CN102126778A - Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation - Google Patents

Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation Download PDF

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CN102126778A
CN102126778A CN 201110028360 CN201110028360A CN102126778A CN 102126778 A CN102126778 A CN 102126778A CN 201110028360 CN201110028360 CN 201110028360 CN 201110028360 A CN201110028360 A CN 201110028360A CN 102126778 A CN102126778 A CN 102126778A
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electrocatalytic oxidation
tank
waste water
groove
organic waste
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梅荣武
韦彦斐
沈浙萍
李欲如
张钢
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Zhejiang Environmental Science Research and Design Institute
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Abstract

本发明公开了一种多相电催化氧化处理有机废水槽型装置及其方法。它包括电催化氧化槽、电极板支架、柱形阳极、板形阴极、中间介质、催化剂、进水口、进气口、出水口、槽体支撑、内介质支撑和溢流槽。酸性有机废水进入多相电催化氧化槽内,同时加入氧化剂,在电催化氧化槽内进行电催化氧化反应。电极为石墨加载二氧化钛;催化剂为耐酸性的磁铁粉和针铁矿粉。中间介质为凹凸棒土和电气石;氧化剂为双氧水、空气、二氧化氯和高锰酸钾。反应后的废水加液碱或石灰水调节pH值至7,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。本发明具有处理效率高、占地少、运行费用低等优点。

The invention discloses a multiphase electrocatalytic oxidation treatment organic wastewater tank type device and a method thereof. It includes an electrocatalytic oxidation tank, an electrode plate support, a cylindrical anode, a plate cathode, an intermediate medium, a catalyst, a water inlet, an air inlet, a water outlet, a tank body support, an inner medium support and an overflow tank. The acidic organic wastewater enters the heterogeneous electrocatalytic oxidation tank, and an oxidant is added at the same time, and the electrocatalytic oxidation reaction is carried out in the electrocatalytic oxidation tank. The electrode is graphite-loaded titanium dioxide; the catalyst is acid-resistant magnet powder and goethite powder. The intermediate medium is attapulgite and tourmaline; the oxidant is hydrogen peroxide, air, chlorine dioxide and potassium permanganate. Add liquid caustic soda or lime water to the reacted wastewater to adjust the pH value to 7, then enter the sedimentation tank for precipitation, and the precipitated wastewater enters the biochemical treatment system for treatment. The invention has the advantages of high processing efficiency, less land occupation, and low operating cost.

Description

一种多相电催化氧化处理有机废水槽型装置及其方法A multiphase electrocatalytic oxidation treatment organic wastewater tank type device and method thereof

技术领域technical field

本发明涉及高浓度有机废水处理装置及其方法,尤其涉及主要是采用多相电催化氧化技术处理高浓度有机废水的方法。属于污水处理技术领域。The invention relates to a high-concentration organic wastewater treatment device and a method thereof, in particular to a method for treating high-concentration organic wastewater mainly by adopting multiphase electrocatalytic oxidation technology. It belongs to the technical field of sewage treatment.

背景技术Background technique

随着我国化工、医药、染料等行业的快速发展,我国的经济实力得到逐步提高;同时,与此平行的是生产过程中所排出的废水对环境污染也日益加剧、对人类的健康形成严重的威胁。化工、医药、染料等行业的废水因成分复杂、有机物含量高、含盐高、色度和毒性大,处理此类废水无论技术上还是经济上都存在较大困难,一般采用能耗较高的焚烧法或经简单的表观处理后大倍数稀释后生化处理,此类方法处理往往投资高,占地面积大,运行费用高,用户难以承受。With the rapid development of my country's chemical industry, medicine, dyestuff and other industries, my country's economic strength has been gradually improved; at the same time, in parallel with this, the waste water discharged in the production process is also increasingly polluting the environment and causing serious damage to human health. threaten. Due to the complex composition, high organic content, high salt content, high chroma and toxicity of wastewater from chemical, pharmaceutical, and dye industries, it is difficult to treat such wastewater both technically and economically. Incineration method or simple surface treatment followed by large multiple dilution followed by biochemical treatment, these methods often require high investment, occupy a large area, and have high operating costs, which are unaffordable for users.

高浓度有机废水氧化处理技术是当今环保领域的研究热点、技术难点。多相电催化氧化法是利用最新开发的高效催化剂,通电后通过氧化剂的作用,将成分复杂、有机物含量高、含盐高、色度和毒性大的废水在较温和的条件下进行破坏性氧化,这是一种把化工领域的最新技术与相应高效催化剂相结合的一种氧化技术,代表了国外此类污水治理的主要趋势。该技术具有处理效率高、适用性广、处理成本较低、操作管理方便等优点,具有广阔的应用前景。High-concentration organic wastewater oxidation treatment technology is a research hotspot and technical difficulty in the field of environmental protection today. The heterogeneous electrocatalytic oxidation method is to use the latest developed high-efficiency catalyst to destructively oxidize the wastewater with complex components, high organic content, high salt content, chromaticity and toxicity under milder conditions through the action of oxidants after electrification , which is an oxidation technology that combines the latest technology in the chemical industry with corresponding high-efficiency catalysts, and represents the main trend of this type of sewage treatment abroad. This technology has the advantages of high processing efficiency, wide applicability, low processing cost, convenient operation and management, etc., and has broad application prospects.

发明内容Contents of the invention

本发明的目的是克服现有技术的不足,提供了一种多相电催化氧化处理有机废水槽型装置及其方法。The object of the present invention is to overcome the deficiencies of the prior art, and provide a multiphase electrocatalytic oxidation treatment organic wastewater tank-type device and method thereof.

多相电催化氧化处理有机废水槽型装置包括:一种多相电催化氧化处理有机废水槽型装置,其特征在于包括电催化氧化槽、电极板支架、柱形阳极、板形阴极、中间介质、催化剂、进水口、进气口、出水口、槽体支撑、内介质支撑和溢流槽;电催化氧化槽下端设有槽体支撑,电催化氧化槽上端设有溢流槽和电极板支架,电极板支架下方设有柱形阳极和板形阴极,电催化氧化槽下部设有内介质支撑,内介质支撑上设有中间介质、催化剂,内介质支撑下方设有进气口,电催化氧化槽底部设有进水口,溢流槽上设有出水口。The multiphase electrocatalytic oxidation treatment organic wastewater tank device includes: a multiphase electrocatalytic oxidation treatment organic wastewater tank device, which is characterized in that it includes an electrocatalytic oxidation tank, an electrode plate support, a cylindrical anode, a plate cathode, and an intermediate medium , catalyst, water inlet, air inlet, water outlet, tank support, inner medium support and overflow tank; the lower end of the electrocatalytic oxidation tank is provided with tank support, and the upper end of the electrocatalytic oxidation tank is provided with overflow tank and electrode plate support , a cylindrical anode and a plate-shaped cathode are arranged under the electrode plate support, an inner medium support is arranged at the lower part of the electrocatalytic oxidation tank, an intermediate medium and a catalyst are arranged on the inner medium support, and an air inlet is arranged under the inner medium support, and the electrocatalytic oxidation A water inlet is provided at the bottom of the tank, and a water outlet is provided on the overflow tank.

所述的多相电催化氧化处理有机废水槽型装置的中间介质、催化剂中的中间介质为:凹凸棒土和电气石。The intermediate medium in the multiphase electrocatalytic oxidation treatment organic wastewater tank-type device and the intermediate medium in the catalyst are: attapulgite and tourmaline.

所述的多相电催化氧化处理有机废水槽型装置的中间介质、催化剂中的催化剂为:耐酸性的磁铁粉三氧化二铁和针铁矿粉。The intermediate medium and the catalyst in the multi-phase electrocatalytic oxidation treatment organic wastewater tank-type device are: acid-resistant magnet powder ferric oxide and goethite powder.

所述的多相电催化氧化处理有机废水槽型装置采用钢制,内衬玻璃钢纤维与环氧树脂防腐。The multi-phase electrocatalytic oxidation treatment organic wastewater tank-type device is made of steel, lined with fiberglass fiber and epoxy resin for anticorrosion.

所述装置的多相电催化氧化处理有机废水方法是:有机废水用硫酸或氢氧化钠先调节pH使其呈酸性,然后有机废水由多相电催化氧化槽底部进入多相电催化氧化槽内,同时,废水中加入氧化剂,其中氧化剂为双氧水、空气、二氧化氯和高锰酸钾,在电催化氧化槽内进行电催化氧化反应,催化氧化反应时间为2~8h,电极间的直流电压为5~15V,电流密度为2~20mA/cm2,反应后的废水加液碱或石灰水调节pH值至7,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。The heterogeneous electrocatalytic oxidation treatment method of the device is as follows: the organic wastewater is first adjusted to pH with sulfuric acid or sodium hydroxide to make it acidic, and then the organic wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank , at the same time, oxidants are added to the wastewater, wherein the oxidants are hydrogen peroxide, air, chlorine dioxide and potassium permanganate, and the electrocatalytic oxidation reaction is carried out in the electrocatalytic oxidation tank. The catalytic oxidation reaction time is 2 to 8h, and the DC voltage between the electrodes 5~15V, current density 2~20mA/cm 2 , add liquid caustic soda or lime water to adjust the pH value to 7, and then enter the sedimentation tank for sedimentation, and the sedimented wastewater enters the biochemical treatment system for treatment.

所述的有机废水由多相电催化氧化槽底部进入多相电催化氧化槽的进水方式为:连续或间歇进出水。The way in which the organic wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank is continuous or intermittent water inflow and outflow.

本发明与现有技术相比具有的有益效果:The present invention has the beneficial effect compared with prior art:

(1) 实现了在酸性条件下的多相电催化氧化。(1) Realized heterogeneous electrocatalytic oxidation under acidic conditions.

(2) 使用了耐酸的催化剂。(2) An acid-resistant catalyst is used.

(3) 电极材料选用了半导体介质,提高了处理效率。(3) The electrode material is selected as a semiconductor medium, which improves the processing efficiency.

(4) 处理流程简单,操作简便,可实现自动化控制。(4) The processing flow is simple, the operation is easy, and automatic control can be realized.

附图说明Description of drawings

图1为本发明的电催化氧化装置的结构图。Fig. 1 is a structural diagram of the electrocatalytic oxidation device of the present invention.

图中,电催化氧化槽1、电极板支架2、柱形阳极3、板形阴极4、中间介质、催化剂5、进水口6、进气口7、出水口8、槽体支撑9、内介质支撑10和溢流槽11。In the figure, electrocatalytic oxidation tank 1, electrode plate support 2, cylindrical anode 3, plate cathode 4, intermediate medium, catalyst 5, water inlet 6, air inlet 7, water outlet 8, tank support 9, inner medium Support 10 and overflow tank 11.

具体实施方式Detailed ways

多相电催化氧化处理有机废水槽型装置包括:电催化氧化槽1、电极板支架2、柱形阳极3、板形阴极4、中间介质、催化剂5、进水口6、进气口7、出水口8、槽体支撑9、内介质支撑10和溢流槽11;电催化氧化槽1下端设有槽体支撑9,电催化氧化槽1上端设有溢流槽11和电极板支架2,电极板支架2下方设有柱形阳极3和板形阴极4,电催化氧化槽1下部设有内介质支撑10,内介质支撑10上设有中间介质、催化剂5,内介质支撑10下方设有进气口7,电催化氧化槽1底部设有进水口6,溢流槽11上设有出水口8。The multiphase electrocatalytic oxidation treatment organic wastewater tank device includes: electrocatalytic oxidation tank 1, electrode plate support 2, cylindrical anode 3, plate cathode 4, intermediate medium, catalyst 5, water inlet 6, air inlet 7, outlet Nozzle 8, tank support 9, inner medium support 10, and overflow tank 11; the lower end of the electrocatalytic oxidation tank 1 is provided with a tank support 9, and the upper end of the electrocatalytic oxidation tank 1 is provided with an overflow tank 11 and an electrode plate support 2, and the electrode A columnar anode 3 and a plate-shaped cathode 4 are arranged under the plate support 2, an inner medium support 10 is arranged at the bottom of the electrocatalytic oxidation tank 1, an intermediate medium and a catalyst 5 are arranged on the inner medium support 10, and an inlet medium is arranged under the inner medium support 10. Gas port 7, water inlet 6 is provided at the bottom of electrocatalytic oxidation tank 1, and water outlet 8 is provided on overflow tank 11.

所述的多相电催化氧化处理有机废水槽型装置的中间介质、催化剂5中的中间介质为:凹凸棒土和电气石。The intermediate medium in the multiphase electrocatalytic oxidation treatment organic wastewater tank-type device and the intermediate medium in the catalyst 5 are: attapulgite and tourmaline.

所述的多相电催化氧化处理有机废水槽型装置的中间介质、催化剂5中的催化剂为:耐酸性的磁铁粉四氧化三铁和针铁矿粉。The intermediate medium and the catalyst in the catalyst 5 of the heterogeneous electrocatalytic oxidation treatment organic wastewater tank-type device are: acid-resistant magnet powder ferric oxide and goethite powder.

所述的多相电催化氧化处理有机废水槽型装置采用钢制,内衬玻璃钢纤维与环氧树脂防腐。The multi-phase electrocatalytic oxidation treatment organic wastewater tank-type device is made of steel, lined with fiberglass fiber and epoxy resin for anticorrosion.

所述装置的多相电催化氧化处理有机废水方法是:有机废水用硫酸或氢氧化钠先调节pH使其呈酸性,然后有机废水由多相电催化氧化槽底部进入多相电催化氧化槽内,同时,废水中加入氧化剂,其中氧化剂为双氧水、空气、二氧化氯和高锰酸钾,在电催化氧化槽内进行电催化氧化反应,催化氧化反应时间为2~8h,电极间的直流电压为5~15V,电流密度为2~20mA/cm2,反应后的废水加液碱或石灰水调节pH值至7,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。The heterogeneous electrocatalytic oxidation treatment method of the device is as follows: the organic wastewater is first adjusted to pH with sulfuric acid or sodium hydroxide to make it acidic, and then the organic wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank , at the same time, oxidants are added to the wastewater, wherein the oxidants are hydrogen peroxide, air, chlorine dioxide and potassium permanganate, and the electrocatalytic oxidation reaction is carried out in the electrocatalytic oxidation tank. The catalytic oxidation reaction time is 2 to 8h, and the DC voltage between the electrodes 5~15V, current density 2~20mA/cm 2 , add liquid caustic soda or lime water to adjust the pH value to 7, and then enter the sedimentation tank for sedimentation, and the sedimented wastewater enters the biochemical treatment system for treatment.

所述的有机废水由多相电催化氧化槽底部进入多相电催化氧化槽的进水方式为:连续或间歇进出水。The way in which the organic wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank is continuous or intermittent water inflow and outflow.

所述装置的多相电催化氧化处理有机废水具体操作方法:先用硫酸或氢氧化钠调节有机废水的pH值,一般控制在1~3。将调整好pH值的废水通过耐腐蚀污水泵打入多相电催化氧化槽内进行催化氧化,氧化时间为2~8h, 电极间的直流电压为5~15V,电流密度为2~20mA/cm2,可根据不同的进水水质及处理程度进行调整。电极为石墨加载二氧化钛;催化剂为耐酸性的磁铁粉四氧化三铁和针铁矿粉。中间介质为凹凸棒土和电气石;投加比例为:1:1~5:1,投加量为总容积的20~60%;氧化剂为双氧水、空气、二氧化氯和高锰酸钾。在外加电场的作用下,进行多相电催化氧化:利用具有助催化与吸附功能的中间介质如凹凸棒土和电气石将有机污染物富集到介质表面;由于各种吸附介质的吸附能力和吸附范围不同,可以吸附各类污染物。污染物从水相连续富集到固相表面,在常温、常压条件下,可以在氧化剂、催化剂、电场的多重协同作用下连续快速的被分解,改变了废水中特征污染物如苯环、杂环等的结构,使大分子有机物转化为小分子或二氧化碳和水,从而达到连续高效处理有机物的目的,也可以提高废水的可生化性。多相电催化氧化反应后的废水pH值可以提高到4~6,加液碱或石灰水调节pH值至7~8,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。The specific operation method of the heterogeneous electrocatalytic oxidation treatment of organic wastewater by the device: first adjust the pH value of the organic wastewater with sulfuric acid or sodium hydroxide, and generally control it at 1-3. The wastewater with adjusted pH value is pumped into the multiphase electrocatalytic oxidation tank through a corrosion-resistant sewage pump for catalytic oxidation. The oxidation time is 2-8h, the DC voltage between the electrodes is 5-15V, and the current density is 2-20mA/cm 2. It can be adjusted according to different influent water quality and treatment degree. The electrode is graphite-loaded titanium dioxide; the catalyst is acid-resistant magnet powder triiron tetroxide and goethite powder. The intermediate medium is attapulgite and tourmaline; the dosage ratio is: 1:1~5:1, and the dosage is 20~60% of the total volume; the oxidant is hydrogen peroxide, air, chlorine dioxide and potassium permanganate. Under the action of an external electric field, multiphase electrocatalytic oxidation is carried out: using intermediate media with catalytic and adsorption functions such as attapulgite and tourmaline to enrich organic pollutants on the surface of the media; due to the adsorption capacity of various adsorption media and The adsorption range is different, and various pollutants can be adsorbed. Pollutants are continuously enriched from the water phase to the surface of the solid phase. Under normal temperature and pressure conditions, they can be continuously and rapidly decomposed under the multiple synergistic effects of oxidants, catalysts, and electric fields, changing the characteristic pollutants in wastewater such as benzene rings, Structures such as heterocycles can convert macromolecular organic matter into small molecules or carbon dioxide and water, so as to achieve the purpose of continuous and efficient treatment of organic matter, and can also improve the biodegradability of wastewater. The pH value of the wastewater after the heterogeneous electrocatalytic oxidation reaction can be increased to 4-6, and the pH value is adjusted to 7-8 by adding liquid caustic soda or lime water, and then enters the sedimentation tank for precipitation, and the precipitated wastewater enters the biochemical treatment system for treatment.

电催化氧化机理:在电催化体系中有强氧化性的活性物质存在,这些活性物质包括H2O2、O3、HO-、HO2 -、O2 -。以及溶剂化电子es等,若溶液中有Cl-存在,还可能有Cl2、HClO-及ClO_等氧化剂存在。这些强氧化性物质的存在,能够大大提高降解有机物的能力。表1列出了部分强氧化性物质标准还原电极电势。 Electrocatalytic oxidation mechanism : In the electrocatalytic system, there are strong oxidizing active substances, including H 2 O 2 , O 3 , HO - , HO 2 - , O 2 - . And solvated electrons e s , etc., if there is Cl - in the solution, there may also be Cl 2 , HClO - and ClO _ and other oxidants. The presence of these strong oxidizing substances can greatly improve the ability to degrade organic matter. Table 1 lists the standard reduction electrode potentials of some strong oxidizing substances.

表1强氧化性物质标准还原电极电势表Table 1 Standard reduction electrode potential table of strong oxidizing substances

强氧化剂种类Types of strong oxidizing agents 标准电位/VStandard potential/V 强氧化剂种类Types of strong oxidizing agents 标准电位/VStandard potential/V HO. HO . 2.802.80 H2O2 H2O2 _ 1.781.78 O2 - O 2 - 2.422.42 HO2 - HO 2 - 1.701.70 O3 O 3 2.072.07 Cl- Cl- 1.361.36

从上表中可以看出,它们都具有相当高的还原电势,能够氧化大多数有机物。As can be seen from the above table, they all have quite high reduction potentials and are capable of oxidizing most organic compounds.

在电催化体系中,通过电解产生的O2或外界提供的O2,在阴极上还原可产生H2O2In the electrocatalytic system, O 2 generated by electrolysis or O 2 provided by the outside can be reduced on the cathode to generate H 2 O 2 .

Figure 2011100283609100002DEST_PATH_IMAGE002
酸性条件下:O2+2H++2e-    H2O2
Figure 2011100283609100002DEST_PATH_IMAGE002
Under acidic conditions: O 2 +2H + +2e - H 2 O 2

Figure 2011100283609100002DEST_PATH_IMAGE004
碱性条件下:O2+H2O+2e-    HO2 -+OH-
Figure 2011100283609100002DEST_PATH_IMAGE004
Under alkaline conditions: O 2 +H 2 O+2e - HO 2 - +OH -

Figure 2011100283609100002DEST_PATH_IMAGE006
HO2 -+H2O+2e-    H2O2+OH-
Figure 2011100283609100002DEST_PATH_IMAGE006
HO 2 - +H 2 O+2e - H 2 O 2 +OH -

而体系中的HO,可以在金属催化剂的作用下产生:And the HO in the system . , which can be produced under the action of metal catalysts:

Figure DEST_PATH_IMAGE004A
酸性条件下:Mred+H++ H2O2   Mox+HO.+H2O
Figure DEST_PATH_IMAGE004A
Under acidic conditions: M red +H + + H 2 O 2 M ox +HO . +H 2 O

Figure DEST_PATH_IMAGE006A
碱性条件下:Mred+H2O2    Mox+HO.+OH-
Figure DEST_PATH_IMAGE006A
Under alkaline conditions: M red +H 2 O 2 Mox+HO . +OH -

在HO-的作用下,有机物发生快速氧化反应及自由基链反应,从而迅速被降解。Under the action of HO - , organic matter undergoes rapid oxidation reaction and free radical chain reaction, thereby being rapidly degraded.

石墨负载的Ti02为半导体材料。半导体粒子的能带结构一般由填满电子的价带和空的高能导带构成,价带和导带之间存在禁带,当通电后,在外电场的作用下,由于能量大于禁带宽度,半导体价带上的电子(e)被激发跃迁到导带形成高能电子(e),在价带上产生空穴(h+),并在电场作用下分别迁移到粒子表面。高能电子 (e)易被水中溶解氧等氧化性物质所捕获,而空穴因具有极强的获取电子的能力而具有很强的氧化能力,可将其表面吸附的有机物或OH-及H20分子氧化成·OH自由基,·OH自由基几乎无选择地将水中有机物氧化。Graphite supported Ti0 2 is a semiconductor material. The energy band structure of semiconductor particles is generally composed of a valence band filled with electrons and an empty high-energy conduction band. There is a forbidden band between the valence band and the conduction band. The electrons (e 1 ) on the valence band of the semiconductor are excited to jump to the conduction band to form high-energy electrons (e 1 ), which generate holes (h + ) in the valence band, and migrate to the surface of the particle under the action of the electric field. High-energy electrons ( e- ) are easily captured by oxidizing substances such as dissolved oxygen in water, while holes have a strong oxidation ability due to their strong ability to obtain electrons, and can absorb organic matter or OH - and H on their surface 2 0 molecules are oxidized into ·OH radicals, and ·OH free radicals oxidize organic matter in water almost non-selectively.

任务上利用化学催化氧化、电催化氧化、化学氧化、电凝聚等藕合技术处理高浓度有机废水,以降低废水的毒性,提高废水的可生化性,为废水提标、达标排放和中水回用创造条件。In terms of tasks, chemical catalytic oxidation, electrocatalytic oxidation, chemical oxidation, electrocoagulation and other coupling technologies are used to treat high-concentration organic wastewater in order to reduce the toxicity of wastewater, improve the biodegradability of wastewater, and improve the standards of wastewater, standard discharge and reclaimed water recycling. Use to create conditions.

实施例1:有机硅废水处理Embodiment 1: organosilicon wastewater treatment

有机硅废水用硫酸先调节pH使其呈酸性,然后有机硅废水由多相电催化氧化槽底部进入多相电催化氧化槽内,同时,废水中加入氧化剂,其中氧化剂为双氧水,在电催化氧化槽内进行电催化氧化反应,催化氧化反应时间为8h,电极间的直流电压为15V,电流密度为20mA/cm2,反应后的废水加液碱调节pH值至7,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。The organic silicon wastewater is first adjusted with sulfuric acid to make it acidic, and then the organic silicon wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank. At the same time, an oxidant is added to the wastewater, and the oxidant is hydrogen peroxide. The electrocatalytic oxidation reaction is carried out in the tank, the catalytic oxidation reaction time is 8h, the DC voltage between the electrodes is 15V, and the current density is 20mA/cm 2 , the reacted wastewater is added with liquid alkali to adjust the pH value to 7, and then enters the sedimentation tank for precipitation. The sedimented wastewater enters the biochemical treatment system for treatment.

有机硅单体生产所排废水有机物浓度高,含盐量高,可生化性差。具体水质参数见表1-1。The effluent from the production of organic silicon monomers has a high concentration of organic matter, high salt content, and poor biodegradability. See Table 1-1 for specific water quality parameters.

表1-1  有机硅废水水质表     单位:mg/lTable 1-1 Water quality table of organic silicon wastewater Unit: mg/l

有机硅废水用电催化氧化方法处理,连续试验8h,每隔2h取一次样,分别测定CODcr、Cl-。试验结果见表1-2(原水CODcr为2850mg/l)。Organosilicon wastewater was treated by electrocatalytic oxidation. The test was continued for 8 hours, and samples were taken every 2 hours to measure COD cr and Cl - respectively. The test results are shown in Table 1-2 (COD cr of raw water is 2850mg/l).

表1-2 电催化氧化试验结果Table 1-2 Electrocatalytic oxidation test results

批次batch 2h2 hours 4h4 hours 6h6 hours 8h8 hours CODcr(mg/L)COD cr (mg/L) 2.48×103 2.48×10 3 1.12×103 1.12×10 3 1.25×103 1.25×10 3 1.27×103 1.27×10 3 去除率(%)Removal rate (%) 13.013.0 70.970.9 56.156.1 55.455.4 Cl-(mg/L)Cl - (mg/L) 2.12×104 2.12×10 4 1.82×104 1.82×10 4 1.73×104 1.73×10 4 1.83×104 1.83×10 4

实施例2:有机磷废水处理Embodiment 2: organic phosphorus wastewater treatment

草甘膦生产废水用硫酸先调节pH使其呈酸性,然后草甘膦生产废水由多相电催化氧化槽底部进入多相电催化氧化槽内,同时,废水中加入氧化剂,其中氧化剂为双氧水,在电催化氧化槽内进行电催化氧化反应,催化氧化反应时间为2h,电极间的直流电压为5V,电流密度为2mA/cm2,反应后的废水加石灰水调节pH值至7,再进入沉淀池沉淀,沉淀后的废水进入生化处理系统处理。The pH of glyphosate production wastewater is first adjusted with sulfuric acid to make it acidic, and then the glyphosate production wastewater enters the multiphase electrocatalytic oxidation tank from the bottom of the multiphase electrocatalytic oxidation tank. At the same time, an oxidant is added to the wastewater, and the oxidant is hydrogen peroxide. The electrocatalytic oxidation reaction is carried out in the electrocatalytic oxidation tank. The catalytic oxidation reaction time is 2h, the DC voltage between the electrodes is 5V, and the current density is 2mA/cm 2 . After the reaction, add lime water to adjust the pH value to 7, and then enter The sedimentation tank settles, and the sedimented wastewater enters the biochemical treatment system for treatment.

草甘膦生产废水有机物浓度高,含盐量高,有机磷含量高,处理难度大。该生产工艺废水pH:1~2,CODcr:20000~30000mg/l;总磷(以有机磷为主)>1000mg/l。Glyphosate production wastewater has a high concentration of organic matter, high salt content, and high organic phosphorus content, making it difficult to treat. The production process wastewater pH: 1 ~ 2, COD cr : 20000 ~ 30000mg/l; total phosphorus (mainly organic phosphorus) > 1000mg/l.

草甘膦生产废水用电催化氧化方法处理,连续试验2h,分别测定CODcr、TP。测得沉淀后上清液 CODcr去除率大于40%,总磷去除率大于75%。Glyphosate production wastewater was treated by electrocatalytic oxidation method, and the test was continued for 2 hours, and COD cr and TP were measured respectively. It is measured that the supernatant CODcr removal rate after precipitation is greater than 40%, and the total phosphorus removal rate is greater than 75%.

Claims (6)

1. the organic waste water slot-type device is handled in a polyphase electrocatalytic oxidation, it is characterized in that comprising that catalytic oxidation groove (1), battery lead plate support (2), cylindricality anode (3), plate shape negative electrode (4), intermediate medium, catalyzer (5), water-in (6), inlet mouth (7), water outlet (8), cell body support (9), interior dielectric support (10) and overflow groove (11); Catalytic oxidation groove (1) lower end is provided with cell body and supports (9), catalytic oxidation groove (1) upper end is provided with overflow groove (11) and battery lead plate support (2), battery lead plate support (2) below is provided with cylindricality anode (3) and plate shape negative electrode (4), catalytic oxidation groove (1) bottom is provided with interior dielectric support (10), interior dielectric support (10) is provided with intermediate medium, catalyzer (5), interior dielectric support (10) below is provided with inlet mouth (7), catalytic oxidation groove (1) bottom is provided with water-in (6), and overflow groove (11) is provided with water outlet (8).
2. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that the intermediate medium in described intermediate medium, the catalyzer (5) is: attapulgite and tourmalinite.
3. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that the catalyzer in described intermediate medium, the catalyzer (5) is: acid proof magnetic iron powder Z 250 and pyrrhosiderite powder.
4. the organic waste water slot-type device is handled in a kind of polyphase electrocatalytic oxidation according to claim 1, it is characterized in that described catalytic oxidation groove (1) adopts steel, and glass inner-lining steel fiber and Resins, epoxy are anticorrosion.
5. the organic waste water method is handled in the use polyphase electrocatalytic oxidation of installing according to claim 1, it is characterized in that organic waste water makes it be acid with sulfuric acid or the adjusting pH of sodium hydroxide elder generation, organic waste water is entered in the polyphase electrocatalytic oxidation groove by polyphase electrocatalytic oxidation trench bottom then, simultaneously, add oxygenant in the waste water, wherein oxygenant is a hydrogen peroxide, air, dioxide peroxide and potassium permanganate, in the catalytic oxidation groove, carry out electrocatalysis oxidation reaction, the catalytic oxidation time is 2~8h, interelectrode volts DS is 5~15V, and current density is 2~20mA/cm 2, reacted wastewater adds liquid caustic soda or liming is regulated pH value to 7, enters the settling tank precipitation again, and the waste water of post precipitation enters biochemical treatment system and handles.
6. the organic waste water method is handled in a kind of polyphase electrocatalytic oxidation according to claim 5, it is characterized in that described organic waste water by the water intake mode that polyphase electrocatalytic oxidation trench bottom enters polyphase electrocatalytic oxidation groove is: Inlet and outlet water continuously or intermittently.
CN 201110028360 2011-01-26 2011-01-26 Groove-type device and method for treating organic wastewater by multiphase electro-catalytic oxidation Pending CN102126778A (en)

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CN113880222A (en) * 2021-11-05 2022-01-04 中国地质大学(北京) A method for degrading organic wastewater based on natural tourmaline synergistic hydrogen peroxide

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