WO2021248899A1 - 一种氧化石墨烯改性聚多巴胺复合纳滤膜及其制备方法 - Google Patents
一种氧化石墨烯改性聚多巴胺复合纳滤膜及其制备方法 Download PDFInfo
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- WO2021248899A1 WO2021248899A1 PCT/CN2020/142057 CN2020142057W WO2021248899A1 WO 2021248899 A1 WO2021248899 A1 WO 2021248899A1 CN 2020142057 W CN2020142057 W CN 2020142057W WO 2021248899 A1 WO2021248899 A1 WO 2021248899A1
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- graphene oxide
- polydopamine
- nanofiltration membrane
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- composite nanofiltration
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 51
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 23
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002346 layers by function Substances 0.000 claims abstract description 9
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 6
- 239000012074 organic phase Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000768 polyamine Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 4
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 12
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- -1 metallurgy Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Definitions
- the invention belongs to the technical field of membrane separation, and specifically relates to a graphene oxide modified polydopamine composite nanofiltration membrane and a preparation method thereof.
- Nanofiltration membrane is a new type of pressure-driven membrane with a pore size between ultrafiltration and reverse osmosis, and can be used for the separation of divalent and monovalent salts.
- Nanofiltration membranes have the characteristics of low operating pressure, high flux and energy saving. Therefore, nanofiltration membranes are widely used in bioengineering, medicine, metallurgy, water treatment, electronics and other fields.
- the commonly used nanofiltration membrane in the industry is the organic nanofiltration membrane, which has many advantages such as high air permeability, low density, good film formation, low cost and good flexibility.
- the organic nanofiltration membrane has low flux in industrial applications. , Poor anti-fouling ability and other shortcomings, so it is necessary to modify the organic nanofiltration membrane to improve the flux and anti-fouling of the membrane layer.
- the purpose of the present invention is to overcome the defects of the prior art and provide a graphene oxide modified polydopamine composite nanofiltration membrane.
- Another object of the present invention is to provide a method for preparing the above-mentioned graphene oxide modified polydopamine composite nanofiltration membrane.
- a graphene oxide modified polydopamine composite nanofiltration membrane comprising a polyethersulfone support and an organic functional layer arranged on the polyethersulfone support.
- the organic functional layer is composed of an aqueous phase monomer, an organic phase monomer and
- the acid acceptor is the raw material to be formed on the polyethersulfone support through the interfacial polymerization reaction;
- the above-mentioned water phase monomer is composed of polydopamine and graphene oxide
- the organic phase monomer is trimesoyl chloride
- the above-mentioned acid acceptor is a polyamine.
- the polyamine is diethylamine.
- the pore size of the polyethersulfone support is 10-30KD.
- the mass ratio of the polydopamine to graphene oxide is 1:0.6-1.
- the mass ratio of the polydopamine, graphene oxide and polyamine is 1:0.6-1:9-11.
- the method for preparing the graphene oxide modified polydopamine composite nanofiltration membrane is characterized in that it includes: using a mixture of polydopamine and graphene oxide as an aqueous monomer, using phthaloyl chloride as an organic monomer, and using a multi-element Amine is an acid acceptor, and the organic functional layer is formed on the polyethersulfone support through an interfacial polymerization reaction to obtain the graphene oxide modified polydopamine composite nanofiltration membrane.
- step (3) After the material obtained in step (3) is dried in the shade, it is heat-treated at 50-80° C., and then cooled in a furnace to obtain the graphene oxide modified polydopamine composite nanofiltration membrane.
- the concentration of the graphene oxide aqueous solution is 1-5 mg/L.
- the concentration of the polyamine in the aqueous solution is 0.8-1.2 wt%.
- the concentration of the n-hexane solution of trimesoyl chloride is 0.08-0.12 wt%.
- the beneficial effect of the present invention is that the present invention adds a polydopamine composite nanofiltration membrane through graphene oxide to improve the hydrophilicity and roughness of the membrane layer surface, thereby increasing the water flux of the membrane layer.
- Figure 1 is a scanning electron micrograph of a graphene oxide modified polydopamine composite nanofiltration membrane prepared in Example 2 of the present invention.
- the modified Hummers method in the following comparative examples and examples specifically includes:
- step (3) Place the material obtained in step (3) in a cool place to air dry, and then put it in a 50°C oven for heat treatment for 15 minutes, and then cool it in the furnace to obtain a contrast film.
- Membrane tube performance test The comparative membrane prepared in this comparative example was tested at room temperature and 0.6MPa pressure. Its pure water flux was 57LHM and the rejection rate of 0.2wt% magnesium sulfate solution was 96%.
- step (3) Place the material obtained in step (3) in a cool place to air dry, and then put it in a 50°C oven for heat treatment for 15 minutes, and then cool it in the furnace to obtain a contrast film.
- Membrane tube performance test the comparative membrane prepared in this comparative example was tested at room temperature and 0.6 MPa pressure. Its pure water flux was 60 LHM, and the rejection rate of 0.2wt% magnesium sulfate solution was 95%.
- step (3) Place the material obtained in step (3) in a cool place to air dry, and then put it in a 50°C oven for heat treatment for 15 minutes, and then cool it in the furnace to obtain a contrast film.
- Membrane tube performance test the comparative membrane prepared in this comparative example was tested at room temperature and 0.6 MPa pressure. Its pure water flux was 64LHM, and the rejection rate of 0.2wt% magnesium sulfate solution was 93%.
- step (3) The material obtained in step (3) is placed in a cool place and air-dried, and then placed in an oven at 50° C. for heat treatment for 15 minutes, and then cooled in the furnace to obtain the graphene oxide modified polydopamine composite nanofiltration membrane.
- step (3) Place the material obtained in step (3) in a cool place to air dry, and then put it in a 50°C oven for heat treatment for 15 minutes, and then cool it down in the furnace to obtain the graphene oxide modified polydopamine composite sodium as shown in Figure 1. Filter membrane.
- step (3) The material obtained in step (3) is placed in a cool place and air-dried, and then placed in an oven at 50° C. for heat treatment for 15 minutes, and then cooled in the furnace to obtain the graphene oxide modified polydopamine composite nanofiltration membrane.
- Membrane tube performance test the graphene oxide modified polydopamine composite nanofiltration membrane prepared in this example was tested at room temperature and 0.6MPa pressure. Its pure water flux was 76LHM, compared with 0.2wt% magnesium sulfate solution The retention rate is 98%.
- the invention discloses a graphene oxide modified polydopamine composite nanofiltration membrane and a preparation method thereof.
- the composite nanofiltration membrane comprises a polyethersulfone support and an organic functional layer arranged on the polyethersulfone support.
- the monomer, organic phase monomer and acid acceptor are formed on the polyethersulfone support through interfacial polymerization reaction as raw materials.
- the invention adds a polydopamine composite nanofiltration membrane through graphene oxide to improve the hydrophilicity and roughness of the membrane layer surface, thereby increasing the water flux of the membrane layer, and has industrial practicability.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
本发明公开了一种氧化石墨烯改性聚多巴胺复合纳滤膜及其制备方法，包括聚醚砜支撑体和设于该聚醚砜支撑体上的有机功能层，该有机功能层以水相单体、有机相单体和酸接受剂为原料通过界面聚合反应于聚醚砜支撑体上形成。本发明通过氧化石墨烯添加聚多巴胺复合纳滤膜，提高膜层表面的亲水性和粗糙度从而提高膜层的水通量。
Description
本发明属于膜分离技术领域，具体涉及一种氧化石墨烯改性聚多巴胺复合纳滤膜及其制备方法。
纳滤膜是一种新型的压力驱动膜，膜孔径介于超滤和反渗透之间，能够用于二价盐和一价盐的分离。纳滤膜具有操作压力低、高通量和节能等特点，因此，纳滤膜被广泛地应用于生物工程、医药、冶金、水处理、电子等领域。工业常用的纳滤膜为有机纳滤膜，它具有透气性高、密度低、成膜性好、成本低和柔韧性好等诸多优点，但是有机纳滤膜在工业应用中存在着通量低，抗污染能力差等缺点，因此需要对有机纳滤膜进行改性，提高膜层的通量和抗污染性。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种氧化石墨烯改性聚多巴胺复合纳滤膜。
本发明的另一目的在于提供上述氧化石墨烯改性聚多巴胺复合纳滤膜的制备方法。
本发明的技术方案如下：
一种氧化石墨烯改性聚多巴胺复合纳滤膜，包括聚醚砜支撑体和设于该聚醚砜支撑体上的有机功能层，该有机功能层以水相单体、有机相单体和酸接受剂为原料通过界面聚合反应于聚醚砜支撑体上形成；
上述水相单体由聚多巴胺和氧化石墨烯组成；
上述有机相单体为均苯三甲酰氯；
上述酸接受剂为多元胺。
在本发明的一个优选实施方案中，所述多元胺为二乙胺。
在本发明的一个优选实施方案中，所述聚醚砜支撑体的孔径为10-30KD。
在本发明的一个优选实施方案中，所述聚多巴胺与氧化石墨烯的质量比为1:0.6-1。
进一步优选的，所述聚多巴胺、氧化石墨烯和多元胺的质量比为1:0.6-1:9-11。
本发明的另一技术方案如下：
上述氧化石墨烯改性聚多巴胺复合纳滤膜的制备方法，其特征在于：包括：以聚多巴胺和氧化石墨烯的混合物作为水相单体，以均苯二甲酰氯作为有机单体，以多元胺为酸接受剂，通过界面聚合反应在所述聚醚砜支撑体上形成所述有机功能层，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
在本发明的一个优选实施方案中，包括如下步骤：
(1)使用改性的Hummers方法制备氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液；
(3)将经过乙醇和水洗后的聚醚砜支撑体浸泡于上述水相溶液中，室温反应后进行泡水和吹干，再浸泡于均苯三甲酰氯的正己烷溶液中，室温下反应后进行泡水和吹干；重复该步骤至少1次；
(4)将步骤(3)所得的物料阴干后，再于50-80℃热处理，之后随炉冷却，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
进一步优选的，所述氧化石墨烯水溶液的浓度为1-5mg/L。
进一步优选的，所述步骤(4)中，所述多元胺在所述水相溶液中的浓度为0.8-1.2wt％。
进一步优选的，所述均苯三甲酰氯的正己烷溶液的浓度为0.08-0.12wt％。
本发明的有益效果是：本发明通过氧化石墨烯添加聚多巴胺复合纳滤膜，提高膜层表面的亲水性和粗糙度从而提高膜层的水通量。
图1为本发明实施例2制得的氧化石墨烯改性聚多巴胺复合纳滤膜的扫描电镜照片。
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述对比例和实施例中的改性的Hummers方法具体包括：
(1)取1000mL的烧杯洗净干燥，加入3g鳞片石墨，在磁力搅拌下缓慢加入 360mL浓硫酸(98％H
2SO
4)和40mL浓磷酸(95％H
3PO
4)，再分批次缓慢加入18g高锰酸钾(KMnO
4)；烧杯移至50℃油浴中，搅拌12h。取出烧杯，自然冷却至室温。反应液缓慢浇在400mL稀双氧水(含18ml 30％H
2O
2)的冰块上，溶液变成亮黄色；
(2)将上述溶液用孔径为0.05μm管式陶瓷膜进行错流过滤进行除杂，获得除杂后的氧化石墨烯溶液；其基本原理是利用陶瓷膜的孔径筛分作用，即陶瓷管式膜过滤孔径尺寸小于GO片层的尺寸，使得GO片层无法通过管式陶瓷膜流出，而是随着管道内液体循环回流至料液桶中，既不会堵塞膜孔，保证膜孔的畅通性，而且也对尺寸较大的GO片层进行粉碎和剥离；陶瓷管式膜过滤孔径尺寸大于GO溶液的杂质离子尺寸，使得H
+、K
+、Mn
2+等酸根和金属离子可以轻松穿过陶瓷管式膜的孔径排出。如此反复循环，实现GO与废酸、K
+、和Mn
2+等金属离子的分离，以及对GO溶液的收集，完成对GO的洗涤除杂；
(3)根据所需浓度进行稀释或浓缩，获得浓度为1-5mg/mL的氧化石墨烯水溶液。
对比例1
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和多元胺于水中搅拌混合均匀，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得对比膜。
膜管性能测试：将本对比例制得的对比膜在室温和0.6MPa的压力条件下进行测试，其纯水通量57LHM，对0.2wt％的硫酸镁溶液截留率96％。
对比例2
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.03wt％，二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得对比膜。
膜管性能测试：将本对比例制得的对比膜在室温和0.6MPa的压力条件下进行测试，其纯水通量60LHM，对0.2wt％的硫酸镁溶液截留率95％。
对比例3
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.12wt％，二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得对比膜。
膜管性能测试：将本对比例制得的对比膜在室温和0.6MPa的压力条件下进行测试，其纯水通量64LHM，对0.2wt％的硫酸镁溶液截留率93％。
实施例1
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.06wt％， 二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
膜管性能测试：将本实施例制得的氧化石墨烯改性聚多巴胺复合纳滤膜在室温和0.6MPa的压力条件下进行测试，其纯水通量74LHM，对0.2wt％的硫酸镁溶液截留率96％。
实施例2
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.08wt％，二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得如图1所示的所述氧化石墨烯改性聚多巴胺复合纳滤膜。
膜管性能测试：将本实施例制得的氧化石墨烯改性聚多巴胺复合纳滤膜在室温和0.6MPa的压力条件下进行测试，其纯水通量80LHM，对0.2wt％的硫酸镁溶液截留率98％。
实施例3
(1)使用改性的Hummers方法制备浓度为1-5mg/mL的氧化石墨烯水溶液；
(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液，其中，聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.1wt％， 二乙胺的浓度为1wt％；
(3)将经过乙醇和水洗后的50KD聚醚砜支撑体浸泡于上述水相溶液中，室温反应10min后进行泡水和吹干，再浸泡于浓度为0.1wt％的均苯三甲酰氯的正己烷溶液中，室温下反应10min后进行泡水和吹干；重复该步骤1次；
(4)将步骤(3)所得的物料放置在阴凉处风干后放入50℃烘箱中热处理15min，之后随炉冷却，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
膜管性能测试：将本实施例制得的氧化石墨烯改性聚多巴胺复合纳滤膜在室温和0.6MPa的压力条件下进行测试，其纯水通量76LHM，对0.2wt％的硫酸镁溶液截留率98％。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
本发明公开了一种氧化石墨烯改性聚多巴胺复合纳滤膜及其制备方法，包括聚醚砜支撑体和设于该聚醚砜支撑体上的有机功能层，该有机功能层以水相单体、有机相单体和酸接受剂为原料通过界面聚合反应于聚醚砜支撑体上形成。本发明通过氧化石墨烯添加聚多巴胺复合纳滤膜，提高膜层表面的亲水性和粗糙度从而提高膜层的水通量,具有工业实用性。
Claims (10)
- 一种氧化石墨烯改性聚多巴胺复合纳滤膜，其特征在于：包括聚醚砜支撑体和设于该聚醚砜支撑体上的有机功能层，该有机功能层以水相单体、有机相单体和酸接受剂为原料通过界面聚合反应于聚醚砜支撑体上形成；上述水相单体由聚多巴胺和氧化石墨烯组成；上述有机相单体为均苯三甲酰氯；上述酸接受剂为多元胺。
- 如权利要求1所述的一种氧化石墨烯改性聚多巴胺复合纳滤膜，其特征在于：所述多元胺为二乙胺。
- 如权利要求1所述的一种氧化石墨烯改性聚多巴胺复合纳滤膜，其特征在于：所述聚醚砜支撑体的孔径为10-30KD。
- 如权利要求1所述的一种氧化石墨烯改性聚多巴胺复合纳滤膜，其特征在于：所述聚多巴胺与氧化石墨烯的质量比为1:0.6-1。
- 如权利要求4所述的一种氧化石墨烯改性聚多巴胺复合纳滤膜，其特征在于：所述聚多巴胺、氧化石墨烯和多元胺的质量比为1:0.6-1:9-11。
- 权利要求1至5中任一权利要求所述的一种氧化石墨烯改性聚多巴胺复合纳滤膜的制备方法，其特征在于：包括：以聚多巴胺和氧化石墨烯的混合物作为水相单体，以均苯二甲酰氯作为有机单体，以多元胺为酸接受剂，通过界面聚合反应在所述聚醚砜支撑体上形成所述有机功能层，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
- 如权利要求6所述的制备方法，其特征在于：包括如下步骤：(1)使用改性的Hummers方法制备氧化石墨烯水溶液；(2)将聚多巴胺和氧化石墨烯水溶液搅拌混合均匀，再加入多元胺，超声处理后，获得水相溶液；所述聚多巴胺的浓度为0.1wt％，氧化石墨烯的浓度为0.06-0.1wt％，二乙胺的浓度为1wt％；(3)将经过乙醇和水洗后的聚醚砜支撑体浸泡于上述水相溶液中，室温反应后进行泡水和吹干，再浸泡于均苯三甲酰氯的正己烷溶液中，室温下反应后进行泡水和吹干；重复该步骤至少1次；(4)将步骤(3)所得的物料阴干后，再于50-80℃热处理，之后随炉冷却，即得所述氧化石墨烯改性聚多巴胺复合纳滤膜。
- 如权利要求7所述的制备方法，其特征在于：所述氧化石墨烯水溶液的浓度为1-5mg/L。
- 如权利要求7所述的制备方法，其特征在于：所述步骤(4)中，所述多元胺在所述水相溶液中的浓度为0.8-1.2wt％。
- 如权利要求7所述的制备方法，其特征在于：所述均苯三甲酰氯的正己烷溶液的浓度为0.08-0.12wt％。
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