Antifouling ultrafiltration membrane and preparation method thereof
By forming an aniline gel layer on the ultrafiltration membrane and treating the ultrafiltration membrane with a mixed solution of aniline, hyaluronic acid, and γ-cyclodextrin, the membrane fouling problem caused by protein adsorption is solved, and the service life of the ultrafiltration membrane is extended.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-11-07
- Publication Date
- 2026-03-27
AI Technical Summary
Existing ultrafiltration membranes are easily adsorbed by proteins during protein separation and purification, leading to membrane fouling and shortening their service life.
By forming an aniline gel layer on the ultrafiltration membrane and treating the ultrafiltration membrane with a mixed solution of aniline, hyaluronic acid and γ-cyclodextrin, the protein adsorption capacity is reduced.
It significantly reduces the adsorption of proteins by the ultrafiltration membrane and extends the service life of the ultrafiltration membrane.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of ultrafiltration membrane preparation, in particular to a kind of antifouling ultrafiltration membrane and its preparation method. BACKGROUND
[0002] The artificial diaphragm used in ultrafiltration process is generally made of high molecular materials such as cellulose acetate, cellulose acetate ester, polyethylene, polysulfone and polyamide, etc. Ultrafiltration membrane is widely used in chemical industry, food and pharmaceutical industry for concentrating, purifying and separating macromolecular substances.
[0003] The inventor found in practical application that when using ultrafiltration membrane to separate and purify biological macromolecules such as proteins, biological macromolecules such as proteins are easily adsorbed on the ultrafiltration membrane, thereby causing pollution of the ultrafiltration membrane and greatly shortening the service life of the ultrafiltration membrane.
[0004] Therefore, it is of important application value to develop an ultrafiltration membrane which is not easy to adsorb proteins. SUMMARY
[0005] In order to overcome at least one of the technical problems existing in the prior art, the present application provides a preparation method of an antifouling ultrafiltration membrane. Studies have shown that the ultrafiltration membrane prepared by the method has the ability to resist protein pollution.
[0006] The technical scheme of the present application is as follows:
[0007] A preparation method of an antifouling ultrafiltration membrane, comprising the following steps:
[0008] (1) aniline is taken and added to water, then hydrochloric acid is added, heated to 90-100℃, and stirred uniformly to obtain an aniline-containing mixed solution;
[0009] (2) the aniline-containing mixed solution is cooled to -15 to -25℃, then an ammonium persulfate aqueous solution at -15 to -25℃ is added to obtain a reaction solution;
[0010] (3) the ultrafiltration membrane is placed in the reaction solution, soaked at 0℃ for 6-12h, and then taken out to obtain the antifouling ultrafiltration membrane.
[0011] The inventor surprisingly found in research that by the above method, a layer of aniline gel layer can be formed on the ultrafiltration membrane, which can reduce the adsorption capacity of the ultrafiltration membrane for proteins and improve the ability to resist protein pollution; during the use of the ultrafiltration membrane to filter proteins, the adsorption of the ultrafiltration membrane for proteins can be reduced, thereby prolonging the service life of the ultrafiltration membrane.
[0012] Preferably, the amount ratio of aniline, hydrochloric acid and water in step (1) is 5-10g: 10-20mL: 100mL.
[0013] Most preferably, the amount ratio of aniline, hydrochloric acid and water in step (1) is 8g: 15mL: 100mL.
[0014] Preferably, the volume ratio of the mixed solution of ammonium persulfate aqueous solution and aniline in step (2) is 1-2: 1-2.
[0015] Preferably, the volume ratio of the mixed solution of ammonium persulfate aqueous solution and aniline in step (2) is 1: 1.
[0016] Preferably, the mass fraction of ammonium persulfate in the ammonium persulfate aqueous solution in step (2) is 5-10%.
[0017] Preferably, hyaluronic acid and γ-cyclodextrin are further added in step (1).
[0018] The inventors have surprisingly found that, by the method of the present application, the anti-fouling ultrafiltration membrane prepared by adding hyaluronic acid and γ-cyclodextrin in step (1) can further reduce the adsorption capacity of the ultrafiltration membrane to proteins.
[0019] Further preferably, the amount ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water in step (1) is 5-10g: 1-3g: 1-3g: 10-20mL: 100mL.
[0020] Most preferably, the amount ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water in step (1) is 8g: 2g: 1g: 15mL: 100mL.
[0021] Preferably, the ultrafiltration membrane in step (3) is a polyether sulfone ultrafiltration membrane.
[0022] The present application also provides an anti-fouling ultrafiltration membrane prepared by the above preparation method.
[0023] Beneficial effects: the present application provides a preparation method of an anti-fouling ultrafiltration membrane; by the method of the present application, a layer of aniline gel can be formed on the ultrafiltration membrane, which can reduce the adsorption capacity of the ultrafiltration membrane to proteins and improve the anti-protein fouling capacity; the adsorption of the ultrafiltration membrane to proteins can be reduced during the filtration of proteins using the ultrafiltration membrane, thereby prolonging the service life of the ultrafiltration membrane. Further, the inventors have found that, by adding hyaluronic acid and γ-cyclodextrin in step (1) of the present application, the anti-fouling ultrafiltration membrane prepared can further reduce the adsorption capacity of the ultrafiltration membrane to proteins. DETAILED DESCRIPTION
[0024] The present application will be further explained in combination with specific embodiments, but the embodiments do not limit the protection scope of the present application.
[0025] Preparation of the antifouling ultrafiltration membrane of Example 1
[0026] (1) Aniline was taken into water, then 25% hydrochloric acid was added, heated to 95℃, and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, hydrochloric acid and water was 8g: 15mL: 100mL;
[0027] (2) The aniline-containing mixture was cooled to -20℃, then 8% ammonium persulfate aqueous solution at -20℃ was added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixture was 1:1.
[0028] (3) The polyether sulfone ultrafiltration membrane was put into the reaction solution, soaked at 0℃ for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0029] Preparation of the antifouling ultrafiltration membrane of Example 2
[0030] (1) Aniline was taken into water, then 20% hydrochloric acid was added, heated to 95℃, and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, hydrochloric acid and water was 5g: 20mL: 100mL;
[0031] (2) The aniline-containing mixture was cooled to -20℃, then 5% ammonium persulfate aqueous solution at -20℃ was added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixture was 1:1.
[0032] (3) The polyether sulfone ultrafiltration membrane was put into the reaction solution, soaked at 0℃ for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0033] Preparation of the antifouling ultrafiltration membrane of Example 3
[0034] (1) Aniline was taken into water, then 30% hydrochloric acid was added, heated to 95℃, and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, hydrochloric acid and water was 10g: 10mL: 100mL;
[0035] (2) The aniline-containing mixture was cooled to -20℃, then 10% ammonium persulfate aqueous solution at -20℃ was added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixture was 1:1.
[0036] (3) The polyether sulfone ultrafiltration membrane was put into the reaction solution, soaked at 0℃ for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0037] Preparation of the antifouling ultrafiltration membrane of Example 4
[0038] (1) aniline is taken into water, then 25% hydrochloric acid is added, then hyaluronic acid and γ-cyclodextrin are added, heated to 95°C, and stirred uniformly to obtain aniline-containing mixed solution; wherein the amount ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water is 8g:2g:1g:15mL:100mL;
[0039] (2) the aniline-containing mixed solution is cooled to -20°C, then 8% ammonium persulfate aqueous solution at -20°C is added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixed solution is 1:1.
[0040] (3) polyether sulfone ultrafiltration membrane is put into the reaction solution, soaked at 0°C for 8h, and then the ultrafiltration membrane is taken out to obtain the antifouling ultrafiltration membrane.
[0041] Example 5 Preparation of antifouling ultrafiltration membrane
[0042] (1) aniline is taken into water, then 20% hydrochloric acid is added, then hyaluronic acid and γ-cyclodextrin are added, heated to 95°C, and stirred uniformly to obtain aniline-containing mixed solution; wherein the amount ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water is 5g:1g:3g:20mL:100mL;
[0043] (2) the aniline-containing mixed solution is cooled to -20°C, then 5% ammonium persulfate aqueous solution at -20°C is added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixed solution is 1:1.
[0044] (3) polyether sulfone ultrafiltration membrane is put into the reaction solution, soaked at 0°C for 8h, and then the ultrafiltration membrane is taken out to obtain the antifouling ultrafiltration membrane.
[0045] Example 6 Preparation of antifouling ultrafiltration membrane
[0046] (1) aniline is taken into water, then 30% hydrochloric acid is added, then hyaluronic acid and γ-cyclodextrin are added, heated to 95°C, and stirred uniformly to obtain aniline-containing mixed solution; wherein the amount ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water is 10g:3g:1g:10mL:100mL;
[0047] (2) the aniline-containing mixed solution is cooled to -20°C, then 10% ammonium persulfate aqueous solution at -20°C is added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixed solution is 1:1.
[0048] (3) polyether sulfone ultrafiltration membrane is put into the reaction solution, soaked at 0°C for 8h, and then the ultrafiltration membrane is taken out to obtain the antifouling ultrafiltration membrane.
[0049] Preparation of the antifouling ultrafiltration membrane of Comparative Example 1
[0050] (1) Aniline was added to water, then 25% hydrochloric acid was added, then hyaluronic acid was added, and the mixture was heated to 95°C and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, hyaluronic acid, hydrochloric acid and water was 8g:3g:15mL:100mL;
[0051] (2) The aniline-containing mixture was cooled to -20°C, then 8% ammonium persulfate aqueous solution at -20°C was added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixture was 1:1.
[0052] (3) The polyether sulfone ultrafiltration membrane was immersed in the reaction solution at 0°C for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0053] The difference between Comparative Example 1 and Example 4 is that Comparative Example 1 further adds only hyaluronic acid in step (1); while Example 4 further adds hyaluronic acid and γ-cyclodextrin in step (1).
[0054] Preparation of the antifouling ultrafiltration membrane of Comparative Example 2
[0055] (1) Aniline was added to water, then 25% hydrochloric acid was added, then γ-cyclodextrin was added, and the mixture was heated to 95°C and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, γ-cyclodextrin, hydrochloric acid and water was 8g:3g:15mL:100mL;
[0056] (2) The aniline-containing mixture was cooled to -20°C, then 8% ammonium persulfate aqueous solution at -20°C was added to obtain a reaction solution; wherein the volume ratio of ammonium persulfate aqueous solution to aniline mixture was 1:1.
[0057] (3) The polyether sulfone ultrafiltration membrane was immersed in the reaction solution at 0°C for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0058] The difference between Comparative Example 2 and Example 4 is that Comparative Example 2 further adds only γ-cyclodextrin in step (1); while Example 4 further adds hyaluronic acid and γ-cyclodextrin in step (1).
[0059] Preparation of the antifouling ultrafiltration membrane of Comparative Example 3
[0060] (1) Aniline was added to water, then 25% hydrochloric acid was added, then chitosan was added, and the mixture was heated to 95°C and stirred uniformly to obtain an aniline-containing mixture; wherein the amount ratio of aniline, chitosan, hydrochloric acid and water was 8g:3g:15mL:100mL;
[0061] (2) The aniline-containing mixture was cooled to -20°C, and then an ammonium persulfate aqueous solution with a mass fraction of 8% at -20°C was added to obtain a reaction solution; wherein the volume ratio of the ammonium persulfate aqueous solution to the aniline-containing mixture was 1:1.
[0062] (3) The polyether sulfone ultrafiltration membrane was placed in the reaction solution and soaked at 0°C for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0063] The difference between Comparative Example 3 and Example 4 is that the Comparative Example 3 further adds chitosan in step (1); while the Example 4 further adds hyaluronic acid and γ-cyclodextrin in step (1).
[0064] Preparation of the antifouling ultrafiltration membrane of Comparative Example 4
[0065] (1) Aniline was taken and added into water, then hydrochloric acid with a mass fraction of 25% was added, followed by the addition of hyaluronic acid and chitosan, and heated to 95°C to obtain an aniline-containing mixture; wherein the amount ratio of aniline, hyaluronic acid, chitosan, hydrochloric acid and water was 8g:2g:1g:15mL:100mL.
[0066] (2) The aniline-containing mixture was cooled to -20°C, and then an ammonium persulfate aqueous solution with a mass fraction of 8% at -20°C was added to obtain a reaction solution; wherein the volume ratio of the ammonium persulfate aqueous solution to the aniline-containing mixture was 1:1.
[0067] (3) The polyether sulfone ultrafiltration membrane was placed in the reaction solution and soaked at 0°C for 8h, and then the ultrafiltration membrane was taken out to obtain the antifouling ultrafiltration membrane.
[0068] The difference between Comparative Example 4 and Example 4 is that the Comparative Example 4 further adds hyaluronic acid and chitosan in step (1); while the Example 4 further adds hyaluronic acid and γ-cyclodextrin in step (1).
[0069] The antifouling ultrafiltration membranes prepared in Examples 1-6 and Comparative Examples 1-4 were respectively soaked in an interleukin-6 solution with a concentration of 10000pg / mL for 30min, and then the antifouling ultrafiltration membranes were taken out; the concentrations of the interleukin-6 solutions soaked in each antifouling ultrafiltration membrane were respectively tested; the adsorption rate was calculated, and the results are shown in Table 1.
[0070] Adsorption rate (%) = {(concentration of interleukin-6 solution before soaking - concentration of interleukin-6 solution after soaking) / concentration of interleukin-6 solution before soaking} x 100.
[0071] Table 1.
[0072]
[0073] As can be seen from the test data in Table 1, the anti-fouling ultrafiltration membrane prepared in Examples 1-3 has an adsorption rate of about 3% for interleukin-6, and has a small protein adsorption rate.
[0074] As can be seen from the test data in Table 1, the anti-fouling ultrafiltration membrane prepared in Examples 4-6 has an adsorption rate of less than 0.3% for interleukin-6, which is much smaller than that of the anti-fouling ultrafiltration membrane prepared in Examples 1-3. This shows that the anti-fouling ultrafiltration membrane prepared by adding hyaluronic acid and γ-cyclodextrin in step (1) of the method of the application can further greatly reduce the adsorption capacity of the ultrafiltration membrane for proteins.
[0075] As can be seen from the test data in Table 1, the anti-fouling ultrafiltration membrane prepared in Comparative Examples 1-4 has an adsorption rate for interleukin-6 that is not greatly reduced compared with Example 1, and the reduction is much smaller than that of Example 4. This shows that adding only hyaluronic acid or only γ-cyclodextrin, or adding other ingredients, or adding combinations of other ingredients in step (1) of the method of the application cannot further greatly reduce the adsorption capacity of the ultrafiltration membrane for proteins; only the anti-fouling ultrafiltration membrane prepared by simultaneously adding hyaluronic acid and γ-cyclodextrin in step (1) of the method of the application can further greatly reduce the adsorption capacity of the ultrafiltration membrane for proteins.
[0076] As can be seen from the test data in Table 1, the anti-fouling ultrafiltration membrane prepared in Example 4 has an adsorption rate for interleukin-6 that is much smaller than that of Comparative Examples 1 and 2; this shows that simultaneously adding hyaluronic acid and γ-cyclodextrin in step (1) of the method of the application can synergistically reduce the adsorption capacity of the ultrafiltration membrane for proteins.
Claims
1. A method for preparing an antifouling ultrafiltration membrane, characterized in that, It includes the following steps: (1) Add aniline to water, then add hydrochloric acid, heat to 90~100℃, and stir until homogeneous to obtain a mixture containing aniline; (2) Cool the aniline-containing mixture to -15~-25℃, and then add an ammonium persulfate aqueous solution at -15~-25℃ to obtain the reaction solution; (3) Place the ultrafiltration membrane in the reaction solution and soak it at 0°C for 6-12 hours. Remove the ultrafiltration membrane to obtain the antifouling ultrafiltration membrane. Hyaluronic acid and γ-cyclodextrin are also added in step (1); In step (1), the ratio of aniline, hyaluronic acid, γ-cyclodextrin, hydrochloric acid and water is 8g:2g:1g:15mL:100mL.
2. The method for preparing the antifouling ultrafiltration membrane according to claim 1, characterized in that, In step (2), the volume ratio of the ammonium persulfate aqueous solution to the aniline mixture is 1~2:1~2.
3. The method for preparing the antifouling ultrafiltration membrane according to claim 2, characterized in that, In step (2), the volume ratio of the ammonium persulfate aqueous solution to the aniline mixture is 1:
1.
4. The method for preparing the antifouling ultrafiltration membrane according to claim 1, characterized in that, In step (2), the mass fraction of ammonium persulfate in the aqueous solution is 5-10%.
5. The method for preparing the antifouling ultrafiltration membrane according to claim 1, characterized in that, The ultrafiltration membrane in step (3) is a polyethersulfone ultrafiltration membrane.
6. The antifouling ultrafiltration membrane prepared by the preparation method according to any one of claims 1 to 5.
Citation Information
Patent Citations
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CN114618320A