CN105967279A - A method of micro-plasma arc discharge catalytic water treatment by changing the electrode position - Google Patents
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- 229910052749 magnesium Inorganic materials 0.000 claims description 3
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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Abstract
Description
技术领域technical field
本发明属于环境工程水处理技术领域，涉及一种改变电极位置进行微等离子体弧放电催化水处理方法。The invention belongs to the technical field of environmental engineering water treatment, and relates to a method for catalytic water treatment by micro-plasma arc discharge by changing electrode positions.
背景技术Background technique
在电场作用下，液相放电过程产生的等离子体中含有大量高能活性粒子，对许多分子有破坏作用。这些高能活性粒子与催化剂相结合，能有效提高放电处理效果，促进有机分子分解，因而成为污染处理技术研究和开发的热点。Under the action of an electric field, the plasma generated during the liquid phase discharge process contains a large number of high-energy active particles, which can damage many molecules. The combination of these high-energy active particles and catalysts can effectively improve the discharge treatment effect and promote the decomposition of organic molecules, so it has become a hot spot in the research and development of pollution treatment technology.
以含钛的阀金属作为阳极进行的微弧放电，可在阳极上原位生成的二氧化钛，在放电产生的等离子体中发挥催化作用，强化羟基自由基的形成。也就是说，放电系统形成了一个自然集成的液相等离子体-催化协同系统。同时，阳极上因电解产生的O2气体，提供易放电的气相空间，O2为OH自由基提供反应物；因浮力向上从阳极逃逸中，对等离子体及活性物质的传播起到促进作用。气泡的压力和在阳极停留时间是和周围液体压力相关。In the micro-arc discharge with titanium-containing valve metal as the anode, titanium dioxide can be generated in situ on the anode, which can play a catalytic role in the plasma generated by the discharge and strengthen the formation of hydroxyl radicals. That is, the discharge system forms a naturally integrated liquid-phase plasma-catalysis synergistic system. At the same time, the O 2 gas generated by electrolysis on the anode provides a gas phase space that is easy to discharge, and O 2 provides reactants for OH radicals; due to buoyancy, it escapes from the anode upwards and promotes the propagation of plasma and active materials. The pressure and residence time of the bubbles at the anode are related to the surrounding liquid pressure.
和其他模式的液相放电不同，微弧放电是阳极形成的绝缘氧化膜击穿的过程，受阳极电解产生的O2影响大，O2的状态将影响放电的强度。O2的状态包括气泡内压力、气泡在阳极的滞留情况、气泡从阳极的逃逸特点。因此，优化O2的状态将使液相等离子体-催化系统更好的协同，发挥气泡提供利于放电的气相、提供O2源、促进物质传输的作用。Different from other modes of liquid phase discharge, micro-arc discharge is a breakdown process of the insulating oxide film formed on the anode, which is greatly affected by the O 2 produced by the electrolysis of the anode, and the state of O 2 will affect the intensity of the discharge. The state of O 2 includes the internal pressure of the bubbles, the retention of the bubbles at the anode, and the escape characteristics of the bubbles from the anode. Therefore, optimizing the state of O2 will make the liquid-phase plasma-catalysis system better synergistic, and play the role of bubbles in providing a gas phase that is conducive to discharge, providing O2 sources, and promoting material transport.
发明内容Contents of the invention
根据微弧放电特点，更好地优化反应器，发挥系统的协同作用，本专利提供一种改变电极位置进行微等离子体弧放电催化水处理方法。According to the characteristics of micro-arc discharge, the reactor is better optimized and the synergistic effect of the system is brought into play. This patent provides a method for catalytic water treatment by changing the electrode position and performing micro-plasma arc discharge.
本发明采用的技术手段如下：The technical means adopted in the present invention are as follows:
一种改变电极位置进行微等离子体弧放电催化水处理方法，其特征在于具有如下步骤：A method for micro-plasma arc discharge catalytic water treatment by changing electrode positions, characterized in that it has the following steps:
S1、在待处理液中加入添加剂；S1, adding additives to the liquid to be treated;
S2、打开冷却水循环系统及搅拌系统；S2, open the cooling water circulation system and the stirring system;
S3、将阳极和阴极水平放入到反应池中，所述阳极位于所述阴极的下方，所述阳极尽可能位于所述反应池的最深处，且不与所述反应池接触，阳极置于阴极下，阳极电解产生的O2垂直于阳极表面向上逃逸，对等离子体及活性物质的传播起到促进作用，在同样浸没深度下，阳极在下放置模式比其他放置模式(或阴阳两级垂直放置、或阴极在下的水平放置，或斜放)处理效果更理想。又由于阳极在下，承受的液体压力较其他放置模式大，增加了气泡在阳极的停留，有利于液相放电，阳极尽可能位于液相更深处，且深度增大，则在气泡逸出液体的传质路径更长，可以与液体更为充分的接触并反应，有利于处理效果的提高；S3. Put the anode and the cathode horizontally into the reaction cell, the anode is located below the cathode, the anode is located in the deepest part of the reaction cell as far as possible, and is not in contact with the reaction cell, and the anode is placed Under the cathode, the O2 produced by the electrolysis of the anode escapes upwards perpendicular to the surface of the anode, which promotes the propagation of plasma and active materials. placed, or the cathode is placed horizontally below, or placed obliquely) the treatment effect is more ideal. And because the anode is on the bottom, the liquid pressure it bears is greater than other placement modes, which increases the residence of the bubbles at the anode, which is conducive to liquid phase discharge. The mass transfer path is longer, which can fully contact and react with the liquid, which is conducive to the improvement of the treatment effect;
S4、将含有添加剂的待处理液加入到所述反应池中；S4, adding the liquid to be treated containing additives into the reaction pool;
S5、接通所述阳极和所述阴极之间的电源，并逐渐升高电压，使所述电源在所述电源的参数下稳定放电，通过所述阳极和所述阴极对反应体系施加电压，使阳极表面能够原位生成负载型催化剂进行放电催化；S5. Turn on the power supply between the anode and the cathode, and gradually increase the voltage, so that the power supply is stably discharged under the parameters of the power supply, and apply a voltage to the reaction system through the anode and the cathode, Enable the in-situ generation of supported catalysts on the surface of the anode for discharge catalysis;
S6、分析水处理效果；S6, analyze water treatment effect;
S7、水处理结束，S7, the water treatment is finished,
上述方法根据待处理液的状态不同可分为静态处理方法和动态处理方法，The above methods can be divided into static treatment methods and dynamic treatment methods according to the state of the liquid to be treated.
所述静态处理方法具有如下步骤：The static processing method has the following steps:
1)在待处理液中加入添加剂；1) Add additives in the liquid to be treated;
2)打开冷却水循环系统及搅拌系统；2) Turn on the cooling water circulation system and stirring system;
3)将阳极和阴极水平放入到反应池中，所述阳极位于所述阴极的下方，所述阳极尽可能位于所述反应池的最深处，且不与所述反应池接触；3) Put the anode and the cathode horizontally into the reaction cell, the anode is located below the cathode, the anode is located in the deepest part of the reaction cell as far as possible, and is not in contact with the reaction cell;
4)将含有添加剂的待处理液加入到所述反应池中；4) adding the liquid to be treated containing additives into the reaction pool;
5)接通所述阳极和所述阴极之间的电源，并逐渐升高电压，使所述电源在所述电源的参数下稳定放电；5) Turn on the power supply between the anode and the cathode, and gradually increase the voltage, so that the power supply can discharge stably under the parameters of the power supply;
6)分析水处理效果：定时取样化验待处理液的水质变化，按预先的计算处理时间，并结合化验结果，确定处理结束时间；6) Analyze the water treatment effect: take samples regularly to test the water quality change of the liquid to be treated, calculate the treatment time in advance, and combine the test results to determine the end time of the treatment;
7)水处理结束：逐渐降低电源电压至10-20V后，再依次关闭电源、搅拌系统和冷却水循环系统，7) End of water treatment: gradually reduce the power supply voltage to 10-20V, then turn off the power supply, stirring system and cooling water circulation system in turn,
所述动态处理方法具有如下步骤：The dynamic processing method has the following steps:
1)在待处理液中加入添加剂：在待处理液体输入管道里加入添加剂；1) Add additives to the liquid to be treated: add additives to the input pipeline of the liquid to be treated;
2)打开冷却水循环系统及搅拌系统；2) Turn on the cooling water circulation system and stirring system;
3)将阳极和阴极水平放入到反应池中，所述阳极位于所述阴极的下方，所述阳极尽可能位于所述反应池的最深处，且不与所述反应池接触；3) Put the anode and the cathode horizontally into the reaction cell, the anode is located below the cathode, the anode is located in the deepest part of the reaction cell as far as possible, and is not in contact with the reaction cell;
4)将含有添加剂的待处理液加入到所述反应池中；4) adding the liquid to be treated containing additives into the reaction pool;
5)接通所述阳极和所述阴极之间的电源，并逐渐升高电压，使所述电源在所述电源的参数下稳定放电；5) Turn on the power supply between the anode and the cathode, and gradually increase the voltage, so that the power supply can discharge stably under the parameters of the power supply;
6)分析水处理效果：分析从反应池流出的处理后的水质，根据化验结果，调节液体进出反应池的流量，使处理效果满足要求；6) Analysis of water treatment effect: analyze the treated water quality flowing out of the reaction tank, and adjust the flow of liquid in and out of the reaction tank according to the test results, so that the treatment effect meets the requirements;
7)水处理结束：停止向所述反应池中输入待处理液，逐渐降低电压至10-20V后，再依次关闭电源、搅拌系统及冷却水循环系统。7) End of water treatment: Stop inputting the liquid to be treated into the reaction pool, gradually reduce the voltage to 10-20V, and then turn off the power supply, the stirring system and the cooling water circulation system in sequence.
所述添加剂的浓度为0.5-50g/L，所述添加剂为硅酸钠、碳酸钠、铝酸钠或硫酸钠中的一种或数种。The concentration of the additive is 0.5-50g/L, and the additive is one or more of sodium silicate, sodium carbonate, sodium aluminate or sodium sulfate.
所述阳极的材质为含钛的阀金属及其合金。The material of the anode is titanium-containing valve metal and its alloys.
所述阀金属为钛、镁或铝。The valve metal is titanium, magnesium or aluminum.
所述阳极的形状为板状或针状。The shape of the anode is plate or needle.
所述阳极位于待处理液中的电极表面积为5mm2-1dm2。The electrode surface area of the anode in the liquid to be treated is 5 mm 2 -1 dm 2 .
所述阳极与所述阴极之间的电极间距为2-50mm。The electrode distance between the anode and the cathode is 2-50mm.
所述电源为电压为80V-1kV的直流电源或电压峰值为80V-1kV的单极脉冲电源。The power supply is a DC power supply with a voltage of 80V-1kV or a unipolar pulse power supply with a peak voltage of 80V-1kV.
本发明具有以下优点：The present invention has the following advantages:
阳极置于阴极下，阳极电解产生的O2垂直于阳极方向向上逃逸，对等离子体及活性物质的传播起到促进作用，在同样浸没深度下，阳极在下放置模式比其他放置模式(或阴阳两级垂直放置、或阴极在下的水平放置，或斜放)处理效果更理想。又由于阳极在下，承受的液体压力较其他放置模式大，增加了气泡在阳极的停留，有利于液相放电。且深度增大，则在气泡逸出液体的传质路径更长，可以与液体更为充分的接触并反应，有利于处理效果的提高。The anode is placed under the cathode, and the O2 produced by the electrolysis of the anode escapes upwards perpendicular to the direction of the anode, which promotes the propagation of plasma and active materials. The level is placed vertically, or the cathode is placed horizontally below, or placed obliquely) the treatment effect is more ideal. And because the anode is on the bottom, the liquid pressure it bears is higher than other placement modes, which increases the residence of bubbles at the anode, which is beneficial to liquid phase discharge. And as the depth increases, the mass transfer path for the bubbles to escape from the liquid will be longer, which can fully contact and react with the liquid, which is beneficial to the improvement of the treatment effect.
基于上述理由本发明可在环境工程水处理技术等领域广泛推广。Based on the above reasons, the present invention can be widely promoted in the fields of environmental engineering water treatment technology and the like.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明作进一步详细的说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1是本发明的具体实施方式中水处理装置结构示意图。Fig. 1 is a schematic structural diagram of a water treatment device in a specific embodiment of the present invention.
具体实施方式detailed description
一种改变电极位置进行微等离子体弧放电催化水处理方法，具有如下步骤：A method for micro-plasma arc discharge catalytic water treatment by changing electrode positions, comprising the following steps:
S1、在待处理液中加入添加剂；S1, adding additives to the liquid to be treated;
S2、打开冷却水循环系统及搅拌系统；S2, open the cooling water circulation system and the stirring system;
S3、将阳极和阴极水平放入到反应池中，所述阳极位于所述阴极的下方，所述阳极尽可能位于所述反应池的最深处，且不与所述反应池接触；S3. Put the anode and the cathode horizontally into the reaction cell, the anode is located below the cathode, the anode is located in the deepest part of the reaction cell as far as possible, and is not in contact with the reaction cell;
S4、将含有添加剂的待处理液加入到所述反应池中；S4, adding the liquid to be treated containing additives into the reaction pool;
S5、接通所述阳极和所述阴极之间的电源，并逐渐升高电压，使所述电源在所述电源的参数下稳定放电；S5. Turn on the power supply between the anode and the cathode, and gradually increase the voltage, so that the power supply can discharge stably under the parameters of the power supply;
S6、分析水处理效果；S6, analyze water treatment effect;
S7、水处理结束，S7, the water treatment is finished,
所述添加剂的浓度为0.5-50g/L，所述添加剂为硅酸钠、碳酸钠、铝酸钠或硫酸钠中的一种或数种。The concentration of the additive is 0.5-50g/L, and the additive is one or more of sodium silicate, sodium carbonate, sodium aluminate or sodium sulfate.
所述阳极的材质为含钛的阀金属及其合金。The material of the anode is titanium-containing valve metal and its alloys.
所述阀金属为钛、镁或铝。The valve metal is titanium, magnesium or aluminum.
所述阳极的形状为板状或针状。The shape of the anode is plate or needle.
所述阳极位于待处理液中的电极表面积为5mm2-1dm2。The electrode surface area of the anode in the liquid to be treated is 5 mm 2 -1 dm 2 .
所述阳极与所述阴极之间的电极间距为2-50mm。The electrode distance between the anode and the cathode is 2-50mm.
所述电源为电压为80V-1kV的直流电源或电压峰值为80V-1kV的单极脉冲电源。The power supply is a DC power supply with a voltage of 80V-1kV or a unipolar pulse power supply with a peak voltage of 80V-1kV.
实施例1Example 1
如图1所示，一种采用阳极放置阴极下面来改进微等离子体弧放电催化水处理方法，具有如下步骤：As shown in Figure 1, a method for improving micro-plasma arc discharge catalytic water treatment by placing the anode under the cathode has the following steps:
S1、在待处理液1中加入添加剂；S1, adding additives to the liquid to be treated 1;
S2、打开冷却水循环系统2及磁力搅拌系统3；S2, open the cooling water circulation system 2 and the magnetic stirring system 3;
S3、将阳极4和阴极5水平放入到反应池6中，所述阳极4位于所述阴极5的下方，所述阳极4尽可能位于所述反应池6的最深处，且不与所述反应池6接触，所述阳极4和所述阴极5的几何中心在液面下深度为65mm；S3, put the anode 4 and the cathode 5 into the reaction cell 6 horizontally, the anode 4 is located below the cathode 5, the anode 4 is located in the deepest part of the reaction cell 6 as far as possible, and is not connected to the reaction cell 6. The reaction pool 6 is in contact, and the geometric center of the anode 4 and the cathode 5 is 65mm below the liquid surface;
S4、将含有添加剂的待处理液1加入到所述反应池6中；S4, adding the liquid to be treated 1 containing additives into the reaction tank 6;
S5、接通所述阳极4和所述阴极5之间的电源7，并逐渐升高电压，使所述电源7在所述电源7的参数下稳定放电；S5, switch on the power supply 7 between the anode 4 and the cathode 5, and gradually increase the voltage, so that the power supply 7 is stably discharged under the parameters of the power supply 7;
S6、分析水处理效果：定时取样化验待处理液1的水质变化，按预先的计算处理时间，并结合化验结果，确定处理结束时间；S6. Analyze the water treatment effect: regularly take samples to test the water quality change of the liquid 1 to be treated, calculate the treatment time in advance, and combine the test results to determine the treatment end time;
S7、水处理结束：逐渐降低电源7电压至10-20V后，再依次关闭电源7、磁力搅拌系统3和冷却水循环系统2，S7, the end of water treatment: gradually reduce the voltage of the power supply 7 to 10-20V, then turn off the power supply 7, the magnetic stirring system 3 and the cooling water circulation system 2 in sequence,
所述阳极4的材质为钛铝合金，包括以下重量份的物质：钛：70份，铝：30份，以及不可避免的微量元素，所述阴极5的材质为不锈钢，The material of the anode 4 is titanium aluminum alloy, including the following materials in parts by weight: titanium: 70 parts, aluminum: 30 parts, and unavoidable trace elements, and the material of the cathode 5 is stainless steel,
所述电源7是电压为500V的直流电源。The power supply 7 is a DC power supply with a voltage of 500V.
所述阳极4与所述阴极5之间的电极间距为10mm。The electrode distance between the anode 4 and the cathode 5 is 10mm.
所述阳极4位于待处理液1中的电极表面积为8000mm2。The electrode surface area of the anode 4 located in the liquid to be treated 1 is 8000mm 2 .
所述阳极4和所述阴极5的形状为板状。The shape of the anode 4 and the cathode 5 is plate.
本实施例中以添加有艳红B的蒸馏水模拟待处理液1，所述艳红B属偶氮类染料弱酸性染料，是印染工业及纺织业中常用的染料，且含有苯环，用化学和生物等方法处理该类废水的效果均不理想。艳红B溶液的初始浓度为20mg/L，所述待处理液1的含量为1500mL。In this embodiment, the distilled water added with Brilliant Red B is used to simulate the liquid 1 to be treated. The Brilliant Red B belongs to the weak acid dye of azo dyes, is a dye commonly used in the printing and dyeing industry and the textile industry, and contains a benzene ring. The effect of treating this kind of wastewater by biological and biological methods is not ideal. The initial concentration of Brilliant Red B solution is 20 mg/L, and the content of the liquid to be treated 1 is 1500 mL.
处理待处理液1的过程中，通过紫外-可见分光光度计测量待处理液1的最大吸收波长处的吸光度变化，以反映艳红B溶液的脱色效果。During the process of treating the liquid 1 to be treated, the change of absorbance at the maximum absorption wavelength of the liquid 1 to be treated is measured by an ultraviolet-visible spectrophotometer to reflect the decolorization effect of the Brilliant Red B solution.
实验结果表明，所述阳极4在所述阴极5之下的放置模式比阳极4在上阴极5在下的放置模式，6min时处理效果提高5％。Experimental results show that the placement pattern of the anode 4 below the cathode 5 is higher than the placement pattern of the anode 4 on the top and the cathode 5 on the bottom, and the treatment effect is increased by 5% in 6 minutes.
实施例2Example 2
如图1所示，一种采用阳极放置阴极下面来改进微等离子体弧放电催化水处理方法，其与实施例1相比的区别特征在于，所述阳极4和所述阴极5的几何中心在液面下深度为125mm。As shown in Figure 1, a method for improving micro-plasma arc discharge catalytic water treatment by placing the anode under the cathode, its difference compared with Example 1 is that the geometric center of the anode 4 and the cathode 5 is at The depth below the liquid surface is 125mm.
实验结果表明：深度为125mm时相比深度为65mm时，6min时处理效果提高8％。The experimental results show that when the depth is 125mm, compared with the depth of 65mm, the treatment effect is increased by 8% in 6 minutes.
实施例3Example 3
如图1所示，一种采用阳极放置阴极下面来改进微等离子体弧放电催化水处理方法，其与实施例1相比的区别特征在于，本实施例处理对象为罗丹明B模拟的印染废水。所述罗丹明B属氧杂蒽酸性染料，是印染工业及纺织业中常用的染料，且含有苯环，用化学和生物等方法处理该类废水的效果均不理想。As shown in Figure 1, a method for improving micro-plasma arc discharge catalytic water treatment by placing the anode under the cathode, its difference compared with Example 1 is that the treatment object of this example is printing and dyeing wastewater simulated by Rhodamine B . The rhodamine B belongs to the xanthene acid dye, is a dye commonly used in the printing and dyeing industry and the textile industry, and contains a benzene ring, and the effect of treating this type of wastewater with chemical and biological methods is not satisfactory.
实验结果表明，所述阳极4在所述阴极5之下的放置模式比阳极4在上阴极5在下的放置模式，6min时处理效果提高7％。Experimental results show that the placement pattern of the anode 4 below the cathode 5 is higher than the placement pattern of the anode 4 on the top and the cathode 5 below, and the treatment effect is increased by 7% in 6 minutes.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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