CN105169962B - Method for preparing nanofiltration membrane by adopting layer-by-layer self-assembly method - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000001338 self-assembly Methods 0.000 title claims abstract description 17
- 238000001728 nano-filtration Methods 0.000 title abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000004907 flux Effects 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 85
- 210000004379 membrane Anatomy 0.000 claims description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000108 ultra-filtration Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 210000002469 basement membrane Anatomy 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 5
- 150000001412 amines Chemical class 0.000 claims 3
- 238000002791 soaking Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000013535 sea water Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000010612 desalination reaction Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003242 anti bacterial agent Substances 0.000 abstract 1
- 229940088710 antibiotic agent Drugs 0.000 abstract 1
- 235000015203 fruit juice Nutrition 0.000 abstract 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 15
- 229930187593 rose bengal Natural products 0.000 description 15
- 229940081623 rose bengal Drugs 0.000 description 15
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 15
- 238000000614 phase inversion technique Methods 0.000 description 7
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
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Abstract
一种层层自组装法制备纳滤膜的方法，本发明涉及一种纳滤膜的制备方法。本发明是要解决现有方法制备的纳滤膜不能同时具有良好的截留性能和较高水通量的问题，方法为：制备聚丙烯腈溶液，制备聚丙烯腈基膜，制备处理后的聚丙烯腈基膜，组装一层聚乙烯亚胺，组装一层氧化石墨烯，重复组装聚乙烯亚胺和氧化石墨烯，即完成。本发明利用层层自组装技术，使聚乙烯亚胺和氧化石墨烯改性PAN膜，使其亲水性和膜表面的孔径大小得到有效的调控，并且膜比较薄，可以获得比较大的通量，同时得到的纳滤膜具有良好的截留性能，本发明应用于抗生素的分离、果汁浓缩和海水除盐领域。The invention relates to a method for preparing a nanofiltration membrane by a layer-by-layer self-assembly method, and the invention relates to a method for preparing a nanofiltration membrane. The present invention aims to solve the problem that the nanofiltration membrane prepared by the existing method cannot have good interception performance and relatively high water flux at the same time. Acrylonitrile-based film, assemble a layer of polyethyleneimine, assemble a layer of graphene oxide, repeat the assembly of polyethyleneimine and graphene oxide, and it is completed. The invention utilizes layer-by-layer self-assembly technology to modify the PAN membrane with polyethyleneimine and graphene oxide, so that the hydrophilicity and the pore size of the membrane surface can be effectively regulated, and the membrane is relatively thin, so that a relatively large passthrough can be obtained. amount, and the obtained nanofiltration membrane has good retention performance, and the invention is applied to the fields of separation of antibiotics, concentration of fruit juice and desalination of sea water.
Description
技术领域technical field
本发明涉及一种纳滤膜的制备方法。The invention relates to a preparation method of a nanofiltration membrane.
背景技术Background technique
由于淡水资源日已枯竭，海水淡化技术正越来越受重视。其中膜分离技术尤其是新型膜分离技术正受到科学家们的广泛关注。Due to the depletion of fresh water resources, seawater desalination technology is getting more and more attention. Among them, membrane separation technology, especially new membrane separation technology, is attracting widespread attention from scientists.
纳滤始于80年代中后期，是一种新型的压力驱动的无相变物理分离的过程。纳滤膜的孔径小于超滤膜的孔径、大于反渗透膜的孔径。纳滤膜的特点在于其对二价和多价离子的较高的截留率，而对单价离子截留率则相对较低，其截留分子量介于200-1000g·mol-1。因而，纳滤过程被广泛应用于染料等活性物质的除盐和浓缩、硬水软化、分子量不同的有机物的物料分离与纯化、水中少量有机物的去除等工业领域。现有纳滤膜研究的主要问题是截留性能优良时，纳滤膜的单位压力的水通量却比较低。Nanofiltration began in the mid-to-late 1980s and is a new pressure-driven physical separation process without phase change. The pore size of the nanofiltration membrane is smaller than that of the ultrafiltration membrane and larger than that of the reverse osmosis membrane. Nanofiltration membranes are characterized by their high rejection rate for divalent and multivalent ions, while their rejection rate for monovalent ions is relatively low, and their molecular weight cutoff is between 200-1000g·mol -1 . Therefore, the nanofiltration process is widely used in industrial fields such as desalination and concentration of active substances such as dyes, softening of hard water, material separation and purification of organic substances with different molecular weights, and removal of small amounts of organic substances in water. The main problem in the existing nanofiltration membrane research is that when the interception performance is excellent, the water flux per unit pressure of the nanofiltration membrane is relatively low.
发明内容Contents of the invention
本发明是要解决现有方法制备的纳滤膜不能同时具有良好的截留性能和较高水通量的问题，提供一种层层自组装法制备纳滤膜的方法。The invention aims to solve the problem that the nanofiltration membrane prepared by the existing method cannot have good interception performance and relatively high water flux at the same time, and provides a method for preparing the nanofiltration membrane by a layer-by-layer self-assembly method.
本发明一种层层自组装法制备纳滤膜的方法，包括以下步骤：A kind of method for preparing nanofiltration membrane by layer-by-layer self-assembly method of the present invention comprises the following steps:
一、将溶剂、成孔剂和聚丙烯腈混合，制得聚丙烯腈溶液；One, solvent, pore-forming agent and polyacrylonitrile are mixed, make polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤3～5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, wash with deionized water for 3 to 5 times, and obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于氢氧化钠溶液中，在20℃～50℃下反应20min～60min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5～2h，再置于盐酸溶液中浸泡1～5h，得到处理后的聚丙烯腈基膜；3. Put the polyacrylonitrile-based membrane in sodium hydroxide solution and react at 20°C-50°C for 20min-60min. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5-2h , and then immersed in hydrochloric acid solution for 1 to 5 hours to obtain the treated polyacrylonitrile-based membrane;
四、将步骤三处理后的聚丙烯腈基膜浸入聚乙烯亚胺溶液中10～90min，取出后放入去离子水浸泡2～10min，得到含有聚乙烯亚胺层的聚丙烯腈基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in the polyethyleneimine solution for 10-90 minutes, take it out and soak it in deionized water for 2-10 minutes, and obtain the polyacrylonitrile-based membrane containing the polyethyleneimine layer;
五、将含有聚乙烯亚胺层的聚丙烯腈基膜置于氧化石墨烯溶液中，浸泡10～90min，取出后放入去离子水浸泡2～10min，得到含有聚乙烯亚胺层和氧化石墨烯层的纳滤膜；5. Put the polyacrylonitrile-based film containing the polyethyleneimine layer in the graphene oxide solution, soak it for 10-90 minutes, take it out, put it in deionized water and soak it for 2-10 minutes, and obtain the polyacrylonitrile-based film containing the polyethyleneimine layer and graphite oxide Nanofiltration membrane of olefin layer;
六、重复步骤四和步骤五的操作0～7次，即完成。6. Repeat steps 4 and 5 for 0 to 7 times, and the process is complete.
本发明利用层层自组装技术，使聚乙烯亚胺和氧化石墨烯改性PAN膜，使其亲水性和膜表面的孔径大小得到有效的调控，并且膜比较薄，可以获得比较大的通量，同时得到的纳滤膜具有良好的截留性能，适用于各种染料的分离，海水淡化等，降低了能耗同时净化了水质，淡化了海水，有重大的应用前景。The invention utilizes layer-by-layer self-assembly technology to modify the PAN membrane with polyethyleneimine and graphene oxide, so that the hydrophilicity and the pore size of the membrane surface can be effectively regulated, and the membrane is relatively thin, so that a relatively large passthrough can be obtained. At the same time, the obtained nanofiltration membrane has good retention performance, which is suitable for the separation of various dyes, seawater desalination, etc., which reduces energy consumption and purifies water quality, desalinates seawater, and has great application prospects.
具体实施方式detailed description
具体实施方式一：本实施方式一种层层自组装法制备纳滤膜的方法，包括以下步骤：Specific embodiment one: present embodiment a kind of method for preparing nanofiltration membrane by self-assembly method layer by layer, comprising the following steps:
一、将溶剂、成孔剂和聚丙烯腈混合，制得聚丙烯腈溶液；One, solvent, pore-forming agent and polyacrylonitrile are mixed, make polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤3～5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, wash with deionized water for 3 to 5 times, and obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于氢氧化钠溶液中，在20℃～50℃下反应20min～60min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5～2h，再置于盐酸溶液中浸泡1～5h，得到处理后的聚丙烯腈基膜；3. Put the polyacrylonitrile-based membrane in sodium hydroxide solution and react at 20°C-50°C for 20min-60min. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5-2h , and then immersed in hydrochloric acid solution for 1 to 5 hours to obtain the treated polyacrylonitrile-based membrane;
四、将步骤三处理后的聚丙烯腈基膜浸入聚乙烯亚胺溶液中10～90min，取出后放入去离子水浸泡2～10min，得到含有聚乙烯亚胺层的聚丙烯腈基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in the polyethyleneimine solution for 10-90 minutes, take it out and soak it in deionized water for 2-10 minutes, and obtain the polyacrylonitrile-based membrane containing the polyethyleneimine layer;
五、将含有聚乙烯亚胺层的聚丙烯腈基膜置于氧化石墨烯溶液中，浸泡10～90min，取出后放入去离子水浸泡2～10min，得到含有聚乙烯亚胺层和氧化石墨烯层的纳滤膜；5. Put the polyacrylonitrile-based film containing the polyethyleneimine layer in the graphene oxide solution, soak it for 10-90 minutes, take it out, put it in deionized water and soak it for 2-10 minutes, and obtain the polyacrylonitrile-based film containing the polyethyleneimine layer and graphite oxide Nanofiltration membrane of olefin layer;
六、重复步骤四和步骤五的操作0～7次，即完成。6. Repeat steps 4 and 5 for 0 to 7 times, and the process is complete.
本实施方式利用层层自组装技术，使聚乙烯亚胺和氧化石墨烯改性PAN膜，使其亲水性和膜表面的孔径大小得到有效的调控，并且膜比较薄，可以获得比较大的通量，同时得到的纳滤膜具有良好的截留性能，适用于各种染料的分离，海水淡化等，降低了能耗同时净化了水质，淡化了海水，有重大的应用前景。In this embodiment, the layer-by-layer self-assembly technology is used to modify the PAN membrane with polyethyleneimine and graphene oxide, so that the hydrophilicity and the pore size of the membrane surface can be effectively regulated, and the membrane is relatively thin, so that a relatively large At the same time, the obtained nanofiltration membrane has good retention performance, which is suitable for the separation of various dyes, seawater desalination, etc., which reduces energy consumption and purifies water quality, desalinates seawater, and has great application prospects.
具体实施方式二：本实施方式与具体实施方式一不同的是：步骤一所述的溶剂为N-甲基吡咯烷酮。其它与具体实施方式一相同。Embodiment 2: The difference between this embodiment and Embodiment 1 is that the solvent in Step 1 is N-methylpyrrolidone. Others are the same as in the first embodiment.
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤一所述的成孔剂为聚乙二醇或聚乙烯吡咯烷酮。其它与具体实施方式一或二相同。Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that the pore-forming agent in step 1 is polyethylene glycol or polyvinylpyrrolidone. Others are the same as in the first or second embodiment.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是：步骤一中聚丙烯腈、成孔剂和溶剂的质量比为(15～25):1:(74～84)。其它与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the mass ratio of polyacrylonitrile, porogen and solvent in step 1 is (15-25):1:(74-84). Others are the same as those in the first to third specific embodiments.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是：步骤三所述的氢氧化钠溶液的质量浓度为5％～20％。其它与具体实施方式一至四之一相同。Embodiment 5: This embodiment is different from Embodiment 1 to Embodiment 4 in that: the mass concentration of the sodium hydroxide solution described in step 3 is 5% to 20%. Others are the same as one of the specific embodiments 1 to 4.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是：步骤三所述的盐酸溶液的浓度为0.05mol/L～0.5mol/L。其它与具体实施方式一至五之一相同。Embodiment 6: This embodiment differs from Embodiments 1 to 5 in that: the concentration of the hydrochloric acid solution in step 3 is 0.05 mol/L-0.5 mol/L. Others are the same as one of the specific embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是：步骤四所述的聚乙烯亚胺溶液的浓度为0.5～3g/L。其它与具体实施方式一至六之一相同。Embodiment 7: This embodiment differs from Embodiment 1 to Embodiment 6 in that: the concentration of the polyethyleneimine solution in step 4 is 0.5-3 g/L. Others are the same as one of the specific embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是：步骤四中浸入聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min。其它与具体实施方式一至七之一相同。Embodiment 8: The difference between this embodiment and one of Embodiments 1 to 7 is that in step 4, immerse in polyethyleneimine solution for 30 minutes, take it out and soak in deionized water for 5 minutes. Others are the same as one of the specific embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是：步骤五所述的氧化石墨烯溶液的浓度为0.05～0.5g/L。其它与具体实施方式一至八之一相同。Embodiment 9: This embodiment is different from Embodiment 1 to Embodiment 8 in that: the concentration of the graphene oxide solution described in step 5 is 0.05-0.5 g/L. Others are the same as one of the specific embodiments 1 to 8.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是：步骤五中置于氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min。其它与具体实施方式一至九之一相同。Embodiment 10: This embodiment differs from Embodiment 1 to Embodiment 9 in that: in step 5, put it in the graphene oxide solution, soak it for 30 minutes, take it out, put it into deionized water and soak it for 5 minutes. Others are the same as one of the specific embodiments 1 to 9.
下面的实施例将对本发明予以进一步的说明，但并不因此而限制本发明。The following examples will further illustrate the present invention, but do not limit the present invention thereby.
实施例1：本实施例层层自组装法制备纳滤膜的方法，包括以下步骤：Embodiment 1: The method for preparing the nanofiltration membrane by the layer-by-layer self-assembly method of this embodiment comprises the following steps:
一、将79g氮甲基吡咯烷酮和1g聚乙二醇，加入20g聚丙烯腈中，制得聚丙烯腈溶液；1. Add 79g nitrogen methylpyrrolidone and 1g polyethylene glycol to 20g polyacrylonitrile to prepare polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, and wash it with deionized water for 5 times to obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于质量浓度为10％的氢氧化钠溶液中，在40℃下反应30min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5h，再置于0.1mol/L盐酸溶液中浸泡3h，得到处理后的聚丙烯腈基膜；3. Place the polyacrylonitrile-based membrane in a sodium hydroxide solution with a mass concentration of 10%, and react at 40°C for 30 minutes. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5h. , and then soaked in 0.1mol/L hydrochloric acid solution for 3 hours to obtain the treated polyacrylonitrile-based film;
四、将步骤三处理后的聚丙烯腈基膜浸入1g/L聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层的聚丙烯腈基膜；4. Immerse the polyacrylonitrile-based film treated in step 3 in a 1g/L polyethyleneimine solution for 30 minutes, take it out, and soak it in deionized water for 5 minutes to obtain a polyacrylonitrile-based film containing a polyethyleneimine layer;
五、将含有聚乙烯亚胺层的聚丙烯腈基膜置于0.1g/L氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层和氧化石墨烯层的纳滤膜；5. Place the polyacrylonitrile-based film containing the polyethyleneimine layer in a 0.1g/L graphene oxide solution, soak for 30 minutes, take it out and soak it in deionized water for 5 minutes, and obtain the polyacrylonitrile-based film containing the polyethyleneimine layer and graphite oxide Nanofiltration membrane of olefin layer;
六、重复步骤四和步骤五的操作0次，即完成。6. Repeat steps 4 and 5 for 0 times to complete.
拥有大的渗透通量同时兼具较高的截留率为理想的纳滤膜膜的指标。It is an ideal indicator of nanofiltration membrane with large permeation flux and high rejection rate.
通量的测定：取一定面积的纳滤膜样品在纳滤测试装置中，在室温及0.5MPa(N2)下用溶剂将纳滤膜压实45min，测试通过膜的甲醇、乙醇、异丙醇的质量m，通过计算得出体积V。每次测试前待溶剂流量大致稳定之后在进行测试。即要保证一定压力不变的条件下，测试一定时间t透过纳滤膜的溶剂体积V。Measurement of flux: Take a nanofiltration membrane sample of a certain area in the nanofiltration test device, and use a solvent to compact the nanofiltration membrane for 45 minutes at room temperature and 0.5MPa (N2), and test the methanol, ethanol, and isopropanol that pass through the membrane. The mass m of the volume V is obtained by calculation. Before each test, wait until the solvent flow is roughly stable before performing the test. That is to say, it is necessary to test the solvent volume V that passes through the nanofiltration membrane for a certain period of time t under the condition that the pressure remains constant.
截留率的测定：以纳滤膜对孟加拉玫瑰红Rose Bengal(RB)的截留率来表征纳滤膜的截留性。Determination of rejection rate: the rejection rate of the nanofiltration membrane to Rose Bengal (RB) was used to characterize the rejection of the nanofiltration membrane.
步骤三处理后的聚丙烯腈基膜的纯水通量为129.45L/m2h bar，对RB的截留率为24.21％，乙醇的通量为120.56L/m2h bar，RB在乙醇当中的截留率为19.87％。The pure water flux of the polyacrylonitrile-based membrane treated in step 3 is 129.45L/m 2 h bar, the rejection rate of RB is 24.21%, the flux of ethanol is 120.56L/m 2 h bar, and RB is in ethanol The rejection rate is 19.87%.
步骤四含有聚乙烯亚胺层的聚丙烯腈基膜的纯水通量为20.49L/m2h bar，对RB的截留率为77.26％，乙醇的通量为34.22L/m2h bar，RB在乙醇当中的截留率为49.19％。Step 4 The pure water flux of the polyacrylonitrile-based membrane containing the polyethyleneimine layer is 20.49L/m 2 h bar, the rejection rate of RB is 77.26%, and the flux of ethanol is 34.22L/m 2 h bar, The rejection rate of RB in ethanol was 49.19%.
本实例获得的纳滤膜的表面组装层数为2层，其纯水通量为22.96L/m2h bar，对RB的截留率为80.46％，乙醇的通量为35.46L/m2h bar，RB在乙醇当中的截留率为51.26％。The surface assembly layer of the nanofiltration membrane obtained in this example is 2 layers, its pure water flux is 22.96L/m 2 h bar, the rejection rate to RB is 80.46%, and the ethanol flux is 35.46L/m 2 h bar, RB has a rejection rate of 51.26% in ethanol.
从本实施例的实验数据可知，含有聚乙烯亚胺层和氧化石墨烯层的纳滤膜与步骤三处理后的聚丙烯腈基膜、步骤四含有聚乙烯亚胺层的聚丙烯腈基膜相比，可以获得比较大的通量同时具有良好的截留性能。From the experimental data of this embodiment, it can be known that the polyacrylonitrile-based membrane containing polyethyleneimine layer and graphene oxide layer and the polyacrylonitrile-based membrane treated in step 3, and the polyacrylonitrile-based membrane containing polyethyleneimine layer in step 4 In comparison, a relatively large flux can be obtained while having good interception performance.
实施例2：本实施例层层自组装法制备纳滤膜的方法，包括以下步骤：Embodiment 2: The method for preparing the nanofiltration membrane by the layer-by-layer self-assembly method of this embodiment comprises the following steps:
一、将79g氮甲基吡咯烷酮和1g聚乙二醇，加入20g聚丙烯腈中，制得聚丙烯腈溶液；1. Add 79g nitrogen methylpyrrolidone and 1g polyethylene glycol to 20g polyacrylonitrile to prepare polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, and wash it with deionized water for 5 times to obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于质量浓度为10％的氢氧化钠溶液中，在40℃下反应30min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5h，再置于0.1mol/L盐酸溶液中浸泡3h，得到处理后的聚丙烯腈基膜；3. Place the polyacrylonitrile-based membrane in a sodium hydroxide solution with a mass concentration of 10%, and react at 40°C for 30 minutes. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5h. , and then soaked in 0.1mol/L hydrochloric acid solution for 3 hours to obtain the treated polyacrylonitrile-based film;
四、将步骤三处理后的聚丙烯腈基膜浸入1g/L聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层的超滤基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in a 1g/L polyethyleneimine solution for 30 minutes, take it out, and soak it in deionized water for 5 minutes to obtain an ultrafiltration base membrane containing a polyethyleneimine layer;
五、将含有聚乙烯亚胺层的超滤基膜置于0.1g/L氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层和氧化石墨烯层的超滤基膜；5. Place the ultrafiltration base membrane containing polyethyleneimine layer in 0.1g/L graphene oxide solution, soak for 30min, take it out and soak it in deionized water for 5min, and obtain the polyethyleneimine layer and graphene oxide layer ultrafiltration basement membrane;
六、重复步骤四和步骤五的操作1次，即完成。6. Repeat step 4 and step 5 for one time to complete.
拥有大的渗透通量同时兼具较高的截留率为理想的纳滤膜膜的指标。It is an ideal indicator of nanofiltration membrane with large permeation flux and high rejection rate.
本实例获得的纳滤膜的表面组装层数为4层，其纯水通量为16.45L/m2h bar，对RB的截留率为90.47％，乙醇的通量为34.34L/m2h bar，RB在乙醇当中的截留率为54.21％。The surface assembly layer of the nanofiltration membrane obtained in this example is 4 layers, its pure water flux is 16.45L/m 2 h bar, the rejection rate to RB is 90.47%, and the ethanol flux is 34.34L/m 2 h bar, the rejection rate of RB in ethanol was 54.21%.
实施例3：本实施例层层自组装法制备纳滤膜的方法，包括以下步骤：Embodiment 3: the method for preparing the nanofiltration membrane by the layer-by-layer self-assembly method of this embodiment comprises the following steps:
一、将79g氮甲基吡咯烷酮和1g聚乙二醇，加入20g聚丙烯腈中，制得聚丙烯腈溶液；1. Add 79g nitrogen methylpyrrolidone and 1g polyethylene glycol to 20g polyacrylonitrile to prepare polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, and wash it with deionized water for 5 times to obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于质量浓度为10％的氢氧化钠溶液中，在40℃下反应30min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5h，再置于0.1mol/L盐酸溶液中浸泡3h，得到处理后的聚丙烯腈基膜；3. Place the polyacrylonitrile-based membrane in a sodium hydroxide solution with a mass concentration of 10%, and react at 40°C for 30 minutes. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5h. , and then soaked in 0.1mol/L hydrochloric acid solution for 3 hours to obtain the treated polyacrylonitrile-based film;
四、将步骤三处理后的聚丙烯腈基膜浸入1g/L聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层的超滤基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in a 1g/L polyethyleneimine solution for 30 minutes, take it out, and soak it in deionized water for 5 minutes to obtain an ultrafiltration base membrane containing a polyethyleneimine layer;
五、将含有聚乙烯亚胺层的超滤基膜置于0.1g/L氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层和氧化石墨烯层的超滤基膜；5. Place the ultrafiltration base membrane containing polyethyleneimine layer in 0.1g/L graphene oxide solution, soak for 30min, take it out and soak it in deionized water for 5min, and obtain the polyethyleneimine layer and graphene oxide layer ultrafiltration basement membrane;
六、重复步骤四和步骤五的操作2次，即完成。6. Repeat step 4 and step 5 twice to complete.
拥有大的渗透通量同时兼具较高的截留率为理想的纳滤膜膜的指标。It is an ideal indicator of nanofiltration membrane with large permeation flux and high rejection rate.
本实例获得的纳滤膜的表面组装层数为6层，其纯水通量为14.56L/m2h bar，对RB的截留率为94.27％，乙醇的通量为29.41L/m2h bar，RB在乙醇当中的截留率为65.26％。The surface assembly layer of the nanofiltration membrane obtained in this example is 6 layers, its pure water flux is 14.56L/m 2 h bar, the rejection rate of RB is 94.27%, and the ethanol flux is 29.41L/m 2 h bar, the rejection rate of RB in ethanol was 65.26%.
实施例4：本实施例层层自组装法制备纳滤膜的方法，包括以下步骤：Embodiment 4: the method for preparing the nanofiltration membrane by the layer-by-layer self-assembly method of this embodiment comprises the following steps:
一、将79g氮甲基吡咯烷酮和1g聚乙二醇，加入20g聚丙烯腈中，制得聚丙烯腈溶液；1. Add 79g nitrogen methylpyrrolidone and 1g polyethylene glycol to 20g polyacrylonitrile to prepare polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, and wash it with deionized water for 5 times to obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于质量浓度为10％的氢氧化钠溶液中，在40℃下反应30min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5h，再置于0.1mol/L盐酸溶液中浸泡3h，得到处理后的聚丙烯腈基膜；3. Place the polyacrylonitrile-based membrane in a sodium hydroxide solution with a mass concentration of 10%, and react at 40°C for 30 minutes. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5h. , and then soaked in 0.1mol/L hydrochloric acid solution for 3 hours to obtain the treated polyacrylonitrile-based film;
四、将步骤三处理后的聚丙烯腈基膜浸入1g/L聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层的超滤基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in a 1g/L polyethyleneimine solution for 30 minutes, take it out, and soak it in deionized water for 5 minutes to obtain an ultrafiltration base membrane containing a polyethyleneimine layer;
五、将含有聚乙烯亚胺层的超滤基膜置于0.1g/L氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层和氧化石墨烯层的超滤基膜；5. Place the ultrafiltration base membrane containing polyethyleneimine layer in 0.1g/L graphene oxide solution, soak for 30min, take it out and soak it in deionized water for 5min, and obtain the polyethyleneimine layer and graphene oxide layer ultrafiltration basement membrane;
六、重复步骤四和步骤五的操作3次，即完成。6. Repeat step 4 and step 5 for 3 times to complete.
拥有大的渗透通量同时兼具较高的截留率为理想的纳滤膜膜的指标。It is an ideal indicator of nanofiltration membrane with large permeation flux and high rejection rate.
本实例获得的纳滤膜的表面组装层数为8层，其纯水通量为12.78L/m2h bar，对RB的截留率为97.65％，乙醇的通量为25.16L/m2h bar，RB在乙醇当中的截留率为71.06％。The surface assembly layer of the nanofiltration membrane obtained in this example is 8 layers, its pure water flux is 12.78L/m 2 h bar, the rejection rate to RB is 97.65%, and the ethanol flux is 25.16L/m 2 h bar, the rejection rate of RB in ethanol was 71.06%.
实施例4：本实施例层层自组装法制备纳滤膜的方法，包括以下步骤：Embodiment 4: the method for preparing the nanofiltration membrane by the layer-by-layer self-assembly method of this embodiment comprises the following steps:
一、将79g氮甲基吡咯烷酮和1g聚乙二醇，加入20g聚丙烯腈中，制得聚丙烯腈溶液；1. Add 79g nitrogen methylpyrrolidone and 1g polyethylene glycol to 20g polyacrylonitrile to prepare polyacrylonitrile solution;
二、利用浸没-沉淀相转化法将聚丙烯腈溶液制成超滤基膜，去离子水洗涤5次，得到聚丙烯腈基膜；2. Utilize the immersion-precipitation phase inversion method to make the polyacrylonitrile solution into an ultrafiltration base membrane, and wash it with deionized water for 5 times to obtain a polyacrylonitrile base membrane;
三、将聚丙烯腈基膜置于质量浓度为10％的氢氧化钠溶液中，在40℃下反应30min，反应结束后，将聚丙烯腈基膜取出，放入去离子水中浸泡清洗0.5h，再置于0.1mol/L盐酸溶液中浸泡3h，得到处理后的聚丙烯腈基膜；3. Place the polyacrylonitrile-based membrane in a sodium hydroxide solution with a mass concentration of 10%, and react at 40°C for 30 minutes. After the reaction, take out the polyacrylonitrile-based membrane and soak it in deionized water for 0.5h. , and then soaked in 0.1mol/L hydrochloric acid solution for 3 hours to obtain the treated polyacrylonitrile-based film;
四、将步骤三处理后的聚丙烯腈基膜浸入1g/L聚乙烯亚胺溶液中30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层的超滤基膜；4. Immerse the polyacrylonitrile-based membrane treated in step 3 in a 1g/L polyethyleneimine solution for 30 minutes, take it out, and soak it in deionized water for 5 minutes to obtain an ultrafiltration base membrane containing a polyethyleneimine layer;
五、将含有聚乙烯亚胺层的超滤基膜置于0.1g/L氧化石墨烯溶液中，浸泡30min，取出后放入去离子水浸泡5min，得到含有聚乙烯亚胺层和氧化石墨烯层的超滤基膜；5. Place the ultrafiltration base membrane containing polyethyleneimine layer in 0.1g/L graphene oxide solution, soak for 30min, take it out and soak it in deionized water for 5min, and obtain the polyethyleneimine layer and graphene oxide layer ultrafiltration basement membrane;
六、重复步骤四和步骤五的操作4次，即完成。6. Repeat step 4 and step 5 4 times to complete.
拥有大的渗透通量同时兼具较高的截留率为理想的纳滤膜膜的指标。It is an ideal indicator of nanofiltration membrane with large permeation flux and high rejection rate.
本实例获得的纳滤膜的表面组装层数为10层，其纯水通量为6.97L/m2h bar，对RB的截留率为99.99％，乙醇的通量为22.98L/m2h bar，RB在乙醇当中的截留率为81.26％。The surface assembly layer of the nanofiltration membrane obtained in this example is 10 layers, its pure water flux is 6.97L/m 2 h bar, the rejection rate to RB is 99.99%, and the ethanol flux is 22.98L/m 2 h bar, the rejection rate of RB in ethanol was 81.26%.
实施例1～4利用层层自组装技术，使聚乙烯亚胺和氧化石墨烯改性PAN膜，使其亲水性和膜表面的孔径大小得到有效的调控，并且膜比较薄，可以获得比较大的通量，同时得到的纳滤膜具有良好的截留性能，适用于各种染料的分离，海水淡化等，降低了能耗同时净化了水质，淡化了海水，有重大的应用前景。Examples 1-4 use layer-by-layer self-assembly technology to modify the PAN membrane with polyethyleneimine and graphene oxide, so that the hydrophilicity and the pore size of the membrane surface can be effectively regulated, and the membrane is relatively thin, which can obtain comparative Large flux, and the nanofiltration membrane obtained at the same time has good retention performance, which is suitable for the separation of various dyes, seawater desalination, etc., reduces energy consumption and purifies water quality, desalinates seawater, and has great application prospects.
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| CN111437739A (en) * | 2020-04-23 | 2020-07-24 | 北京工业大学 | Preparation method of polyacrylonitrile-based composite loose nanofiltration membrane |
| CN113797773B (en) * | 2020-06-12 | 2023-04-14 | 三达膜科技（厦门）有限公司 | Molybdenum disulfide oxide-graphene oxide-PEI composite ceramic nanofiltration membrane and preparation method thereof |
| CN114950148A (en) * | 2022-05-23 | 2022-08-30 | 厦门大学 | Layer-by-layer self-assembly preparation method of graphene oxide nanofiltration membrane |
| CN119056252B (en) * | 2024-08-30 | 2025-03-14 | 兰州理工大学 | A hydrolyzed polyacrylonitrile-based nanofiltration membrane and its preparation method and application |
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| US20130284338A1 (en) * | 2012-04-26 | 2013-10-31 | Gm Global Technology Operations Llc. | Self assembly of graphene materials |
| CN102824856B (en) * | 2012-08-31 | 2015-07-08 | 北京工业大学 | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology |
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