CN109516527A - 一种连续流电化学过滤***及其在降解氨氮废水中的应用 - Google Patents
一种连续流电化学过滤***及其在降解氨氮废水中的应用 Download PDFInfo
- Publication number
- CN109516527A CN109516527A CN201811480290.9A CN201811480290A CN109516527A CN 109516527 A CN109516527 A CN 109516527A CN 201811480290 A CN201811480290 A CN 201811480290A CN 109516527 A CN109516527 A CN 109516527A
- Authority
- CN
- China
- Prior art keywords
- anode
- continuous flow
- cathode
- filtration system
- flow electrochemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000001914 filtration Methods 0.000 title claims abstract description 29
- 239000002351 wastewater Substances 0.000 title claims abstract description 18
- 230000015556 catabolic process Effects 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910009848 Ti4O7 Inorganic materials 0.000 claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 18
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 16
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002474 experimental method Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 nitrogenous compound Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明公开了一种连续流电化学过滤***及其在降解氨氮废水中的应用。所述连续流电化学过滤***包括阳极与阴极，其特征在于，所述阳极采用Ti4O7薄膜，阴极采用Pd/Cu改性的Ni泡沫，阳极、阴极相对一侧的表面各设有一层PTFE基底膜，且阳极的一侧为进水口，阴极的一侧为出水口，出水口处设有Ag/AgCl参比电极；阳极、阴极分别通过一集流体与电源的正极、负极连接。本发明采用了膜分离与电化学技术相结合的改进方法，并以一种连续流操作方式进行。在这种体系中，对流强化传质可显著增强目标污染物分子向膜表面活性位点的传递过程，具有易控制和可放大等优点，有望实现工程应用。
Description
技术领域
本发明涉及一种基于Ti4O7阳极的连续流电化学过滤***及其在降解氨氮废水中的应用，属于水处理技术领域。
背景技术
随着经济的快速发展和生活水平的日益提高，致使含氮化合物的排放量急剧增加，氨氮已经给我国的水体环境带来了巨大的压力，引起社会各界的普遍关注。氨氮浓度过高时，会消耗水中大量的氧气，造成水体的富营养化和水生生物的死亡，同时对人体健康也有不利影响。目前国内外广泛采用的氨氮废水处理技术包括离子交换法、折点加氯法、生物法、和光催化法等。例如，离子交换法可采用具有阳离子交换能力的树脂或其他材料，对氨氮废水进行高效处理，但技术成本偏高。生物法则可通过硝化和反硝化作用将氨氮转化为氮气，但是需要对碳源进行精准调控，以维持恒定的C/N比。因此，发展高效、低耗、环保的氨氮降解新技术，对缓解日益严峻的环境压力有着重要的现实意义。
目前，电化学高级氧化技术因为其环保高效的特点成为人们研究的新热点，有望解决氨氮污染的难题。电化学高级氧化技术可以分为电化学直接氧化和间接氧化，电化学直接氧化过程是靠电子转移来实现，而间接氧化过程是通过活性自由基氧化来实现有机污染物的降解。前人将电化学应用于氨氮废水处理已有诸多有益的尝试。例如，Ji等设计了一种新型太阳光驱动的光电催化氯自由基反应***，利用WO3阳极对可见光响应特性，在光照条件下产生光穴，将[Cl-]氧化为Cl·，从而对氨氮进行降解(Water Res.,2017,125,512-519)。尽管氨氮去除效率有所提高，但由于传质过程具有扩散限制，限制了上述***的实际应用。此外，氨氮氧化会产生一定量的硝态氮和亚硝态氮，导致脱氮的不完全。
此外，Liu等的研究表明电化学过滤体系的传质速率比传统序批式体系提升了6倍(J.Phys.Chem.C,2012,116,374-383)。Zhang等的研究表明该阴极对硝态氮的去除速率是Pt阴极的33倍(Environ.Sci.Technol.,2018,52,1413-1420)。
发明内容
本发明所要解决的技术问题是：现有氨氮废水在处理过程中脱氮不完全的问题。
为了解决上述问题，本发明提供了一种连续流电化学过滤***，包括阳极与阴极，其特征在于，所述阳极采用Ti4O7薄膜，阴极采用Pd/Cu改性的Ni泡沫，阳极、阴极相对一侧的表面各设有一层PTFE基底膜，且阳极的一侧为进水口，阴极的一侧为出水口，出水口处设有Ag/AgCl参比电极；阳极、阴极分别通过一集流体与电源的正极、负极连接。
优选地，所述Ti4O7薄膜的制备方法为：将Ti4O7置于容器中，在水中超声1h使之分散均匀；将得到的分散液抽滤到PTFE基底膜上，制成Ti4O7薄膜。
优选地，所述Pd/Cu改性的Ni泡沫的制备方法为：将Ni泡沫依次浸没在浓度0.1M的硫酸、丙酮、去离子水中各超声10-30min去除表面氧化物；将氯化钯、五水合硫酸铜、盐酸溶液置于容器混合均匀，得到混合液；在三电极***中，将作为工作电极的Ni泡沫、作为对电极的Pt，以及作为参比电极的饱和Ag/AgCl电极共同浸入混合液中，在应用电位为-1.0Vvs.Ag/AgCl的条件下进行电沉积实验，沉积完成后即得Pd/Cu改性的Ni泡沫。
更优选地，所述氯化钯的浓度为2mM，五水合硫酸铜的浓度为4mM，盐酸溶液的浓度为0.1M，三者的体积比为1：1：1。
优选地，所述集流体采用Ti棒。
本发明还提供了一种上述连续流电化学过滤***在降解氨氮废水中的应用。
优选地，将硫酸铵溶液导入所述连续流电化学过滤***；然后，控制阳极的电势范围为1～3V vs.Ag/AgCl，pH值的范围为1～12，[Cl-]初始浓度的范围为0.01～1.0mol/L。
优选地，所述硫酸铵溶液的流速为1～10mL/min。
优选地，所述[Cl-]在阳极被氧化生成氯自由基，即Cl·，Cl·选择性地与NH4+反应生成氮气，阳极的副产物进一步在阴极选择性还原为N2。
更优选地，所述阳极的副产物为NO3 -和NO2 -中的至少一种。
本发明采用了膜分离与电化学技术相结合的改进方法，并以一种连续流操作方式进行。在这种体系中，对流强化传质可显著增强目标污染物分子向膜表面活性位点的传递过程，具有易控制和可放大等优点，有望实现工程应用。
本发明采用真空抽滤技术制得Ti4O7薄膜，采用电沉积技术制得的高选择性的阴极改性Ni泡沫，在辅助电场作用下，将氨氮快速高效地转换为氮气，进而实现氨氮废水的高效处理。与现有技术相比，本发明的有益效果在于：
1、该Ti4O7薄膜的制备原料简单易得、制备周期较短、制备条件温和，原料和制备的成本都较低；
2、该Ti4O7薄膜具有高析氧电位，在用于电化学反应中呈现出极强的耐腐蚀和极强的稳定性；
3、在适当的外部电位的作用下，原位阳极氧化[Cl-]可有效且持续地产生Cl·，这些产生的Cl·可选择性地与NH4 +反应生成N2，阳极副反应产生的NO3 -和NO2 -可进一步在选择性阴极还原为N2，阳极和阴极的高孔隙率和对流增强了氨氮的传质和转化性能。
附图说明
图1为本发明提供的连续流电化学过滤***的示意图；
图2为氨氮废水在三种模式下进行电氧化过滤实验的降解效果图。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。
实施例1-3提供的连续流电化学过滤***如图1所示，其包括阳极2与阴极4，所述阳极2采用Ti4O7薄膜，阴极4采用Pd/Cu改性的Ni泡沫，阳极2、阴极4相对一侧的表面各设有一层PTFE基底膜3，且阳极2的一侧为进水口1，阴极4的一侧为出水口7，出水口7处设有Ag/AgCl参比电极6；阳极2、阴极4分别通过一集流体5与电源的正极、负极连接。所述集流体5采用Ti棒。
实施例1
取50mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，Ti4O7薄膜过薄。取150mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约30kΩ，电阻过大。取100mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约10kΩ，电阻过大。取100mg Ti4O7和5mg酸化CNT加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约100Ω，导电性很好，将制备好的Ti4O7薄膜在电化学过滤器中做阳极。
取氯化钯(2mM)、五水合硫酸铜(4mM)、盐酸(0.1M)各100mL于同一烧杯中超声15min使其混合均匀；在三电极***中，采用Ni泡沫为工作电极、Pt为对电极，以及饱和Ag/AgCl为参比电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，将制备好的Pd/Cu改性Ni泡沫在电化学过滤器中做阴极。
实施例2
取100mg Ti4O7和5mg酸化CNT加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上。将制备好的Ti4O7薄膜在电化学过滤器中做阳极。
取氯化钯(2mM)、五水合硫酸铜(4mM)、盐酸(0.1M)各100mL于同一烧杯中超声15min使其混合均匀；在三电极***中，采用Ni泡沫为工作电极、Pt为对电极，以及饱和Ag/AgCl为参比电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，将制备好的Pd/Cu改性Ni泡沫在电化学过滤器中做阴极。
控制阳极电势在1.5V vs.Ag/AgCl，pH为7，Cl-的初始浓度在0.1mol/L，控制流速从1到4mL/min，氨氮去除率从87％上升到大于99％。
实施例3
阳极Ti4O7薄膜和阴极Pd/Cu改性Ni泡沫制备方法与实施例2相同。加入0.175g氯化钠的30mL氨氮废水通过电化学过滤装置后回到原来的烧杯中，然后又重新进入过滤装置进行循环过滤；加入0.175g氯化钠的30mL氨氮废水通过电化学过滤装置后滴入新的烧杯中，做单次过滤实验；加入0.175g氯化钠的30mL氨氮废水进行batch实验。控制阳极电势在2.5Vvs.Ag/AgCl，pH为7，[Cl-]的初始浓度在0.1mol/L。如图2所示，反应1.5h后单次过滤实验的氨氮去除率为11.8％，batch实验的氨氮去除率为63.6％，循环过滤实验的氨氮去除率大于99.9％。
Claims (10)
1.一种连续流电化学过滤***，包括阳极(2)与阴极(4)，其特征在于，所述阳极(2)采用Ti4O7薄膜，阴极(4)采用Pd/Cu改性的Ni泡沫，阳极(2)、阴极(4)相对一侧的表面各设有一层PTFE基底膜(3)，且阳极(2)的一侧为进水口(1)，阴极(4)的一侧为出水口(7)，出水口(7)处设有Ag/AgCl参比电极(6)；阳极(2)、阴极(4)分别通过一集流体(5)与电源的正极、负极连接。
2.如权利要求1所述的连续流电化学过滤***，其特征在于，所述Ti4O7薄膜的制备方法为：将Ti4O7置于容器中，在水中超声1h使之分散均匀；将得到的分散液抽滤到PTFE基底膜(3)上，制成Ti4O7薄膜。
3.如权利要求1所述的连续流电化学过滤***，其特征在于，优选地，所述Pd/Cu改性的Ni泡沫的制备方法为：将Ni泡沫依次浸没在浓度0.1M的硫酸、丙酮、去离子水中各超声10-30min去除表面氧化物；将氯化钯、五水合硫酸铜、盐酸溶液置于容器混合均匀，得到混合液；在三电极***中，将作为工作电极的Ni泡沫、作为对电极的Pt，以及作为参比电极的饱和Ag/AgCl电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，沉积完成后即得Pd/Cu改性的Ni泡沫。
4.如权利要求1所述的连续流电化学过滤***，其特征在于，所述氯化钯的浓度为2mM，五水合硫酸铜的浓度为4mM，盐酸溶液的浓度为0.1M，三者的体积比为1：1：1。
5.如权利要求1所述的连续流电化学过滤***，其特征在于，所述集流体(5)采用Ti棒。
6.一种权利要求1-5任意一项所述的连续流电化学过滤***在降解氨氮废水中的应用。
7.如权利要求6所述的连续流电化学过滤***在降解氨氮废水中的应用，其特征在于，将硫酸铵溶液导入所述连续流电化学过滤***；然后，控制阳极的电势范围为1～3Vvs.Ag/AgCl，pH值的范围为1～12，[Cl-]初始浓度的范围为0.01～1.0mol/L。
8.如权利要求7所述的连续流电化学过滤***在降解氨氮废水中的应用，其特征在于，所述硫酸铵溶液的流速为1～10mL/min。
9.如权利要求6所述的连续流电化学过滤***在降解氨氮废水中的应用，其特征在于，所述[Cl-]在阳极被氧化生成氯自由基，即Cl·，Cl·选择性地与NH4 +反应生成氮气，阳极的副产物进一步在阴极选择性还原为N2。
10.如权利要求9所述的连续流电化学过滤***在降解氨氮废水中的应用，其特征在于，所述阳极的副产物为NO3 -和NO2 -中的至少一种。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811480290.9A CN109516527B (zh) | 2018-12-05 | 2018-12-05 | 一种连续流电化学过滤***及其在降解氨氮废水中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811480290.9A CN109516527B (zh) | 2018-12-05 | 2018-12-05 | 一种连续流电化学过滤***及其在降解氨氮废水中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109516527A true CN109516527A (zh) | 2019-03-26 |
| CN109516527B CN109516527B (zh) | 2022-05-06 |
Family
ID=65794066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811480290.9A Active CN109516527B (zh) | 2018-12-05 | 2018-12-05 | 一种连续流电化学过滤***及其在降解氨氮废水中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109516527B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683616A (zh) * | 2019-10-17 | 2020-01-14 | 东华大学 | 一种连续流光电化学过滤***及其应用 |
| CN111392822A (zh) * | 2020-04-13 | 2020-07-10 | 上海交通大学 | 还原硝态氮为氨氮的方法 |
| CN112250144A (zh) * | 2020-09-25 | 2021-01-22 | 暨南大学 | 一种基于电化学氧化-还原顺序转换的Cr(VI)去除与回收方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473337A (zh) * | 2017-09-22 | 2017-12-15 | 天津碧水源膜材料有限公司 | 电催化膜与三维电极耦合处理难降解废水的装置和方法 |
-
2018
- 2018-12-05 CN CN201811480290.9A patent/CN109516527B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107473337A (zh) * | 2017-09-22 | 2017-12-15 | 天津碧水源膜材料有限公司 | 电催化膜与三维电极耦合处理难降解废水的装置和方法 |
Non-Patent Citations (2)
| Title |
|---|
| YAN ZHANG ET AL: ""Exhaustive conversion of inorganic nitrogen to nitrogen gas based on a photoelectro-chlorine cycle reaction and a highly selective nitrogen gas generation cathode"", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY》 * |
| YANBIAO LIU ET AL: ""Electrochemical wastewater treatment with carbon nanotube filters coupled with in situ generated H2O2"", 《ENVIRONMENTAL SCIENCE: WATER RESEARCH & TECHNOLOGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110683616A (zh) * | 2019-10-17 | 2020-01-14 | 东华大学 | 一种连续流光电化学过滤***及其应用 |
| CN111392822A (zh) * | 2020-04-13 | 2020-07-10 | 上海交通大学 | 还原硝态氮为氨氮的方法 |
| CN112250144A (zh) * | 2020-09-25 | 2021-01-22 | 暨南大学 | 一种基于电化学氧化-还原顺序转换的Cr(VI)去除与回收方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109516527B (zh) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103739043B (zh) | 一种光催化三维电极/电芬顿体系的粒子电极及制备方法 | |
| Cho et al. | Effects of electric voltage and sodium chloride level on electrolysis of swine wastewater | |
| CN109534453B (zh) | 一种氯自由基介导的电化学过滤***及其应用 | |
| CN108423776A (zh) | 一种电容去离子耦合电催化协同去除重金属和有机物的方法 | |
| CN109516527A (zh) | 一种连续流电化学过滤***及其在降解氨氮废水中的应用 | |
| CN102211830B (zh) | 电催化氧化处理切削液废水的方法 | |
| CN110980895B (zh) | 一种从水中电吸附并降解去除抗生素的方法及装置 | |
| CN103435134B (zh) | 一种基于CNTs/Fe3O4三维电-Fenton提高兰炭废水可生化性的方法 | |
| CN102701329A (zh) | 一种多孔纳晶电极的制备方法及其应用 | |
| CN110240221A (zh) | 一种光电催化体系及降解有机污染物同时回收贵金属银的方法 | |
| CN106673140B (zh) | 电化学反应器及电催化去除氯离子的方法 | |
| CN108017120A (zh) | 一种采用新型阳极电催化氧化处理苯酚有机废水的方法 | |
| CN105776441A (zh) | 一种三维多孔钛基体二氧化铅电极及其制备方法和应用 | |
| CN206814454U (zh) | 一种用于污水处理的曝气强化微电解反应装置 | |
| CN112978874A (zh) | 利用流动电极电容去离子装置净化含碘盐废水的方法 | |
| CN106630116B (zh) | 一种强化微生物电化学脱氮的方法与大阴极室连续流生物电化学反应装置 | |
| CN108793344A (zh) | 微流体反应器对低盐废水的电化学氧化处理装置及方法 | |
| CN112723494B (zh) | 电活化过硫酸盐促进难降解有机物与氮元素同步去除的水处理技术 | |
| CN106186593B (zh) | 一种可回收氮磷的尿液废水处理装置及可回收氮磷的方法 | |
| CN205653218U (zh) | 多维电解污水处理设备 | |
| CN104860397A (zh) | 一种电化学-生物流化床反应器及其废水处理方法 | |
| CN109626513A (zh) | 光催化燃料电池与过硫酸盐耦合降解污染物并提高产电的方法 | |
| CN104310671A (zh) | 一种采用间歇供电的三维电极电催化反应器废水处理方法 | |
| CN103420456B (zh) | 一种三维电极除氨氮的方法 | |
| CN113697938B (zh) | 一种微生物燃料电池装置及其耦合电活化过硫酸盐方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240524 Address after: Room 2215, No. 933 Zhongshan West Road, Changning District, Shanghai, 200000 Patentee after: Shanghai Baitan Environmental Technology Co.,Ltd. Country or region after: China Address before: 201600 No. 2999 North Renmin Road, Shanghai, Songjiang District Patentee before: DONGHUA University Country or region before: China |