CN105600879A - Electrocatalytic oxidation reaction device for treating toxic organic wastewater - Google Patents
Electrocatalytic oxidation reaction device for treating toxic organic wastewater Download PDFInfo
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 231100000331 toxic Toxicity 0.000 title claims abstract description 26
- 230000002588 toxic effect Effects 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000003411 electrode reaction Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 40
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 40
- 238000005192 partition Methods 0.000 claims description 24
- 239000006260 foam Substances 0.000 claims description 16
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010815 organic waste Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- -1 oxalic acid modified titanium Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
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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
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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Abstract
Description
技术领域technical field
本发明涉及一种特别适用于有机工业废水深度处理的金属氧化物电极反应装置，属于电化学技术领域。The invention relates to a metal oxide electrode reaction device particularly suitable for advanced treatment of organic industrial wastewater, belonging to the technical field of electrochemistry.
背景技术Background technique
电催化氧化反应技术是利用电化学方法持续产生具有高活性的羟基自由基，使有机物得以降解矿化。传统的电催化氧化反应装置采用的是多组极板装配在同一反应槽中，存在传质效果差，电流效率低，水力停留时间短以及能耗高等缺点。后经过改进，通过引入新型电极、投加药剂等手段，增大了电极的工作面积，改善了传质效果，提高了电流效率，但是，现有的电催化氧化电极反应装置仍有很多不足，具体如下：Electrocatalytic oxidation reaction technology uses electrochemical methods to continuously generate highly active hydroxyl radicals to degrade and mineralize organic matter. The traditional electrocatalytic oxidation reaction device uses multiple sets of plates assembled in the same reaction tank, which has disadvantages such as poor mass transfer effect, low current efficiency, short hydraulic retention time and high energy consumption. After improvement, the working area of the electrode has been increased, the mass transfer effect has been improved, and the current efficiency has been improved by introducing new electrodes and adding chemicals. However, the existing electrocatalytic oxidation electrode reaction device still has many deficiencies. details as follows:
1.现有反应装置采用大容积反应槽内安装多组电极同时工作，造成水力停留时间过长，处理效果和处理效率低下；1. The existing reaction device uses multiple sets of electrodes installed in a large-volume reaction tank to work at the same time, resulting in too long hydraulic retention time and low treatment effect and efficiency;
2.现有电催化氧化电极反应装置对于阳极板的活性表面层利用率低；2. The existing electrocatalytic oxidation electrode reaction device has a low utilization rate of the active surface layer of the anode plate;
3.现有反应装置进水布水设备形式单一，废水容易在反应装置内形成水力学短流或死角，影响处理效果；3. The water inlet and distribution equipment of the existing reaction device has a single form, and the wastewater is easy to form a hydraulic short flow or dead angle in the reaction device, which affects the treatment effect;
4.现有反应装置在使用过程中会放出大量的热，随着工作时间的延长，装置内的温度会不断升高，这会严重影响装置的工作效率和使用寿命；4. The existing reaction device will release a lot of heat during use, and with the extension of working time, the temperature inside the device will continue to rise, which will seriously affect the working efficiency and service life of the device;
5.现有反应装置规格大小不一，不能标准化拼接安装，不适用于水量水质多变的工业废水处理现状。5. Existing reaction devices have different specifications and sizes, cannot be installed in standardized splicing, and are not suitable for the status quo of industrial wastewater treatment with variable water quantity and quality.
发明内容Contents of the invention
本发明的目的在于提供一种用于毒性有机工业废水深度处理的电催化氧化反应装置，用以改变传统金属氧化物电极反应装置构造单一，效率低下，处理效果差以及能耗高的现状。The purpose of the present invention is to provide an electrocatalytic oxidation reaction device for the advanced treatment of toxic organic industrial wastewater, which is used to change the current situation of the traditional metal oxide electrode reaction device with single structure, low efficiency, poor treatment effect and high energy consumption.
为解决上述问题，本发明装置采用如下技术方案：In order to solve the above problems, the device of the present invention adopts the following technical solutions:
一种处理毒性有机废水的电催化氧化反应装置，包括壳体、进水口及出水口，所述壳体内设有多个依次相连的反应槽，所述金属氧化物电极反应装置还包括设置在各所述反应槽内的金属氧化物电极反应单元，各所述金属氧化物电极反应单元包括正极及负极；同一所述金属氧化物电极反应单元内的所述正极是由1个阳极板构成，所述负极是由2个阴极板并联构成，且同一所述金属氧化物电极反应单元内的所述阳极板与所述阴极板是交替间隔且相对设置；所述多个金属氧化物电极反应单元内的所述正极并联，所述负极并联。An electrocatalytic oxidation reaction device for treating toxic organic wastewater, comprising a housing, a water inlet and a water outlet, the housing is provided with a plurality of sequentially connected reaction tanks, and the metal oxide electrode reaction device also includes The metal oxide electrode reaction unit in the reaction tank, each metal oxide electrode reaction unit includes a positive electrode and a negative electrode; the positive electrode in the same metal oxide electrode reaction unit is composed of an anode plate, so The negative electrode is composed of two cathode plates connected in parallel, and the anode plates and the cathode plates in the same metal oxide electrode reaction unit are alternately spaced and oppositely arranged; in the plurality of metal oxide electrode reaction units The positive poles are connected in parallel, and the negative poles are connected in parallel.
在本发明的一实施例中，所述壳体内设置有隔板，所述隔板将所述壳体内的空间分割成多个所述反应槽，且相邻两个所述反应槽之间有缓冲槽间隔，每一所述反应槽内设置有一个所述金属氧化物电极反应单元。In one embodiment of the present invention, a partition is provided inside the housing, and the partition divides the space in the housing into a plurality of reaction tanks, and there is a gap between two adjacent reaction tanks. The buffer tanks are spaced apart, and one metal oxide electrode reaction unit is arranged in each of the reaction tanks.
在本发明的一实施例中，各所述反应槽是由位于进水一侧的第一隔板和位于出水一侧的第二隔板限定，且所述第一隔板比所述第二隔板高。In one embodiment of the present invention, each of the reaction tanks is defined by a first partition on the water inlet side and a second partition on the water outlet side, and the first partition is larger than the second partition. The partitions are high.
在本发明的一实施例中，每一所述金属氧化物电极反应单元的所述阴极板是分别设置在所述第一隔板和所述第二隔板的内壁上。In an embodiment of the present invention, the cathode plates of each metal oxide electrode reaction unit are respectively disposed on inner walls of the first separator and the second separator.
在本发明的一实施例中，所述缓冲槽将一个所述反应槽的顶部和与之相邻的另一个所述反应槽的底部相连通。In an embodiment of the present invention, the buffer tank connects the top of one reaction tank with the bottom of another adjacent reaction tank.
在本发明的一实施例中，各所述反应槽的底部设有布水板，所述布水板上具有多个布水穿孔。In an embodiment of the present invention, a water distribution plate is provided at the bottom of each of the reaction tanks, and the water distribution plate has a plurality of water distribution perforations.
在本发明的一实施例中，所述进水口和所述出水口分别位于所述壳体的两侧，且所述进水口和所述出水口相对位置一致，尺寸一致。In an embodiment of the present invention, the water inlet and the water outlet are respectively located on two sides of the housing, and the relative positions and sizes of the water inlet and the water outlet are consistent.
在本发明的一实施例中，所述处理毒性有机废水的电催化氧化反应装置还包括设置在所述壳体上部的泡沫清除装置。In an embodiment of the present invention, the electrocatalytic oxidation reaction device for treating toxic organic wastewater further includes a foam removal device arranged on the upper part of the housing.
在本发明的一实施例中，所述泡沫清除装置包括：设置在所述壳体上方的清除刮板和电机，用于将所述清除刮板同所述电机相连的传动链条，用于将所述泡沫清除装置清除的泡沫收集的收集槽。In an embodiment of the present invention, the foam removal device includes: a removal scraper and a motor arranged above the housing, a transmission chain for connecting the removal scraper to the motor, and a transmission chain for connecting the removal scraper to the motor. A collection tank into which the foam removed by the foam removal device collects.
在本发明的一实施例中，所述阳极板为钛基锆掺杂纳晶多孔二氧化铅电极或钛基铈掺杂纳晶多孔二氧化铅电极，所述阴极板为草酸改性钛电极。In an embodiment of the present invention, the anode plate is a titanium-based zirconium-doped nanocrystalline porous lead dioxide electrode or a titanium-based cerium-doped nanocrystalline porous lead dioxide electrode, and the cathode plate is an oxalic acid modified titanium electrode .
由于以上技术方案的采用，本发明与现有技术相比有如下优势：Due to the adoption of the above technical solutions, the present invention has the following advantages compared with the prior art:
采用本发明的电催化氧化反应装置来处理废水，有效解决了废水处理不完全导致阳电极表面容易沉积杂质和有机积碳的不足，废水处理效果提高，特别是对于高浓度有机废水的处理效果增强，同时电耗降低，处理成本降低The electrocatalytic oxidation reaction device of the present invention is used to treat wastewater, which effectively solves the problem that impurities and organic carbon deposits are easily deposited on the surface of the positive electrode due to incomplete wastewater treatment, and the wastewater treatment effect is improved, especially for high-concentration organic wastewater. , while reducing power consumption and processing costs
附图说明Description of drawings
图1为根据本发明的处理毒性有机废水的电催化氧化反应装置的结构示意图；Fig. 1 is the structural representation of the electrocatalytic oxidation reaction device of processing toxic organic waste water according to the present invention;
图2为根据本发明的处理毒性有机废水的电催化氧化反应装置的起始端(末端)示意图；Fig. 2 is the initial end (end) schematic diagram of the electrocatalytic oxidation reaction device of processing toxic organic waste water according to the present invention;
图3为根据本发明的处理毒性有机废水的电催化氧化反应装置的布水板示意图；3 is a schematic diagram of a water distribution plate of an electrocatalytic oxidation reaction device for treating toxic organic wastewater according to the present invention;
图4为根据本发明的处理毒性有机废水的电催化氧化反应装置的阳极板(阴极板)示意图；Fig. 4 is the schematic diagram of the anode plate (cathode plate) of the electrocatalytic oxidation reaction device for the treatment of toxic organic waste water according to the present invention;
图5为根据本发明的处理毒性有机废水的电催化氧化反应装置的壳体侧面示意图；Fig. 5 is the schematic side view of the housing of the electrocatalytic oxidation reaction device for treating toxic organic wastewater according to the present invention;
图6为根据本发明的处理毒性有机废水的电催化氧化反应装置的动力装置的示意图；Fig. 6 is the schematic diagram of the power unit of the electrocatalytic oxidation reaction device for treating toxic organic wastewater according to the present invention;
图7为根据本发明的处理毒性有机废水的电催化氧化反应装置的冷却装置的示意图。Fig. 7 is a schematic diagram of a cooling device of an electrocatalytic oxidation reaction device for treating toxic organic wastewater according to the present invention.
其中：1、壳体；2、进水口；3、出水口；4、金属氧化物电极反应单元；40、反应槽；41、阳极板；411、阳极接电柄；42、阴极板；421、阴极接电柄；43、隔板；431、第一隔板；432、第二隔板；44、布水板；441、布水穿孔；5、缓冲槽；51、排渣口；6、出水槽；7、泡沫消除装置；8、动力装置；I、入口；O、出口；9、冷却装置；91、冷凝管道。Among them: 1. shell; 2. water inlet; 3. water outlet; 4. metal oxide electrode reaction unit; 40. reaction tank; 41. anode plate; 411. anode connection handle; 42. cathode plate; 421. Cathode connection handle; 43, partition; 431, first partition; 432, second partition; 44, water distribution plate; 441, water distribution perforation; 5, buffer tank; 51, slag discharge port; 6, outlet Water tank; 7, foam elimination device; 8, power unit; I, inlet; O, outlet; 9, cooling device; 91, condensation pipe.
具体实施方式detailed description
下面，将结合本发明实施例中的附图，对本发明实施例中的技术方案进行详细的描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。In the following, the technical solutions in the embodiments of the present invention will be described in detail with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。It should be noted that, in this document, the term "comprising", "comprising" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article or apparatus comprising a set of elements includes not only those elements, It also includes other elements not expressly listed, or elements inherent in the process, method, article, or apparatus.
参见图1，本发明的处理毒性有机废水的电催化氧化反应装置主要包括壳体1、进水口2、出水口3、五个金属氧化物电极反应单元4、动力装置(参见图6)以及冷却装置(参见图7)。壳体1内的空间通过隔板43被分割成五个反应槽40，每个反应槽40内设置有一个金属氧化物电极反应单元4，从而形成五个各自独立的金属氧化物电极反应单元4。Referring to Fig. 1, the electrocatalytic oxidation reaction device for the treatment of toxic organic wastewater of the present invention mainly includes a housing 1, a water inlet 2, a water outlet 3, five metal oxide electrode reaction units 4, a power unit (see Fig. 6) and cooling device (see Figure 7). The space in the casing 1 is divided into five reaction tanks 40 through the partition 43, and each reaction tank 40 is provided with a metal oxide electrode reaction unit 4, thereby forming five independent metal oxide electrode reaction units 4 .
在本发明中，各所述反应槽40是由位于进水一侧的第一隔板431和位于出水一侧的第二隔板432限定，且所述第一隔板431比所述第二隔板432高。并且，各反应槽40的底部设有布水板44，所述布水板44上具有多个布水穿孔441，如图3所示。结合参考图3，在一较佳实施例中，所述布水穿孔441的半径为4mm，并呈两排平行排列，两排布水穿孔之间的中心间距为10mm，所述布水板44距离所述壳体的底部10cm。In the present invention, each of the reaction tanks 40 is defined by a first partition 431 on the water inlet side and a second partition 432 on the water outlet side, and the first partition 431 is larger than the second partition 432. The bulkhead 432 is tall. Moreover, a water distribution plate 44 is provided at the bottom of each reaction tank 40, and the water distribution plate 44 has a plurality of water distribution perforations 441, as shown in FIG. 3 . With reference to Fig. 3, in a preferred embodiment, the radius of the water distribution perforation 441 is 4mm, and they are arranged in two parallel rows, the center distance between the two rows of water distribution perforations is 10mm, and the water distribution plate 44 10 cm from the bottom of the housing.
在本发明中，相邻的两个反应槽40之间可通过缓冲槽5在顶部或底部相连通。在如图1所示的实施例中，相邻两个反应槽40之间是通过一个缓冲槽5作为间隔，将一个反应槽40的顶部的出水口和与之相邻的另一个反应槽40的底部的布水板44相连通。优选的，所述缓冲槽的宽度为2～4cm。通过所述缓冲槽连接各个金属氧化物电极反应单元，可以充分利用所述阳极板的表面活性层，使进入所述金属氧化物电极反应装置的废水全部经过所述阳极板的表明活性层，使废水得到充分处理。In the present invention, two adjacent reaction tanks 40 can communicate at the top or bottom through the buffer tank 5 . In the embodiment shown in Figure 1, a buffer tank 5 is used as a gap between two adjacent reaction tanks 40, and the water outlet on the top of one reaction tank 40 is connected to another reaction tank 40 adjacent to it. The water distribution plate 44 at the bottom is connected. Preferably, the buffer tank has a width of 2-4 cm. Connecting each metal oxide electrode reaction unit through the buffer tank can make full use of the surface active layer of the anode plate, so that all the waste water entering the metal oxide electrode reaction device passes through the surface active layer of the anode plate, so that Wastewater is adequately treated.
在本发明中，各金属氧化物电极反应单元4包括正极及负极。如图1所示的实施例中，在同一个金属氧化物电极反应单元4内，由1个阳极板41构成正极，由2个阴极板42并联构成负极。并且，在同一金属氧化物电极反应单元4内的所述阳极板41与所述阴极板42是交替间隔且相对设置，例如，将所述阴极板42紧靠所述反应槽40的内壁放置(即分别设置在所述第一隔板431和所述第二隔板432的内壁上)，将所述阳极板41放置在所述反应槽40的中间位置，且与2块所述阴极板42的间距相等，并且，正极与负极之间间距(即图1中阳极板41与阴极板42之间间距)为1～4cm。在各个金属氧化物电极反应单元4之间，多个阳极板41并联，多个阴极板42并联。In the present invention, each metal oxide electrode reaction unit 4 includes a positive electrode and a negative electrode. In the embodiment shown in FIG. 1 , in the same metal oxide electrode reaction unit 4 , one anode plate 41 forms the positive pole, and two cathode plates 42 are connected in parallel to form the negative pole. Moreover, the anode plates 41 and the cathode plates 42 in the same metal oxide electrode reaction unit 4 are alternately spaced and oppositely arranged, for example, the cathode plates 42 are placed close to the inner wall of the reaction tank 40 ( That is, they are respectively arranged on the inner walls of the first partition 431 and the second partition 432), the anode plate 41 is placed in the middle of the reaction tank 40, and is connected with the two cathode plates 42 The spacing between them is equal, and the spacing between the positive electrode and the negative electrode (that is, the spacing between the anode plate 41 and the cathode plate 42 in FIG. 1 ) is 1-4 cm. Between each metal oxide electrode reaction unit 4 , a plurality of anode plates 41 are connected in parallel, and a plurality of cathode plates 42 are connected in parallel.
在本发明中，如图2和图4所示，所述阳极板41和所述阴极板42的尺寸可为500*500mm，且所述阳极板41和所述阴极板42的一边分别焊接有100*50mm的阳极接电柄411和阴极接电柄421，所述阳极接电柄411和所述阴极接电柄421是横向设置并从壳体1的侧壁穿出。在本发明中，所述正极可选自由金属掺杂的钛基二氧化铅极板组成的阳极板群组，极板表面金属氧化物晶粒的平均直径为500nm±100nm；所述负极可选自由800目砂纸打磨处理，草酸改性的钛极板组成的阴极板群组。优选的，可采用钛基锆掺杂纳晶多孔二氧化铅电极或钛基铈掺杂纳晶多孔二氧化铅电极作为所述阳极板。更优选的，所述阳极板采用锆掺杂钛基锡锑二氧化铅纳晶多孔极板，极板表面晶粒粒径为500nm±100nm，所述阴极板采用2％浓度的草酸溶液改性钛板。In the present invention, as shown in FIG. 2 and FIG. 4 , the size of the anode plate 41 and the cathode plate 42 may be 500*500mm, and one side of the anode plate 41 and the cathode plate 42 are respectively welded with An anode connection handle 411 and a cathode connection handle 421 of 100*50 mm are arranged laterally and pass through the side wall of the housing 1 . In the present invention, the positive electrode may be an anode plate group consisting of metal-doped titanium-based lead dioxide plates, and the average diameter of the metal oxide grains on the surface of the plates is 500nm±100nm; the negative electrode may be The cathode plate group is composed of oxalic acid-modified titanium plate after grinding with 800-grit sandpaper. Preferably, a titanium-based zirconium-doped nanocrystalline porous lead dioxide electrode or a titanium-based cerium-doped nanocrystalline porous lead dioxide electrode can be used as the anode plate. More preferably, the anode plate is made of zirconium-doped titanium-based tin-antimony lead dioxide nanocrystalline porous plate, the grain size on the surface of the plate is 500nm±100nm, and the cathode plate is modified with 2% concentration of oxalic acid solution Titanium plate.
在本发明中，所述壳体1还包括设置在壳体末端的出水槽6，所述出水槽6的宽度为10～20cm。所述进水口2和所述出水口3分别位于所述壳体1的两侧，且所述进水口2和所述出水口3的相对位置一致，尺寸一致。例如，结合参考图1和图2，所述进水口2和所述出水口3是设置在所述壳体1的外侧，且所述进水口2是设置在所述壳体1的起始端的底部，其内直径为40cm，所述进水口2的数量可为9个；所述出水口3是设置在所述出水槽6的外侧底部，其内直径为40cm，所述出水口3的数量也为9个。废水通过所述进水管2依次经过五个金属氧化物电极反应单元4处理后汇入出水槽6，从所述出水口3排出。In the present invention, the casing 1 further includes a water outlet groove 6 arranged at the end of the casing, and the width of the water outlet groove 6 is 10-20 cm. The water inlet 2 and the water outlet 3 are located on both sides of the housing 1 respectively, and the relative positions and sizes of the water inlet 2 and the water outlet 3 are consistent. For example, referring to FIG. 1 and FIG. 2, the water inlet 2 and the water outlet 3 are arranged on the outside of the housing 1, and the water inlet 2 is arranged at the starting end of the housing 1. Bottom, its internal diameter is 40cm, and the quantity of described water inlet 2 can be 9; Described water outlet 3 is arranged on the outer bottom of described water outlet tank 6, and its internal diameter is 40cm, and the quantity of described water outlet 3 Also for 9. The waste water passes through the water inlet pipe 2 and is processed by five metal oxide electrode reaction units 4 sequentially, and then flows into the water outlet tank 6 and is discharged from the water outlet 3 .
在本发明中，结合参考图1、图5，所述处理毒性有机废水的电催化氧化反应装置还包括有排渣口51，其可设置在所述缓冲槽5的底部，用于在所述金属氧化物电极反应装置运行过程中可间歇排渣，并取样检测各个金属氧化物电极反应单元的处理效率。在处理效率过低时，减小所述动力装置流速或提高所述反应装置的接入电流电压；在处理效率过高时，例如在图1中的第三、第四排渣口取样检测结果低于检测限时，提高所述动力装置流速或降低所述电催化氧化电极反应装置的接入电流电压。In the present invention, with reference to Fig. 1 and Fig. 5, the electrocatalytic oxidation reaction device for treating toxic organic wastewater also includes a slagging outlet 51, which can be arranged at the bottom of the buffer tank 5 for During the operation of the metal oxide electrode reaction device, the slag can be discharged intermittently, and the processing efficiency of each metal oxide electrode reaction unit can be tested by sampling. When the processing efficiency is too low, reduce the flow rate of the power unit or increase the access current voltage of the reaction device; when the processing efficiency is too high, for example, the third and fourth slag outlets in Fig. When it is lower than the detection limit, increase the flow rate of the power device or reduce the input current and voltage of the electrocatalytic oxidation electrode reaction device.
在本发明中，如图6所示，所述动力装置8用于将废水连续输送到整个电催化氧化反应装置中，其可包括潜水泵、流量计、以及与所述进水口2和所述出水口4相连的管路。较佳地，动力装置8可采用低压高流直流电源，电压0–30V，电流0–1000A可调。其中，动力装置8的第一线路81是与所述金属氧化物电极反应单元4的正极连接，第二线路82是与所述金属氧化物电极反应单元4的负极连接。In the present invention, as shown in FIG. 6 , the power unit 8 is used to continuously deliver waste water to the entire electrocatalytic oxidation reaction device, which may include a submersible pump, a flow meter, and the water inlet 2 and the The pipeline connected to the water outlet 4. Preferably, the power device 8 can adopt a low-voltage high-current DC power supply with an adjustable voltage of 0-30V and an adjustable current of 0-1000A. Wherein, the first line 81 of the power device 8 is connected to the positive pole of the metal oxide electrode reaction unit 4 , and the second line 82 is connected to the negative pole of the metal oxide electrode reaction unit 4 .
在本发明中，如图7所示，所述冷却装置9是用于所述电催化氧化反应装置的冷却，其可包括水箱(图中未示)、循环水泵(图中未示)、以及排布在所述壳体1上的冷凝管道91。所述冷凝管道91具有入口I和出口O，其中冷凝液经由所述入口流入，并经由所述出口流出。较佳地，所述冷却装置9是设置于所述电催化氧化反应装置的壳体外侧或所述电催化氧化反应装置的壳体与金属氧化物电极反应单元之间，用于传递反应单元运行过程中产生的反应热。In the present invention, as shown in Figure 7, the cooling device 9 is used for the cooling of the electrocatalytic oxidation reaction device, which may include a water tank (not shown in the figure), a circulating water pump (not shown in the figure), and Condensation pipes 91 arranged on the casing 1 . The condensation pipe 91 has an inlet I and an outlet O, wherein condensate flows in through the inlet and flows out through the outlet. Preferably, the cooling device 9 is arranged outside the shell of the electrocatalytic oxidation reaction device or between the shell of the electrocatalytic oxidation reaction device and the metal oxide electrode reaction unit, for transferring the operation of the reaction unit The heat of reaction generated in the process.
在本发明中，所述电催化氧化电极反应装置还可包括设置在所述壳体1上部的泡沫清除装置7。所述泡沫消除装置7采用链式刮脱或气体吹脱，用以消除装置运行过程产生的泡沫膨胀问题。所述泡沫清除装置可包括：设置在所述壳体1上方的清除刮板和电机，用于将所述清除刮板同所述电机相连的传动链条，用于将所述泡沫清除装置7清除的泡沫收集的收集槽。In the present invention, the electrocatalytic oxidation electrode reaction device may further include a foam removal device 7 arranged on the upper part of the casing 1 . The foam elimination device 7 adopts chain scraping or gas blowing to eliminate the foam expansion problem generated during the operation of the device. The foam removal device may include: a removal scraper and a motor arranged above the housing 1, a transmission chain for connecting the removal scraper to the motor, and a drive chain for removing the foam removal device 7 collection tank for foam collection.
比较例comparative example
采用本发明的电催化氧化反应装置对进行废水处理的部分条件如下：Adopt the electrocatalytic oxidation reaction device of the present invention to carry out the partial condition of wastewater treatment as follows:
1)废水电导率≥2000μS/cm；1) Wastewater conductivity ≥ 2000μS/cm;
2)潜水泵流量为1～3t/h；2) The flow rate of the submersible pump is 1~3t/h;
3)电压≤10V，电流≤40mA/cm2；3) Voltage ≤ 10V, current ≤ 40mA/cm 2 ;
4)泡沫消除装置工作频率为6～12次/h。4) The working frequency of the foam elimination device is 6-12 times/h.
其他未注明条件参照电催化氧化电极反应装置常规处理条件。For other unspecified conditions, refer to the conventional treatment conditions of the electrocatalytic oxidation electrode reaction device.
应用实例，分别采用传统装置和本发明装置对农药厂含吡啶废水进行处理，对比结果见表1。Application example, the traditional device and the device of the present invention are respectively used to treat pyridine-containing wastewater from pesticide factories, and the comparison results are shown in Table 1.
表1Table 1
由表可知，处理相同浓度的吡啶废水，本发明装置比传统装置在单位时间内处理更多废水，处理效率明显提升，能耗明显下降。在连续运行中，未见阳极板表面有机积碳沉淀，而传统装置在连续运行过程中，处理效率下降明显，阳极板表面有机积碳沉淀堆积。It can be seen from the table that, when treating pyridine wastewater with the same concentration, the device of the present invention can process more wastewater per unit time than the traditional device, the treatment efficiency is significantly improved, and the energy consumption is significantly reduced. During continuous operation, there is no organic carbon deposition on the surface of the anode plate, while the treatment efficiency of the traditional device drops significantly during continuous operation, and the organic carbon deposition on the surface of the anode plate accumulates.
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和应用本发明。任何熟悉本领域的技术人员在本发明揭露的技术范围内，可以轻易对本实施例做出各种修改，并把在此说明的原理应用到其它实例施而不必经过创造性劳动。因此，本发明不限于这里的实施例，不脱离本发明范畴所做出改进和修改都应涵盖在本发明的保护范围之内。The above description of the embodiments is for those of ordinary skill in the technical field to understand and apply the present invention. Any person skilled in the art can easily make various modifications to this embodiment within the technical scope disclosed in the present invention, and apply the principles described here to other embodiments without creative efforts. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made without departing from the scope of the present invention shall be covered within the protection scope of the present invention.
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