CN106000130B - 一种PVDF/碳纤维基MFe2O4型光催化导电过滤膜耦合MBR/MFC的方法 - Google Patents
一种PVDF/碳纤维基MFe2O4型光催化导电过滤膜耦合MBR/MFC的方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 42
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 41
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 40
- 238000001914 filtration Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910000708 MFe2O4 Inorganic materials 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 13
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 206010006895 Cachexia Diseases 0.000 description 1
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J35/23—
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明属于新能源与环境污染控制领域,一种PVDF/碳纤维基MFe2O4型光催化导电过滤膜耦合MBR/MFC的方法,采用该膜作为微生物燃料电池的阴极,在生物阳极产电驱动下,阴极辅以光催化提升污染物的去除效率,最后膜过滤出水实现了废水的高效节能处理。该PVDF/碳纤维基MFe2O4光催化导电过滤膜的制备方法如下:在PVDF铸膜液中通过先后添加碳纳米粉末和MFe2O4光催化剂,后以一定厚度涂覆在碳纤维布表面,经相转化法制得了PVDF/碳纤维基MFe2O4光催化导电过滤膜。在H型微生物燃料电池中,将该膜置于阴极,耦合生物产电和光催化及膜过滤实现废水的节能高效处理。
Description
技术领域
本发明属于新能源与环境污染控制领域,特别涉及到耦合生物光电催化与过滤膜实现污水高效处理,提出了一种制备MFe2O4型光催化导电过滤膜在 MBR/MFC体系处理废水的方法。
背景技术
膜生物反应器(Membrane Bioreactor,MBR)是目前废水处理领域常见的二级处理技术,但是膜污染及高能耗两大瓶颈问题严重影响了其广泛应用。近几年,有研究将微生物燃料电池(Microbial Fuel Cell,MFC)与MBR耦合,制备导电膜用作阴极,可大大减缓膜污染程度,提升膜的抗污染性能并延长其使用周期。并且,MFC用作污水处理是往往出水水质不达标准,采用导电膜作为阴极过滤出水,其水质较好,完全达到排放标准。
目前污水处理领域面临的难题较多,并且,各种医药费水,养殖废水、农业废水中含有大量的抗生素,富N有机物、持久性难降解污染物等,这大大增加了废水处理的难度。常规的生化处理法不能将这些污染物高效去除,光催化法可产生羟基自由基、超氧自由基等活性物种,可高效降解水中污染物。将光催化法引入到MFC与MBR耦合体系(MFC/MBR),可实现复杂废水的高效节能处理。徐璇等人(CN103159331A)公开了一种光催化协同微生物燃料电池技术处理污水同时发电的方法及装置,其装置是采用紫外光催化在阳极辅助微生物颜料电池降解废水中有机物好氨氮。李娜娜等人(CN)公开了一种具有导电和光催化功能聚合物/无机物粒子杂化分离膜,在高压反应釜中加入二氧化钛,并与铸膜液高速搅拌后凝固而成。到目前为止,在废水处理领域采用生物阳极产电驱动并在阴极辅以光催化和MBR过滤实现废水处理还未见报道。
发明内容
本发明要解决的技术问题是针对MBR方法处理废水时的膜污染和高能耗问题,制备了一种MFe2O4型光催化剂负载的碳纤维基/PVDF光催化导电过滤膜,并将该膜用在阴极在微生物燃料电池产电驱动下处理污水并辅助光催化及 MBR实现废水的高效处理。
本发明的技术方案:
一种PVDF/碳纤维基MFe2O4型光催化导电过滤膜耦合MBR/MFC的方法,步骤如下:
(1)采用微波加热法制备MFe2O4磁性光催化纳米材料
将三价铁系物和二价金属化合物按照摩尔比为2:1混合,加入乙二醇溶剂中,通过5-13mol/L NaOH溶液调节体系为碱性,搅拌均匀后超声3-20min,然后微波快速加热至溶剂完全蒸发,用去离子水洗涤,过滤,真空干燥得到MFe2O4磁性光催化纳米材料;
所述的三价铁系物是三价铁化合物,如氯化铁、硝酸铁、硫酸铁等;
所述的二价金属化合物包括二价镁化合物,二价锰化合物,二价铁化合物,二价镍化合物,二价锌化合物、二价钴化合物、二价钡化合物等;
(2)PVDF/碳纤维基MFe2O4型光催化导电过滤膜的制备
在质量百分比浓度为5%-16%的PVDF铸膜液中加入碳粉末,碳粉末的质量为PVDF铸膜液质量的1%-10%,搅拌均匀,添加PVDF铸膜液质量的0.5%-10%的MFe2O4磁性光催化纳米材料,继续搅拌,脱泡静置,在碳纤维基上进行涂覆,厚度为200-2000μm,浸水相转化后成膜,得到PVDF/碳纤维基MFe2O4型光催化导电过滤膜;
所述的PVDF铸膜液是PVDF粉末分散在N-甲基吡咯烷酮或N,N-二甲基甲酰胺中,搅拌均匀;PVDF铸膜液的质量百分比浓度是指PVDF质量与总混合体系质量的比值。
所述的碳粉末是碳材料的纳米粒径粉末,如碳纤维粉、碳纳米管、石墨烯、活性炭粉等。
(3)将上述得到的PVDF/碳纤维基MFe2O4型光催化导电过滤膜用在MFC系统阴极,实现MFC、MBR及光催化作用相结合,高效快速的处理污水。
本发明的效果和益处是:
(1)在导电膜基础上制备出光催化导电膜,可进一步提高污水处理效率;
(2)MFe2O4具有光催化特性,在可见光下也具有光催化性能,故制备MFe2O4光催化导电过滤膜在废水处理时可耦合光电催化与过滤出水双重结合,高效节能处理废水。
(3)本发明为废水处理提供了新理念,即采用光催化膜耦合膜过滤、光催化、能源转化等处理工艺,体现多重优势。
附图说明
图1是MFe2O4催化剂在K3Fe(CN)6电解液中的循环伏安图,各催化剂在图中都呈现出氧化还原活性。图中◇表示ZnFe2O4,--表示CoFe2O4,—表示 NiFe2O4,…表示Fe3O4。
图2是PVDF/碳纤维基CoFe2O4光催化导电过滤膜在K3Fe(CN)6电解液中的循环伏安图。图中--表示CoFe2O4添加比例为0.49%,﹎表示CoFe2O4添加比例为1%,—表示CoFe2O4添加比例为1.48%。
图3是采用PVDF/碳纤维基CoFe2O4光催化导电过滤膜在阴极对盐酸四环素的去除效率。图中●表示加光照条件;■表示不加光照条件。
具体实施方式
以下结合技术方案和附图,详细叙述本发明的具体实施方式。
实施例1
称取0.90g FeCl3·6H2O和0.40g CoCl2·6H2O,依次加入50mL乙二醇和20mL5mol/L的NaOH溶液,搅拌均匀后超声5min,然后将溶液倒入微波专用的玻璃皿中,微波加热至溶剂完全蒸发,得到CoFe2O4纳米颗粒。结合产物具有磁性的特征,用去离子水清洗产物,以去除离子杂质,然后用水相滤膜抽滤。将所得固体置于真空干燥箱中进行干燥,最终得到纯净的CoFe2O4纳米颗粒。
在5%PVDF铸膜液中,添加0.2g碳粉末,搅拌均匀,后添加0.1g CoFe2O4,搅拌均匀后,脱泡静置,在平整的玻璃板上铺设一张碳纤维布(厚度约为250 μm),在其表面涂覆200μm的PVDF膜,浸入去离子水中相转化一整夜,得到 PVDF/碳纤维基CoFe2O4光催化导电过滤膜。
采用同样的方法将0.40g CoCl2·6H2O换成0.23g ZnCl2、0.48g Ni(NO3)2·6H2O、0.47g FeSO4·7H2O制备出PVDF/碳纤维基ZnFe2O4(NiFe2O4、 Fe3O4)光催化导电过滤膜。
实施例2
称取0.90g FeCl3·6H2O和0.23g CoCl2·6H2O,依次加入100mL乙二醇和5mL13mol/L的NaOH溶液,搅拌均匀后超声20min,然后将溶液倒入玻璃皿中,微波加热至溶剂完全蒸发,得到CoFe2O4纳米颗粒。结合产物具有磁性的特征,用去离子水清洗产物,以去除离子杂质,然后用水相滤膜抽滤。将所得固体置于真空干燥箱中进行干燥,最终得到纯净的CoFe2O4纳米颗粒。
在16%PVDF铸膜液中,添加2g碳粉末,搅拌均匀,后添加2g CoFe2O4,搅拌均匀后,脱泡静置,在平整的玻璃板上铺设一张碳纤维布(厚度约为250 μm),在其表面涂覆2000μm的PVDF膜,浸入去离子水中相转化一整夜,得到 PVDF/碳纤维基CoFe2O4光催化导电过滤膜。
采用同样的方法将0.40g CoCl2·6H2O换成0.23g ZnCl2、0.48g Ni(NO3)2·6H2O、0.47g FeSO4·7H2O制备出PVDF/碳纤维基ZnFe2O4(NiFe2O4、 Fe3O4)光催化导电过滤膜。
实施例3
称取0.90g FeCl3·6H2O和0.48g CoCl2·6H2O,依次加入80mL乙二醇和8mL7.5mol/L的NaOH溶液,搅拌均匀后置于超声波细胞粉碎机中超声15min,然后将溶液倒入微波专用的玻璃皿中,微波加热至溶剂完全蒸发,得到CoFe2O4纳米颗粒。结合产物具有磁性的特征,用去离子水清洗产物,以去除离子杂质,然后用水相滤膜抽滤。将所得固体置于真空干燥箱中进行干燥,最终得到纯净的CoFe2O4纳米颗粒。
在10%PVDF铸膜液中,添加0.3g碳粉末,搅拌均匀,后添加0.1-0.3g CoFe2O4,搅拌均匀后,脱泡静置,在平整的玻璃板上铺设一张碳纤维布(厚度约为250μm),在其表面涂覆300μm的PVDF膜,浸入去离子水中相转化一整夜,得到PVDF/碳纤维基CoFe2O4光催化导电过滤膜。
采用同样的方法将0.40g CoCl2·6H2O换成0.23g ZnCl2、0.48g Ni(NO3)2·6H2O、0.47g FeSO4·7H2O制备出PVDF/碳纤维基ZnFe2O4(NiFe2O4、 Fe3O4)光催化导电过滤膜。制备的四种MFe2O4光催化剂在5mmol/L的 K3Fe(CN)6和1mol/L KCl溶液中中扫描,测定其循环伏安特性曲线,结果可知 (如图1),催化剂均表现出催化活性。
制备的PVDF/碳纤维基CoFe2O4光催化导电过滤膜在5mmol/L的K3Fe(CN)6和1mol/LKCl溶液中扫描,测定其循环伏安特性曲线,如图2所示。结果表明,该PVDF/碳纤维基CoFe2O4光催化导电过滤膜具有催化活性。
实施例4
将实施例3制备的PVDF/碳纤维基CoFe2O4光催化导电过滤膜置于H型 MFC,作为阴极,阳极采用希瓦氏菌负载的石墨颗粒填充,采用碳棒导出电子,外接电阻,后连接阴极膜,阳极与阴极之间用多孔有机隔板隔开(孔径0.2cm),阴极底部放置曝气(空气)设备。模拟污水先通过阳极,后通过阴极,后经膜减压抽滤出水。运行稳定后,出水中COD处理效率均达到90%以上。阴极室加光照,运行一段时间后,发现系统产能电势在加光后有所提高。说明阴极引入光催化作用后对产能有提升效果。
实施例5
将实施例2制备的PVDF/碳纤维基CoFe2O4光催化导电过滤膜置于MFC(左侧阳极,右侧阴极,左右平行放置)阴极,左侧阳极采用希瓦氏菌负载的石墨颗粒填充,采用碳棒导出电子,外接电阻,后连接阴极膜,阳极与阴极之间采用质子交换膜隔开,阴极底部放置曝气(空气)设备。阳极注入模拟污水,阴极室配制50mg/L的盐酸四环素抗生素溶液,每隔一段时间测试阴极液中盐酸四环素浓度。比较体系在加光不加光条件下对盐酸四环素的降解效率。结果如图3 所示,在加光条件下体系对盐酸四环素的降解速率和降解效率有很大提升。
Claims (5)
1.一种PVDF/碳纤维基MFe2O4型光催化导电过滤膜耦合MBR/MFC的方法,其特征在于,步骤如下:
(1)采用微波加热法制备MFe2O4磁性光催化纳米材料
将三价铁系物和二价金属化合物按照摩尔比为2:1混合,加入乙二醇溶剂中,通过5-13mol/L NaOH溶液调节体系为碱性,搅拌均匀后超声3-20 min,然后微波快速加热至溶剂完全蒸发,用去离子水洗涤,过滤,真空干燥得到MFe2O4磁性光催化纳米材料;
(2) PVDF/碳纤维基MFe2O4型光催化导电过滤膜的制备
在质量百分比浓度为5%-16%的PVDF铸膜液中加入碳粉末,碳粉末的质量为PVDF铸膜液质量的1%-10%,搅拌均匀,添加PVDF铸膜液质量的0.5%-10% 的MFe2O4磁性光催化纳米材料,继续搅拌,脱泡静置,在碳纤维基上进行涂覆,厚度为200-2000 μm,浸水相转化后成膜,得到PVDF/碳纤维基MFe2O4型光催化导电过滤膜;
(3)将上述得到的PVDF/碳纤维基MFe2O4型光催化导电过滤膜用在MFC系统阴极,实现MFC、MBR及光催化作用相结合,高效快速地处理污水。
2.根据权利要求1所述的方法,其特征在于,所述的三价铁系物是氯化铁、硝酸铁、硫酸铁中的一种或两种以上混合。
3.根据权利要求1或2所述的方法,其特征在于,所述的二价金属化合物包括二价镁化合物、二价锰化合物、二价铁化合物、二价镍化合物、二价锌化合物、二价钴化合物和二价钡化合物。
4.根据权利要求1或2所述的方法,其特征在于,所述的碳粉末是碳材料的纳米粒径粉末,选自碳纤维粉、碳纳米管、石墨烯或活性炭粉。
5.根据权利要求3所述的方法,其特征在于,所述的碳粉末是碳材料的纳米粒径粉末,选自碳纤维粉、碳纳米管、石墨烯或活性炭粉。
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