CN106830457A - Electrode couples ozone oxidation integral reactor - Google Patents
Electrode couples ozone oxidation integral reactor Download PDFInfo
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 76
- 230000003647 oxidation Effects 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 113
- 238000006243 chemical reaction Methods 0.000 claims description 86
- 238000005868 electrolysis reaction Methods 0.000 claims description 67
- 239000003054 catalyst Substances 0.000 claims description 62
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 238000005273 aeration Methods 0.000 claims description 24
- 238000005192 partition Methods 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000006378 damage Effects 0.000 claims description 9
- 238000004062 sedimentation Methods 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011152 fibreglass Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 3
- 230000001154 acute effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 25
- 238000011282 treatment Methods 0.000 abstract description 16
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 43
- 239000003344 environmental pollutant Substances 0.000 description 32
- 231100000719 pollutant Toxicity 0.000 description 32
- 239000007789 gas Substances 0.000 description 30
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 230000005684 electric field Effects 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
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- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- 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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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Abstract
本发明涉及一种污水处理装置，特别涉及一种将电极技术和臭氧氧化技术耦合处理污水的反应器。本发明将电极技术和臭氧氧化技术在同一反应器中实现耦合，提供一种设备成本低，零部件耗用少，可规避臭氧氧化选择性的缺点，极大提高臭氧氧化效率，降低臭氧用量，缩短臭氧反应时间，达到有效处理生化出水和提高处理效率的电极耦合臭氧氧化一体式反应器。
The invention relates to a sewage treatment device, in particular to a reactor for coupling electrode technology and ozone oxidation technology to treat sewage. In the present invention, the electrode technology and the ozone oxidation technology are coupled in the same reactor to provide a device with low cost and less component consumption, which can avoid the shortcomings of ozone oxidation selectivity, greatly improve the efficiency of ozone oxidation, and reduce the amount of ozone used. Shorten the ozone reaction time, achieve the effective treatment of biochemical effluent and improve the treatment efficiency of the electrode-coupled ozone oxidation integrated reactor.
Description
技术领域technical field
本发明涉及一种污水处理装置，特别涉及一种将电极技术和臭氧氧化技术耦合处理污水的反应器。The invention relates to a sewage treatment device, in particular to a reactor for coupling electrode technology and ozone oxidation technology to treat sewage.
背景技术Background technique
臭氧氧化技术在水处理领域得到了广泛应用，如城市给水的杀菌消毒、工业废水的深度处理等。目前该技术在有机废水特别是难生物降解有机废水处理方法受到越来越多的重视。但由于其氧化选择性、臭氧利用率低、运行成本高等问题，臭氧氧化技术的推广应用受到了严重限制。臭氧作为一种强氧化剂可直接将有机物氧化分解，但其与有机物的反应具有较强的选择性，往往只能使废水中大分子有机物转变为小分子有机物，产生羟基自由基的效率也较低。Ozone oxidation technology has been widely used in the field of water treatment, such as sterilization and disinfection of urban water supply, advanced treatment of industrial wastewater, etc. At present, this technology has received more and more attention in the treatment of organic wastewater, especially refractory organic wastewater. However, due to its oxidation selectivity, low ozone utilization rate, and high operating costs, the popularization and application of ozone oxidation technology has been severely limited. As a strong oxidizing agent, ozone can directly oxidize and decompose organic matter, but its reaction with organic matter has strong selectivity, and often can only convert large molecular organic matter in wastewater into small molecular organic matter, and the efficiency of generating hydroxyl radicals is also low. .
电化学方法治理废水一般无需添加氧化剂，设备简单、体积小，污泥量少，后处理简单，通常被称为“环境友好”的绿色氧化技术。同时，传统的三维电极反应处理难生物降解有机废水，多数以简单的外加电场作用下进行有机废水的电化学降解，因此废水中有机污染物的转化和去除效率不高，无法实现废水中有机物的转化。Electrochemical treatment of wastewater generally does not require the addition of oxidants, the equipment is simple, the volume is small, the amount of sludge is small, and the post-treatment is simple. It is often called an "environmentally friendly" green oxidation technology. At the same time, the traditional three-dimensional electrode reaction treatment of refractory organic wastewater is mostly electrochemically degraded under the action of a simple external electric field, so the conversion and removal efficiency of organic pollutants in wastewater is not high, and the organic matter in wastewater cannot be achieved. transform.
臭氧氧化技术与电极技术的结合能够提高废水处理效果，但现有技术只是简单的将电解与臭氧氧化组合，处理效率低、成本高。如申请号为201510816139.8的中国专利申请“一种废水处理装置及通过该装置处理废水的方法”，包括臭氧发生器、三维电极反应器和直流稳压电源，其中在所述三维电极反应器内设有臭氧布气底托，在所述臭氧布气底托下方设有臭氧曝气头，在所述臭氧曝气头上方设有粒子电极、主电极，在所述三维电极反应器的腔体壁上贯通设置有废液进料口和取样口。该技术方案直接在电极反应器内通入臭氧，对废水的处理效率低，不能充分发挥各自作用，存在不可预测的干扰。The combination of ozone oxidation technology and electrode technology can improve the wastewater treatment effect, but the existing technology simply combines electrolysis and ozone oxidation, resulting in low treatment efficiency and high cost. For example, the Chinese patent application with application number 201510816139.8 "a waste water treatment device and a method for treating waste water through the device" includes an ozone generator, a three-dimensional electrode reactor and a DC stabilized power supply, wherein the three-dimensional electrode reactor is equipped with There is an ozone gas distribution bottom bracket, an ozone aeration head is provided below the ozone gas distribution bottom bracket, a particle electrode and a main electrode are arranged above the ozone aeration head, and the cavity wall of the three-dimensional electrode reactor A waste liquid feeding port and a sampling port are arranged through the upper part. This technical solution directly feeds ozone into the electrode reactor, which has a low treatment efficiency for wastewater, cannot fully exert their respective functions, and has unpredictable interference.
如申请号为201610051298.8的中国专利申请“一种臭氧催化氧化与电吸附结合的焦化废水深度处理系统”，该系统包括臭氧催化氧化反应器、臭氧发生器、氧气罐、气液分离装置、过滤器、电吸附装置、回用水箱、浓水箱、产水电磁阀、浓水电磁阀以及连接管道；其中，经过生化处理后并经混凝沉淀后的焦化废水的出口与所述臭氧催化氧化反应器的进水口连接；所述臭氧催化氧化反应器的出水口与气液分离装置连接；所述气液分离装置的出水口与过滤器的入水口连接；所述的过滤器出水口与电吸附装置的入水口相连，电吸附装置的出水口通过产水电磁阀与回用水箱相连，同时通过浓水电磁阀与浓水箱相连。该技术方案中臭氧催化氧化反应器与电吸附装置为简单串联形式，只能各自先后发挥作用，并没有起到真正的协同作用，因而不能克服各自单独处理时存在的缺点。For example, the Chinese patent application with the application number 201610051298.8 "A Advanced Treatment System for Coking Wastewater Combining Ozone Catalytic Oxidation and Electric Adsorption", the system includes an ozone catalytic oxidation reactor, an ozone generator, an oxygen tank, a gas-liquid separation device, and a filter , an electric adsorption device, a recycled water tank, a concentrated water tank, a water production solenoid valve, a concentrated water solenoid valve and connecting pipes; wherein, the outlet of coking wastewater after biochemical treatment and coagulation and precipitation is connected with the ozone catalytic oxidation reactor The water inlet is connected; the water outlet of the ozone catalytic oxidation reactor is connected with the gas-liquid separation device; the water outlet of the gas-liquid separation device is connected with the water inlet of the filter; the water outlet of the filter is connected with the electric adsorption device The water inlet of the electric adsorption device is connected to the water inlet, and the water outlet of the electro-adsorption device is connected to the reuse water tank through the water production solenoid valve, and is connected to the concentrated water tank through the concentrated water solenoid valve. In this technical solution, the ozone catalytic oxidation reactor and the electro-adsorption device are in a simple series connection, and they can only function one after the other, without a real synergistic effect, so they cannot overcome the shortcomings of each of them when they are treated separately.
如专利号为201310236853.0的中国发明专利“一种臭氧尾气强化臭氧氧化废水处理的方法及装置”，该处理装置包括连通的预电解单元和臭氧氧化单元，所述臭氧氧化单元的尾气出口连入预电解单元。该方法使废水首先进入预电解单元进行电解反应，电解反应后的废水流入臭氧氧化单元，在臭氧氧化单元内通入臭氧进行反应，臭氧氧化单元产生的臭氧尾气接入预电解单元中曝气。该技术方案在将预电解单元和臭氧氧化单元串联的同时，又将臭氧尾气通入预电解单元，但预电解单元和臭氧氧化单元彼此仍是两个相对独立的装置，因而设备成本高。For example, the Chinese invention patent No. 201310236853.0 "A Method and Device for Ozone Tail Gas Enhanced Ozonation Oxidation Wastewater Treatment", the treatment device includes a connected pre-electrolysis unit and an ozone oxidation unit, and the tail gas outlet of the ozone oxidation unit is connected to the pre-electrolysis unit. electrolysis unit. In the method, waste water first enters the pre-electrolysis unit for electrolysis reaction, the waste water after the electrolysis reaction flows into the ozonation unit, and ozone is passed into the ozonation unit for reaction, and the ozone tail gas generated by the ozonation unit is connected to the pre-electrolysis unit for aeration. In this technical solution, while the pre-electrolysis unit and the ozone oxidation unit are connected in series, the ozone tail gas is passed into the pre-electrolysis unit, but the pre-electrolysis unit and the ozone oxidation unit are still two relatively independent devices, so the equipment cost is high.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种设备成本低，零部件耗用少，可规避臭氧氧化选择性的缺点，极大提高臭氧氧化效率，降低臭氧用量，缩短臭氧反应时间，达到有效处理生化出水和提高处理效率的电极耦合臭氧氧化一体式反应器。The purpose of the present invention is to overcome the deficiencies of the prior art, to provide a device with low cost, less parts consumption, which can avoid the shortcomings of ozone oxidation selectivity, greatly improve the efficiency of ozone oxidation, reduce the amount of ozone, shorten the ozone reaction time, An electrode-coupled ozone oxidation integrated reactor that can effectively treat biochemical effluent and improve treatment efficiency.
为了达到上述目的，本发明所设计的一种电极耦合臭氧氧化一体式反应器，反应器主体为内部中空，外部封闭的腔室结构，其内部通过隔板分隔为电解反应室和臭氧反应室，且隔板与反应器顶板和反应器底板之间均存在间距，隔板上方的反应器顶板高度低于电解反应室顶板和臭氧反应室顶板高度；隔板上方的反应器顶板与电解反应室侧壁的连接处设有上进水挡板，上进水挡板向电解反应室方向倾斜；电解反应室的顶部设有进水口，电解反应室内设有多组电极板，电极板通过设置在导线管内的导线与外部电源连接；隔板底部设有下进水挡板，下进水挡板向臭氧反应室方向倾斜；臭氧反应室底部设有曝气系统，曝气系统包括进气管和微孔曝气盘，进气管连通臭氧源，微孔曝气盘设置在进气管上；臭氧反应室的顶部设有气体收集罩，气体收集罩为倒置漏斗形，气体收集罩顶端通过排气管与尾气破坏装置连接；气体收集罩下方的臭氧反应室侧壁上设有出水口，出水口为出水堰形式。In order to achieve the above object, a kind of electrode-coupled ozone oxidation integrated reactor designed by the present invention, the main body of the reactor is hollow inside, and the chamber structure of the outside is closed, and its interior is divided into electrolysis reaction chamber and ozone reaction chamber by partition, And there is a distance between the partition plate and the top plate of the reactor and the bottom plate of the reactor, the height of the top plate of the reactor above the partition plate is lower than the height of the top plate of the electrolysis reaction chamber and the top plate of the ozone reaction chamber; There is an upper water inlet baffle at the connection of the wall, and the upper water inlet baffle is inclined to the direction of the electrolysis reaction chamber; the top of the electrolysis reaction chamber is provided with a water inlet, and there are multiple sets of electrode plates in the electrolysis reaction chamber, and the electrode plates are arranged on the wires The wire in the tube is connected to the external power supply; the bottom of the partition is provided with a lower water inlet baffle, and the lower water inlet baffle is inclined to the direction of the ozone reaction chamber; an aeration system is installed at the bottom of the ozone reaction chamber, and the aeration system includes an air inlet pipe and a micropore The aeration pan, the air intake pipe is connected to the ozone source, and the microporous aeration pan is set on the air intake pipe; the top of the ozone reaction chamber is equipped with a gas collection cover, which is in the shape of an inverted funnel, and the top of the gas collection cover passes through the exhaust pipe and the exhaust gas Destroy the connection of the device; the side wall of the ozone reaction chamber under the gas collection hood is provided with a water outlet in the form of a water outlet weir.
作为优选，所述上进水挡板与水平面的夹角为20°-80°。Preferably, the angle between the upper water inlet baffle and the horizontal plane is 20°-80°.
作为优选，所述下进水挡板与水平面的夹角为90°-165°。Preferably, the angle between the lower water inlet baffle and the horizontal plane is 90°-165°.
作为优选，所述电极板通过卡槽固定于电解反应室内；为了与反应器绝缘，并且避免电解过程被腐蚀，卡槽采用玻璃钢、聚四氟乙烯或UPVC材质；电极板的阳极板采用具有钌、铱、钽等稀土元素镀层的钛板，阴极板可采用钛板、石墨板或不锈钢板等材料。Preferably, the electrode plate is fixed in the electrolysis reaction chamber through a card slot; in order to insulate the reactor and avoid corrosion during the electrolysis process, the card slot is made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC; the anode plate of the electrode plate is made of ruthenium , iridium, tantalum and other rare earth elements coated titanium plate, the cathode plate can be made of titanium plate, graphite plate or stainless steel plate and other materials.
作为优选，所述电极板间距为1-500cm，电极板厚度为1-5mm，电极组数为1-10组。Preferably, the distance between the electrode plates is 1-500 cm, the thickness of the electrode plates is 1-5 mm, and the number of electrode groups is 1-10 groups.
作为优选，出水口低于气体收集罩底部10-100cm。Preferably, the water outlet is 10-100 cm lower than the bottom of the gas collection hood.
作为优选，在反应器内通入粉末状催化材料，进行电极耦合臭氧催化氧化反应，可采用固定床形式或者流化床形式；所述的粉末状催化材料，其活性组分对臭氧氧化和电解反应均具有催化性能，属于多效催化剂。As preferably, feed powdery catalytic material in the reactor, carry out electrode coupling ozone catalytic oxidation reaction, can adopt fixed bed form or fluidized bed form; Described powdery catalytic material, its active component is to ozone oxidation and electrolysis The reactions all have catalytic properties and belong to multi-effect catalysts.
所述固定床形式的反应器进行如下改进设计：电解反应室顶板上还设置进水搅拌器，电解反应室底部还设置潜水搅拌器，电解反应室的顶部侧壁上设有进水口；电极板底部还设置承托网，承托网上放置催化剂固体床；臭氧反应室顶部气体收集罩改为三相分离器，三相分离器为倒置漏斗形状，三相分离器顶端通过排气管与尾气破坏装置连接；微孔曝气盘的上方还设置承托网，承托网上放置催化剂固体床，固定床下层为大粒径砾石，固定床中上层为催化剂；三相分离器底部上方的臭氧反应室侧壁上设有出水口，出水口为出水堰形式。The reactor in the form of a fixed bed is designed as follows: a water inlet agitator is also arranged on the top plate of the electrolysis reaction chamber, a submersible agitator is also arranged at the bottom of the electrolysis reaction chamber, and a water inlet is provided on the top side wall of the electrolysis reaction chamber; There is also a supporting net at the bottom, on which a catalyst solid bed is placed; the gas collection cover on the top of the ozone reaction chamber is changed to a three-phase separator, which is in the shape of an inverted funnel, and the top of the three-phase separator is destroyed by the exhaust pipe and the exhaust gas. The device is connected; a supporting net is also set above the microporous aeration disc, and a catalyst solid bed is placed on the supporting net. The lower layer of the fixed bed is large-size gravel, and the middle and upper layers of the fixed bed are catalysts; the ozone reaction chamber above the bottom of the three-phase separator A water outlet is arranged on the side wall, and the water outlet is in the form of a water outlet weir.
作为进一步优选，所述电极板的间距为100-500cm，电极板厚度为1-5mm，电极组数为1-2组；电解反应室中承托网的网孔直径为1-2mm，固定床中的催化剂为球状，其粒径为3-5mm，催化剂固定床的填充度为30%-80%；进水搅拌器的搅拌速率为60-500rad/min，潜水搅拌器的搅拌强度为1-10w/m3；臭氧反应室中承托网采用钛合金材质，网孔直径为5-10mm，砾石粒径为12-30mm，催化剂为球状，其粒径为3-5mm；出水堰堰口底部高度高于三相分离器底部5~50cm；所述的催化剂，是以γ-Al2O3为载体，负载Zn、Ti、Mn、Sn、Fe、Bi中的一种或几种氧化物为活性组分的催化材料；优选的是，所述的γ-Al2O3为球体，直径为3-5mm，活性组分为Ti、Sn和Mn的氧化物，活性组分摩尔比为Ti：Sn：Mn=（10~200）:（1~30）:（5~100）。As a further preference, the distance between the electrode plates is 100-500cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 1-2 groups; the mesh diameter of the supporting net in the electrolysis reaction chamber is 1-2mm, and the fixed bed The catalyst in the catalyst is spherical, its particle size is 3-5mm, and the filling degree of the catalyst fixed bed is 30%-80%; the stirring rate of the water inlet mixer is 60-500rad/min, and the stirring intensity of the submersible mixer is 1- 10w/m 3 ; the support net in the ozone reaction chamber is made of titanium alloy, the mesh diameter is 5-10mm, the gravel particle size is 12-30mm, the catalyst is spherical, and its particle size is 3-5mm; the height of the bottom of the outlet weir 5~50cm higher than the bottom of the three-phase separator; the catalyst is based on γ-Al 2 O 3 as the carrier, and supports one or more oxides of Zn, Ti, Mn, Sn, Fe, Bi as the active The catalytic material of the component; preferably, the γ-Al 2 O 3 is a sphere with a diameter of 3-5mm, the active components are oxides of Ti, Sn and Mn, and the molar ratio of the active components is Ti:Sn : Mn=(10~200):(1~30):(5~100).
所述流化床形式的反应器进行如下改进设计：电解反应室顶板上还设置进水搅拌器，电解反应室底部侧壁上还设置潜水搅拌器，电解反应室的顶部侧壁上设有进水口和催化剂投加口；臭氧反应室顶部气体收集罩改为三相分离器，三相分离器为倒置漏斗形状，外部设有倒置鳞片型叶片，三相分离器顶端通过排气管与尾气破坏装置连接；在三相分离器底部上方还设置斜管沉淀装置，在与斜管沉淀装置底部处于同一水平位置的臭氧反应室侧壁上设有出水口，出水口为出水堰形式。The reactor in the form of a fluidized bed is designed as follows: a water inlet agitator is arranged on the top plate of the electrolysis reaction chamber, a submersible agitator is also arranged on the bottom side wall of the electrolysis reaction chamber, and an inlet agitator is arranged on the top side wall of the electrolysis reaction chamber. Water port and catalyst feeding port; the gas collection cover on the top of the ozone reaction chamber is changed to a three-phase separator, the three-phase separator is in the shape of an inverted funnel, with inverted scale-shaped blades on the outside, and the top of the three-phase separator is destroyed by the exhaust pipe and the exhaust gas. The device is connected; an inclined tube sedimentation device is also installed above the bottom of the three-phase separator, and a water outlet is provided on the side wall of the ozone reaction chamber at the same level as the bottom of the inclined tube sedimentation device, and the water outlet is in the form of an outlet weir.
作为进一步优选，所述隔板呈平行四边形，平行四边形锐角夹角γ为45°-85°；所述电极板的间距为2-20cm，更优选为2-6cm，电极板厚度为1-5mm，电极组数为2-5组；进水搅拌器的搅拌速率为60-500rad/min，潜水搅拌器的搅拌强度为1-10w/m3；出水口底部高度高于三相分离器底部5-50cm；所述斜管倾角为50°-70°；投加的催化剂，是以粉末活性炭为载体，负载Zn、Ti、Mn、Sn、Fe、Bi中的一种或几种氧化物为活性组分的催化材料；优选的是，所述的粉末活性炭颗粒为80-100目，活性组分为Ti、Sn和Mn的氧化物，活性组分摩尔比为Ti：Sn：Mn=（10-200）:（1-30）:（5-100）。As a further preference, the separator is in the shape of a parallelogram, and the included angle γ of the acute angle of the parallelogram is 45°-85°; the distance between the electrode plates is 2-20 cm, more preferably 2-6 cm, and the thickness of the electrode plates is 1-5 mm , the number of electrode groups is 2-5 groups; the stirring rate of the water inlet mixer is 60-500rad/min, the stirring intensity of the submersible mixer is 1-10w/m 3 ; the height of the bottom of the water outlet is higher than the bottom of the three-phase separator 5 -50cm; the inclination angle of the inclined tube is 50°-70°; the catalyst added is based on powdered activated carbon as a carrier, and one or more oxides of Zn, Ti, Mn, Sn, Fe, Bi are loaded as active The catalytic material of component; Preferably, described powder activated carbon particle is 80-100 order, and active component is the oxide compound of Ti, Sn and Mn, and active component molar ratio is Ti:Sn:Mn=(10- 200):(1-30):(5-100).
本发明将电极技术和臭氧氧化技术在同一反应器中实现耦合，工作原理如下：废水进入反应器内，经上进水挡板导流首先进入电解室，进行电极电解氧化还原反应，将废水中环状、长链的大分子有机物进行开环、断链，有效的降低了污染物被氧化所需的化学能，提高后续臭氧氧化的氧化效率，降低了臭氧用量，同时解决了臭氧氧化技术具有选择性的缺点；经初次电解反应后的废水通过隔板与反应器底板之间的空间经下进水挡板导流进入臭氧反应室内，废水在臭氧反应室充分溶解臭氧并进行氧化反应，含饱和臭氧的废水通过隔板与反应器顶板之间的空间在上进水挡板的导流下进入电解反应室，溶解饱和的臭氧在电极处得失电子，迅速进行电极电解和臭氧氧化的耦合反应，废水再经下进水挡板导流重新进入臭氧反应室溶解臭氧，加速气液传质速率，形成稳定的内循环模式，大幅提高臭氧利用效率；数次循环后，气体经气体收集罩并通过尾气破坏装置破坏后排出反应器外，废水经出水堰排出反应器。该技术主要存在以下反应机制：（1）臭氧反应室内，气态臭氧溶解于废水中，臭氧分子在废水酸碱条件下直接氧化污染物；（2）电极体系：阳极板处高氧化电位直接氧化污染物，阴极板处高还原电位直接还原污染物；（3）臭氧电极耦合反应体系：阳极板周围的酸性环境促进臭氧分子直接氧化污染物，阴极板周围的碱性环境促进臭氧产生•OH间接氧化污染物；臭氧分子在阴极得电子产生•O、•O3-等中间产物，间接氧化污染物；氧气分子在阴极得电子与水反应生成H2O2，H2O2可直接氧化污染物；H2O2与臭氧分子具有协同作用，反应可产生•OH。In the present invention, the electrode technology and the ozone oxidation technology are coupled in the same reactor, and the working principle is as follows: the waste water enters the reactor, and firstly enters the electrolysis chamber through the upper water inlet baffle to carry out the electrode electrolysis redox reaction, and the waste water Ring-shaped and long-chain macromolecular organics are opened and chain-broken, which effectively reduces the chemical energy required for the oxidation of pollutants, improves the oxidation efficiency of subsequent ozone oxidation, reduces the amount of ozone, and solves the problem of ozone oxidation technology. The disadvantage of selectivity; the waste water after the initial electrolysis reaction passes through the space between the partition plate and the bottom plate of the reactor and enters the ozone reaction chamber through the space between the lower water inlet baffle, and the waste water fully dissolves ozone in the ozone reaction chamber and undergoes oxidation reaction, containing The ozone-saturated wastewater enters the electrolysis reaction chamber through the space between the separator and the top plate of the reactor under the diversion of the upper inlet baffle, and the dissolved and saturated ozone gains and loses electrons at the electrode, and the coupled reaction of electrode electrolysis and ozone oxidation rapidly proceeds , the waste water re-enters the ozone reaction chamber to dissolve ozone through the diversion of the lower water inlet baffle, accelerates the gas-liquid mass transfer rate, forms a stable internal circulation mode, and greatly improves the ozone utilization efficiency; after several cycles, the gas passes through the gas collection hood and After being destroyed by the tail gas destruction device, it is discharged out of the reactor, and the waste water is discharged out of the reactor through the outlet weir. The technology mainly has the following reaction mechanism: (1) In the ozone reaction chamber, gaseous ozone is dissolved in the wastewater, and the ozone molecules directly oxidize pollutants under the acid-base condition of the wastewater; (2) Electrode system: the high oxidation potential at the anode plate directly oxidizes the pollution (3) Ozone electrode coupling reaction system: the acidic environment around the anode plate promotes the direct oxidation of pollutants by ozone molecules, and the alkaline environment around the cathode plate promotes the generation of ozone and the indirect oxidation of OH Pollutants; Ozone molecules get electrons at the cathode to produce intermediate products such as •O, •O3 - , which indirectly oxidize pollutants; Oxygen molecules get electrons at the cathode and react with water to generate H 2 O 2 , H 2 O 2 can directly oxidize pollutants; H 2 O 2 has a synergistic effect with ozone molecules, and the reaction can produce •OH.
本发明固定床形式的反应器将三维电极技术和臭氧催化氧化技术组合于同一反应器中，以固定床形式同步实现了两项技术的串联应用和耦合应用；工作原理如下：废水进入反应器内，经上进水挡板和进水搅拌器导流首先进入电解室，配合固定床中的催化剂进行三维电极电解氧化还原反应，将废水中环状、长链的大分子有机物进行开环、断链，有效的降低了污染物被氧化所需的化学能，提高后续臭氧氧化的氧化效率，降低了臭氧用量，同时解决了臭氧氧化技术具有选择性的缺点；经初次电解反应后的废水在潜水搅拌器的推流作用下，通过隔板与反应器底板之间的空间经下进水挡板导流进入臭氧反应室内，废水和固定床中的催化剂在臭氧反应室充分溶解臭氧并进行催化氧化反应，含饱和臭氧的废水通过隔板与反应器顶板之间的空间在上进水挡板的导流下进入电解反应室，溶解饱和的臭氧在三维电极处得失电子，迅速进行三维电极和臭氧催化氧化的耦合反应，废水再经下进水挡板导流重新进入臭氧反应室溶解臭氧，加速气液传质速率，形成稳定的内循环模式，大幅提高臭氧利用效率；数次循环后废水经三相分离器分离，气体经尾气破坏装置排出反应器外，催化剂留在反应器内循环反应，废水经出水堰排出反应器。以固定床形式在反应器内添加催化剂，相比二维电极，极大的提高了臭氧与污染物接触的比表面积、电极体系面体比，协同活性组分的催化效能，使反应效率大大提高；主要存在以下反应机制：（1）臭氧催化氧化体系，气态臭氧溶解于废水中，臭氧分子在废水中直接氧化污染物，污染物和臭氧分子被吸附于催化剂表面，催化剂表面的活性位点参与水中臭氧分解反应，加速臭氧分解产生•OH的速率；污染物在金属氧化物表面形成易与臭氧分子反应的络合物；（2）三维电极体系：阳极板处高氧化电位直接氧化污染物，阴极板处高还原电位直接还原污染物，催化剂在电场中因静电感应而带电，每个催化剂颗粒均形成微小原电池，污染物吸附于催化剂表面被电解降解，大大提高了电解的面体比，电流效率提升，反应能耗下降；（3）三维电极耦合臭氧催化氧化反应体系：阳极板周围的酸性环境促进臭氧分子直接氧化污染物，阴极板周围的碱性环境促进臭氧产生•OH间接氧化污染物；臭氧分子在阴极和催化剂表面得电子产生•O、•O3-等中间产物，间接氧化污染物；氧气分子在阴极得电子与水反应生成H2O2，H2O2可直接氧化污染物；H2O2与臭氧分子具有协同作用，反应可产生•OH；催化剂在电场静电感应条件下形成原电池，催化剂负载的金属氧化物在通电条件与O2反应产生•OH，污染物、臭氧分子吸附于催化剂表面，与新生态•OH迅速接触，反应效率大大提高（4）催化剂体系：Sn和Ti两种金属氧化物具有协同作用，臭氧分子和电场均可利用SnO2和TiO2导带能级相差0.5V的特性，在臭氧及其中间产物氧化作用下或电场作用下，TiO2表面电子向SnO2移动，在TiO2表面形成电子空穴，SnO2可减少TiO2表面电子与空穴复合几率，空穴具有极强的氧化性，易与水和氧气产生•OH。The reactor in the form of a fixed bed of the present invention combines the three-dimensional electrode technology and the ozone catalytic oxidation technology in the same reactor, and simultaneously realizes the serial application and coupled application of the two technologies in the form of a fixed bed; the working principle is as follows: the waste water enters the reactor , through the upper water inlet baffle and water inlet agitator diversion, first enter the electrolysis chamber, cooperate with the catalyst in the fixed bed to carry out three-dimensional electrode electrolytic redox reaction, and open the ring and long chain macromolecular organic substances in the wastewater. Chain, which effectively reduces the chemical energy required for the oxidation of pollutants, improves the oxidation efficiency of subsequent ozone oxidation, reduces the amount of ozone, and solves the selective shortcomings of ozone oxidation technology; the wastewater after the initial electrolysis reaction Under the action of the push flow of the agitator, the water flows into the ozone reaction chamber through the space between the partition plate and the bottom plate of the reactor through the lower water baffle, and the wastewater and the catalyst in the fixed bed fully dissolve ozone in the ozone reaction chamber and carry out catalytic oxidation Reaction, the wastewater containing saturated ozone enters the electrolysis reaction chamber through the space between the separator and the top plate of the reactor under the diversion of the upper inlet baffle, and the dissolved and saturated ozone gains and loses electrons at the three-dimensional electrode, and the three-dimensional electrode and ozone The coupling reaction of catalytic oxidation, the waste water enters the ozone reaction chamber to dissolve ozone through the diversion of the lower water inlet baffle, accelerates the gas-liquid mass transfer rate, forms a stable internal circulation mode, and greatly improves the ozone utilization efficiency; after several cycles, the waste water is passed through The three-phase separator is separated, the gas is discharged out of the reactor through the tail gas destruction device, the catalyst is left in the reactor to circulate and react, and the waste water is discharged out of the reactor through the outlet weir. The catalyst is added in the reactor in the form of a fixed bed. Compared with the two-dimensional electrode, the specific surface area of the contact between ozone and pollutants and the surface-to-body ratio of the electrode system are greatly improved, and the catalytic performance of the active components is coordinated to greatly improve the reaction efficiency; There are mainly the following reaction mechanisms: (1) Ozone catalytic oxidation system, gaseous ozone dissolves in wastewater, ozone molecules directly oxidize pollutants in wastewater, pollutants and ozone molecules are adsorbed on the catalyst surface, and the active sites on the catalyst surface participate in the water Ozone decomposition reaction accelerates the rate of OH produced by ozone decomposition; pollutants form complexes on the surface of metal oxides that are easy to react with ozone molecules; (2) Three-dimensional electrode system: the high oxidation potential at the anode plate directly oxidizes pollutants, and the cathode The high reduction potential at the plate directly reduces pollutants. The catalyst is charged due to electrostatic induction in the electric field. Each catalyst particle forms a tiny primary battery. The pollutants are adsorbed on the surface of the catalyst and degraded by electrolysis, which greatly improves the surface-to-body ratio of electrolysis and improves the current efficiency. , the reaction energy consumption is reduced; (3) three-dimensional electrode coupling ozone catalytic oxidation reaction system: the acidic environment around the anode plate promotes the direct oxidation of pollutants by ozone molecules, and the alkaline environment around the cathode plate promotes the generation of ozone. OH indirectly oxidizes pollutants; ozone Molecules gain electrons at the cathode and the surface of the catalyst to produce intermediate products such as O, O 3 -, and indirectly oxidize pollutants; oxygen molecules gain electrons at the cathode and react with water to generate H 2 O 2 , which can directly oxidize pollutants ; H 2 O 2 has a synergistic effect with ozone molecules, and the reaction can produce OH; the catalyst forms a primary battery under the condition of electric field electrostatic induction, and the metal oxide supported by the catalyst reacts with O 2 to produce OH, pollutants and ozone molecules adsorb On the surface of the catalyst, the rapid contact with the new ecology OH greatly improves the reaction efficiency (4) Catalyst system: the two metal oxides of Sn and Ti have a synergistic effect, and both the ozone molecule and the electric field can use the conduction band energy level of SnO 2 and TiO 2 The difference is 0.5V. Under the oxidation of ozone and its intermediate products or under the action of an electric field, electrons on the surface of TiO 2 move to SnO 2 and form electron holes on the surface of TiO 2. SnO 2 can reduce the recombination of electrons and holes on the surface of TiO 2 Possibility, the hole has a strong oxidizing property, and it is easy to generate •OH with water and oxygen.
本发明流化床形式的反应器将三维电极技术和臭氧催化氧化技术组合于同一反应器中，以流化床形式同步实现了两项技术的串联应用和耦合应用；工作原理如下：废水进入反应器内，然后加入粉末催化剂，废水和催化剂的混合物经上进水挡板导流、进水搅拌器推流均质后进入电解反应室，进行三维电解氧化还原反应，将废水中环状、长链的大分子有机物进行开环、断链，有效的降低了污染物被氧化所需的化学能，提高后续臭氧氧化的氧化效率，降低了臭氧用量，同时解决了臭氧氧化技术具有选择性的缺点；经初次电解反应后，在潜水搅拌器的推流作用下，废水和粉末催化剂通过隔板与反应器底板之间的空间经下进水挡板导流进入臭氧反应室内，废水和催化剂在臭氧反应室充分溶解臭氧并进行催化氧化反应，含饱和臭氧的废水和催化剂通过隔板与反应器顶板之间的空间在上进水挡板的导流下进入电解反应室，溶解饱和的臭氧在三维电极处得失电子，迅速进行三维电极和臭氧催化氧化的耦合反应，然后废水和催化剂经下进水挡板导流重新进入臭氧反应室溶解臭氧，加速气液传质速率，形成稳定的内循环模式，大幅提高臭氧利用效率；经数次循环后的废水在三相分离器的作用下实现粉末催化剂、废水和气体的分离，气体经尾气破坏装置排出反应器外，粉末催化剂留在反应器内循环反应，废水先通过斜管沉淀装置沉淀，后经过出水堰排出反应器，水中未被三相分离器分离的粉末催化剂在斜管沉淀装置中进行二次固液分离，避免催化剂流失的同时保证出水SS达标。粉末催化剂以流化态形式在反应器内循环，相比固定床，极大的提高了与臭氧及污染物接触的比表面积，催化效能更加；主要存在以下反应机制：（1）臭氧催化氧化体系，气态臭氧溶解于废水中，臭氧分子在废水中直接氧化污染物，污染物和臭氧分子被吸附于催化剂表面，催化剂表面的活性位点参与水中臭氧分解反应，加速臭氧分解产生·OH的速率；污染物在金属氧化物表面形成易与臭氧分子反应的络合物；（2）三维电极体系：阳极板处高氧化电位直接氧化污染物，阴极板处高还原电位直接还原污染物，催化剂在电场中因静电感应而带电，每个催化剂颗粒均形成微小原电池，污染物吸附于催化剂表面被电解降解，大大提高了电解的面体比，电流效率提升，反应能耗下降；（3）三维电极耦合臭氧催化氧化反应体系：阳极板周围的酸性环境促进臭氧分子直接氧化污染物，阴极板周围的碱性环境促进臭氧产生·OH间接氧化污染物；臭氧分子在阴极得电子产生·O、·O3 -等中间产物，间接氧化污染物；氧气分子在阴极得电子与水反应生成H2O2，H2O2可直接氧化污染物；H2O2与臭氧分子具有协同作用，反应可产生·OH；催化剂在电场静电感应条件下形成原电池，催化剂负载的金属氧化物在通电条件与O2反应产生·OH，污染物、臭氧分子吸附于催化剂表面，与新生态·OH迅速接触，反应效率大大提高。The reactor in the form of a fluidized bed of the present invention combines the three-dimensional electrode technology and the ozone catalytic oxidation technology in the same reactor, and simultaneously realizes the serial application and coupling application of the two technologies in the form of a fluidized bed; the working principle is as follows: the waste water enters the reaction Then add the powdered catalyst, the mixture of waste water and catalyst is diverted through the upper water inlet baffle, pushed and homogenized by the water inlet agitator, and then enters the electrolysis reaction chamber for three-dimensional electrolytic redox reaction. The macromolecular organic matter of the chain is opened and chain broken, which effectively reduces the chemical energy required for the oxidation of pollutants, improves the oxidation efficiency of subsequent ozone oxidation, reduces the amount of ozone, and solves the selective shortcomings of ozone oxidation technology. ; After the initial electrolysis reaction, under the push flow action of the submersible mixer, the waste water and powder catalyst flow into the ozone reaction chamber through the space between the partition plate and the bottom plate of the reactor, and the waste water and catalyst flow into the ozone reaction chamber through the lower water inlet baffle. The reaction chamber fully dissolves ozone and carries out catalytic oxidation reaction. The wastewater and catalyst containing saturated ozone enter the electrolysis reaction chamber through the space between the separator and the top plate of the reactor under the guidance of the upper inlet baffle, and the saturated ozone is dissolved in three dimensions. Electrons are gained and lost at the electrode, and the coupling reaction between the three-dimensional electrode and ozone catalytic oxidation is quickly carried out, and then the wastewater and catalyst are diverted through the lower inlet baffle to re-enter the ozone reaction chamber to dissolve ozone, accelerate the gas-liquid mass transfer rate, and form a stable internal circulation mode , greatly improving the efficiency of ozone utilization; the waste water after several cycles is separated from the powder catalyst, waste water and gas under the action of the three-phase separator, the gas is discharged out of the reactor through the tail gas destruction device, and the powder catalyst remains in the reactor for circulation Reaction, the wastewater is first precipitated through the inclined tube sedimentation device, and then discharged from the reactor through the outlet weir. The powder catalyst in the water that has not been separated by the three-phase separator is subjected to a second solid-liquid separation in the inclined tube sedimentation device to avoid catalyst loss and ensure water outlet SS up to standard. The powder catalyst circulates in the reactor in a fluidized state. Compared with the fixed bed, the specific surface area in contact with ozone and pollutants is greatly improved, and the catalytic efficiency is better. The main reaction mechanism is as follows: (1) Ozone catalytic oxidation system , gaseous ozone dissolves in wastewater, ozone molecules directly oxidize pollutants in wastewater, pollutants and ozone molecules are adsorbed on the catalyst surface, and the active sites on the catalyst surface participate in the ozone decomposition reaction in water, accelerating the rate of ozone decomposition to produce OH; Pollutants form complexes on the surface of metal oxides that are easy to react with ozone molecules; (2) Three-dimensional electrode system: the high oxidation potential at the anode plate directly oxidizes the pollutants, and the high reduction potential at the cathode plate directly reduces the pollutants. Each catalyst particle is charged due to electrostatic induction, and each catalyst particle forms a tiny primary battery. Pollutants are adsorbed on the surface of the catalyst and degraded by electrolysis, which greatly improves the surface-to-body ratio of electrolysis, improves current efficiency, and reduces reaction energy consumption; (3) three-dimensional electrode coupling ozone Catalytic oxidation reaction system: the acidic environment around the anode plate promotes the direct oxidation of pollutants by ozone molecules, and the alkaline environment around the cathode plate promotes the generation of ozone and indirect oxidation of pollutants by OH; the ozone molecules get electrons at the cathode to generate O, O 3 - and other intermediate products, indirectly oxidizing pollutants; oxygen molecules get electrons at the cathode and react with water to generate H 2 O 2 , H 2 O 2 can directly oxidize pollutants; H 2 O 2 has a synergistic effect with ozone molecules, and the reaction can produce OH ;The catalyst forms a primary battery under the condition of electric field electrostatic induction, and the metal oxide supported by the catalyst reacts with O 2 to generate OH under the condition of electrification. Pollutants and ozone molecules are adsorbed on the surface of the catalyst, and quickly contact with the new ecological OH, and the reaction efficiency is greatly improved. .
附图说明Description of drawings
图1为本发明实施例1的结构示意图。Fig. 1 is a schematic structural diagram of Embodiment 1 of the present invention.
图2为本发明实施例2的结构示意图。Fig. 2 is a schematic structural diagram of Embodiment 2 of the present invention.
图3为本发明实施例3的结构示意图。Fig. 3 is a schematic structural diagram of Embodiment 3 of the present invention.
具体实施方式detailed description
下面结合附图对本发明作进一步的描述。The present invention will be further described below in conjunction with the accompanying drawings.
实施例1Example 1
如图1所示，本实施例描述的一种电极耦合臭氧氧化一体式反应器，反应器主体为内部中空，外部封闭的腔室结构，其内部通过隔板1分隔为电解反应室2和臭氧反应室3，且隔板与反应器顶板和反应器底板之间均存在间距，隔板上方的反应器顶板高度低于电解反应室顶板和臭氧反应室顶顶板高度；隔板上方的反应器顶板与电解反应室侧壁的连接处设有上进水挡板4，上进水挡板向电解反应室方向倾斜，上进水挡板与水平面的夹角为20°-80°；电解反应室的顶部设有进水口5，电解反应室内设有多组电极板6，电极板通过卡槽固定于电解反应室内，卡槽采用玻璃钢、聚四氟乙烯或UPVC材质；电极板通过设置在导线管内的导线与外部电源连接，电极板的阳极板采用具有钌、铱、钽等稀土元素镀层的钛板，阴极板采用钛板、石墨板或不锈钢板等材料；极板间距为1-500cm，极板厚度为1-5mm，电极组数为1-10组；隔板底部设有下进水挡板7，下进水挡板向臭氧反应室方向倾斜，下进水挡板与水平面的夹角为90°-165°；臭氧反应室底部设有曝气系统8，曝气系统包括进气管和微孔曝气盘，进气管连通臭氧源，微孔曝气盘设置在进气管上；臭氧反应室的顶部设有气体收集罩9，气体收集罩为倒置漏斗形，气体收集罩顶端通过排气管与尾气破坏装置10连接；气体收集罩下方的臭氧反应室侧壁上设有出水口11，出水口为出水堰形式，出水堰低于气体收集罩底部10-100cm。As shown in Figure 1, an electrode-coupled ozone oxidation integrated reactor described in this embodiment, the main body of the reactor is a hollow chamber structure with a closed exterior, and the interior is divided into an electrolytic reaction chamber 2 and an ozone chamber by a partition 1. Reaction chamber 3, and there is a distance between the partition plate and the reactor top plate and the reactor bottom plate, the height of the reactor top plate above the partition plate is lower than the height of the top plate of the electrolysis reaction chamber and the top plate of the ozone reaction chamber; the height of the reactor top plate above the partition plate The connection with the side wall of the electrolysis reaction chamber is provided with an upper water inlet baffle 4, the upper water inlet baffle is inclined to the direction of the electrolysis reaction chamber, and the angle between the upper water inlet baffle and the horizontal plane is 20°-80°; the electrolysis reaction chamber There is a water inlet 5 on the top of the electrolytic reaction chamber, and there are multiple sets of electrode plates 6 in the electrolytic reaction chamber. The electrode plates are fixed in the electrolytic reaction chamber through the card groove, and the card groove is made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC; the electrode plate is arranged in the wire tube The lead wire of the electrode plate is connected to the external power supply. The anode plate of the electrode plate is made of titanium plate coated with rare earth elements such as ruthenium, iridium, tantalum, and the cathode plate is made of titanium plate, graphite plate or stainless steel plate. The thickness of the plate is 1-5mm, the number of electrode groups is 1-10 groups; the bottom of the separator is provided with a lower water inlet baffle 7, the lower water inlet baffle is inclined to the direction of the ozone reaction chamber, and the angle between the lower water inlet baffle and the horizontal plane 90°-165°; the bottom of the ozone reaction chamber is equipped with an aeration system 8, the aeration system includes an air intake pipe and a microporous aeration plate, the air intake pipe is connected to the ozone source, and the microporous aeration plate is arranged on the air intake pipe; the ozone reaction The top of the chamber is provided with a gas collection cover 9, the gas collection cover is an inverted funnel shape, the top of the gas collection cover is connected to the exhaust gas destruction device 10 through an exhaust pipe; the side wall of the ozone reaction chamber below the gas collection cover is provided with a water outlet 11, The water outlet is in the form of a water outlet weir, and the water outlet weir is 10-100cm lower than the bottom of the gas collection cover.
实施例2Example 2
如图2所示，本实施例描述的一种电极耦合臭氧氧化一体式固定床反应器，反应器主体为内部中空，外部封闭的腔室结构，其内部通过隔板1分隔为电解反应室2和臭氧反应室3，且隔板与反应器顶板和反应器底板之间均存在间距，隔板上方的反应器顶板高度低于电解反应室顶板和臭氧反应室顶顶板高度；隔板上方的反应器顶板与电解反应室侧壁的连接处设有上进水挡板4，上进水挡板向电解反应室方向倾斜，上进水挡板与水平面的夹角为20°-80°；电解反应室的顶部侧壁上设有进水口5，电解反应室顶板上设有进水搅拌器6，电解反应室底部侧壁上设有潜水搅拌器7，进水搅拌器的搅拌速率为60-500rad/min，潜水搅拌器的搅拌强度为1-10w/m3；电解反应室内设有多组电极板8，电极板通过卡槽固定于电解反应室内，卡槽采用玻璃钢、聚四氟乙烯或UPVC材质；电极板通过设置在导线管内的导线与外部电源连接，电极板的阳极板采用具有钌、铱、钽等稀土元素镀层的钛板，阴极板采用钛板、石墨板或不锈钢板等材料，极板间距为100-500cm，极板厚度为1-5mm，电极组数为1-2组；电极板底部设置承托网，承托网上放置催化剂固体床9，承托网的网孔直径为1-2mm，固定床中的催化剂为球状，其粒径为3-5mm，催化剂固定床的填充度为30%-80%；隔板底部设有下进水挡板10，下进水挡板向臭氧反应室方向倾斜，下进水挡板与水平面的夹角为90°-165°；臭氧反应室底部设有曝气系统11，曝气系统包括进气管和微孔曝气盘，进气管连通臭氧源，微孔曝气盘设置在进气管上；微孔曝气盘的上方设置承托网，承托网上放置催化剂固体床12，固定床下层为大粒径砾石13，固定床中上层为催化剂，承托网采用钛合金材质，网孔直径为5-10mm，砾石粒径为12-30mm，催化剂为球状，其粒径为3-5mm；臭氧反应室顶部设有三相分离器14，三相分离器为倒置漏斗形状，三相分离器顶端通过排气管与尾气破坏装置15连接；三相分离器底部上方的臭氧反应室侧壁上设有出水口16，出水口为出水堰形式，出水堰堰口底部高度高于三相分离器底部5~50cm。所述电解反应室和臭氧反应室中的催化剂是以直径为3-5mm的球体γ-Al2O3为载体，负载Ti、Sn和Mn氧化物为活性组分的催化材料，活性组分摩尔比为Ti：Sn：Mn=（10~200）:（1~30）:（5~100）。As shown in Figure 2, an electrode-coupled ozone oxidation integrated fixed-bed reactor described in this embodiment, the main body of the reactor is a cavity structure with a hollow interior and a closed exterior, and the interior is divided into an electrolytic reaction chamber 2 by a partition 1 and the ozone reaction chamber 3, and there is a distance between the partition plate and the reactor top plate and the reactor bottom plate, the height of the reactor top plate above the partition plate is lower than the height of the top plate of the electrolytic reaction chamber and the top plate of the ozone reaction chamber; the reaction above the partition plate The connection between the top plate of the device and the side wall of the electrolysis reaction chamber is provided with an upper water inlet baffle 4, the upper water inlet baffle is inclined to the direction of the electrolysis reaction chamber, and the angle between the upper water inlet baffle and the horizontal plane is 20°-80°; The top side wall of the reaction chamber is provided with a water inlet 5, the top plate of the electrolysis reaction chamber is provided with a water inlet agitator 6, and the bottom side wall of the electrolysis reaction chamber is provided with a submersible agitator 7, and the stirring rate of the water inlet agitator is 60- 500rad/min, the stirring intensity of the submersible mixer is 1-10w/m 3 ; there are multiple groups of electrode plates 8 in the electrolysis reaction chamber, and the electrode plates are fixed in the electrolysis reaction chamber through the card groove, and the card groove is made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC material; the electrode plate is connected to the external power supply through the wire set in the wire tube, the anode plate of the electrode plate is made of titanium plate with rare earth element coating such as ruthenium, iridium, tantalum, etc., and the cathode plate is made of titanium plate, graphite plate or stainless steel plate and other materials , the distance between the pole plates is 100-500cm, the thickness of the pole plates is 1-5mm, and the number of electrode groups is 1-2 groups; the bottom of the electrode plate is provided with a supporting net, and a catalyst solid bed 9 is placed on the supporting net, and the mesh diameter of the supporting net is 1-2mm, the catalyst in the fixed bed is spherical, its particle size is 3-5mm, the filling degree of the catalyst fixed bed is 30%-80%; The plate is inclined towards the direction of the ozone reaction chamber, and the angle between the lower water inlet baffle and the horizontal plane is 90°-165°; the bottom of the ozone reaction chamber is provided with an aeration system 11, and the aeration system includes an air inlet pipe and a microporous aeration disc, The trachea is connected to the ozone source, and the microporous aeration pan is arranged on the air intake pipe; a support net is set above the microporous aeration pan, and a catalyst solid bed 12 is placed on the support net, and the lower layer of the fixed bed is large-sized gravel 13. The upper layer is a catalyst, the support net is made of titanium alloy, the mesh diameter is 5-10mm, the gravel particle size is 12-30mm, the catalyst is spherical, and its particle size is 3-5mm; the top of the ozone reaction chamber is equipped with a three-phase separator 14 , the three-phase separator is in the shape of an inverted funnel, and the top of the three-phase separator is connected to the exhaust gas destruction device 15 through an exhaust pipe; the side wall of the ozone reaction chamber above the bottom of the three-phase separator is provided with a water outlet 16, and the water outlet is an outlet weir Form, the height of the bottom of the outlet weir is 5~50cm higher than the bottom of the three-phase separator. The catalyst in the electrolysis reaction chamber and the ozone reaction chamber is a 3-5mm diameter sphere γ-Al 2 O 3 as a carrier, a catalyst material loaded with Ti, Sn and Mn oxides as active components, and the active component moles The ratio is Ti:Sn:Mn=(10~200):(1~30):(5~100).
实施例3Example 3
如图3所示，本实施例描述的一种电极耦合臭氧氧化一体式流化床反应器，反应器主体为内部中空，外部封闭的腔室结构，其内部通过隔板1分隔为电解反应室2和臭氧反应室3，且隔板与反应器顶板和反应器底板之间均存在间距，隔板呈平行四边形，平行四边形锐角夹角γ为45°-85°；隔板上方的反应器顶板高度低于电解反应室顶板和臭氧反应室顶顶板高度；隔板上方的反应器顶板与电解反应室侧壁的连接处设有上进水挡板4，上进水挡板向电解反应室方向倾斜，上进水挡板与水平面的夹角为20°-80°；电解反应室的顶部侧壁上设有进水口5和催化剂投加口15，电解反应室顶板上设有进水搅拌器6，电解反应室底部侧壁上设有潜水搅拌器7，进水搅拌器的搅拌速率为60-500rad/min，潜水搅拌器的搅拌强度为1-10w/m3；电解反应室内设有多组电极板8，电极板通过卡槽固定于电解反应室内，卡槽采用玻璃钢、聚四氟乙烯或UPVC材质；电极板通过设置在导线管内的导线与外部电源连接，电极板的阳极板采用具有钌、铱、钽等稀土元素镀层的钛板，阴极板采用钛板、石墨板或不锈钢板等材料，极板间距为2-6cm，极板厚度为1-5mm，电极组数为2-5组；隔板底部设有下进水挡板9，下进水挡板向臭氧反应室方向倾斜，下进水挡板与水平面的夹角为90°-165°；臭氧反应室底部设有曝气系统10，曝气系统包括进气管和微孔曝气盘，进气管连通臭氧源，微孔曝气盘设置在进气管上；臭氧反应室顶部设有三相分离器11，三相分离器为倒置漏斗形状，外部设有倒置鳞片型叶片，三相分离器顶端通过排气管与尾气破坏装置12连接；在三相分离器底部上方还设有斜管沉淀装置13，斜管倾角为50°-70°；在与斜管沉淀装置底部处于同一水平位置的臭氧反应室侧壁上设有出水口14，出水口为出水堰形式，出水堰底部高度高于三相分离器底部5-50cm。投加的催化剂是以80-100目的粉末活性炭为载体，负载Ti、Sn和Mn的氧化物为活性组分的催化材料，活性组分摩尔比为Ti：Sn：Mn=（10-200）:（1-30）:（5-100）。As shown in Figure 3, an electrode-coupled ozone oxidation integrated fluidized bed reactor described in this embodiment, the main body of the reactor is hollow inside and a closed chamber structure outside, and the inside of the reactor is divided into an electrolytic reaction chamber by a partition 1 2 and the ozone reaction chamber 3, and there is a distance between the partition plate and the reactor top plate and the reactor bottom plate, the partition plate is a parallelogram, and the angle γ of the acute angle of the parallelogram is 45°-85°; The height is lower than the height of the top plate of the electrolytic reaction chamber and the top plate of the ozone reaction chamber; the connection between the top plate of the reactor above the partition and the side wall of the electrolytic reaction chamber is provided with an upper water inlet baffle 4, and the upper water inlet baffle faces the direction of the electrolytic reaction chamber Inclined, the angle between the upper water inlet baffle and the horizontal plane is 20°-80°; the top side wall of the electrolysis reaction chamber is provided with a water inlet 5 and a catalyst feeding port 15, and the top plate of the electrolysis reaction chamber is provided with a water inlet agitator 6. A submersible mixer 7 is arranged on the side wall of the bottom of the electrolytic reaction chamber. A group of electrode plates 8, the electrode plates are fixed in the electrolytic reaction chamber through the card slot, the card slot is made of glass fiber reinforced plastics, polytetrafluoroethylene or UPVC; Titanium plate coated with rare earth elements such as ruthenium, iridium, tantalum, etc. The cathode plate is made of titanium plate, graphite plate or stainless steel plate. The distance between the plates is 2-6cm, the thickness of the plates is 1-5mm, and the number of electrode groups is 2-5 group; the bottom of the clapboard is provided with a lower water inlet baffle 9, the lower water inlet baffle is inclined to the direction of the ozone reaction chamber, and the angle between the lower water inlet baffle and the horizontal plane is 90°-165°; the bottom of the ozone reaction chamber is provided with an exposure Air system 10, the aeration system comprises air intake pipe and microporous aeration pan, the air intake pipe is connected with the ozone source, and the microporous aeration pan is arranged on the air intake pipe; the top of the ozone reaction chamber is provided with a three-phase separator 11, and the three-phase separator is Inverted funnel shape, with inverted scale-shaped blades on the outside, the top of the three-phase separator is connected to the exhaust gas destruction device 12 through the exhaust pipe; there is also an inclined pipe sedimentation device 13 above the bottom of the three-phase separator, and the inclined pipe has an inclination angle of 50° -70°; On the side wall of the ozone reaction chamber at the same level as the bottom of the inclined tube sedimentation device, a water outlet 14 is provided. The water outlet is in the form of a water outlet weir, and the height of the bottom of the water outlet weir is 5-50cm higher than the bottom of the three-phase separator. The catalyst to be added is a catalytic material with powdered activated carbon of 80-100 mesh as the carrier, and oxides of Ti, Sn and Mn as the active components. The molar ratio of the active components is Ti:Sn:Mn=(10-200): (1-30): (5-100).
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