CN113663535B - High-performance thin-layer composite membrane and preparation method and application thereof - Google Patents
High-performance thin-layer composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-performance thin-layer composite membrane and a preparation method and application thereof. The thin-layer composite membrane comprises a matrix and glycerin or cane sugar attached to the upper surface and the lower surface of the matrix, wherein the matrix comprises a supporting layer and a separating layer, the supporting layer comprises a bottom lining layer and a porous supporting layer, and the separating layer is located on the upper surface of the porous supporting layer. The thin-layer composite membrane is obtained by the steps of soaking a substrate into a glycerol solution or a sucrose solution, drying and performing microwave treatment. The thin-layer composite membrane prepared by the method has high water flux and high salt rejection rate. The preparation method is simple, convenient and efficient, and the morphological structure of the composite membrane cannot be damaged.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a thin-layer composite membrane and a preparation method and application thereof.
Background
The thin-layer composite membrane consists of a supporting layer and a separating layer. In the specific preparation process, a layer of thin and compact different materials with special separation functions is compounded on the porous supporting base film to form the separation material with proper permeation quantity or salt rejection rate. Compared with an integrated membrane, the thin-layer composite membrane has higher solute separation rate and higher water permeation rate, so that more than 90% of separation membranes on the market are thin-layer composite membranes. The thin-layer composite membrane is widely applied to the fields of petrifaction, electronics, textile, light industry, metallurgy, medicine, bioengineering, food, environmental protection and the like.
In order to further improve the filtration performance of the composite membrane and better meet the application requirements, the permeability of the membrane can be effectively improved by respectively modifying and controlling the supporting layer and the active layer of the composite membrane or optimizing the membrane preparation process. In the work of modifying the active layer, post-treatment and surface modification methods are numerous, and specific methods include additive modification, plasma treatment, surface grafting modification, surface coating modification and the like. For example, in patent CN110180415a, fenton reagent is dropped on the surface of the composite membrane and heated, and then hydrophilic agent is dropped on the surface of the composite membrane to perform hydrophilic post-treatment modification. The united states patent US5028453 improves the contamination resistance of the composite membrane by introducing hydrophilic groups on the membrane surface by using a plasma post-treatment method, but the current plasma post-treatment method is limited by technical conditions and cost and cannot realize mass production. In the united states patent US5151183, fluorine gas is used to fluorinate the surface of the membrane to improve the anti-fouling performance of the membrane, but at the same time, the fluorine gas treatment easily breaks the polyamide molecular chains on the surface of the membrane, thereby affecting the separation performance and the service life of the membrane. In patent CN109289551A, the composite membrane is contacted with a polyphenol compound, and the polyphenol compound and polyamide are subjected to a crosslinking reaction, so that the crosslinking density of the polyamide surface is improved, and the salt rejection rate of the membrane is obviously improved. Compared with surface modification treatment, the surface grafting method involves more complex chemical reaction and relatively complicated process. Belfer et al (Journal of membrane science,1998,139, 175-181) graft methacrylic acid and polyethylene glycol methacrylic acid branched chains, respectively, to a polyamide composite membrane by a radiation grafting method, thereby improving the anti-contamination capability of the membrane. In addition, the surface coating method is a modification method which is most easy to realize industrial production due to the relative simple process. Both the chinese patent application CN1468649a and the US patent application US6913694 disclose that the surface of the composite film is coated with a coating layer of an epoxy compound containing more than 2 epoxy groups to improve the stain resistance of the composite film, but the improvement of the stain resistance of the composite film is limited due to the limitation of the density of hydrophilic groups. In conclusion, a simple and efficient post-treatment method is proposed and invented to improve the performance of the composite membrane.
Disclosure of Invention
The present invention is directed to overcoming the above problems of the prior art and providing a high performance thin layer composite membrane having both high water flux and high salt rejection, a method for preparing the same, and applications thereof.
One of the objects of the present invention is to provide a high performance thin composite membrane comprising a base and glycerin or sucrose adhered to upper and lower surfaces of the base, wherein the base comprises a support layer comprising a backing layer and a porous support layer, and a separation layer disposed on an upper surface of the porous support layer.
In the present invention, the support layer is not particularly limited and may be selected conventionally in the art. The source of the support layer is not particularly limited, and may be, for example, commercially available.
Wherein the bottom lining layer can be selected conventionally in the field, for example, the bottom lining layer is at least one of non-woven fabric, polyester screen and electrostatic spinning film. The non-woven fabric can be various non-woven fabrics in the prior art, is not limited in material type, and specifically can be polyester non-woven fabric, polypropylene non-woven fabric, polyphenyl ether non-woven fabric and the like.
The porous support layer may be a membrane conventionally selected in the art, and is preferably at least one of polysulfone, sulfonated polysulfone, bisphenol a-type polysulfone, polyethersulfone, sulfonated polyethersulfone, phenolphthalein-type nonsulfonated polyarylethersulfone, polyacrylonitrile, and polyvinylidene fluoride.
The separation layer may be one conventionally selected in the art, and is preferably a film of at least one of polyvinyl alcohol, sulfonated polyether sulfone, polydopamine, polyethylene glycol, monohydroxy polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, hydroxyl-terminated polytetrahydrofuran, hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polyethylene, hydroxyl-terminated nitrile rubber, hydroxyl-terminated styrene-butadiene liquid rubber, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, ethylene-vinyl alcohol copolymer, and polyamide.
The thin-layer composite membrane is obtained by the steps of soaking a substrate into a glycerol solution or a sucrose solution, drying and performing microwave treatment.
The invention also aims to provide a preparation method of the high-performance thin-layer composite membrane, which comprises the steps of soaking the whole matrix in glycerol solution or sucrose solution, drying and carrying out microwave treatment.
The concentration of the glycerol is preferably 50 to 300g/L, more preferably 100 to 200g/L.
The concentration of sucrose is preferably 50 to 300g/L, more preferably 100 to 200g/L.
The soaking time is preferably 5 to 20 seconds, more preferably 10 to 15 seconds.
The solvent of the glycerol solution or the sucrose solution is preferably water.
Preferably, the glycerol solution or the sucrose solution is sonicated to homogeneity and then allowed to stand for use.
According to a preferred embodiment of the invention, during the soaking process, the substrate is placed in a big beaker or a finishing box filled with glycerol or sucrose aqueous solution for 5 to 20s, preferably 10 to 15s, and is taken out after the upper surface and the lower surface of the substrate are fully soaked with glycerol or sucrose.
After soaking in glycerol or sucrose, the obtained composite membrane is dried at room temperature.
The microwave treatment is preferably carried out at a power of 500 to 900w for 10 to 600 seconds, more preferably at a power of 800 to 900w for 180 to 300 seconds.
In the method of the present invention, the source of the matrix of the composite film is not particularly limited, and the matrix may be commercially available or may be prepared by a method generally used in the art.
According to a preferred embodiment of the present invention, the method for preparing the thin composite film may specifically include the steps of:
(1) Preparing a separation layer on the upper surface of the porous support layer of the support layer to obtain a matrix;
(2) Soaking the whole matrix into a glycerol solution or a sucrose solution, and drying at room temperature to obtain a composite membrane;
preferably, the whole matrix is soaked in a large beaker or a finishing box filled with a glycerol solution or a sucrose solution for 5 to 20 seconds, preferably 10 to 15 seconds, and the matrix is taken out and dried after being soaked;
(3) Performing microwave treatment on the composite membrane obtained in the step (2),
preferably, the microwave treatment is preferably carried out at a power of 500 to 900w for 10 to 600s, more preferably at a power of 800 to 900w for 180 to 300s.
In the present invention, the source of the support layer is not particularly limited, and for example, it can be obtained commercially, such as a commercial ultrafiltration membrane or microfiltration membrane; or may be obtained by a production method generally used in the art.
The support layer includes a backing layer and a porous support layer.
The backing layer may be selected as is conventional in the art, for example, the backing layer is at least one of a nonwoven, a polyester screen, an electrospun film.
The porous supporting layer is a porous supporting base film, preferably one or a combination of a polysulfone porous supporting base film, a sulfonated polysulfone porous supporting base film, a bisphenol A type polysulfone porous supporting base film, a polyether sulfone porous supporting base film, a sulfonated polyether sulfone porous supporting base film, a phenolphthalein type non-sulfonated polyarylethersulfone porous supporting base film, a polyacrylonitrile porous supporting base film and a polyvinylidene fluoride porous supporting layer base film.
In the step (1), the separation layer is prepared by a coating method or an interfacial polymerization method. And preparing a separation layer on the upper surface of the porous supporting layer by a coating method or an interfacial polymerization method.
Wherein, the matrix prepared by the coating method is mainly to coat a layer of polymer solution on the upper surface of the porous supporting layer and then dry the polymer solution to obtain a separation layer; the matrix prepared by the interfacial polymerization method is prepared by adopting an amino compound containing two or more amino groups and an acyl chloride compound containing two or more acyl chloride groups through interfacial polymerization on a porous supporting layer.
The polymer which can be used as the separation layer in the coating method is one or more of polyvinyl alcohol, sulfonated polyether sulfone, polydopamine, polyethylene glycol, monohydroxy polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, hydroxyl-terminated polytetrahydrofuran, hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polyethylene, hydroxyl-terminated nitrile rubber, hydroxyl-terminated butylbenzene liquid rubber, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene or ethylene-vinyl alcohol copolymer.
The interfacial polymerization method is not particularly limited, and interfacial polymerization methods generally used in the art, such as interfacial polymerization using an aqueous phase of an amino compound having two or more amino groups and an organic phase of an acid chloride compound having two or more acid chloride groups, can be used. Wherein, the amino compound containing two or more amino groups is one or more of aromatic polyfunctional amines. The aromatic polyfunctional amine is preferably at least one of m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amonol, xylylenediamine, and piperazine.
The acyl chloride compound containing two or more acyl chloride groups is one or more of aromatic polyfunctional acyl chloride compounds. The aromatic polyfunctional acid chloride compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl chloride, biphenyldicarbonyl chloride, benzenedisulfonyl chloride, and trimesoyl chloride.
The organic solvent of the organic phase solution is one or more of n-hexane, cyclohexane, trichlorotrifluoroethane, n-heptane, n-octane, toluene, ethylbenzene and ISOPAR solvent oil.
The concentration of the compound containing two or more amino groups in the aqueous phase solution is 0.05-40 g/L, preferably 2-30 g/L; the concentration of the acyl chloride compound containing two or more acyl chloride groups in the organic phase solution is 0.5-5 g/L, preferably 0.5-2 g/L.
The aqueous solution can also comprise common basic auxiliary agents for preparing composite membranes, such as surfactants, acid absorbents, interfacial polymerization cosolvents and the like.
The surfactant can be one commonly used in the art for preparing composite membranes, such as at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl trimethyl ammonium bromide and sodium laurate.
The acid absorbent may be one commonly used in the art for preparing composite membranes, such as at least one of triethylamine, sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate, sodium hydroxide, and potassium hydroxide.
The interfacial polymerization cosolvent can be at least one interfacial polymerization cosolvent commonly used in the field of composite membrane preparation, such as dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, phenol, isopropanol, ethylene glycol, triphenyl phosphate, tributyl phosphate, acetone and ethyl acetate.
The amounts of surfactant, acid absorber and interfacial polymerization co-solvent are also conventional and may be preferred in the present invention: the concentration of the surfactant is 0.1-5 g/L; the concentration of the acid absorbent is 1-10 g/L; the concentration of the interfacial polymerization cosolvent is 1-200 g/L.
The third purpose of the invention is to provide the application of the high-performance thin-layer composite membrane or the thin-layer composite membrane obtained by the preparation method in a reverse osmosis membrane, a nanofiltration membrane and a forward osmosis membrane.
The invention is characterized in that the substrate is post-treated and modified by a microwave method, so that glycerin or cane sugar is attached to the back surface of the bottom lining layer and the upper surface of the separation layer of the thin-layer composite membrane, and the obtained thin-layer composite membrane has higher water flux and good retention rate.
The microwave post-treatment method is adopted, the microwave post-treatment is a characteristic mode which cannot be simulated by other post-treatment methods, and the microwave post-treatment method has the advantages of high post-treatment speed, high efficiency, small temperature gradient of the heated material, suitability for most polymers and the like. The composite membrane separation layer prepared by the invention has larger specific surface area, the microwave post-treatment can initiate the surface and interface action of the composite membrane, larger adhesive force can be achieved in a short time, the combination effect of the separation layer and the support layer is enhanced, the defect influence is overcome, and the excellent long-term stability and separation permeability of the composite membrane are maintained. In the microwave aftertreatment process, microwave energy is converted into heat energy. The heat absorbed by the material is related to the dielectric coefficient of the material, and most polymer materials have low dielectric loss factors and are not sensitive to microwaves. In addition, most of the converted energy is concentrated on the interface rather than in each body, so that each body is not heated, the shape and the size of each body are kept stable, and the morphological structure of the composite membrane is not damaged. The microwave aftertreatment method is simple, convenient and efficient and is worthy of study.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
In the following examples and comparative examples: all drug and composite membrane support layers are commercially available.
The salt rejection rate and the water flux of the thin-layer composite membrane are obtained by the following tests: loading the thin-layer composite membrane into a membrane pool, and testing the concentration change of sodium chloride in a sodium chloride raw water solution with initial concentration of 2000ppm and a permeate liquid within 1h by using a reverse osmosis composite membrane under the conditions that the pressure is 1.5MPa and the temperature is 25 ℃; the nanofiltration composite membrane is tested under 0.5MPa for the concentration change of a magnesium sulfate raw aqueous solution with initial concentration of 2000ppm and magnesium sulfate in a permeate within 1h, and the salt rejection rate R and the water flux J of the composite membrane are calculated by the following formulas:
R＝(C f -C p )/C f x 100%, wherein R is salt cut rate, C f Is the concentration of salt in the stock solution, C p Is the concentration of salt in the permeate; j = Q/(A.t), wherein J is water flux, Q is water permeability (L), and A is effective membrane area (m) of the composite membrane 2 ) And t is time (h).
Example 1
A commercial polysulfone ultrafiltration membrane A was used as a support layer and was brought into wet contact with an aqueous solution of m-phenylenediamine at a concentration of 20g/L for 60 seconds. And then pouring out the redundant aqueous solution, rolling the surface of the membrane by using a clean rubber roller, then contacting the membrane with an ISOPAR E solution containing 1g/L of trimesoyl chloride for 60s, then airing the formed polyamide separation layer in the air, treating the polyamide separation layer in an oven at 70 ℃ for 2min, and rinsing the polyamide separation layer in water at 25 ℃ for 10min to obtain the thin-layer composite reverse osmosis membrane substrate. Preparing 50g/L of glycerol aqueous solution in a big beaker, and soaking the whole composite membrane matrix in the big beaker filled with the glycerol aqueous solution for 10s. Taking out the composite reverse osmosis membrane, drying at room temperature, airing, putting the composite reverse osmosis membrane into a microwave oven, and performing microwave 900w treatment for 300s to obtain the composite membrane.
Example 2
A thin layer composite reverse osmosis membrane was prepared according to the method of example 1, except that 100g/L aqueous glycerol solution was used at the post-treatment modification stage.
Example 3
A thin layer composite reverse osmosis membrane was prepared according to the method of example 1, except that 200g/L of an aqueous glycerol solution was used in the post-treatment modification stage.
Example 4
A thin layer composite reverse osmosis membrane was prepared according to the method of example 1, except that 300g/L aqueous glycerol solution was used at the post-treatment modification stage.
Comparative example 1
A thin layer composite reverse osmosis membrane was prepared according to the method of example 1, except that the post-treatment modification stage was not impregnated with an aqueous glycerol solution, dried directly at room temperature and then treated with microwave 900w for 300s.
Comparative example 2
A thin layer composite reverse osmosis membrane was prepared according to the method of example 1, except that the composite membrane was not subjected to the glycerol impregnation and the microwave post-treatment, but was stored in deionized water.
The performance of the thin layer composite reverse osmosis membranes prepared in the above examples 1 to 4 and comparative examples 1 to 2 was tested using an aqueous solution of sodium chloride having a concentration of 2000ppm under test conditions of an operating pressure of 1.5MPa and a temperature of 25 ℃. The results of the tests are shown in table 1.
TABLE 1
As can be seen from examples 1-4 and comparative examples 1-2, the water flux of the thin-layer composite reverse osmosis membrane can be effectively improved by carrying out post-treatment modification on the thin-layer composite reverse osmosis membrane by adopting a microwave method, and meanwhile, the salt rejection rate of the composite membrane is slightly reduced. In addition, a glycerin soaking step before microwave treatment is indispensable, and the soaking concentration of the glycerin aqueous solution has little influence on the performance of the composite membrane.
Example 5
A composite reverse osmosis membrane was prepared under the same preparation conditions and procedures as in example 3 and post-treated with 900w of microwave for 300 seconds after being wetted with 200g/L of an aqueous glycerol solution. Except that commercial polysulfone ultrafiltration membrane B was used as the porous support base membrane.
Example 6
A composite reverse osmosis membrane was prepared under the same preparation conditions and procedures as in example 3 and post-treated with 900w of microwave for 300 seconds after being wetted with 200g/L of an aqueous glycerol solution. Except that a commercial polysulfone ultrafiltration membrane C was used as the porous support base membrane.
Comparative example 3
A composite reverse osmosis membrane was prepared under the same preparation conditions and procedures as in example 5, except that 200g/L of an aqueous glycerol solution was directly soaked in the post-treatment stage and dried without microwave post-treatment.
Comparative example 4
A composite reverse osmosis membrane was fabricated under the same fabrication conditions and procedures as in example 6, except that 200g/L of an aqueous glycerol solution was directly soaked in air and dried in the post-treatment stage without microwave post-treatment.
The performance of the thin layer composite reverse osmosis membranes prepared in examples 5 to 6 and comparative examples 3 to 4 described above was tested using an aqueous solution of sodium chloride having a concentration of 2000ppm under test conditions of an operating pressure of 1.5MPa and a temperature of 25 ℃. The results of the tests are shown in table 2.
TABLE 2
It can be seen from examples 5-6 and comparative examples 3-4 that the microwave post-treatment modification method is also applicable to composite membranes made with different types of support layers.
Example 7
A commercial polyacrylonitrile ultrafiltration membrane was used in wetted contact with a 10g/L aqueous solution of piperazine for 30s. And then pouring out the redundant aqueous solution, drying the surface of the membrane by using a clean rubber roller, then contacting the membrane with an ISOPAR solution oil solution containing 1g/L trimesoyl chloride for 30s, then airing the formed polyamide separation layer in the air, treating the polyamide separation layer in an oven at 70 ℃ for 2min, and rinsing the polyamide separation layer in water at 25 ℃ for 10min to obtain the thin-layer composite nanofiltration membrane matrix. Preparing 200g/L of glycerol aqueous solution in a big beaker, soaking the prepared composite membrane matrix in the big beaker filled with the glycerol aqueous solution for 10s, drying the composite nanofiltration membrane at room temperature after soaking, putting the composite nanofiltration membrane into a microwave oven after air drying, and performing microwave 900w treatment for 20s to obtain the composite membrane.
Example 8
A thin-layer composite nanofiltration membrane was prepared as in example 7, except that microwave 900w was used for 60s in the post-treatment modification stage.
Example 9
A thin-layer composite nanofiltration membrane was prepared as in example 7, except that microwave 900w was used for 180s in the post-treatment modification stage.
Example 10
A thin-layer composite nanofiltration membrane was prepared as in example 7, except that microwave 900w was used for 300s in the post-treatment modification stage.
Comparative example 5
A composite nanofiltration membrane was prepared under the same preparation conditions and procedures as in example 7, soaked in glycerol and then dried, except that no microwave treatment was performed.
The performance of the composite nanofiltration membranes prepared in examples 7 to 10 and comparative example 5 above was tested using an aqueous solution of magnesium sulfate at a concentration of 2000ppm under test conditions of an operating pressure of 0.5MPa and a temperature of 25 ℃. The results of the tests are shown in table 3.
TABLE 3
From the examples 7-10 and the comparative example 5, it can be seen that the water flux of the thin-layer composite nanofiltration membrane can be effectively improved by carrying out post-treatment modification on the thin-layer composite nanofiltration membrane by using a microwave method, and meanwhile, the salt rejection rate of the composite membrane is not obviously reduced.
Example 11
A commercial polyacrylonitrile ultrafiltration membrane was used in wetted contact with a 10g/L aqueous solution of piperazine for 30s. And then pouring out the redundant aqueous solution, drying the surface of the membrane by using a clean rubber roller, then contacting the membrane with an ISOPAR solution oil solution containing 1g/L of trimesoyl chloride for 30s, then airing the formed polyamide separation layer in the air, treating the polyamide separation layer in a drying oven at 70 ℃ for 2min, and rinsing the polyamide separation layer in water at 25 ℃ for 10min to obtain the thin-layer composite nanofiltration membrane matrix. Preparing 200g/L of glycerol aqueous solution in a big beaker, soaking the prepared composite membrane matrix in the big beaker filled with the glycerol aqueous solution for 10s, then placing the composite nanofiltration membrane at room temperature for drying, airing, placing the composite nanofiltration membrane in a microwave oven, and performing microwave treatment for 300s at 500w to obtain the composite membrane.
Example 12
A thin layer composite nanofiltration membrane was prepared as in example 11, except that microwave 700w was used for 300s in the post-treatment modification stage.
Example 13
A thin layer composite nanofiltration membrane was prepared as in example 11, except that microwave 900w was used for 300s in the post-treatment modification stage.
The performance of the composite nanofiltration membranes prepared in examples 11 to 13 above was tested using an aqueous solution of magnesium sulfate at a concentration of 2000ppm under test conditions of an operating pressure of 0.5MPa and a temperature of 25 ℃. The results of the tests are shown in Table 4.
TABLE 4
It can be seen from examples 11-13 that the use of different microwave powers for the same treatment time does not have a significant effect on the performance of the composite membrane.
Example 14
A commercial polysulfone ultrafiltration membrane A is used as a supporting layer, a layer of polyvinyl alcohol aqueous solution of 10g/L is coated on the supporting layer, then the supporting layer is placed in an oven of 70 ℃ for treatment for 2min, and then the supporting layer is rinsed in water of 25 ℃ for 10min, so that a composite membrane matrix is obtained. Preparing 200g/L of glycerol aqueous solution in a big beaker, soaking the prepared composite membrane matrix in the big beaker filled with the glycerol aqueous solution for 10s, drying the composite reverse osmosis membrane at room temperature after soaking, putting the composite reverse osmosis membrane in a microwave oven after air drying, and performing microwave 900w treatment for 300s to obtain the composite membrane.
Example 15
A composite membrane was prepared under the same preparation conditions and procedures as in example 14, and impregnated with glycerin and then dried, except that the coating polymer was changed to a 10g/L solution of sulfonated polyethersulfone in N, N-dimethylformamide.
Comparative example 6
A composite membrane was prepared under the same preparation conditions and procedures as in example 14, and impregnated with glycerin and then dried, except that the microwave treatment was not carried out.
Comparative example 7
A composite membrane was prepared under the same preparation conditions and procedures as in example 15, and impregnated with glycerin and then dried, except that the microwave treatment was not carried out.
The composite membranes prepared in examples 14 to 15 and comparative examples 6 to 7 described above were tested for performance using an aqueous solution of magnesium sulfate at a concentration of 2000ppm under test conditions of an operating pressure of 0.5MPa and a temperature of 25 c. The results of the tests are shown in Table 5.
TABLE 5
As can be seen from examples 14-15 and comparative examples 6-7, the microwave post-treatment modification method is also applicable to composite membranes made by coating.
Example 16
A composite membrane was prepared under the same preparation conditions and procedures as in example 3 and subjected to microwave post-treatment, except that the composite membrane was soaked in 200g/L sucrose aqueous solution for 10 seconds before the microwave post-treatment.
The performance of the thin layer composite reverse osmosis membrane prepared above for example 16 was tested using an aqueous solution of sodium chloride at a concentration of 2000ppm under test conditions of an operating pressure of 1.5MPa and a temperature of 25 ℃. The results of the tests are shown in Table 6.
TABLE 6
It can be seen from examples 16 and 3 that the performance of the composite membrane is not greatly affected by soaking in glycerol or sucrose aqueous solution before microwave post-treatment modification.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A high-performance thin-layer composite membrane is characterized by comprising a matrix and glycerol or sucrose attached to the upper and lower surfaces of the matrix, wherein the matrix comprises a support layer and a separation layer, the support layer comprises a bottom lining layer and a porous support layer, and the separation layer is positioned on the upper surface of the porous support layer; the thin-layer composite membrane is obtained by the steps of soaking a substrate into a glycerol solution or a sucrose solution, drying and performing microwave treatment.
2. The high performance thin composite film according to claim 1, wherein:
the porous supporting layer is a membrane of at least one of polysulfone, sulfonated polysulfone, bisphenol A type polysulfone, polyethersulfone, sulfonated polyethersulfone, phenolphthalein type non-sulfonated polyarylethersulfone, polyacrylonitrile and polyvinylidene fluoride.
3. The high performance thin composite film according to claim 1, wherein:
the separation layer is a film of at least one of polyvinyl alcohol, sulfonated polyether sulfone, polydopamine, polyethylene glycol, monohydroxy polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, hydroxyl-terminated polytetrahydrofuran, hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated polyethylene, hydroxyl-terminated butadiene-acrylonitrile rubber, hydroxyl-terminated butadiene-styrene liquid rubber, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, ethylene-vinyl alcohol copolymer and polyamide.
4. A method of making a high performance thin composite film according to any one of claims 1~3 comprising the steps of soaking the substrate in a glycerol or sucrose solution, drying, and microwave treatment.
5. The method of preparing a high performance thin composite film according to claim 4, wherein:
the concentration of the glycerol is 50-300 g/L; or the like, or, alternatively,
the concentration of the sucrose is 50-300 g/L.
6. The method of preparing a high performance thin composite film according to claim 5, wherein:
the concentration of the glycerol is 100 to 200 g/L; or the like, or, alternatively,
the concentration of the sucrose is 100 to 200g/L.
7. The method of preparing a high performance thin composite film according to claim 4, wherein:
the microwave treatment is carried out at a power of 500 to 900w for 10 to 600s.
8. The method of preparing a high performance thin composite film according to claim 7, wherein:
the microwave treatment is carried out at a power of 800 to 900w for 180 to 300s.
9. The method of making a high performance thin layer composite membrane of any one of claims 4~8 comprising the steps of:
(1) Preparing a separation layer on the upper surface of the porous supporting layer of the supporting layer to obtain a matrix;
(2) Soaking the whole matrix into a glycerol solution or a sucrose solution, and drying at room temperature;
(3) And (4) microwave treatment.
10. A method of manufacturing a thin composite film according to claim 9, wherein:
in the step (1), the separation layer is prepared by a coating method or an interfacial polymerization method.
11. The method of preparing a thin composite film according to claim 10, wherein:
the interfacial polymerization method is to carry out polymerization by adopting an aqueous phase of an amino compound containing two or more amino groups and an organic phase of an acyl chloride compound containing two or more acyl chloride groups.
12. Use of the high performance thin layer composite membrane according to any one of claims 1~3 or the thin layer composite membrane obtained by the preparation method according to any one of claims 4 to 11 in a reverse osmosis membrane, a nanofiltration membrane or a forward osmosis membrane.
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