 microns；The thickness of the anti-pollution layer
Spend for 0.05-0.5 microns, be preferably 0.08-0.2 microns.
3. reverse osmosis membrane according to claim 1 or 2, wherein, in the separating layer, the crosslinked polyamide passes through
Polyamine is carried out interfacial polymerization with polynary acyl chlorides to obtain；Preferably, the weight ratio of the polyamine and polynary acyl chlorides is (1-
100):1；Preferably, the polyamine is at least one in m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine
Kind, the polynary acyl chlorides is at least one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride；Preferably,
The condition of the interfacial polymerization includes polymerization temperature and is 40-150 DEG C, is preferably 50-120 DEG C, polymerization time 0.5-20min,
Preferably 1-10min.
4. reverse osmosis membrane according to claim 1 or 2, wherein, the cross-linking reaction is in crosslinking agent, catalysts and solvents
In the presence of carry out；Preferably, relative to the solvent of 100 parts by weight, the dosage of the sulfonated polyethylene alcohol is 0.1-50 weights
Part is measured, the dosage of the amine substance is 0.01-50 parts by weight, and the dosage of the crosslinking agent is 0.001-5 parts by weight, described to urge
Agent is acid and its dosage so that the pH value of cross-linking system is 1-5.
5. reverse osmosis membrane according to claim 4, wherein, the ion exchange capacity of the sulfonated polyethylene alcohol is 0.1-
3mmol/g, is preferably 0.5-2mmol/g；Preferably, the amine substance is chitosan, chitosan quaternary ammonium salt, gamma-amino third
Base trimethoxy silane, γ aminopropyltriethoxy silane and dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group]
At least one of ammonium chloride, is preferably chitosan quaternary ammonium salt and/or dimethyl stearyl [3- (trimethoxy silicon substrate) third
Base] ammonium chloride；Preferably, the crosslinking agent for formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, malonaldehyde, butanedial and
At least one of glutaraldehyde；Preferably, the catalyst be sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid at least
It is a kind of；Preferably, the condition of the cross-linking reaction includes reaction temperature for 20-150 DEG C, more preferably 50-120 DEG C, during reaction
Between for 1min-1h, more preferably 2min-30min.
6. reverse osmosis membrane according to claim 1 or 2, wherein, the supporting layer is by polyester, polyacrylonitrile, polyvinylidene fluoride
At least one of the non-sulfonated polyether sulphone of alkene, phenolphthalein type, polyether sulfone and polysulfones are made.
7. a kind of preparation method of reverse osmosis membrane, this method is included on supporting layer forms separating layer using crosslinked polyamide,
Then cross-linking reaction is carried out by sulfonated polyethylene alcohol and amine substance in the separating layer and forms anti-pollution layer.
8. according to the method described in claim 7, wherein, forming the mode of the separating layer is included polyamine and polynary acyl chlorides
Then absorption carries out interfacial polymerization on the supporting layer；Preferably, the weight ratio of the polyamine and polynary acyl chlorides is (1-
100):1；Preferably, the polyamine is at least one in m-phenylene diamine (MPD), p-phenylenediamine, o-phenylenediamine, piperazine and equal benzene triamine
Kind, the polynary acyl chlorides is at least one of pyromellitic trimethylsilyl chloride, m-phthaloyl chloride and paraphthaloyl chloride；Preferably,
The condition of the interfacial polymerization includes polymerization temperature and is 40-150 DEG C, is preferably 50-120 DEG C, polymerization time 0.5-20min,
Preferably 1-10min.
9. according to the method described in claim 7, wherein, formed the mode of the anti-pollution layer include by sulfonated polyethylene alcohol,
Amine substance, crosslinking agent and catalyst, which are dissolved in solvent, is made coating liquid, and the coating liquid then is coated in the separating layer
On, cross-linking reaction is carried out afterwards；Preferably, relative to the solvent of 100 parts by weight, the dosage of the sulfonated polyethylene alcohol is 0.1-
50 parts by weight, the dosage of the amine substance are 0.01-50 parts by weight, and the dosage of the crosslinking agent is 0.001-5 parts by weight, institute
It is acid and its dosage so that the pH value of cross-linking system is 1-5 to state catalyst.
10. according to the method described in claim 9, wherein, the ion exchange capacity of the sulfonated polyethylene alcohol is 0.1-
3mmol/g, is preferably 0.5-2mmol/g；Preferably, the amine substance is chitosan, chitosan quaternary ammonium salt, gamma-amino third
Ethyl triethoxy silicane alkane, gamma-amino propyl trimethoxy silicane and dimethyl stearyl [3- (trimethoxy silicon substrate) propyl group]
At least one of ammonium chloride, is preferably chitosan quaternary ammonium salt and/or dimethyl stearyl [3- (trimethoxy silicon substrate) third
Base] ammonium chloride；Preferably, the crosslinking agent for formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, glyoxal, malonaldehyde, butanedial and
At least one of glutaraldehyde；Preferably, the catalyst be sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, formic acid and nitric acid at least
It is a kind of；Preferably, the condition of the cross-linking reaction includes reaction temperature for 20-150 DEG C, more preferably 50-120 DEG C, during reaction
Between for 1min-1h, more preferably 2min-30min.
11. method according to any one of claims of claim 7-10, wherein, the supporting layer is by polyester, polyacrylonitrile, poly-
At least one of the non-sulfonated polyether sulphone of vinylidene, phenolphthalein type, polyether sulfone and polysulfones are made.
12. method according to any one of claims of claim 7-10, wherein, the thickness of the supporting layer is micro- for 90-150
Rice, is preferably 100-120 microns；The thickness of the separating layer is 0.05-0.5 microns, is preferably 0.1-0.3 microns；It is described resistance to
The thickness of pollution layer is 0.05-0.5 microns, is preferably 0.08-0.2 microns.
13. the reverse osmosis membrane being prepared as the method described in any one in claim 7-12.
14. application of the reverse osmosis membrane in claim 1-6 and 13 described in any one in water treatment field.
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| CN113522065A (en) * | 2020-04-22 | 2021-10-22 | 万华化学集团股份有限公司 | Chlorine-resistant and pollution-resistant polyamide reverse osmosis composite membrane and preparation method thereof |
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| CN114247298A (en) * | 2022-03-01 | 2022-03-29 | 湖南沁森高科新材料有限公司 | Post-treatment method for improving stability of reverse osmosis membrane and reverse osmosis membrane product |
| CN114247298B (en) * | 2022-03-01 | 2022-07-12 | 湖南沁森高科新材料有限公司 | Post-treatment method for improving stability of reverse osmosis membrane and reverse osmosis membrane product |
| CN114749035A (en) * | 2022-04-14 | 2022-07-15 | 浙江美易膜科技有限公司 | Low-pressure large-flux hollow fiber nanofiltration membrane as well as preparation method and application thereof |
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