CN113600040B - High-flux polyethylene-based reverse osmosis membrane and preparation method and application thereof - Google Patents
High-flux polyethylene-based reverse osmosis membrane and preparation method and application thereof Download PDFInfo
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- CN113600040B CN113600040B CN202110853756.0A CN202110853756A CN113600040B CN 113600040 B CN113600040 B CN 113600040B CN 202110853756 A CN202110853756 A CN 202110853756A CN 113600040 B CN113600040 B CN 113600040B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a high-flux polyethylene-based reverse osmosis membrane, a preparation method and application thereof, wherein the reverse osmosis membrane comprises a hydrophilized polyethylene porous support layer, an intermediate layer and a polyamide desalting layer formed on the intermediate layer; the intermediate layer is prepared by coating a mixed solution of a benzene compound containing amino and sulfonic groups, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether on a hydrophilized polyethylene porous supporting layer and then heating the mixed solution for reaction. The polyvinyl reverse osmosis membrane prepared by the invention has obviously higher flux and desalination rate.
Description
Technical Field
The invention relates to a reverse osmosis membrane, in particular to a high-flux polyethylene-based reverse osmosis membrane and a preparation method and application thereof, and belongs to the technical field of water treatment.
Background
Reverse osmosis membranes have been widely used in the fields of household water purifiers, industrial pure water manufacturing, wastewater treatment, seawater desalination, and the like, because of the characteristics of high separation efficiency, low energy consumption, less pollution, and the like. At present, the main stream of reverse osmosis membranes on the market are crosslinked aromatic polyamide composite reverse osmosis membranes, which comprise a three-layer structure, namely a PET non-woven fabric supporting layer, a polysulfone porous layer and a polyamide desalting layer. Wherein, the cost of PET non-woven fabrics and polysulfone raw materials accounts for more than 2/3 of the cost of the reverse osmosis membrane, and the core production technology is monopoly by a few chemical companies for a long time, so the cost of raw materials for producing the reverse osmosis membrane is difficult to reduce.
In recent years, research on a polyethylene microporous membrane as a substrate has appeared, and a polyethylene composite reverse osmosis membrane with low cost and certain permeability is prepared. The related patents are mainly focused on the problem that the surface of the traditional polyethylene film is poor in hydrophilicity, and hydrophilic modification is carried out to solve the problem that the water phase is difficult to uniformly disperse on the surface of the polyethylene film in the interfacial polymerization process, so that remarkable progress is achieved. The presently disclosed patents are mainly modified by pure water replacement after wetting with an organic solvent (e.g., chinese publication No. CN 112246104A), impregnated hydrophilic material modification (e.g., chinese publication No. CN 111760464A), low pressure plasma and PVA cross-linking coating modification (e.g., chinese publication No. CN109126483 a). In terms of pure water replacement after wetting with an organic solvent, chinese patent publication CN112246104a uses an organic solvent with low surface tension such as alcohols or phenols to wet a polyethylene material in advance, and then removes the solvent for use, thereby successfully preparing a reverse osmosis membrane sheet. In the aspect of modification of impregnated hydrophilic materials, the polyethylene film is subjected to hydrophilic modification by a polymer solution with hydroxyl groups in Chinese published patent CN111760464A, and then the modified polyethylene film is further processed to prepare a reverse osmosis film, so that the separation performance is remarkably improved. In the aspect of low-pressure plasma and PVA crosslinking coating modification, the method for preparing the reverse osmosis membrane by coating crosslinked PVA after treating the polyethylene membrane by using low-pressure plasma in China published patent CN109126483A has more industrial feasibility and promotes the wide application of the polyethylene membrane in the field of reverse osmosis base membranes.
Although some technical solutions for preparing reverse osmosis membranes using polyethylene membranes have been formed in the prior art, there is room for improvement in terms of both industrial feasibility and flux improvement.
Disclosure of Invention
The invention aims to provide a high-flux polyethylene-based reverse osmosis membrane, which has the characteristics of industrial feasibility, high flux and high desalination rate.
The invention further aims to provide a preparation method of the high-flux polyethylene-based reverse osmosis membrane, which has the characteristics of simplicity in operation, easiness in industrial production and the like.
It is a further object of the present invention to provide the use of the high flux polyethylene-based reverse osmosis membrane in a water treatment module or apparatus and/or in a water treatment process.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a first aspect of the present invention is to provide a high flux polyethylene-based reverse osmosis membrane comprising a hydrophilized polyethylene porous support layer, an intermediate layer, and a polyamide desalination layer formed on the intermediate layer;
the intermediate layer is prepared by coating a mixed solution of a benzene compound containing amino and sulfonic groups, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether on a hydrophilized polyethylene porous supporting layer and then heating the mixed solution for reaction.
The benzene-based compound having an amino group and a sulfonic acid group is a compound having 1 or more active amino groups, 1 or more sulfonic acid groups, and 1 or more benzene ring groups, and is preferably one or more of sodium aminobenzenesulfonate, sodium metaaminobenzenesulfonate, sodium 2-aminobenzenesulfonate, 3-aminobenzenesulfonate, sulfanilic acid, 2-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, sodium 3, 4-diaminobenzenesulfonate, 2, 4-diaminobenzenesulfonate, 3, 4-diaminobenzenesulfonate, and 4, 4-diaminodiphenylamine-2-sulfonic acid, and more preferably sodium aminobenzenesulfonate.
In the present invention, the polyamide desalting layer is obtained by interfacial polymerization of an aqueous phase containing an active amino compound having 2 or more and an organic phase containing a polyfunctional acyl halide.
The compound having 2 or more active amino groups may be any polyfunctional amine, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines, which may be used alone or as a mixture.
Examples of the aromatic polyfunctional amine include m-phenylenediamine, o-phenylenediamine, 1,3, 5-triaminobenzene, 1,2, 4-triaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 2, 4-diaminoanisoyl, amisole, and xylylenediamine;
examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, and tris (2-aminoethyl) amine;
examples of the alicyclic polyfunctional amine include 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine, 2, 5-dimethylpiperazine and 4-aminomethylpiperazine;
among the above polyfunctional amines, m-phenylenediamine is more preferable.
Examples of the polyfunctional acid halide include aromatic, aliphatic, and alicyclic polyfunctional acid halides, and the polyfunctional acid halide may be used alone or as a mixture.
Examples of the aromatic polyfunctional acid halide include trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarboxylic acid chloride, naphthalenedicarboxylic acid dichloride, trimesoyl chloride, and xylylene disulfonyl chloride, and monochlorosulfonyl-benzene dicarboxylic acid dichloride;
examples of the aliphatic polyfunctional acid halide include propane tricarboxylic acid chloride, butane tricarboxylic acid chloride, pentane tricarboxylic acid chloride, glutaryl halide, adipoyl halide;
examples of the alicyclic polyfunctional acid halide include cyclopropane tricarboxylic acid chloride, cyclobutane tetracarboxylic acid chloride, cyclopentane tricarboxylic acid chloride, cyclopentene tetracarboxylic acid chloride, cyclohexane tricarboxylic acid chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentene dicarboxylic acid chloride, cyclobutane dicarboxylic acid chloride, cyclohexane dicarboxylic acid chloride, and tetrahydrofuran dicarboxylic acid chloride;
among the above polyfunctional acid halides, trimesoyl chloride is more preferable.
In the invention, the hydrophilized polyethylene porous support layer is a hydrophilized porous support film which is formed by processing a polyethylene film by low-pressure plasma, and the pore diameter is 20-40nm.
The inventors of the present application have unexpectedly found that hydrophilization of a polyethylene-based film by low-pressure plasma treatment is extremely prone to occurrence of film surface crack defects, and that it is difficult to obtain a high desalination rate if directly applied to reverse osmosis membrane production. Further, a reverse osmosis membrane is prepared by coating crosslinked PVA on a treated polyethylene-based membrane with crack defects, and it is difficult to obtain high flux although the desalination rate is improved. And after the mixed solution of sodium aminobenzenesulfonate, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether is coated on the hydrophilized polyethylene porous supporting layer and then heated for reaction to generate an intermediate layer, the reverse osmosis membrane is prepared, and the flux and the desalination rate are both obviously improved. Because the poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether with linear structures and certain molecular weights have crosslinking reaction in the heating process, the crack defect of the film surface can be effectively covered with lower coating quantity; on one hand, the sodium aminobenzenesulfonate participates in the crosslinking reaction, and the carried benzene ring structure can effectively enlarge the molecular chain gap of the intermediate layer, so that the intermediate layer is endowed with higher water flux; on the other hand, the carried sulfonate groups can impart excellent hydrophilic properties to the intermediate layer, thereby further reducing the water molecule passage resistance of the intermediate layer. Therefore, the mixed solution of sodium aminobenzenesulfonate, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether is coated on the surface of the hydrophilized polyethylene film to heat the middle layer, and then the mixture is used for preparing the reverse osmosis film, so that the desalination rate of the reverse osmosis film can be improved, and the film can be endowed with excellent water flux.
In a preferred embodiment of the high flux polyethylene-based reverse osmosis membrane of the invention, said porous support layer is a hydrophilized polyethylene membrane. The hydrophilized polyethylene film can be produced by known techniques known in the art, and is not particularly limited. The polyethylene film is generally treated with a low pressure plasma treatment technique to obtain a hydrophilized polyethylene film, which can be manufactured, for example, by the method of chinese laid-open patent CN109126483 a.
The second aspect of the present invention provides a method for preparing the high-flux polyethylene-based reverse osmosis membrane, comprising the steps of:
1) Coating a mixed solution of a benzene compound containing amino and sulfonic groups, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether on a hydrophilized polyethylene porous supporting layer, and heating for reaction to prepare an intermediate layer;
2) Soaking the hydrophilized polyethylene porous support film with the intermediate layer in the soaking liquid, and then placing the soaking liquid in pure water for washing;
3) Soaking the soaked porous support membrane in an aqueous phase with more than 2 active amino compounds for 15-30s, removing superfluous aqueous phase on the surface, contacting the porous support membrane with an organic phase containing polyfunctional acyl halide, performing interfacial polymerization reaction, removing excessive liquid, and drying to obtain the reverse osmosis membrane.
The benzene series compound containing amino and sulfonic acid groups, the compound with more than 2 active amino groups and the polyfunctional acyl halide in the preparation method have the same definition as the previous, namely:
the benzene-based compound containing amino groups and sulfonic acid groups is a compound having 1 or more active amino groups, 1 or more sulfonic acid groups, and 1 or more benzene ring groups, preferably sodium aminobenzenesulfonate, sodium metaaminobenzenesulfonate, sodium 2-aminobenzenesulfonate, 3-aminobenzenesulfonate, sulfanilic acid, 2-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, sodium 3, 4-diaminobenzenesulfonate, 2, 4-diaminobenzenesulfonate, 3, 4-diaminobenzenesulfonate, 4-diaminodiphenylamine-2-sulfonic acid, more preferably sodium aminobenzenesulfonate;
the compound having 2 or more active amino groups is an aromatic, aliphatic, or alicyclic polyfunctional amine, preferably one or more of m-phenylenediamine, o-phenylenediamine, 1,3, 5-diaminobenzene, 1,2, 4-diaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 2, 4-diaminoanisoyl, amiol, xylylenediamine, ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine, 2, 5-dimethylpiperazine, and 4-aminomethylpiperazine, more preferably m-phenylenediamine;
the polyfunctional acid halide is one or more of aromatic, aliphatic, or alicyclic polyfunctional acid halides, preferably trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarboxyl chloride, naphthalenedicarboxyl dichloride, trimesoyl chloride, benzenedicarboxyl chloride, monochlorosulfonylbenzenedicarboxyl chloride, propanetricarboxylic acid chloride, butanetricarboxylic acid chloride, pentanetricarboxylic acid chloride, glutaryl halide, adipoyl halide, cyclopropane tricarboxylic acid chloride, cyclobutane tetracarboxylic acid chloride, cyclopentane tricarboxylic acid chloride, cyclopentanetetracarboxylic acid chloride, cyclohexane tricarboxylic acid chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentanedicarboxylic acid chloride, cyclobutane dicarboxyl chloride, cyclohexane dicarboxyl chloride, tetrahydrofuran dicarboxyl chloride, more preferably trimesoyl chloride.
In a preferred embodiment, step 1) comprises the following components in the mixed solution coated on the hydrophilic polyethylene porous support layer: 0.01 to 0.05 weight percent of benzene compound containing amino and sulfonic group, 0.01 to 0.05 weight percent of poly-2-ethyl-2-oxazoline and 0.01 to 0.1 weight percent of polyethylene glycol diglycidyl ether.
The reaction of the mixed solution of the benzene series compound containing the amino group and the sulfonic acid group, the poly-2-ethyl-2-oxazoline and the polyethylene glycol diglycidyl ether in the step 1) under the heating condition comprises the reaction of the amino group in the benzene series compound containing the amino group and the sulfonic acid group and the epoxy group of the polyethylene glycol diglycidyl ether, and also comprises the reaction of the amino group formed by the poly-2-ethyl-2-oxazoline under the heating condition and the epoxy group of the polyethylene glycol diglycidyl ether. Specifically, the heating reaction condition in the step 1) is 50-80 ℃ for 1-5min.
In a preferred embodiment, the infiltration liquid in step 2) is at least one of isopropanol, ethanol and methanol, preferably ethanol; the soaking time is about 1 min.
In a preferred embodiment, step 3) the mass concentration of the active amino compound in the aqueous phase is 2.0 to 6.0wt% and the mass concentration of the polyfunctional acyl halide in the organic phase is 0.05 to 0.2wt%;
preferably, the contact time for interfacial polymerization of the organic phase with the aqueous phase in the porous support membrane is 10 to 30 seconds.
A third aspect of the present invention is to provide the use of a high flux polyethylene-based reverse osmosis membrane as hereinbefore described for the preparation of a water treatment module or apparatus and/or for use in a water treatment process. The water treatment component or device can be any component or device which can be applied to the water treatment process and is provided with the high-flux polyethylene-based reverse osmosis membrane. The "application in a water treatment module or device" includes application to a module or device product having the high flux polyethylene-based reverse osmosis membrane of the present invention installed, as well as to the preparation of such a module or device product. The modules may be, for example, spiral wound modules, disc tube flat sheet modules, and the like. The device can be, for example, a household/commercial reverse osmosis water purifier, an industrial water supply reverse osmosis water purifier, and the like. The water treatment method may be, for example: drinking water production, industrial water supply and the like.
The technical scheme provided by the invention has the following beneficial effects:
(1) The reverse osmosis membrane provided by the invention has the characteristics of high flux and high desalination rate, and is well known in the industry for treatment 50The permeation flux can reach 50L/(m) under the test conditions of 0ppm sodium chloride and 0.69MPa 2 H) or more, and the salt rejection of sodium chloride can reach 99.4% or more. Therefore, the method can be applied to the water treatment fields of household water purification, industrial water supply and the like.
(2) Compared with the traditional preparation method of the reverse osmosis membrane by adopting PET non-woven fabrics and polysulfone-based membranes, the preparation method of the high-flux polyethylene-based reverse osmosis membrane provided by the invention has lower manufacturing cost. The preparation method of the invention is also easy for industrial production and the like.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw materials used in the following examples or comparative examples were commercially available industrial-grade conventional raw materials unless otherwise specified, and the main raw material information is shown in Table 1 below.
TABLE 1 Main raw Material information
The methods used or possible to be used in the examples or comparative examples of the present invention are described below:
1. evaluation of desalination Rate and permeation flux
Desalination rate and permeate flux are two important parameters for evaluating reverse osmosis membrane separation performance. The invention evaluates the separation performance of the reverse osmosis membrane according to GB/T32373-2015 reverse osmosis membrane test method.
The desalination rate (R) is defined as: under certain operating conditions, the salt concentration (C f ) And the salt concentration (C) in the permeate p ) The difference is divided by the salt concentration (C) f ) As shown in formula (1).
The permeate flux is defined as: at a certain operationUnder the condition that the volume of water which is transmitted through the unit membrane area in unit time is L/(m) 2 ·h)。
The operating conditions adopted for measuring the performance of the reverse osmosis membrane in the invention are as follows: the feed solution was 500ppm sodium chloride in water at a pH of 7.0.+ -. 0.5, an operating pressure of 0.69MPa and an operating temperature of 25 ℃.
Examples 1 to 3
A polyvinyl reverse osmosis membrane was prepared according to the following procedure, except that the raw material concentrations and reaction parameters in each example were different in table 1:
(1) Hydrophilizing polyethylene film: the low-pressure oxygen plasma was applied to the polyethylene film at a treatment power of 50W, a treatment pressure of 25Pa, and a treatment time of 180 s. And then the treated membrane is stored stably for 3 days to obtain the hydrophilized polyethylene porous support membrane.
(2) Preparing an intermediate layer: preparing 500g of mixed solution C of sodium aminobenzenesulfonate and poly-2-ethyl-2-oxazoline and 500g of solution D of polyethylene glycol diglycidyl ether, and then mixing C, D solution at room temperature to obtain mixed solution E. And uniformly coating the E solution on the surface of the hydrophilized polyethylene film, then heating in an oven, and drying at 60 ℃ for 3min to obtain the intermediate layer.
(3) And (3) soaking treatment: soaking the hydrophilic polyethylene porous support membrane with the intermediate layer in ethanol soaking solution for 1min at normal temperature, and then placing the support membrane in pure water to wash out the soaking solution in the membrane to obtain the polyethylene membrane with the intermediate layer after soaking treatment, namely the support membrane.
(4) Preparation of an aromatic polyamide desalting layer: firstly, preparing 500g of aqueous phase A containing m-phenylenediamine; immersing the wet support film into the solution A to remove superfluous water on the surface; then carrying out contact reaction on the polyamide and 25g of organic phase B containing trimesoyl chloride, and carrying out interfacial polycondensation to form a polyamide composite membrane; and finally, soaking the obtained crosslinked aromatic polyamide reverse osmosis membrane in deionized water to be tested.
The concentration of each substance, the process conditions, and the salt rejection rate and the permeate flux performance of the reverse osmosis membrane in the examples are recorded in table 1.
Comparative examples 1 to 3
A polyvinyl reverse osmosis membrane was prepared according to the method in examples, but the difference from the examples was that: the intermediate layer was not prepared and treated, and the raw material concentration and reaction parameters in each comparative example were different as shown in table 1.
Comparative examples 4 to 7
A polyvinyl reverse osmosis membrane was prepared according to the method in examples, but the difference from the examples was that: the intermediate layer was prepared with incomplete raw materials, and the raw material concentrations and reaction parameters in each comparative example are shown in table 1.
The concentration of each substance, the process conditions, and the salt rejection rate and the permeate flux performance of the reverse osmosis membrane in the comparative example are recorded in table 1.
Table 1, preparation conditions and product evaluation results in examples 1 to 3 and comparative examples 1 to 7
Examples 4 to 8
A polyvinyl reverse osmosis membrane was prepared according to the method of example 3, except that the types and amounts of the respective raw materials were different as shown in Table 2 below. The results of evaluating the desalination rate and permeation flux performance of the reverse osmosis membrane are shown in Table 2.
Table 2, preparation conditions and product evaluation results in examples 4 to 8
Based on the experimental results shown in tables 1 and 2, the intermediate layer of the invention is adopted to modify the polyethylene-based membrane, and the prepared reverse osmosis membrane has obviously higher flux and desalination rate.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (19)
1. A high flux polyethylene-based reverse osmosis membrane, comprising a hydrophilized polyethylene porous support layer, an intermediate layer, and a polyamide desalination layer formed on the intermediate layer;
the intermediate layer is prepared by coating a mixed solution of a benzene compound containing amino and sulfonic groups, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether on a hydrophilized polyethylene porous supporting layer and then heating the mixed solution for reaction.
2. The high-flux polyethylene-based reverse osmosis membrane according to claim 1, wherein the benzene-based compound containing an amino group and a sulfonic acid group is a compound having 1 or more active amino groups, 1 or more sulfonic acid groups, and 1 or more benzene ring groups.
3. The high flux polyvinyl reverse osmosis membrane of claim 2, wherein the benzene-based compound containing amino and sulfonic acid groups is one or more of sodium aminobenzenesulfonate, sodium metaaminobenzenesulfonate, sodium 2-aminobenzenesulfonate, 3-aminobenzenesulfonate, sulfanilic acid, 2-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, sodium 3, 4-diaminobenzenesulfonate, 2, 4-diaminobenzenesulfonate, 3, 4-diaminobenzenesulfonate, 4-diaminodiphenylamine-2-sulfonic acid.
4. The high-flux polyethylene-based reverse osmosis membrane according to claim 3, wherein the benzene-based compound containing an amino group and a sulfonic acid group is sodium aminobenzenesulfonate.
5. The high flux polyethylene-based reverse osmosis membrane according to claim 1, wherein the polyamide desalination layer is obtained by interfacial polymerization of an aqueous phase comprising an amino compound having 2 or more activities with an organic phase comprising a polyfunctional acyl halide.
6. The high flux polyethylene based reverse osmosis membrane according to any one of claims 1 to 5, wherein the compound having 2 or more active amino groups is an aromatic, aliphatic or alicyclic polyfunctional amine.
7. The high flux polyethylene based reverse osmosis membrane according to claim 6, wherein the compound having more than 2 active amino groups is one or more of m-phenylenediamine, o-phenylenediamine, 1,3, 5-diaminobenzene, 1,2, 4-diaminobenzene, 3, 5-diaminobenzoic acid, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 2, 4-diaminoanisoyl, amiloride, xylylenediamine, ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, 1, 3-diaminocyclohexane, 1, 2-diaminocyclohexane, 1, 4-diaminocyclohexane, piperazine, 2, 5-dimethylpiperazine and 4-aminomethylpiperazine.
8. The high flux polyethylene based reverse osmosis membrane according to claim 7, wherein the compound having more than 2 active amino groups is m-phenylenediamine.
9. The high flux polyethylene based reverse osmosis membrane according to claim 6, wherein the multifunctional acid halide is an aromatic, aliphatic or alicyclic multifunctional acid halide.
10. The high flux polyvinyl reverse osmosis membrane of claim 9, wherein the polyfunctional acid halide is one or more of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, biphenyldicarboxyl chloride, naphthalenedicarboxyl dichloride, trimesoyl chloride, benzenedisulfonyl chloride, monochlorosulfonylbenzenedicarboxyl chloride, propanetricarboxylic acid chloride, butanetricarboxylic acid chloride, pentanetricarboxylic acid chloride, glutaryl halide, adipoyl halide, cyclopropane tricarboxylic acid chloride, cyclobutane tetracarboxylic acid chloride, cyclopentane tricarboxylic acid chloride, cyclopentanetetracarboxylic acid chloride, cyclohexane tricarboxylic acid chloride, tetrahydrofuran tetracarboxylic acid chloride, cyclopentanedicarboxylic acid chloride, cyclobutane dicarboxyl chloride, cyclohexane dicarboxyl chloride, tetrahydrofuran dicarboxyl chloride.
11. The high flux polyethylene based reverse osmosis membrane according to claim 10, wherein the multifunctional acid halide is trimesoyl chloride.
12. A method of preparing a high flux polyethylene-based reverse osmosis membrane according to any one of claims 1-11, comprising the steps of:
1) Coating a mixed solution of a benzene compound containing amino and sulfonic groups, poly-2-ethyl-2-oxazoline and polyethylene glycol diglycidyl ether on a hydrophilized polyethylene porous supporting layer, and heating for reaction to prepare an intermediate layer;
2) Soaking the hydrophilized polyethylene porous support film with the intermediate layer in the soaking liquid, and then placing the soaking liquid in pure water for washing;
3) Soaking the soaked porous support membrane in an aqueous phase with more than 2 active amino compounds for 15-30s, removing superfluous aqueous phase on the surface, contacting the porous support membrane with an organic phase containing polyfunctional acyl halide, performing interfacial polymerization reaction, removing excessive liquid, and drying to obtain the reverse osmosis membrane.
13. The method for preparing a high-flux polyethylene-based reverse osmosis membrane according to claim 12, wherein in the step 1), the content of each component in the mixed solution coated on the hydrophilized polyethylene porous support layer is: 0.01 to 0.05 weight percent of benzene compound containing amino and sulfonic group, 0.01 to 0.05 weight percent of poly-2-ethyl-2-oxazoline and 0.01 to 0.1 weight percent of polyethylene glycol diglycidyl ether.
14. The method for preparing a high flux polyethylene based reverse osmosis membrane according to claim 13, wherein the heating reaction condition in step 1) is 50-80 ℃ for 1-5min.
15. The method for preparing a high flux polyethylene based reverse osmosis membrane according to claim 12, wherein the impregnating solution in step 2) is at least one of isopropanol, ethanol and methanol.
16. The method for preparing a high flux polyethylene based reverse osmosis membrane according to claim 15, wherein the impregnating solution in step 2) is ethanol.
17. The method for preparing a high flux polyethylene based reverse osmosis membrane according to claim 12, wherein the mass concentration of the active amino compound in the aqueous phase in step 3) is 2.0-6.0wt% and the mass concentration of the polyfunctional acyl halide in the organic phase is 0.05-0.2wt%.
18. The method for preparing a high flux polyethylene-based reverse osmosis membrane according to claim 17, wherein the contact time of interfacial polymerization of the organic phase and the aqueous phase in the porous support membrane in the step 3) is 10 to 30s.
19. Use of a high flux polyethylene-based reverse osmosis membrane according to any one of claims 1 to 11 in a water treatment module or device or in a water treatment process.
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