WO2022041925A1 - Photocatalyst-loaded fluorocarbon fiber membrane for sewage station and preparation method therefor - Google Patents
Photocatalyst-loaded fluorocarbon fiber membrane for sewage station and preparation method therefor Download PDFInfo
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- WO2022041925A1 WO2022041925A1 PCT/CN2021/099328 CN2021099328W WO2022041925A1 WO 2022041925 A1 WO2022041925 A1 WO 2022041925A1 CN 2021099328 W CN2021099328 W CN 2021099328W WO 2022041925 A1 WO2022041925 A1 WO 2022041925A1
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- fiber membrane
- photocatalyst
- fluorocarbon fiber
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- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 239000010865 sewage Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 208000028659 discharge Diseases 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 5
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005070 sampling Methods 0.000 description 21
- 239000010408 film Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B01J35/59—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Definitions
- the odor source is enclosed in the covered space. Because the covered space is generally large, the load of the back-end collection and treatment is high, so the investment and operation costs are high.
- the odor intensity of sedimentation tank and anaerobic tank is lower than that of concentration tank and mud storage tank, and the internal environment is not positive pressure; )
- the light transmittance of the film can even reach more than 90%.
- Figure 1 Schematic diagram of the valve prefabricated in the sampling bag.
Abstract
The present invention relates to a photocatalyst-loaded fluorocarbon fiber membrane for a sewage station and a preparation method therefor. Fluorocarbon fibers are grafted with acrylic acid by means of plasma discharge and ultraviolet irradiation, and the binding ability with a photocatalytic material is improved by means of increasing carboxyl groups on a surface thereof to obtain a fluorocarbon fiber membrane of a visible light photocatalyst loaded with WO3-modified Bi2WO6. The loading capacity and surface morphology of the photocatalyst is easy to control, the preparation process is simple and pollution-free, is convenient for industrialized production, and has a good degradation effect on various pollutants in a sewage station in the visible light range that has a wavelength of 420-650 nm.
Description
本发明涉及环保技术领域，具体涉及一种污水站用负载光催化剂的氟碳纤维膜及其制备方法。The invention relates to the technical field of environmental protection, in particular to a photocatalyst-loaded fluorocarbon fiber membrane for a sewage station and a preparation method thereof.
市政污水处理厂往往位于工业集中区或者居民区附近，在污水处理过程中会向外界环境释放大量恶臭性气体，这些气体会对人们的生活环境和身体健康造成一定的潜在危害，市政污水处理厂的异味扰民问题成为热点的民生问题之一，逐渐引起各级主管部门的重视。Municipal sewage treatment plants are often located near industrial concentration areas or residential areas. During the sewage treatment process, a large amount of malodorous gases will be released to the external environment. These gases will cause certain potential harm to people's living environment and health. Municipal sewage treatment plants The problem of peculiar smell disturbing the people has become one of the hot issues of people's livelihood, and has gradually attracted the attention of the competent authorities at all levels.
解决污水处理厂的异味扰民问题，关键是杜绝臭味气体的无组织溢散问题，所以需要对污水处理的构筑物进行加盖。臭气源加盖应便于污水处理设施的正常运行、维护和管理，并符合以下基本要求：(1)正常运行时，加盖不应影响对构筑物内部和设备的采光要求；(2)应设置检修通道，加盖不应妨碍设备的操作和维护检修；(3)应采取防止因抽吸负压引起的加盖损坏的措施；(4)应采取防止雨水在盖板上累积的措施。目前针对城镇污水处理厂的常规加盖方式主要有：玻璃钢加盖、反吊膜加盖和充气膜加盖，其中反吊膜和充气膜常用的膜材为氟碳纤维膜，氟碳纤维膜材具有透光性能好、弹性大、强度高、抗酸碱腐蚀及紫外线老化、具有一定自洁净功能，以上功能主要通过玻璃纤维和聚脂纤维等高强度基材涂覆聚四氟乙烯(PTFE)、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)或者乙烯-四氟乙烯(ETFE)等功能性涂层而实现。The key to solving the problem of peculiar smell disturbing the people in the sewage treatment plant is to eliminate the problem of unorganized escape of odorous gas, so it is necessary to cover the structure of sewage treatment. The capping of the odor source shall facilitate the normal operation, maintenance and management of the sewage treatment facility, and shall meet the following basic requirements: (1) During normal operation, the capping shall not affect the lighting requirements for the interior of the structure and equipment; (2) It shall be set In the maintenance channel, the cover should not hinder the operation and maintenance of the equipment; (3) measures should be taken to prevent damage to the cover caused by suction negative pressure; (4) measures should be taken to prevent rainwater from accumulating on the cover. At present, the conventional capping methods for urban sewage treatment plants mainly include: glass fiber reinforced plastic capping, anti-hanging film capping and inflatable membrane capping. It has good light transmission performance, high elasticity, high strength, acid and alkali corrosion resistance and ultraviolet aging, and has a certain self-cleaning function. The above functions are mainly coated with polytetrafluoroethylene (PTFE), glass fiber and polyester fiber and other high-strength substrates. It is realized by functional coatings such as polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) or ethylene-tetrafluoroethylene (ETFE).
污水站加盖后，臭气源被封闭在加盖空间内，由于加盖空间一般较大导致后端收集处理的负荷较高，从而投资和运行费用较高。沉淀池和厌氧池的臭气强度相比于浓缩池和储泥池较低，且内部加盖环境非正压；加盖膜材的透光性一般比较高，乙烯-四氟乙烯(ETFE)膜材的透光性甚至可以达到90％以上。通过在加盖膜材内侧涂覆可见光光催化剂，在可见光作用下可以分解加盖空间内的臭气，将处理和加盖措施有效集成，此种方式光催化反应时间充足，是一种理想的主动净化方式。After the sewage station is covered, the odor source is enclosed in the covered space. Because the covered space is generally large, the load of the back-end collection and treatment is high, so the investment and operation costs are high. The odor intensity of sedimentation tank and anaerobic tank is lower than that of concentration tank and mud storage tank, and the internal environment is not positive pressure; ) The light transmittance of the film can even reach more than 90%. By coating the visible light photocatalyst on the inside of the capping film, the odor in the capping space can be decomposed under the action of visible light, and the treatment and capping measures can be effectively integrated. This method has sufficient photocatalytic reaction time, which is an ideal Active purification method.
因此，研制出一种制备工艺简单，成本低廉，光催化剂可见光响应良好且与膜材附着力强的氟碳纤维膜，对于削减市政污水站臭气浓度具有重要意义，具有良好的应用前景。Therefore, the development of a fluorocarbon fiber membrane with simple preparation process, low cost, good photocatalyst visible light response and strong adhesion to the membrane material is of great significance for reducing the odor concentration of municipal sewage stations and has good application prospects.
经检索，关于光催化材料与膜材料复合的专利报道已有相关公开。After searching, there have been relevant publications on patent reports on the composite of photocatalytic materials and membrane materials.
如，中国专利申请CN110652974A公开了一种具有光催化功能的吸附型复合纳米纤维膜及制备方法，该申请案是将5-15％质量分数的TiO
2光催化剂、1-8％质量分数的Zr-MOF吸附 材料与14-24％质量分数的PVDF以及DMF和丙酮进行混合，通过静电纺丝的方式制备具有光催化功能的吸附型复合纳米纤维膜，然后与铜网载体进行复合，可用于空气净化领域。该申请案使用的TiO
2光催化剂无法在可见光波段有效分解污染物，而且不是涂敷在纤维膜表面，内部的催化剂无法得到有效光照，制备工艺复杂，无法用于污水处理站加盖膜内的臭气净化。
For example, Chinese patent application CN110652974A discloses an adsorption - type composite nanofiber membrane with photocatalytic function and its preparation method. -MOF adsorption material is mixed with 14-24% mass fraction of PVDF, DMF and acetone to prepare adsorption-type composite nanofiber membrane with photocatalytic function by electrospinning, and then composite with copper mesh carrier, which can be used for air Purify the field. The TiO 2 photocatalyst used in this application cannot effectively decompose pollutants in the visible light band, and it is not coated on the surface of the fiber membrane. The catalyst inside cannot be effectively illuminated, and the preparation process is complicated. Odor purification.
又如，中国专利CN 105749762 B的申请案公开了一种具有光催化活性的高分子复合膜材料及其制备方法，该申请案(1)将氧化石墨烯、去离子水和无水乙醇混合，超声分散后滴加钛酸，加热反应，反应液冷却后过滤、洗涤得包含TiO
2-氧化石墨烯纳米材料的悬浮体系；(2)将悬浮体系移入高压釜中，加入还原剂，密闭后热处理，冷却后分离，洗涤、烘干后得TiO
2-氧化石墨烯纳米粉末材料；(3)TiO
2-氧化石墨烯纳米粉末材料悬浮于甲基丙烯酸甲酯中，超声分散后加入引发剂，水浴中搅拌反应制得铸膜液，将铸膜液均匀刮涂在基底上，烘干后即得复合膜材料。同样的该申请案制备工序复杂，TiO
2无可见光活性，膜材材料受限且内部的光催化材料无法得到有效光照，无法用于污水处理站加盖膜内的臭气净化。
For another example, the application of Chinese patent CN 105749762 B discloses a polymer composite membrane material with photocatalytic activity and a preparation method thereof. The application (1) mixes graphene oxide, deionized water and absolute ethanol, After ultrasonic dispersion, titanic acid is added dropwise, and the reaction is heated. After cooling, the reaction solution is filtered and washed to obtain a suspension system comprising TiO 2 -graphene oxide nanomaterials; (2) the suspension system is moved into an autoclave, a reducing agent is added, and a heat treatment is performed after sealing. , separated after cooling, washed and dried to obtain TiO 2 -graphene oxide nano-powder material; (3) TiO 2 -graphene oxide nano-powder material was suspended in methyl methacrylate, after ultrasonic dispersion, an initiator was added, and a water bath was used. The casting liquid is prepared by stirring and reacting in the middle, the casting liquid is evenly scraped on the substrate, and the composite film material is obtained after drying. Similarly, the preparation process of this application is complicated, TiO 2 has no visible light activity, the film material is limited, and the photocatalytic material inside cannot get effective light, so it cannot be used for odor purification in the cover film of the sewage treatment station.
发明内容SUMMARY OF THE INVENTION
本发明主要解决的技术问题是提供一种污水站用负载光催化剂的氟碳纤维膜及其制备方法，该方法合成工艺简单，光催化材料为WO
3修饰Bi
2WO
6，可以充分利用透过氟碳纤维膜的可见光，光催化材料通过接枝丙烯酸的方式提高了与氟碳纤维膜的附着力，可以工业化应用于污水站加盖内部空间的臭味净化。
The main technical problem to be solved by the present invention is to provide a photocatalyst-loaded fluorocarbon fiber membrane for sewage station and a preparation method thereof. The method has a simple synthesis process, and the photocatalytic material is WO 3 modified Bi 2 WO 6 , which can make full use of the fluorine-transmitting fluorine. The visible light and photocatalytic material of the carbon fiber membrane improves the adhesion with the fluorocarbon fiber membrane by grafting acrylic acid, and can be industrially applied to the odor purification of the interior space of the sewage station.
为实现上述目的，本发明提供的技术方案是：For achieving the above object, the technical scheme provided by the present invention is:
一种污水站用负载光催化剂的氟碳纤维膜，通过对氟碳纤维进行等离子放电和紫外辐照的方式接枝丙烯酸，通过增加其表面上的羧基提高对光催化材料的结合能力，制备方法包括以下步骤：A photocatalyst-loaded fluorocarbon fiber membrane for a sewage station is grafted with acrylic acid by plasma discharge and ultraviolet irradiation on the fluorocarbon fiber, and the binding ability to photocatalytic materials is improved by increasing carboxyl groups on its surface. The preparation method includes the following step:
(1)将氟碳纤维膜裁剪成氟碳纤维膜材样条，放置于等离子发生器中进行等离子放电处理；(1) The fluorocarbon fiber membrane is cut into fluorocarbon fiber membrane splines, and placed in a plasma generator for plasma discharge treatment;
(2)将氟碳纤维膜材样条进行了放电预处理后的一面涂覆丙烯酸溶液，将涂覆了丙烯酸溶液的氟碳纤维膜材样条放置在紫外灯下进行接枝反应；(2) coating the fluorocarbon fiber membrane spline with acrylic acid solution on one side after discharge pretreatment, and placing the fluorocarbon fiber membrane spline coated with the acrylic solution under an ultraviolet lamp to carry out the grafting reaction;
(3)将一定量的二水合钨酸钠溶于蒸馏水中得到钨酸钠溶液，通过滴定管滴加五水合硝酸铋溶于硝酸中得到的硝酸铋溶液，将钨酸钠溶液与硝酸铋溶液混合均匀后得到前驱体溶液；(3) Dissolving a certain amount of sodium tungstate dihydrate in distilled water to obtain a sodium tungstate solution, dropwise adding a bismuth nitrate solution obtained by dissolving bismuth nitrate pentahydrate in nitric acid through a burette, and mixing the sodium tungstate solution with the bismuth nitrate solution The precursor solution is obtained after homogenization;
(4)将接枝后的氟碳纤维膜材样条均匀放置于盛有前驱体溶液的水热反应釜中进行水热反应，自然冷却洗涤后，干燥得到负载WO
3修饰Bi
2WO
6的可见光光催化剂的氟碳纤维膜。
( 4 ) The grafted fluorocarbon fiber membrane splines are evenly placed in a hydrothermal reactor containing the precursor solution for hydrothermal reaction, after natural cooling and washing, drying to obtain visible light loaded with WO3 modified Bi2WO6 Fluorocarbon fiber membranes for photocatalysts.
所述的氟碳纤维膜为常规市售的以高强玻璃纤维或高强聚脂纤维为基材涂覆涂层的膜材。The fluorocarbon fiber membrane is a conventional commercially available membrane material coated with high-strength glass fiber or high-strength polyester fiber as the base material.
所述的氟碳纤维膜选自聚四氟乙烯PTFE膜材、聚偏二氟乙烯PVDF膜材或乙烯-四氟乙 烯共聚物ETFE膜材中的一种。Described fluorocarbon fiber membrane is selected from the one in polytetrafluoroethylene PTFE membrane material, polyvinylidene fluoride PVDF membrane material or ethylene-tetrafluoroethylene copolymer ETFE membrane material.
步骤(1)中，等离子发生器的放电形式为常压辉光放电或者介质阻挡放电，放电间距1-10mm，放电电压10kV-40kV，放电处理时间0.5-20min。In step (1), the discharge form of the plasma generator is normal pressure glow discharge or dielectric barrier discharge, the discharge distance is 1-10mm, the discharge voltage is 10kV-40kV, and the discharge treatment time is 0.5-20min.
步骤(2)中，丙烯酸的涂覆采用旋涂机进行，涂覆转速为100-1000r/min，丙烯酸溶液的质量分数为5-30％，涂覆时间为3-60s。In step (2), the coating of acrylic acid is carried out by a spin coater, the coating speed is 100-1000 r/min, the mass fraction of the acrylic acid solution is 5-30%, and the coating time is 3-60 s.
步骤(2)中，接枝用紫外灯波长为254nm或者365nm，反应时间1-10min，反应温度20-60℃。In step (2), the wavelength of the ultraviolet lamp used for grafting is 254nm or 365nm, the reaction time is 1-10min, and the reaction temperature is 20-60°C.
所述步骤(3)中，硝酸铋溶液的浓度为0.05-0.2mol/L，硝酸的浓度为0.5-5mol/L，钨酸钠溶液的浓度为0.05-0.1mol/L；钨酸钠溶液通过滴定管滴加到硝酸铋溶液中，30-40℃均匀搅拌1-24h，得到混合均匀的前驱体溶液。In the step (3), the concentration of bismuth nitrate solution is 0.05-0.2 mol/L, the concentration of nitric acid is 0.5-5 mol/L, and the concentration of sodium tungstate solution is 0.05-0.1 mol/L; The burette is added dropwise to the bismuth nitrate solution, and the mixture is uniformly stirred at 30-40°C for 1-24 hours to obtain a uniformly mixed precursor solution.
步骤(4)中，水热反应温度为100-180℃，水热反应时间为5-30h；自然冷却后使用的洗涤液为蒸馏水和乙醇，洗涤次数1-5次。In step (4), the hydrothermal reaction temperature is 100-180° C., and the hydrothermal reaction time is 5-30 h; the washing solution used after natural cooling is distilled water and ethanol, and the washing times are 1-5 times.
步骤(4)中，洗涤后膜材干燥温度为40-80℃，干燥时间为4-10h。In step (4), the drying temperature of the membrane material after washing is 40-80° C., and the drying time is 4-10 h.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明的一种污水站用负载光催化剂的氟碳纤维膜，光催化剂为WO
3修饰的Bi
2WO
6可见光光催化剂，可以充分利用透过聚四氟乙烯(PTFE)膜材、聚偏二氟乙烯(PVDF)膜材和乙烯-四氟乙烯共聚物(ETFE)膜材的太阳光，在波长为420-650nm波段的可见光范围内，对污水站各类有机污染物具有良好的降解作用。
(1) A photocatalyst-loaded fluorocarbon fiber membrane for a sewage station of the present invention, the photocatalyst is a Bi 2 WO 6 visible light photocatalyst modified by WO 3 , which can make full use of the permeable polytetrafluoroethylene (PTFE) membrane material, poly The sunlight of vinylidene fluoride (PVDF) film and ethylene-tetrafluoroethylene copolymer (ETFE) film has good degradation of various organic pollutants in sewage stations in the visible light range of 420-650nm wavelength. effect.
(2)本发明的一种污水站用负载光催化剂的氟碳纤维膜的制备方法，膜的外侧为疏水性涂层材料，自洁净能力强可以保证较高的透光率；膜的内侧通过等离子放电和紫外辐照的方式接枝丙烯酸增加表面羧基，从而实现在光滑的氟碳纤维膜表面负载光催化剂，且附着力良好，使用寿命长。(2) A preparation method of a photocatalyst-loaded fluorocarbon fiber membrane for a sewage station of the present invention, the outer side of the membrane is a hydrophobic coating material, and the self-cleaning ability is strong and can ensure higher light transmittance; the inner side of the membrane passes through the plasma Grafting acrylic acid by means of discharge and ultraviolet irradiation increases the surface carboxyl groups, so that the photocatalyst can be loaded on the surface of the smooth fluorocarbon fiber membrane, and the adhesion is good and the service life is long.
(3)膜材负载光催化剂是通过水热法合成，光催化剂的负载量和表面形貌易于调控，制备过程简单无污染，方便工业化生产。(3) The film-supported photocatalyst is synthesized by a hydrothermal method, the loading amount and surface morphology of the photocatalyst are easy to control, the preparation process is simple and pollution-free, and the industrial production is convenient.
图1：采样袋预制的阀门的结构示意图。Figure 1: Schematic diagram of the valve prefabricated in the sampling bag.
图2：实施例1、实施例2、对比例1、对比例2净化性能测试分析对比图。Figure 2: Example 1, Example 2, Comparative Example 1, Comparative Example 2 purification performance test analysis comparison diagram.
图中：1-取样口，2-硅胶取样垫，3-阀体，4-阀门进出气口。In the picture: 1-Sampling port, 2-Silica gel sampling pad, 3-Valve body, 4-Valve inlet and outlet.
下面结合具体实施例对本发明作进一步详细的说明。以下实施例仅用于说明本发明而不用 于限制本发明的范围。The present invention will be described in further detail below with reference to specific embodiments. The following examples are only intended to illustrate the present invention and not to limit the scope of the present invention.
实施例1Example 1
1)将市售高强玻璃纤维为基材，上下涂覆聚四氟乙烯(PTFE)涂层的膜材裁剪成2个13cm×13cm样条放置于常压辉光放电等离子发生器中放电处理10min，放电电压30kV；1) The commercially available high-strength glass fiber is used as the base material, and the membrane material coated with polytetrafluoroethylene (PTFE) coating is cut into two 13cm×13cm splines and placed in a normal pressure glow discharge plasma generator for discharge treatment for 10min. , the discharge voltage is 30kV;
2)放电预处理后的膜材，利用旋涂机涂覆丙烯酸溶液，涂覆丙烯酸溶液的氟碳纤维膜材在紫外灯下进行接枝反应；2) The membrane material after the discharge pretreatment is coated with an acrylic acid solution by a spin coater, and the fluorocarbon fiber membrane material coated with the acrylic acid solution is subjected to a grafting reaction under an ultraviolet lamp;
上述旋涂机转速为200r/min，丙烯酸浓度为15wt％，涂覆时间30s；涂覆后进行紫外接枝反应，反应时间5min，反应温度25℃，所用紫外灯波长为254nm。The rotation speed of the spin coater was 200 r/min, the concentration of acrylic acid was 15 wt%, and the coating time was 30 s; after coating, an ultraviolet grafting reaction was performed, the reaction time was 5 min, the reaction temperature was 25° C., and the wavelength of the ultraviolet lamp used was 254 nm.
3)称取36.278g的二水合钨酸钠溶于蒸馏水中得到钨酸钠溶液，称取97g的五水合硝酸铋溶于硝酸得到硝酸铋溶液，将钨酸钠溶液通过滴定管滴加到硝酸铋溶液中得到前驱体溶液；3) Weigh 36.278g of sodium tungstate dihydrate and dissolve it in distilled water to obtain a sodium tungstate solution, weigh 97g of bismuth nitrate pentahydrate and dissolve it in nitric acid to obtain a bismuth nitrate solution, and add the sodium tungstate solution dropwise to the bismuth nitrate solution through a burette. The precursor solution is obtained in the solution;
上述溶液配制均充分搅拌均匀，搅拌和滴加均在水浴锅中40℃恒温进行；前驱体溶液共计1L，含0.2mol的硝酸铋、0.11mol的钨酸钠和1mol硝酸。The above solutions were fully stirred and evenly added, and the stirring and dropping were carried out in a water bath at a constant temperature of 40°C; the total precursor solution was 1 L, containing 0.2 mol of bismuth nitrate, 0.11 mol of sodium tungstate and 1 mol of nitric acid.
4)将接枝反应后的膜材放置于盛有上述前驱体溶液的水热反应釜中，160℃下水热反应12h，自然冷却后采用蒸馏水和乙醇分别洗涤两次后50℃干燥5h，得到10％WO
3·Bi
2WO
6负载聚四氟乙烯(PTFE)的加盖膜材。
4) The membrane material after the grafting reaction was placed in a hydrothermal reactor containing the above-mentioned precursor solution, hydrothermally reacted at 160 °C for 12 h, and after natural cooling, washed twice with distilled water and ethanol, respectively, and dried at 50 °C for 5 h to obtain 10% WO 3 · Bi 2 WO 6 supported polytetrafluoroethylene (PTFE) capping membrane.
5)将上述2个尺寸为13cm×13cm，负载10％WO
3·Bi
2WO
6可见光光催化剂的聚四氟乙烯加盖膜材，通过膜材热合机做成尺寸为12cm×12cm气体采样袋，采样袋预制有阀门，阀门详见图1所示。
5) The above-mentioned two 13cm×13cm, 10% WO 3 · Bi 2 WO 6 visible light photocatalyst loaded polytetrafluoroethylene covered film materials were made into gas sampling bags with a size of 12cm×12cm through a film material heat sealing machine , the sampling bag is prefabricated with a valve, the valve is shown in Figure 1.
上述阀门材质为PP，嘴外径为4mm；阀门上端取样垫材质为硅胶，可用针筒注射器反复取样。The material of the above valve is PP, and the outer diameter of the mouth is 4mm; the material of the sampling pad at the upper end of the valve is silica gel, which can be repeatedly sampled with a syringe with a syringe.
实施例2Example 2
1)将市售乙烯-四氟乙烯(ETFE)膜材裁剪成2个13cm×13cm样条放置于介质阻挡放电等离子发生器中放电处理5min，放电电压20kV；1) Cut the commercially available ethylene-tetrafluoroethylene (ETFE) film material into two 13cm×13cm splines and place them in a dielectric barrier discharge plasma generator for 5min discharge treatment with a discharge voltage of 20kV;
2)放电预处理后的膜材，利用旋涂机涂覆丙烯酸溶液，涂覆丙烯酸溶液的氟碳纤维膜材在紫外灯下进行接枝反应；2) The membrane material after the discharge pretreatment is coated with an acrylic acid solution by a spin coater, and the fluorocarbon fiber membrane material coated with the acrylic acid solution is subjected to a grafting reaction under an ultraviolet lamp;
上述旋涂机转速为400r/min，丙烯酸浓度为30wt％，涂覆时间40s；涂覆后进行紫外接枝反应，反应时间10min，反应温度25℃，所用紫外灯波长为365nm。The rotation speed of the spin coater was 400 r/min, the acrylic acid concentration was 30 wt%, and the coating time was 40 s; after coating, the UV grafting reaction was performed, the reaction time was 10 min, the reaction temperature was 25° C., and the wavelength of the UV lamp used was 365 nm.
3)称取36.278g的二水合钨酸钠溶于蒸馏水中得到钨酸钠溶液，称取97g的五水合硝酸铋溶于硝酸得到硝酸铋溶液，将钨酸钠溶液通过滴定管滴加到硝酸铋溶液中得到前驱体溶液；3) Weigh 36.278g of sodium tungstate dihydrate and dissolve it in distilled water to obtain a sodium tungstate solution, weigh 97g of bismuth nitrate pentahydrate and dissolve it in nitric acid to obtain a bismuth nitrate solution, and add the sodium tungstate solution dropwise to the bismuth nitrate solution through a burette. The precursor solution is obtained in the solution;
上述溶液配制均充分搅拌均匀，搅拌和滴加均在水浴锅中40℃恒温进行；前驱体溶液共 计1L，含0.2mol的硝酸铋、0.11mol的钨酸钠和1mol硝酸。The above-mentioned solution preparations were all fully stirred, and the stirring and dropping were carried out at a constant temperature of 40°C in a water bath; the precursor solution was 1 L in total, containing 0.2 mol of bismuth nitrate, 0.11 mol of sodium tungstate and 1 mol of nitric acid.
4)将接枝反应后的膜材放置于盛有上述前驱体溶液的水热反应釜中，120℃下水热反应15h，自然冷却后采用蒸馏水和乙醇分别洗涤两次后50℃干燥5h，得到10％WO
3·Bi
2WO
6负载乙烯-四氟乙烯(ETFE)的加盖膜材。
4) The membrane material after the grafting reaction is placed in a hydrothermal reactor containing the above precursor solution, hydrothermally reacted at 120 ° C for 15 h, after natural cooling, washed twice with distilled water and ethanol respectively, and then dried at 50 ° C for 5 h to obtain 10% WO 3 · Bi 2 WO 6 supported ethylene-tetrafluoroethylene (ETFE) capped membrane.
5)将上述2个尺寸为13cm×13cm，负载10％WO
3·Bi
2WO
6可见光光催化剂的乙烯-四氟乙烯(ETFE)加盖膜材样条，通过膜材热合机做成尺寸为12cm×12cm气体采样袋，采样袋预制有阀门。
5) The above two ethylene-tetrafluoroethylene (ETFE) with a size of 13 cm × 13 cm, loaded with 10% WO 3 · Bi 2 WO 6 visible light photocatalyst, and covered with film material splines, were made into a film material with a size of 12cm×12cm gas sampling bag, the sampling bag is prefabricated with a valve.
上述阀门材质为PP，嘴外径为4mm；阀门上端取样垫材质为硅胶，可用针筒注射器反复取样。The material of the above valve is PP, and the outer diameter of the mouth is 4mm; the material of the sampling pad at the upper end of the valve is silica gel, which can be repeatedly sampled with a syringe with a syringe.
对比例1Comparative Example 1
为实施例1的对比例，将市售高强玻璃纤维为基材，上下涂覆聚四氟乙烯(PTFE)涂层的膜材裁剪成2个13cm×13cm样条，通过膜材热合机做成尺寸为12cm×12cm气体采样袋，采样袋预制有阀门。For the comparative example of Example 1, the commercially available high-strength glass fiber is used as the base material, and the film material coated with polytetrafluoroethylene (PTFE) coating on the upper and lower sides is cut into two 13cm×13cm splines, which are made by film material heat sealing machine. The size of the gas sampling bag is 12cm×12cm, and the sampling bag is prefabricated with a valve.
上述阀门材质为PP，嘴外径为4mm；阀门上端取样垫材质为硅胶，可用针筒注射器反复取样。The material of the above valve is PP, and the outer diameter of the mouth is 4mm; the material of the sampling pad at the upper end of the valve is silica gel, which can be repeatedly sampled with a syringe with a syringe.
对比例2Comparative Example 2
为实施例2的对比例，将乙烯-四氟乙烯(ETFE)膜材裁剪成2个13cm×13cm样条，通过膜材热合机做成尺寸为12cm×12cm气体采样袋，采样袋预制有阀门。For the comparative example of Example 2, the ethylene-tetrafluoroethylene (ETFE) film material was cut into two 13cm×13cm splines, and a gas sampling bag with a size of 12cm×12cm was made by a film material heat sealing machine, and the sampling bag was prefabricated with a valve. .
上述阀门材质为PP，嘴外径为4mm；阀门上端取样垫材质为硅胶，可用针筒注射器反复取样。The material of the above valve is PP, and the outer diameter of the mouth is 4mm; the material of the sampling pad at the upper end of the valve is silica gel, which can be repeatedly sampled with a syringe with a syringe.
净化性能测试Purification performance test
将实施例1、实施例2、对比例1和对比例2，采用氟碳纤维膜材试制的采样袋充满大约1L的空气，采用微量注射器通过采样袋阀门上端的取样垫注入50μl的甲醛分析纯溶液，充分混合均匀后，放置于模拟的可见光光源下进行净化性能测试。采样袋竖直固定，距离采样袋10cm的两侧放置125W的自镇流荧光高压汞灯，通过420nm的截止滤光片对高压汞灯发出的光进行处理，以得到模拟污水处理站加盖膜内透过的可见光。实验开始后，每半小时采用注射器通过阀门上端取样垫取样进入气相色谱进行分析。结果见图2所示。The sampling bags of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were filled with about 1 L of air, and 50 μl of analytically pure formaldehyde solution was injected through the sampling pad at the upper end of the sampling bag valve using a micro-syringe. , After fully mixing and evenly, it is placed under a simulated visible light source for purification performance test. The sampling bag was fixed vertically, and 125W self-ballasted fluorescent high-pressure mercury lamps were placed on both sides of the sampling bag at a distance of 10 cm. The light emitted by the high-pressure mercury lamps was processed through a 420nm cut-off filter to obtain a simulated sewage treatment station. visible light passing through. After the start of the experiment, every half hour, a syringe was used to take samples through the sampling pad at the upper end of the valve into the gas chromatograph for analysis. The results are shown in Figure 2.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何形式上的限制，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，依据本发明的技术实质，对以上实施例所作的任何简单的修改、等同替换与改进等，均仍属于本发明技术方案的保护范围之内。The above are only preferred embodiments of the present invention, and do not limit the present invention in any form. Any person skilled in the art, without departing from the scope of the technical solution of the present invention, according to the technical essence of the present invention, Any simple modifications, equivalent replacements and improvements made in the above embodiments still fall within the protection scope of the technical solutions of the present invention.
Claims (9)
- 一种污水站用负载光催化剂的氟碳纤维膜，其特征在于：通过对氟碳纤维进行等离子放电和紫外辐照的方式接枝丙烯酸，通过增加其表面上的羧基提高对光催化材料的结合能力，制备方法包括以下步骤：A photocatalyst-loaded fluorocarbon fiber membrane for a sewage station is characterized in that: the fluorocarbon fiber is grafted with acrylic acid by means of plasma discharge and ultraviolet irradiation, and the binding capacity to the photocatalytic material is improved by increasing the carboxyl groups on the surface thereof, The preparation method includes the following steps:(1)将氟碳纤维膜裁剪成氟碳纤维膜材样条，放置于等离子发生器中进行等离子放电处理；(1) The fluorocarbon fiber membrane is cut into fluorocarbon fiber membrane splines, and placed in a plasma generator for plasma discharge treatment;(2)将氟碳纤维膜材样条进行等离子放电处理后的一面涂覆丙烯酸溶液，将涂覆了丙烯酸溶液的氟碳纤维膜材样条放置在紫外灯下进行接枝反应；(2) Coating acrylic acid solution on one side of the fluorocarbon fiber membrane spline after plasma discharge treatment, placing the fluorocarbon fiber membrane spline coated with the acrylic solution under an ultraviolet lamp to carry out the grafting reaction;(3)将一定量的二水合钨酸钠溶于蒸馏水中得到钨酸钠溶液，通过滴定管滴加五水合硝酸铋溶于硝酸中得到硝酸铋溶液，将钨酸钠溶液与硝酸铋溶液混合均匀后得到前驱体溶液；(3) Dissolve a certain amount of sodium tungstate dihydrate in distilled water to obtain a sodium tungstate solution, add bismuth nitrate pentahydrate and dissolve it in nitric acid through a burette to obtain a bismuth nitrate solution, and mix the sodium tungstate solution and the bismuth nitrate solution evenly Then the precursor solution is obtained;(4)将接枝后的氟碳纤维膜材样条均匀放置于盛有前驱体溶液的水热反应釜中进行水热反应，自然冷却洗涤后，干燥得到负载WO 3修饰Bi 2WO 6的可见光光催化剂的氟碳纤维膜。 ( 4 ) The grafted fluorocarbon fiber membrane splines are evenly placed in a hydrothermal reactor containing the precursor solution for hydrothermal reaction, after natural cooling and washing, drying to obtain visible light loaded with WO3 modified Bi2WO6 Fluorocarbon fiber membranes for photocatalysts.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：所述的氟碳纤维膜为常规市售的以高强玻璃纤维或高强聚脂纤维为基材涂覆涂层的膜材。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, wherein the fluorocarbon fiber membrane is a conventional commercially available high-strength glass fiber or high-strength polyester fiber coated with a coating as a base material. Membrane.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：所述的氟碳纤维膜选自聚四氟乙烯PTFE膜材、聚偏二氟乙烯PVDF膜材或乙烯-四氟乙烯共聚物ETFE膜材中的一种。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, wherein the fluorocarbon fiber membrane is selected from the group consisting of polytetrafluoroethylene PTFE membrane, polyvinylidene fluoride PVDF membrane or ethylene-tetrafluoroethylene One of the vinyl fluoride copolymer ETFE membrane materials.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：步骤(1)中，等离子发生器的放电形式为常压辉光放电或者介质阻挡放电，放电间距1-10mm，放电电压10kV-40kV，放电处理时间0.5-20min。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, wherein in step (1), the discharge form of the plasma generator is atmospheric pressure glow discharge or dielectric barrier discharge, and the discharge spacing is 1-10mm , the discharge voltage is 10kV-40kV, and the discharge treatment time is 0.5-20min.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：步骤(2)中，丙烯酸的涂覆采用旋涂机进行，涂覆转速为100-1000r/min，丙烯酸溶液的质量分数为5-30％，涂覆时间为3-60s。The photocatalyst-loaded fluorocarbon fiber membrane for sewage station according to claim 1, characterized in that: in step (2), the coating of acrylic acid is carried out by a spin coater, and the coating speed is 100-1000 r/min, and the acrylic acid solution The mass fraction is 5-30%, and the coating time is 3-60s.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：步骤(2)中，接枝用紫外灯波长为254nm或者365nm，反应时间1-10min，反应温度20-60℃。The photocatalyst-loaded fluorocarbon fiber membrane for sewage station according to claim 1, characterized in that: in step (2), the wavelength of the ultraviolet lamp used for grafting is 254 nm or 365 nm, the reaction time is 1-10 min, and the reaction temperature is 20-60 nm. °C.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：所述步骤(3)中，前驱体溶液中，硝酸铋溶液的浓度为0.05-0.2mol/L，硝酸的浓度为0.5-5mol/L，钨酸钠溶液的浓度为0.05-0.1mol/L；钨酸钠溶液通过滴定管滴加到硝酸铋溶液中，30-40℃均匀搅拌1-24h，得到混合均匀的前驱体溶液。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, wherein in the step (3), in the precursor solution, the concentration of the bismuth nitrate solution is 0.05-0.2 mol/L, and the concentration of the nitric acid is 0.05-0.2 mol/L. The concentration of sodium tungstate solution is 0.5-5mol/L, and the concentration of sodium tungstate solution is 0.05-0.1mol/L; precursor solution.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：步骤(4)中，水热反应温度为100-180℃，水热反应时间为5-30h。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, wherein in step (4), the hydrothermal reaction temperature is 100-180°C, and the hydrothermal reaction time is 5-30h.
- 根据权利要求1所述的污水站用负载光催化剂的氟碳纤维膜，其特征在于：步骤(4)中， 自然冷却后使用的洗涤液为蒸馏水和乙醇，洗涤次数1-5次；洗涤后膜材干燥温度为40-80℃，干燥时间为4-10h。The photocatalyst-loaded fluorocarbon fiber membrane for a sewage station according to claim 1, characterized in that: in step (4), the washing liquid used after natural cooling is distilled water and ethanol, and the washing times are 1-5 times; The drying temperature is 40-80℃, and the drying time is 4-10h.
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