BICONTINUOUS HIGHLY INTERCONNECTED POROUS POLYMER ULTRAFILTRATION MEMBRANE AS WELL AS PREPARATION METHOD AND APPLICATION THEREOF

Abstract

A polymer ultrafiltration membrane with a bicontinuous highly interconnected porous structure, a preparation method and applications thereof are provided. The ultrafiltration membrane has a bottom layer and a polymer layer. The polymer layer is divided into a sublayer and a surface layer. The surface layer is of a uniform small pore structure with a narrow pore size distribution. The sublayer is of a bicontinuous highly interconnected three-dimensional network porous structure. The bicontinuous highly interconnected porous structure of the bicontinuous highly interconnected porous ultrafiltration membrane is characterized as follows: in the thickness direction of the sublayer, the cross-sectional porosity on any XY cross-section perpendicular to the thickness direction is 40-90%, preferably 60-90%, and further preferably 70-90%; and the difference in the cross-sectional porosities between any two XY cross-sections does not exceed 10%, preferably not exceed 8%, and also preferably not exceed 5%.

Claims

1. A bicontinuous highly interconnected porous ultrafiltration membrane, which comprises a bottom layer and a polymer layer, wherein the polymer layer is divided into a sublayer and a surface layer, the surface layer is of a uniform small pore structure with a narrow pore size distribution, and the sublayer is of a bicontinuous highly interconnected three-dimensional network porous structure; wherein a bicontinuous highly interconnected porous structure of the bicontinuous highly interconnected porous ultrafiltration membrane is characterized as follows: in a thickness direction of the sublayer, a cross-sectional porosity on any XY cross-section perpendicular to the thickness direction is 40-90%, preferably 60-90%, and further preferably 70-90%; and a difference in the cross-sectional porosities between any two XY cross-sections does not exceed 10%, preferably not exceed 8%, and also preferably not exceed 5%.

2. The ultrafiltration membrane according to claim 1, characterized in that: in a length direction of the sublayer, a cross-sectional porosity on any YZ cross-section perpendicular to the length direction is 40-90%, preferably 60-90%, and further preferably 70-90%; and a difference in the cross-sectional porosities between any two YZ cross-sections does not exceed 10%, preferably not exceed 8%, and also preferably not exceed 5%; and in a width direction of the sublayer, a cross-sectional porosity on any XZ cross-section perpendicular to the width direction is 40-90%, preferably 60-90%, and further preferably 70-90%; and a difference in the cross-sectional porosities between any two XZ cross-sections in the width direction does not exceed 10%, preferably not exceed 8%, and also preferably not exceed 5%.

3. The ultrafiltration membrane according to claim 2, characterized in that: a difference in the cross-sectional porosities between any one XY cross-section, any one YZ cross-section and any one XZ cross-section does not exceed 10%, preferably not exceed 8%, and also preferably not exceed 5%.

4. The ultrafiltration membrane according to claim 1, characterized in that: the polymer is at least one of polyvinyl chloride, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, polyacrylic acid, polylactic acid, polyamide, chitosan, polyetherimide, polystyrene, polyolefin, polyester, polytrifluorochloroethylene, silicone resin, acrylonitrile-styrene copolymer, and their modified polymers; and/or, the bottom layer is selected from at least one of nonwoven fabrics, woven fabrics, polyester screens, and electrospun films.

5. The ultrafiltration membrane according to claim 4, characterized in that the polymer is polysulfone; and a water flux of the ultrafiltration membrane obtained by using polysulfone is approximately 1200 LMH or higher, approximately 1500 LMH or higher, or approximately 1800 LMH or higher; and/or a water flux volume equivalent of the ultrafiltration membrane obtained by using polysulfone is approximately 1700 or higher, approximately 2000 or higher, or approximately 2300 or higher; and/or a water flux surface equivalent of the ultrafiltration membrane obtained by using polysulfone is approximately 10 or higher, approximately 40 or higher, approximately 60 or higher, or approximately 70 or higher.

6. The ultrafiltration membrane according to claim 4, characterized in that the polymer is polyacrylonitrile; and a water flux of the ultrafiltration membrane obtained by using polyacrylonitrile is approximately 300 LMH or higher, approximately 400 LMH or higher, or approximately 500 LMH or higher; and/or a water flux volume equivalent of the ultrafiltration membrane obtained by using polyacrylonitrile is approximately 400 or higher, approximately 500 or higher, or approximately 600 or higher; and/or a water flux surface equivalent of the ultrafiltration membrane obtained by using polyacrylonitrile is approximately 5 or higher, approximately 10 or higher, or approximately 15 or higher.

7. The ultrafiltration membrane according to claim 1, characterized in that: a mean pore size of the surface layer is 2-100 nm.

8. The ultrafiltration membrane according to claim 1, characterized in that: a thickness of the bottom layer is 50-300 ?m, a thickness of the sublayer is 10-60 ?m, and a thickness of the surface layer is 0.5-5 ?m.

9. The ultrafiltration membrane according to claim 1, characterized in that: a porosity of the polymer layer is 40-90%, preferably 60-90%.

10. The ultrafiltration membrane according to claim 1, characterized in that: the polymer layer is prepared by an atomization pretreatment and a non-solvent induced phase separation method, the atomization pretreatment being staying in an atomized droplet bath, wherein one side of the bottom layer is faced towards atomized droplets and another side of the membrane coated with a membrane casting solution is protected from contacting with the atomized droplets.

11. A method for preparing the ultrafiltration membrane according to claim 1, comprising the following steps: 1. dissolving components containing a polymer in a solvent to prepare a membrane casting solution; 2. blade-coating the membrane casting solution into a film on a bottom layer to form a bottom layer coated with the membrane casting solution; 3. performing an atomization pretreatment on the bottom layer coated with the membrane casting solution, including staying in a droplet bath, wherein one side of the bottom layer coated with the membrane casting solution is protected from contacting with atomized droplets, and another side of the bottom layer uncoated with the membrane casting solution is faced towards the atomized droplets to obtain an atomization pretreated membrane; 4. immersing the atomization pretreated membrane in a coagulation bath to obtain the ultrafiltration membrane.

12. The method for preparing the ultrafiltration membrane according to claim 11, characterized in that in step 1), a concentration of the polymer in the membrane casting solution is 60-200 g/L, preferably 80-180 g/L; and/or, the solvent is selected from a good solvent for the polymer.

13. The method for preparing the ultrafiltration membrane according to claim 11, characterized in that: in step 2), a thickness of the blade-coated films is 50-500 ?m, preferably 75-300 ?m.

14. The method for preparing the ultrafiltration membrane according to claim 11, characterized in that in step 3), a size of the droplets in the droplet bath is 1-50 ?m, preferably 5-18 ?m; and/or, an atomization pretreatment time is 1-60 seconds, preferably 2-40 seconds; and/or, a required atomization amount per unit membrane area is 2.5-20 L/m.sup.2.Math.h, preferably 10-17 L/m.sup.2 .Math.h; and/or, the droplets are a poor solvent for the polymer.

15. The method for preparing the ultrafiltration membrane according to claim 11, characterized in that: in step 4), the coagulation bath is a poor solvent for the polymer.

16. The method for preparing the ultrafiltration membrane according to claim 12, characterized in that: the good solvent for the polymer is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, acetone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylsulfoxide, tetrahydrofuran, dioxane, acetonitrile, chloroform, polarclean solvent, triethyl phosphate, trimethyl phosphate, hexamethylammonium phosphate, tetramethylurea, acetonitrile, toluene, hexane, and octane; the poor solvent for the polymer is selected from at least one of water, ethanol, and ethylene glycol.

17. The ultrafiltration membrane obtained by the method according to claim 11.

18. A composite nanofiltration membrane, sequentially comprising a bottom layer, a porous support layer, and an active separation layer which is a polyamide layer, wherein the porous support layer is divided into a sublayer and a surface layer, the surface layer is of a small pore structure with a narrow pore size distribution, and the sublayer is attached to the bottom layer and is of an interconnected three-dimensional network porous structure.

19. The composite nanofiltration membrane according to claim 18, characterized in that the ultrafiltration membrane is used as the bottom layer and porous support layer, wherein the polymer layer is used as the porous support layer.

20. The composite nanofiltration membrane according to claim 18, characterized in that a mean pore size of the surface layer of the porous support layer is 10-50 nm; and/or a thickness of the active separation layer is 5-100 nm.

21. The composite nanofiltration membrane according to claim 18, characterized in that: the active separation layer is prepared by an interfacial polymerization reaction of an aliphatic multifunctional amine compound and an aromatic multifunctional acyl chloride compound, wherein the aliphatic multifunctional amine compound is preferably at least one of polyethylene imine, ethylenediamine, piperazine, and 4-aminomethylpiperazine, and the aromatic multifunctional acyl chloride compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl dichloride, biphenyldicarbonyl chloride, benzene disulfo chloride, trimesoyl chloride.

22. The composite nanofiltration membrane according to claim 18, characterized in that the polymer is polysulfone; and a water flux of the composite nanofiltration membrane obtained by using polysulfone is approximately 100 LMH or higher; and/or a water flux volume equivalent of the composite nanofiltration membrane support layer obtained by using polysulfone is approximately 1800 or higher, approximately 2300 or higher, or approximately 2500 or higher; and/or a water flux surface equivalent of the composite nanofiltration membrane support layer obtained by using polysulfone is about 5 or higher, about 10 or higher, about 40 or higher, or about 60 or higher.

23. The composite nanofiltration membrane according to claim 18, characterized in that the polymer is polyacrylonitrile; and a water flux of the composite nanofiltration membrane obtained by using polyacrylonitrile is approximately 80 LMH or higher; and/or a water flux volume equivalent of the composite nanofiltration membrane support layer obtained by using polyacrylonitrile is about 400 or higher, about 600 or higher, or about 1000 or higher; and/or a water flux surface equivalent of the composite nanofiltration membrane support layer obtained by using polyacrylonitrile is about 5 or higher, about 10 or higher, or about 20 or higher.

24. A composite forward osmosis membrane, sequentially comprising a bottom layer, a porous support layer, and an active separation layer which is an aromatic polyamide layer; wherein the porous support layer is divided into a sublayer and a surface layer, the surface layer is of a small pore structure with a narrow pore size distribution, and the sublayer is attached to the bottom layer and is of an interconnected three-dimensional network porous structure.

25. The composite forward osmosis membrane according to claim 24, characterized in that the ultrafiltration membrane is used as the bottom layer and the porous support layer, wherein the polymer layer is used as the porous support layer.

26. The composite forward osmosis membrane according to claim 24, characterized in that a mean pore size of the surface layer of the porous support layer is 5-100 nm; and/or a thickness of the active separation layer is 5-180 nm.

27. The composite forward osmosis membrane according to claim 24, characterized in that: the active separation layer is prepared by an interfacial polymerization reaction of an aromatic multifunctional amine compound and an aromatic multifunctional acyl chloride compound; wherein the aromatic multifunctional amine compound is preferably at least one of m-phenylenediamine, 1,2-diaminobenzene, p-phenylenediamine, 1,3,5-benzenetriamine, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol, xylylene diamine, and the aromatic multifunctional acyl chloride compound is preferably at least one of terephthaloyl chloride, isophthaloyl chloride, phthaloyl dichloride, biphenyldicarbonyl chloride, benzene disulfo chloride, trimesoyl chloride.

28. The composite forward osmosis membrane according to claim 24, characterized in that the polymer is polysulfone; and a water flux of the composite forward osmosis membrane obtained by using polysulfone is approximately 10 LMH or higher (AL-FS), or approximately 18 LMH or higher (AL-DS); and/or a water flux volume equivalent of the composite forward osmosis membrane support layer obtained by using polysulfone is about 10 or higher (AL-FS), or about 30 or higher (AL-DS); and/or a water flux surface equivalent of the composite forward osmosis membrane support layer obtained by using polysulfone is approximately 0.4 or higher (AL-FS), or approximately 1 or higher (AL-DS).

29. The composite forward osmosis membrane according to claim 24, characterized in that the polymer is polyacrylonitrile; and a water flux of the composite forward osmosis membrane obtained by using polyacrylonitrile is approximately 8 LMH or higher (AL-FS), or approximately 18 LMH or higher (AL-DS); and/or a water flux volume equivalent of the composite forward osmosis membrane support layer obtained by using polyacrylonitrile is approximately 10 or higher (AL-FS), or approximately 30 or higher (AL-DS); and/or a water flux surface equivalent of the composite forward osmosis membrane support layer obtained by using polyacrylonitrile is approximately 0.4 or higher (AL-FS), or approximately 1 or higher (AL-DS).

Description

DESCRIPTION OF THE DRAWINGS

[0119] FIG. 1A is a surface morphological image of the ultrafiltration membrane of Example I-3.

[0120] FIG. 1B is a surface morphological image of the ultrafiltration membrane of Example I-5.

[0121] FIG. 1C is a surface morphological image of the ultrafiltration membrane of Comparative Example 1.

[0122] FIG. 1D is a surface morphological image of the ultrafiltration membrane of Comparative Example 2.

[0123] FIG. 1E is a surface morphological image of the ultrafiltration membrane of Example I-8.

[0124] FIG. 1F is a cross-sectional morphological image of the ultrafiltration membrane of Example I-8.

[0125] FIG. 1G is a partially enlarged view of FIG. 1F.

[0126] FIG. 1H is a surface morphological image of the ultrafiltration membrane of Example I-9.

[0127] FIG. 1I is a surface morphological image of the ultrafiltration membrane of Example I-10.

[0128] FIG. 1J is a surface morphological image of the ultrafiltration membrane of Comparative Example I-3.

[0129] FIG. 1K is a cross-sectional morphological image of the ultrafiltration membrane of Comparative Example I-3.

[0130] FIG. 2A is a cross-sectional morphological image of the porous support layer of the nanofiltration membrane obtained in Example II-3.

[0131] FIG. 2B is a surface morphological image of the nanofiltration membrane obtained in Example II-3.

[0132] FIG. 2C is a cross-sectional morphological image of the porous support layer of the nanofiltration membrane obtained in Comparative Example II-1.

[0133] FIG. 3A is a cross-sectional morphological image of the porous support layer of the composite forward osmosis membrane obtained in Example III-5.

[0134] FIG. 3B is a surface morphological image of the composite forward osmosis membrane obtained in Example III-5.

[0135] FIG. 3C is a cross-sectional morphological image of the support layer of the composite forward osmosis membrane obtained in Comparative Example III-1.

SPECIFIC EMBODIMENTS

[0136] The present invention is described specifically with specific Examples as follows. It is necessary to point out that the following Examples only serve for further explanation of the present invention and cannot be understood as a limitation of the protection scope of the present invention. Some non-essential improvements and adjustments of the present invention made by those skilled in the art based on the contents of the present invention still fall within the protection scope of the present invention.

[0137] In addition, it should be explained that each specific technical feature described in the following specific embodiments can be combined in any suitable way without causing contradiction. In order to avoid unnecessary repetition, various possible manners of combinations would not be explained separately in the present invention.

[0138] In addition, various different embodiments of the present invention can also be combined arbitrarily, as long as they do not go against the ideas of the present invention, and the technical solutions formed thereby belong to a part of the initial disclosure of the present description and also fall within the protection scope of the present invention at the same time.

[0139] In the following Examples, the present application provides a high-performance ultrafiltration membrane, which is formed by subjecting the polymer to an atomization pretreatment in combination with a non-solvent induced phase separation, wherein the polymer layer of the ultrafiltration membrane is divided into a sublayer and a surface layer, the sublayer is of a highly interconnected bicontinuous porous structure which consists of a three-dimensional random skeleton.

[0140] As mentioned earlier, the rejection rate is another important indicator that characterizes the performance of the ultrafiltration membrane. The rejection rate of the ultrafiltration membrane towards the substance is required to be 90% or more. Under an operating pressure of 0.1 MPa, by using a 0.1 g.Math.L.sup.?1 bovine serum albumin (BSA) phosphate buffer aqueous solution at 25? C. as a test solution, a BSA rejection rate test was carried out on the self-made ultrafiltration membranes. The molecular weight of BSA used as the test solution was 67 KDa. During testing, after collecting the filtrate at room temperature, the absorbance value A of the BSA test solution and the filtrate was measured by using an ultraviolet grating spectrophotometer at a wavelength of 280 nm. The rejection rate of the ultrafiltration membrane towards BSA was calculated according to formula (2).

[00001]$\begin{array}{cc}R=\left[1-\left(\frac{C_P}{C_J}\right)\right]?100\%=\left[1-\left(\frac{A_P}{A_J}\right)\right]?100\%,& \left(2\right)\end{array}$

[0141] In formula (2), R represents the rejection rate of BSA; C.sub.p represents the concentration of the filtrate; C.sub.j represents the concentration of the test solution; A.sub.p represents the absorbance of the filtrate; A.sub.j represents the absorbance of the test solution.

[0142] With regard to the microscopic morphology of the membrane, the surface and cross-sectional morphologies of the membrane sample were observed by using Hitachi S-4800 high-resolution field emission scanning electron microscopy (FESEM); the mean pore size of the membrane was determined by a liquid-liquid displacement method, wherein when determining the pore size by the method, deionized water and isobutanol were used as a displacing agent and a wetting agent respectively; the cross-sectional porosity of the membrane was obtained by processing and analyzing the SEM morphology of the membrane using Image J software; the bulk porosity of the membrane was determined by using a weighing method, and the bulk porosity of the membrane can be calculated according to formula (3).

[00002]$\begin{array}{cc}?=1-\frac{v_m}{v_t},& \left(3\right)\end{array}$

[0143] In formula (3), V.sub.m is the solid volume of the membrane sample, V.sub.t is the total volume of the membrane sample, V.sub.m=m/?, m is the weight of the dry membrane, ? is the density of the membrane material.

[0144] Unless otherwise defined, all technical and scientific terms used in the present invention belong to the general definitions in the field of the present application.

Example I

[0145] The series of Example I illustrate the ultrafiltration membrane according to the present invention.

[0146] In the Examples of the present invention, all the chemical reagents used are commercially available products, without any special purification treatment unless otherwise specified.

[0147] Spray equipment: Haoqi HQ-JS130H is selected as an ultrasonic humidifier; [0148] Pore size testing equipment: Nanjing Gaoqian PSDA-20 ultrafiltration membrane pore size analyzer.

Example I-1

[0149] 12 g of polysulfone was dissolved in 88 g of polarclean solvent, and heated with stirring at 100? C. to form a homogeneous solution (membrane casting solution), which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric (bottom layer) with a continuous casting machine, with the initial casting height being controlled at 200 ?m during coating, followed by facing one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 5 s and protecting another side coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 6.2 L/m.sup.2.Math.h; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, an ultrafiltration membrane was obtained.

[0150] Therein, the thickness of the nonwoven fabric of the ultrafiltration membrane was 85 ?m, the thickness of the sublayer was 45 ?m, the thickness of the surface layer was 2.2 ?m, the mean pore size of the surface layer is 20 nm.

Example I-2

[0151] An ultrafiltration membrane was prepared according to the method in Example I-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 10 L/m.sup.2.Math.h.

[0152] Therein, the thickness of the sublayer was 47 ?m, the thickness of the surface layer was 1.7 ?m, the mean pore size of the surface layer was 21 nm.

Example I-3

[0153] An ultrafiltration membrane was prepared according to the method in Example I-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 17 L/m.sup.2.Math.h. See FIG. 1A for the surface morphology.

[0154] Therein, the thickness of the sublayer was 50 ?m, the thickness of the surface layer was 1.5 ?m, the mean pore size of the surface layer was 23 nm.

Example I-4

[0155] An ultrafiltration membrane was prepared according to the method in Example I-3, except that in the atomization pretreatment stage, face one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 3 s.

[0156] Therein, the thickness of the sublayer was 48 ?m, the thickness of the surface layer was 1.6 ?m, the mean pore size of the surface layer was 21 nm.

Example I-5

[0157] A filtration membrane was prepared according to the method in Example I-3, except that in the atomization pretreatment stage, face one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 8 s. See FIG. 1B for the surface morphology of the membrane.

[0158] Therein, the thickness of the sublayer was 52 ?m, the thickness of the surface layer was 1.2 ?m, the mean pore size of the surface layer was 178 nm.

Comparative Example I-1

[0159] A filtration membrane was prepared according to the method in Example I-3, except that during the preparation of the filtration membrane, face one side of the coated nonwoven fabric coated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 5 s, obtaining a filtration membrane after washing with water. See FIG. 1C for the surface morphology of the membrane.

[0160] Therein, the mean pore size of the membrane was 410 nm.

Comparative Example I-2

[0161] An ultrafiltration membrane was prepared according to the method in Example I-1, except that during the preparation of the ultrafiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the coated nonwoven fabric in a deionized water coagulation bath for a complete phase separation, and obtain a filtration membrane after washing with water. See FIG. 1D for the surface morphology of the membrane.

[0162] Therein, the mean pore size of the membrane was 17 nm.

[0163] Under the test conditions of an operating pressure of 0.1 MPa and a temperature of 25? C., the pure water fluxes of the ultrafiltration membranes prepared in the above Examples I-1 to 5 and Comparative Examples I-1 to 2 were tested with deionized water. Further, under the testing conditions of 0.1 MPa and a temperature of 25? C., the BSA rejection rates of the ultrafiltration 10 membrane prepared in Examples I-1 to 5 and Comparative Examples I-1 to 2 were tested. The results obtained from the tests are shown in Table I-1.

TABLE-US-00001 TABLE I-1 atomization amount of time of BSA atomization atomization direction of bulk rejection polymer pretreatment pretreatment atomization porosity water flux rate membrane (L/m.sup.2 .Math. h) (s) pretreatment (%) (L/m.sup.2 .Math. h) (%) Example I-1 6.2 5 reverse 68 1211 97.5 direction Example I-2 10 5 reverse 71 1484 96.8 direction Example I-3 17 5 reverse 74 1684 96.3 direction Example I-4 17 3 reverse 70 1355 97.7 direction Example I-5 17 8 reverse 79 1931 68.6 direction Comparative 17 5 forward 77 2045 50.2 Example I-1 direction Comparative 0 0 / 65 923 98.7 Example I-2

[0164] As can be seen from Examples I-1 to 3 and Comparative Example I-2, after the atomization pretreatment on the side of the coated nonwoven fabric uncoated with the membrane casting solution, the pure water fluxes of the resulting ultrafiltration membranes are improved significantly and the atomization amount has a great influence on the pure water flux of the membrane which is increased as the atomization amount increases. As can be seen from Examples I-3 to 5 and Comparative Example I-1 to 2, after the atomization pretreatment on the side of the coated nonwoven fabric uncoated with the membrane casting solution, the pure water flux of the membrane is increased as the atomization time increases; when the atomization time is within 5 s, the BSA rejection rate of the membrane remains basically constant; when the atomization time reaches 8 s, the BSA rejection rate of the membrane decreases significantly; after the atomization pretreatment of the side of the coated nonwoven fabric coated with the membrane casting solution, the BSA rejection rate of the membrane is significantly reduced.

[0165] In terms of morphology, within 5 s of the pretreatment of the side of the coated nonwoven fabric uncoated with the membrane casting solution facing the atomized droplets, the upper surface of the ultrafiltration membrane presents a uniform small pore structure, the mean pore size distributions on the surfaces of the ultrafiltration membranes without and with the atomization pretreatment are both narrow, and the mean pore sizes remain constant at 20?3 nm. The number of pores on the membrane surface and the membrane bulk porosity increase with the increase of atomization time. As the atomization time further increases (greater than 5 s) and the side of the coated nonwoven fabric coated with the membrane casting solution is faced towards the atomized droplet bath, the upper surfaces of the membranes becomes rougher and presents a large pore structure of micrometer scale.

Example I-6

[0166] 12 g of polyacrylonitrile was dissolved in 88 g of DMF solvent, and heated with stirring at 50? C. to form a homogeneous solution, which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric with a continuous casting machine, with the initial casting height being controlled at 200 ?m during coating, followed by facing the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 10 s and protecting the side of the membrane coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 17 L/m.sup.2.Math.h; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, an ultrafiltration membrane was obtained.

[0167] Therein, the thickness of the sublayer was 45 ?m, the thickness of the surface layer was 2.4 ?m, the mean pore size of the surface layer was 18 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 65-67%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 67-72%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 65-71%.

Example I-7

[0168] An ultrafiltration membrane was prepared according to the method in Example I-6, except that in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 20 s.

[0169] Therein, the thickness of the sublayer was 47 ?m, the thickness of the surface layer was 1.9 ?m, the mean pore size of the surface layer was 20 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 68-72%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 66-75%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 67-74%.

Example I-8

[0170] An ultrafiltration membrane was prepared according to the method in Example I-6, except that in the atomization pretreatment stage, face the back side of the coated membrane towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 30 s. See FIG. 1E to FIG. 1G for the surface and cross-sectional morphologies.

[0171] Therein, the thickness of the sublayer was 50 ?m, the thickness of the surface layer was 1.8 ?m, the mean pore size of the surface layer was 24 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 70-74%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 69-78%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 70-76%.

Example I-9

[0172] An ultrafiltration membrane was prepared according to the method in Example I-6, except that in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 40 s. See FIG. 1H for the surface morphology.

[0173] Therein, the thickness of the sublayer was 52 ?m, the thickness of the surface layer was 1.6 ?m, the mean pore size of the surface layer was 62 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 71-77%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 72-79%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 74-78%.

Example I-10

[0174] A filtration membrane was prepared according to the method in Example I-6, except that in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 50 s. See FIG. 1I for the surface morphology.

[0175] Therein, the thickness of the sublayer was 55 ?m, the thickness of the surface layer was 1.5 ?m, the mean pore size of the surface layer was 254 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 75-83%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 75-80%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 76-81%.

Example I-11

[0176] An ultrafiltration membrane was prepared according to the method in Example I-8, except that during the formulation of a membrane casting solution, the addition amount of PAN in a system of membrane casting solution was 14%.

[0177] Therein, the thickness of the sublayer was 53 ?m, the thickness of the surface layer was 2.1 ?m, the mean pore size of the surface layer was 17 nm.

Example I-12

[0178] An ultrafiltration membrane was prepared according to the method in Example I-8, except that during the formulation of a membrane casting solution, 0.5% of a polymer additive of polyvinylpyrrolidone, with a molecular weight of 58000 Da, was added to a system of membrane casting solution.

[0179] Therein, the thickness of the sublayer was 51 ?m, the thickness of the surface layer was 1.5 ?m, the mean pore size of the surface layer was 22 nm.

Comparative Example I-3

[0180] An ultrafiltration membrane was prepared according to the method in Example I-6, except that during the preparation of the ultrafiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the ultrafiltration membrane in a solvent coagulation bath for a complete phase separation, and obtain an ultrafiltration membrane after washing with water. See FIG. 1J to FIG. 1K for the surface and the cross-sectional morphologies of the membrane.

[0181] Therein, the mean pore size of the membrane was 17 nm; in the thickness direction of the sublayer, 5 arbitrary XY cross-sections perpendicular to the thickness direction were counted, with a cross-sectional porosity of 58-62%, and in the length direction of the sublayer, 10 arbitrary YZ cross-sections perpendicular to the length direction were counted, with a cross-sectional porosity of 62-66%, and in the width direction of the sublayer, 10 arbitrary XZ cross-sections perpendicular to the width direction were counted, with a cross-sectional porosity of 61-66%.

Comparative Example I-4

[0182] An ultrafiltration membrane was prepared according to the method in Example I-11, except that during the preparation of the ultrafiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the coated membrane in a deionized water coagulation bath for a complete phase separation, and obtain an ultrafiltration membrane after washing with water.

[0183] Therein, the mean pore size of the membrane was 15 nm.

Comparative Example I-5

[0184] An ultrafiltration membrane was prepared according to the method in Example I-12, except that during the preparation of the ultrafiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the coated membrane in a solvent coagulation bath for a complete phase separation, and obtain an ultrafiltration membrane after washing with water.

[0185] Therein, the mean pore size of the membrane was 21 nm.

[0186] Under the test conditions of an operating pressure of 0.1 MPa and a temperature of 25? C., the pure water fluxes of the ultrafiltration membranes prepared in the above Examples I-6 to 12 and Comparative Examples I-3 to 5 were tested with deionized water. Under the testing conditions of 0.1 MPa and a temperature of 25? C., the BSA rejection rates of the ultrafiltration membranes prepared in the above Examples I-6 to 12 and Comparative Examples I-3 to 5 were tested. The results obtained from the tests are shown in Table I-2.

TABLE-US-00002 TABLE I-2 PAN PVP content in content in atomization membrane membrane amount of time of BSA casting casting atomization atomization bulk water rejection polymer solution solution pretreatment pretreatment porosity flux rate membrane (wt %) (wt %) (L/m.sup.2 .Math. h) (s) (%) (L/m.sup.2 .Math. h) (%) Example I-6 12 0 17 10 75 342 97.6 Example I-7 12 0 17 20 77 389 97.4 Example I-8 12 0 17 30 80 439 94.6 Example I-9 12 0 17 40 84 578 80.5 Example I-10 12 0 17 50 88 1016 69.6 Example I-11 14 0 17 30 76 297 96.1 Example I-12 12 0.5 17 30 81 644 94.2 Comparative 12 0 0 0 73 209 98.2 Example I-3 Comparative 14 0 0 0 70 141 98.5 Example I-4 Comparative 12 0.5 0 0 72 312 97.8 Example I-5

[0187] As can be seen from Examples I-6 to 10 and Comparative Example I-3, after the pretreatment of the side of the coated nonwoven fabric uncoated with the membrane casting solution facing the atomized droplets, the pure water flux of the resulting ultrafiltration membrane is increased as the atomization time increases; within 0 to 40 s of the atomization time, the BSA rejection rate of the ultrafiltration membrane remains basically constant while when the atomization time reaches and exceeds 40 s, the rejection rate of the membrane decrease significantly.

[0188] In terms of morphology, within 0 to 40 s of the atomization time, the upper surface of the ultrafiltration membrane presents a uniform small pore structure, the mean pore size distributions on the surface of the ultrafiltration membranes without and with the atomization pretreatment are both narrow with 20?3 nm. The number of pores on the ultrafiltration membrane surface and the bulk porosity increase with the increase of the atomization time. Compared with the ultrafiltration membrane without an atomization pretreatment, the atomization pretreated ultrafiltration membrane has a significant difference in the cross-sectional morphology, presenting a uniform bicontinuous highly interconnected three-dimensional porous structure, while the cross-section of the ultrafiltration membrane without atomization is of the traditional finger-shaped large pore and sponge pore structure; when the atomization time reaches and exceeds 40 s, the membrane tends to form a microfiltration membrane with the rough large pores on the surface and the bicontinuous highly interconnected porous structure in the cross-section.

[0189] From Examples I-11 to 12 and Comparative Examples I-4 to 5, it can be seen that the influence of the atomization pretreatment on the membrane structure and the performance is also applicable to ultrafiltration membranes prepared by increasing the solid content of the membrane casting solution and using an additive.

Example II

[0190] The series of Example II illustrate the composite nanofiltration membrane according to the present invention.

[0191] According to one preferable embodiment II of the present invention, the preparation method of the composite nanofiltration membrane can be carried out according to the following steps: [0192] 1) dissolving components containing a polymer in a solvent to prepare a membrane casting solution; [0193] 2) blade-coating the membrane casting solution into a film on a bottom layer; [0194] 3) performing an atomization pretreatment, i.e. staying in an atomized droplet bath for a certain period of time, wherein one side of the bottom layer uncoated with the membrane casting solution is faced towards atomized droplets, and another side coated with the membrane casting solution is protected from contacting with the atomized droplets; [0195] 4) immersing in a coagulation bath to obtain a polymer porous support layer with the bottom layer; [0196] 5) sequentially contacting the porous support layer with the bottom layer with an aqueous phase solution of an aliphatic compounds containing two or more amino groups after dilution for 5 to 150 s; [0197] 6) rolling the porous support layer with the bottom layer after immersion in the aqueous phase solution with a rubber roller to remove the excess aqueous phase solution; [0198] 7) contacting the porous support layer with the bottom layer from which the excess aqueous phase solution is removed with an organic phase solution of an acyl chloride compound containing two or more acyl chloride groups for 5 to 150 s, and generating a dense functional layer on the surface of the porous support layer through an interfacial polymerization reaction; [0199] 8) finally, after naturally drying in air, treating the above resulting primary membrane for 1-5 min at a certain temperature; after washing with water, the nanofiltration composite membrane of the present invention is obtained

[0200] In the following Examples and Comparative Examples: [0201] (1) the water flux of the composite nanofiltration membrane is measured by the following method: loading the composite nanofiltration membrane into a cross-flow filtration system, pre-pressing at 0.5 MPa for 0.5 h, and measuring the water permeation amount of the composite nanofiltration membrane within 1 h under conditions of a pressure of 0.5 MPa and a temperature of 25? C., and calculating according to the following formula:

J=Q/A.Math.t, [0202] wherein, J is water flux, Q is water permeation amount (L), A is an effective membrane area of the composite nanofiltration membrane (m.sup.2), and t is the time (h); [0203] (2) the desalination rate of the composite nanofiltration membrane is measured by the following method: loading the composite nanofiltration membrane into a cross-flow filtration system, pre-pressing at 0.5 MPa for 0.5 h, and measuring the concentration change of MgSO.sub.4 in a primary aqueous solution having an initial concentration of 2 g.Math.L.sup.?1 MgSO.sub.4 and in a permeate within 1 h under the conditions of a pressure of 0.5 MPa and a temperature of 25? C., and calculating according to the following formula:

R=(C.sub.p?C.sub.f)/C.sub.p?100%, [0204] wherein, R is the desalination rate (%), C.sub.p is the concentration (g/L or mol/L) of MgSO.sub.4 in the primary solution, and C.sub.f is the concentration (g/L or mol/L) of MgSO.sub.4 in the permeate;

[0205] In the Examples of the present invention, all the chemical reagents used are commercially available products without special purification treatment, unless otherwise specified.

[0206] Spray equipment: Haoqi HQ-JS130H is selected as ultrasonic humidifier.

Example II-1

[0207] (1) Preparation of a porous support layer with a bottom layer: 12 g of polyacrylonitrile was dissolved in 88 g of DMF solvent, and heated with stirring at 50? C. to form a homogeneous solution (membrane casting solution), which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric (bottom layer) with a continuous casting machine, with the initial casting height being controlled at 200 ?m during coating, followed by facing one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 20 s and protecting another side coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 6.2 L/m.sup.2.Math.h per unit membrane area; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, a porous support layer with a bottom layer was obtained. [0208] (2) Preparation of a composite membrane: a certain amount of an aqueous phase monomer piperazine (PIP) was weighed out into a volumetric flask, brought to the graduation with deionized water for a constant volume, and dissolved under ultrasound to form a homogeneous aqueous phase solution containing 0.5w/v % PIP. A certain amount of an organic phase monomer trimesoyl chloride (TMC) was weighed out into a volumetric flask, brought to the graduation with ISOPAR solvent oil for a constant volume, and dissolved under ultrasound to form a homogeneous organic phase solution containing 0.1w/v % TMC. The polyacrylonitrile porous support membrane prepared in step (1) was used for immersion in and contact with the above aqueous phase solution for 30 s. Afterwards, the excess aqueous phase solution was poured out, the surface of the membrane was dried by rolling with a clean rubber roller, and then the membrane was immersed in and brought into contact with an organic phase solution of trimesoyl chloride for 30 s. Afterwards, the excess organic phase solution was poured out, and the formed polyamide layer was dried in air. After treatment at room temperature for 4 min, a composite nanofiltration membrane was obtained. The prepared composite nanofiltration membrane was stored in deionized water for use in testing.

[0209] In the composite nanofiltration membrane obtained from Example II-1, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 44 ?m, the thickness of the surface layer of the porous support layer was 2.1 ?m, the thickness of the active separation layer was 46 nm, the mean pore size of the surface layer of the support layer was 17 nm.

Example II-2

[0210] A nanofiltration membrane was prepared according to the method in Example II-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 10 L/m.sup.2.Math.h during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1).

[0211] In the composite nanofiltration membrane obtained in Example II-2, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 45 ?m, the thickness of the surface layer of the porous support layer was 2.0 ?m, the thickness of the active separation layer was 43 nm. The mean pore size of the surface layer of the support layer was 18 nm.

Example II-3

[0212] A nanofiltration membrane was prepared according to the method in Example II-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 17 L/m.sup.2.Math.h during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1). See FIG. 2A for the cross-sectional morphology of the porous support layer of the nanofiltration membrane. See FIG. 2B for the surface morphology of the nanofiltration membrane.

[0213] In the composite nanofiltration membrane obtained in Example II-3, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 43 ?m, the thickness of the surface layer of the porous support layer was 1.9 ?m, the thickness of the active separation layer was 43 nm. The mean pore size of the surface layer of the support layer is 19 nm.

Example II-4

[0214] A nanofiltration membrane was prepared according to the method in Example II-3, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 10 s.

[0215] In the composite nanofiltration membrane obtained in Example II-4, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 44 ?m, the thickness of the surface layer of the porous support layer was 2.2 ?m, the thickness of the active separation layer was 45 nm. The mean pore size of the surface layer of the support layer was 17 nm.

Example II-5

[0216] A nanofiltration membrane was prepared according to the method in Example II-3, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 30 s.

[0217] In the composite nanofiltration membrane obtained in Example II-5, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 48 ?m, the thickness of the surface layer of the porous support layer was 1.7 ?m, the thickness of the active separation layer was 41 nm. The mean pore size of the surface layer of the support layer was 23 nm.

Example II-6

[0218] A nanofiltration membrane was prepared according to the method in Example II-3, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 40 s.

[0219] In the composite nanofiltration membrane obtained in Example II-6, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 51 ?m, the thickness of the surface layer of the porous support layer was 1.7 ?m, the thickness of the active separation layer was 38 nm. The mean pore size of the surface layer of the support layer was 57 nm.

Example II-7

[0220] A nanofiltration membrane was prepared according to the method in Example II-3, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, facing the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 50 s.

[0221] In the composite nanofiltration membrane obtained in Example II-7, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 54 ?m, the thickness of the surface layer of the porous support layer was 1.5 ?m, the thickness of the active separation layer was 36 nm. The mean pore size of the surface layer of the support layer was 223 nm.

Comparative Example II-1

[0222] A nanofiltration membrane was prepared according to the method in Example II-3, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the ultrafiltration membrane in a solvent coagulation bath for a complete phase separation, and obtain a support layer after washing with water. See FIG. 2C for the cross-sectional morphology of the support layer.

[0223] In the composite nanofiltration membrane obtained in Comparative Example II-1, the thickness of the active separation layer was 46 nm. The mean pore size of the support layer was 14 nm.

[0224] Under the test conditions of an operating pressure of 0.5 MPa and a temperature of 25? C., the water flux and the rejection rate of the nanofiltration membranes prepared in the above Examples I-1 to 7 and Comparative Example II-1 were tested with 2 g.Math.L.sup.?1 MgSO.sub.4 aqueous solution. The results obtained from the tests are shown in Table II-1.

TABLE-US-00003 TABLE II-1 atomization support layer amount per atomization support support layer unit membrane pretreatment layer bulk water rejection nanofiltration polymer area time porosity flux rate membrane material (L/m.sup.2 .Math. h) (s) (%) (L/m.sup.2 .Math. h) (%) Example II-1 Polyacrylonitrile 6.2 20 73 81 ? 5 97.9 ? 0.1 Example II-2 Polyacrylonitrile 10 20 76 87 ? 4 97.7 ? 0.2 Example II-3 Polyacrylonitrile 17 20 78 89 ? 6 97.1 ? 0.6 Example II-4 Polyacrylonitrile 17 10 75 85 ? 5 97.6 ? 0.3 Example II-5 Polyacrylonitrile 17 30 80 87 ? 5 93.8 ? 0.5 Example II-6 Polyacrylonitrile 17 40 84 85 ? 5 78.5 ? 0.8 Example II-7 Polyacrylonitrile 17 50 88 80 ? 7 52.6 ? 1.sup. Comparative Polyacrylonitrile 0 0 71 74 ? 4 98.2 ? 0.5 Example II-1

[0225] From the results of the above Examples II-3 to 5 and Comparative Example II-1, it can be seen that the composite nanofiltration membrane prepared by using the support layer undergoing an atomization pretreatment has excellent water flux and salt rejection rate, and the water flux of the nanofiltration membrane increases with the increase of atomization time on the premise of maintaining a constant salt rejection rate. From Examples II-6 to 7, it can be seen that as the atomization time further increases, the surface pore size of the support layer increases, as is not conducive to the formation of a complete polyamide separation layer, and results in a significant decrease in the salt rejection rate of the nanofiltration membrane. From Examples II-1 to 3, it can be seen that the permeation flux of the nanofiltration membrane increases with the increase of atomization amount.

Example II-8

[0226] (1) Preparation of a porous support layer with a bottom layer: 12 g of polysulfone, 0.5 g of polyvinylpyrrolidone (PVP) were dissolved in 87.5 g of polarclean solvent, and heated with stirring at 100? C. to form a homogeneous solution, which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric with a continuous casting machine, with the initial casting height being controlled at 200 ?m during coating, followed by facing one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 4 s and protecting another side coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 17 L/m.sup.2.Math.h per unit membrane area; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, a porous support layer with a bottom layer was obtained. [0227] (2) Preparation of a composite membrane: a certain amount of an aqueous phase monomer piperazine (PIP) was weighed out into a volumetric flask, brought to the graduation with deionized water for a constant volume, and dissolved under ultrasound to form a homogeneous aqueous phase solution containing 0.5 w/v % PIP. A certain amount of an organic phase monomer trimesoyl chloride (TMC) was weighed out into a volumetric flask, brought to the graduation with ISOPAR solvent oil for a constant volume, and dissolved under ultrasound to form a homogeneous organic phase solution containing 0.1 w/v % TMC. The polysulfone porous support membrane prepared in step (1) was used for immersion in and contact with the above aqueous phase solution for 30 s. Afterwards, the excess aqueous phase solution was poured out, the surface of the membrane was dried by rolling with a clean rubber roller, and then the membrane was immersed in and brought into contact with an organic phase solution of trimesoyl chloride for 30 s. Afterwards, the excess organic phase solution was poured out, and the formed polyamide layer was dried in air. After treatment at room temperature for 4 min, a composite nanofiltration membrane was obtained. The prepared composite nanofiltration membrane was stored in deionized water for use in testing.

[0228] In the composite nanofiltration membrane obtained in Example II-8, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 47 ?m, the thickness of the surface layer of the porous support layer was 1.5 ?m, the thickness of the active separation layer was 46 nm. The mean pore size of the surface layer of the support layer was 21 nm.

Example II-9

[0229] A nanofiltration membrane was prepared according to the method in Example II-8, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 6 s.

[0230] In the composite nanofiltration membrane obtained in Example II-9, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 51 ?m, the thickness of the surface layer of the porous support layer was 1.4 ?m, the thickness of the active separation layer was 42 nm. The mean pore size of the surface layer of the support layer was 24 nm.

Example II-10

[0231] A nanofiltration membrane was prepared according to the method in Example II-8, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 8 s.

[0232] In the composite nanofiltration membrane obtained in Example II-10, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 53 ?m, the thickness of the surface layer of the porous support layer was 1.3 ?m, the thickness of the active separation layer was 39 nm. The mean pore size of the surface layer of the support layer was 167 nm.

Example II-11

[0233] A nanofiltration membrane was prepared according to the method in Example II-8, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 12 s.

[0234] In the composite nanofiltration membrane obtained in Example II-11, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 55 ?m, the thickness of the surface layer of the porous support layer was 1.1 ?m, the thickness of the active separation layer was 35 nm. The mean pore size of the surface layer of the support layer was 289 nm.

Example II-12

[0235] A nanofiltration membrane was prepared according to the method in Example II-8, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane in step (1), in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 24 s.

[0236] In the composite nanofiltration membrane obtained in Example II-12, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 57 ?m, the thickness of the surface layer of the porous support layer was 1.0 ?m, the thickness of the active separation layer was 34 nm. The mean pore size of the surface layer of the support layer was 402 nm.

Comparative Example II-2

[0237] A nanofiltration membrane was prepared according to the method in Example II-8, except that during the preparation of a porous support layer with a bottom layer in the nanofiltration membrane, without undergoing an atomization pretreatment stage, directly immerse the ultrafiltration membrane in a solvent coagulation bath for a complete phase separation, and obtain a porous support layer with a bottom layer after washing with water.

[0238] In the composite nanofiltration membrane obtained in Comparative Example II-2, the thickness of the active separation layer was 49 nm. The mean pore size of the support layer was 16 nm.

[0239] Under the test conditions of an operating pressure of 0.5 MPa and a temperature of 25? C., the water flux and the rejection rate of the nanofiltration membranes prepared in the above Examples I-8 to 12 and Comparative Example II-2 were tested with 2 g.Math.L.sup.?1 MgSO.sub.4 aqueous solution. The results obtained from the tests are shown in Table II-2.

TABLE-US-00004 TABLE II-2 support layer support layer atomization support layer nanofiltration polymer pretreatment bulk porosity water flux rejection rate membrane material time (s) (%) (L/m.sup.2 .Math. h) (%) Example II-8 Polysufone 4 72 113 ? 2 94.7 ? 0.4 Example II-9 Polysufone 6 76 120 ? 1 95.2 ? 1.1 Example II-10 Polysufone 8 79 108 ? 2 81.2 ? 0.6 Example II-11 Polysufone 12 81 105 ? 4 72.7 ? 1.7 Example II-12 Polysufone 24 84 88 ? 2 57.4 ? 0.9 Comparative Polysufone 0 65 90 ? 1 97.1 ? 1.4 Example II-2

[0240] From the results of the above Examples II-8 to 9 and Comparative Example II-2, it can be seen that the nanofiltration membrane prepared by using the porous support layer with a bottom layer undergoing atomization pretreatment has excellent water flux and salt rejection rate. Therein, the atomization time has a great influence on the permeability of the nanofiltration membrane. When the atomization pretreatment time is within a certain range, the pore size of the surface layer of the support layer is relatively small, as is conducive to the formation of a complete polyamide active layer during the interfacial polymerization, and improves the separation permeability of the membrane. The water flux and the salt rejection rate of the nanofiltration membrane reduce dramatically with the continued increase of the atomization pretreatment time.

Example III

[0241] The series of Example III illustrate the composite forward osmosis membrane according to the present invention.

[0242] According to one preferable embodiment III of the present invention, the preparation method of the composite forward osmosis membrane can be carried out according to the following steps: [0243] 1) dissolving components containing a polymer in a solvent to prepare a membrane casting solution; [0244] 2) blade-coating the membrane casting solution into a film on a bottom layer; [0245] 3) performing an atomization pretreatment, i.e. staying in an atomized droplet bath for a certain period of time, wherein one side of the bottom layer uncoated with the membrane casting solution is faced towards atomized droplets and another side coated with the membrane casting solution is protected from contacting with the atomized droplets; [0246] 4) immersing in a coagulation bath to obtain the polymer porous support layer with the bottom layer; [0247] 5) contacting the porous support layer with the bottom layer with an aqueous phase solution of an aromatic compounds containing two or more amino groups after dilution for 5 to 150 s; [0248] 6) rolling the porous support layer with the bottom layer after immersion in the aqueous phase solution with a rubber roller to remove an excess aqueous phase solution; [0249] 7) contacting the porous support layer with the bottom layer from which the excess aqueous phase solution is removed with an organic phase solution of acyl chloride compound containing two or more acyl chloride groups for 5 to 150 s, and generating a dense functional layer on the surface of the porous support layer through an interfacial polymerization reaction; [0250] 8) finally, after naturally drying in air, treating the above resulting primary membrane for 1-5 min at a certain temperature; after washing with water, the forward osmosis composite membrane of the present invention is obtained.

[0251] The water flux and the reverse diffusion salt flux are important parameters for evaluating a forward osmosis composite membrane.

[0252] The water flux of the membrane is a parameter that characterizes the permeability of the membrane, refers to the volume of water penetrating through the membrane per unit area and per unit time, and has a common unit of L/m.sup.2.Math.h. The prepared forward osmosis composite membrane was placed inside a testing device, and at room temperature, the volume of water in a feed solution, which reached an draw solution side through the forward osmosis membrane within a certain period of time, was determined. The specific calculation method is as follows:

J.sub.w=?V/?t.Math.A.sub.m [0253] wherein: [0254] J.sub.wwater flux (L/m.sup.2.Math.h); [0255] ?Vvolume change of feed solution within time t (L); [0256] A.sub.marea of the test film (m.sup.2); [0257] ?ttest time (h).

[0258] The reverse diffusion salt flux is a parameter that characterizes the separation performance of a composite membrane, and has a common unit of g/m.sup.2h. A conductivity meter is used to test the change in conductance in the feed solution, and a standard curve is drawn to fit the change in concentration of the feed solution. The calculation is carried out according to the following formula:

J.sub.s=(C.sub.tV.sub.t?C.sub.0V.sub.0)/?t.Math.?.sub.m [0259] wherein: [0260] J.sub.sreverse diffusion salt flux (g/m.sup.2.Math.h); [0261] C.sub.tconcentration (g/L) of feed solution at time t; [0262] V.sub.tvolume (L) of feed solution at time t; [0263] C.sub.0concentration (g/L) of feed solution at time t=0; [0264] V.sub.0volume (L) of feed solution at time t=0; [0265] A.sub.marea (m.sup.2) of the test film; [0266] ?.sub.ttest time (h).

[0267] The water flux and the reverse diffusion salt flux of the forward osmosis composite membrane were tested on a forward osmosis testing device. The test conditions are as follows: at 25? C., by using 1 M MgCl.sub.2 as an draw solution and deionized water as feed solution, the water flux and the reverse diffusion salt flux of the forward osmosis composite membrane are tested using a forward osmosis testing device.

[0268] In the Examples of the present invention, all the chemical reagents used are commercially available products, without a special purification treatment unless otherwise specified.

[0269] Spray equipment: Haoqi HQ-JS130H is selected as an ultrasonic humidifier;

Example III-1

[0270] (3) Preparation of a porous support layer with a bottom layer: 12 g of polyacrylonitrile was dissolved in 88 g of DMF solvent, and heated with stirring at 50? C. to form a homogeneous solution (membrane casting solution), which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric (bottom layer) with a continuous casting machine, with the initial casting height being controlled at 150 ?m during coating, followed by facing one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 20 s and protecting another side coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 6.2 L/m.sup.2.Math.h per unit membrane area; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, a porous support layer with a bottom layer was obtained. [0271] (4) Preparation of a composite membrane: a certain amount of an aqueous phase monomer m-Phenylenediamine (MPD) was weighed out into a volumetric flask, brought to the graduation with deionized water for a constant volume, and dissolved under ultrasound to form a homogeneous aqueous phase solution containing 2 w/v % MPD. A certain amount of an organic phase monomer trimesoyl chloride (TMC) was weighed out into a volumetric flask, brought to the graduation with ISOPAR solvent oil for a constant volume, and dissolved under ultrasound to form a homogeneous organic phase solution containing 0.1 w/v % TMC. The polyacrylonitrile porous support membrane prepared in step (1) was used for immersion in and contact with the above aqueous phase solution for 60 s. Afterwards, the excess aqueous solution was poured out, the surface of the membrane was dried by rolling with a clean rubber roller, and then the membrane was immersed in and brought into contact with an organic phase solution of trimesoyl chloride for 60 s. Afterwards, the excess organic phase solution was poured out, and then the formed polyamide layer was dried in air. After treatment at room temperature for 4 min, a composite forward osmosis membrane was obtained. The prepared composite forward osmosis membrane was stored in deionized water for use in testing.

[0272] In the composite forward osmosis membrane obtained in Example III-1, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 43 ?m, the thickness of the surface layer of the porous support layer was 2.2 ?m, the thickness of the active separation layer was 45 nm. The mean pore size of the surface layer of the support layer was 16 nm. The bulk porosity of the porous support layer was 72%.

Example III-2

[0273] (1) Preparation of a porous support layer with a bottom layer: a porous support layer with a bottom layer in the forward osmosis membrane was prepared according to the method in Example III-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 10 L/m.sup.2.Math.h during the preparation. [0274] (2) Preparation of a composite membrane: the same as Example III-1.

[0275] In the composite forward osmosis membrane obtained in Example III-2, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 45 ?m, the thickness of the surface layer of the porous support layer was 2.1 ?m, the thickness of the active separation layer was 43 nm. The mean pore size of the surface layer of the support layer was 17 nm. The bulk porosity of the porous support layer was 75%.

Example III-3

[0276] (1) Preparation of a porous support layer with a bottom layer: a porous support layer with a bottom layer in the forward osmosis membrane was prepared according to the method in Example III-1, except that the atomization amount of the atomized droplets used in the atomization pretreatment stage was 17 L/m.sup.2.Math.h during the preparation. [0277] (2) Preparation of a composite membrane: the same as Example III-1.

[0278] In the composite forward osmosis membrane obtained in Example III-3, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 47 ?m, the thickness of the surface layer of the porous support layer was 1.9 ?m, the thickness of the active separation layer was 42 nm. The mean pore size of the surface layer of the support layer was 18 nm. The bulk porosity of the porous support layer was 79%.

Example III-4

[0279] (1) Preparation of a porous support layer with a bottom layer: a porous support layer with a bottom layer in the forward osmosis membrane was prepared according to the method in Example III-3, except that during preparation, in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 10 s. [0280] (2) Preparation of a composite membrane: the same as Example III-1.

[0281] In the composite forward osmosis membrane obtained in Example III-4, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 45 ?m, the thickness of the surface layer of the porous support layer was 2.1 ?m, the thickness of the active separation layer was 44 nm. The mean pore size of the surface layer of the support layer was 17 nm. The bulk porosity of the porous support layer was 74%.

Example III-5

[0282] (1) Preparation of a porous support layer with a bottom layer: a porous support layer with a bottom layer in the forward osmosis membrane was prepared according to the method in Example III-3, except that in the atomization pretreatment stage, face the side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 30 s. See FIG. 3A for the cross-sectional morphology of the porous support layer in the forward osmosis membrane and see FIG. 3B for the surface morphology of the forward osmosis membrane. [0283] (2) Preparation of a composite membrane: the same as Example III-1.

[0284] In the composite forward osmosis membrane obtained in Example III-5, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 47 ?m, the thickness of the surface layer of the porous support layer was 1.6 ?m, the thickness of the active separation layer was 40 nm. The mean pore size of the surface layer of the support layer was 24 nm. The bulk porosity of the porous support layer was 83%.

Example III-6

[0285] (1) Preparation of a porous support layer with a bottom layer: 12 g of polysulfone was dissolved in 88 g of polarclean solvent, and heated with stirring at 100? C. to form a homogeneous solution, which was vacuumized for degassing; then, it was blade-coated on a nonwoven fabric with a continuous casting machine, with the initial casting height being controlled at 150 ?m during coating, followed by facing one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, staying in the droplet bath for 4 s and protecting the side coated with the membrane casting solution from contacting with atomized droplets, with an atomization amount of 17 L/m.sup.2.Math.h per unit membrane area; then the above thin film was immersed in a deionized water coagulation bath for a complete phase separation; after washing with water, a porous support layer with a bottom layer was obtained. [0286] (2) Preparation of a composite membrane: the same as Example III-1.

[0287] In the composite forward osmosis membrane obtained in Example III-6, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 45 ?m, the thickness of the surface layer of the porous support layer was 1.6 ?m, the thickness of the active separation layer was 44 nm. The mean pore size of the surface layer of the support layer was 22 nm. The bulk porosity of the porous support layer was 73%.

Example III-7

[0288] (1) A forward osmosis membrane was prepared according to the method in Example III-6, except that during the preparation of a porous support layer with a bottom layer in the forward osmosis membrane, in the atomization pretreatment stage, face one side of the coated nonwoven fabric uncoated with the membrane casting solution towards a droplet bath obtained by a deonized water ultrasonic atomization, and stay in the droplet bath for 6 s. [0289] (2) Preparation of a composite membrane: the same as Example III-1.

[0290] In the composite forward osmosis membrane obtained in Example III-7, the thickness of the bottom layer was 85 ?m, the thickness of the sublayer of the porous support layer was 49 ?m, the thickness of the surface layer of the porous support layer was 1.4 ?m, the thickness of the active separation layer was 41 nm. The mean pore size of the surface layer of the support layer was 26 nm. The bulk porosity of the porous support layer was 75%.

Comparative Example III-1

[0291] (1) A forward osmosis membrane was prepared according to the method in Example III-3, except that during the preparation of a porous support layer with a bottom layer in the forward osmosis membrane, without undergoing an atomization pretreatment stage, directly immerse the ultrafiltration membrane in a solvent coagulation bath for a complete phase separation, and obtain a porous support layer with a bottom layer after washing with water. See FIG. 3C for the cross-sectional morphology of the support layer. [0292] (2) Preparation of a composite membrane: the same as Example III-3.

[0293] In the composite forward osmosis membrane obtained in Comparative Example III-1, the thickness of the active separation layer was 50 nm. The mean pore size of the support layer was 13 nm. The bulk porosity of the support layer was 70%.

Example III-2

[0294] (1) A forward osmosis membrane was prepared according to the method in Example III-6, except that during the preparation of a porous support layer with a bottom layer in the forward osmosis membrane, without undergoing an atomization pretreatment stage, directly immerse the ultrafiltration membrane in a solvent coagulation bath for a complete phase separation, and obtain a porous support layer with a bottom layer after washing with water. [0295] (2) Preparation of a composite membrane: the same as Example III-6.

[0296] In the composite forward osmosis membrane obtained in Comparative Example III-2, the thickness of the active separation layer was 52 nm. The mean pore size of the support layer was 16 nm. The bulk porosity of the support layer was 67%.

[0297] Performance tests of the water flux, the reverse diffusion salt flux and the salt rejection rate were carried out on the composite forward osmosis membranes prepared in Examples III-1 to 7 and Comparative Examples III-1 to 2.

[0298] The water flux and the reverse diffusion salt flux of the forward osmosis composite membrane were tested in a forward osmosis testing system.

[0299] At 25? C., by using 1 M MgCl.sub.2 aqueous solution as an draw solution and deionized water as feed solution, the water flux and the reverse diffusion salt flux of the composite forward osmosis membrane were tested using a forward osmosis testing device. The results obtained from the tests are shown in Table III-1.

TABLE-US-00005 TABLE III-1 interfacial interfacial support layer atomization reverse salt polymerization polymerization atomization amount per water flux (LMH) diffusion flux (gMH) forward support layer aqueous phase organic phase pretreatment unit membrane AL-FS AL-DS AL-FS AL-DS osmosis polymer monomer and monomer and time area test test test test membrane material content content (s) (LMH) mode mode mode mode Example III-1 polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 20 6.2 8 ? 3 23 ? 2 2 ? 2 3 ? 1 Example III-2 polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 20 10 11 ? 2 26 ? 1 2 ? 1 4 ? 2 Example III-3 polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 20 17 13 ? 1 31 ? 2 2 ? 1 5 ? 1 Example III-4 polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 10 17 9 ? 2 25 ? 3 2 ? 2 4 ? 1 Example III-5 polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 30 17 11 ? 3 22 ? 4 12 ? 1 42 ? 5 Example III-6 polysulfone 2 w/v % MPD 0.1 w/v % TMC 4 17 10 ? 1 23 ? 2 2 ? 1 4 ? 2 Example III-7 polysulfone 2 w/v % MPD 0.1 w/v % TMC 6 17 12 ? 2 26 ? 3 4 ? 1 7 ? 3 Comparative polyacrylonitrile 2 w/v % MPD 0.1 w/v % TMC 0 0 6 ? 1 22 ? 3 3 ? 1 3 ? 2 Example III-1 Comparative polysulfone 2 w/v % MPD 0.1 w/v % TMC 0 0 7 ? 2 19 ? 3 4 ? 2 5 ? 1 Example III-2

[0300] From the testing results of the above Examples III-1 to 7 and Comparative Example III-2, it can be seen that the composite forward osmosis membrane prepared by using the porous support layer with the bottom layer undergoing atomization pretreatment has excellent water flux, and has a significantly improved water flux while keeping the reverse diffusion salt flux relatively low. When the atomization time continues to increase, the pore size of the support layer surface increases gradually, as is not conducive to the formation of a complete polyamide separation layer during the interfacial polymerization, and leads to a dramatic increase of the reverse diffusion salt flux and a reduction in membrane performance. As can be seen from Examples III-1 to 3, the permeation flux of the forward osmosis membrane increases with the increase of atomization amount. In addition, the process of atomization pretreatment can be applied in many polymer membrane production materials and can effectively improve the permeation performance of the composite membrane.