CN202519114U - Combined treatment device for chemical oxygen demand (COD) in polychlorinated biphenyl (PCB) waste water - Google Patents
Combined treatment device for chemical oxygen demand (COD) in polychlorinated biphenyl (PCB) waste water Download PDFInfo
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Abstract
本实用新型涉及一种去除PCB废水中COD的联合处理装置,用于含重金属的高浓度有机废水处理。所述装置依次包括以下组成单元:铁碳池,其顶端设有入水口和pH自动调节装置,调节入水为酸性,且其底部设有曝气系统;芬顿池,其入水口设有自动加药装置,加入双氧水,且其底部设有曝气系统;混凝池,其入水口装有pH自动调节装置,调节入水为碱性,入水口还设有自动加药装置,加入混凝剂;沉淀池,底部设有排泥口。该装置的优点在于:不用调节芬顿池的pH和无需外在添加亚铁离子,因此可节约成本,而且可以快速高效降解高浓度有机废水,如印染废水、PCB废水等,自动化程度高。
The utility model relates to a combined treatment device for removing COD in PCB waste water, which is used for treating high-concentration organic waste water containing heavy metals. The device includes the following components in turn: an iron-carbon pool, with a water inlet and an automatic pH adjustment device on its top, to adjust the water to be acidic, and an aeration system at its bottom; The medicine device, add hydrogen peroxide, and an aeration system is installed at the bottom; the coagulation tank, the water inlet is equipped with a pH automatic adjustment device to adjust the water to be alkaline, and the water inlet is also equipped with an automatic dosing device to add coagulant; The sedimentation tank has a mud discharge port at the bottom. The advantage of the device is that it does not need to adjust the pH of the Fenton pool and does not need to add ferrous ions externally, so it can save costs, and can quickly and efficiently degrade high-concentration organic wastewater, such as printing and dyeing wastewater, PCB wastewater, etc., with a high degree of automation.
Description
技术领域 technical field
本实用新型涉及到污水处理领域,特别是污水中COD处理领域。 The utility model relates to the field of sewage treatment, in particular to the field of COD treatment in sewage.
背景技术 Background technique
印制线路板、电镀、五金加工、皮革等行业生产中会产生含重金属离子及高浓度难降解的COD有机废水,排入江河将造成严重的环境污染,进而造成水资源缺乏和水环境质量恶化。对于难降解有机废水常采用的方法有(1)湿式氧化法、(2)蒸发后燃烧法、(3)厌氧生物处理法。其中前两种方法设备投资大,技术要求高,能耗也大,第三种方法占地面积大,停留时间长且容易产生异味。国内治理PCB的COD有机废水多采用酸化-好氧生物处理,此种方法虽然能有效地去除COD,但由于微生物生长环境要求苛刻,对原水的酸碱度及重金属离子敏感,在运行过程中经常因为控制操作不当,造成整个生化系统瘫痪,出水COD严重超标。 Printed circuit boards, electroplating, hardware processing, leather and other industries will produce heavy metal ions and high-concentration refractory COD organic wastewater, which will cause serious environmental pollution when discharged into rivers, resulting in lack of water resources and deterioration of water environment quality. . The commonly used methods for refractory organic wastewater are (1) wet oxidation method, (2) combustion method after evaporation, and (3) anaerobic biological treatment method. Wherein the first two methods have large investment in equipment, high technical requirements, and large energy consumption. The third method occupies a large area, has a long residence time and is prone to peculiar smell. Domestic treatment of PCB COD organic wastewater mostly adopts acidification-aerobic biological treatment. Although this method can effectively remove COD, it is often sensitive to the pH and heavy metal ions of the raw water due to the harsh requirements of the microbial growth environment. Improper operation caused the paralysis of the entire biochemical system, and the COD of the effluent seriously exceeded the standard.
发明内容 Contents of the invention
本实用新型提供一种处理时间短、处理效果好、节约成本、自动化程度高、方便管理的PCB废水中COD的联合处理装置。 The utility model provides a combined treatment device for COD in PCB waste water with short treatment time, good treatment effect, cost saving, high degree of automation and convenient management.
为解决上述技术问题,本实用新型采用的技术方案是:一种PCB废水中COD的联合处理装置,依次包括以下组成单元:铁碳池,其顶端设有入水口和pH自动调节装置,调节入水为酸性,且其底部设有曝气系统;芬顿池,其入水口设有自动加药装置,加入双氧水,且其底部设有曝气系统;混凝池,其入水口装有pH自动调节装置,调节入水为碱性,入水口还设有自动加药装置,加入混凝剂;沉淀池,底部设有排泥口。 In order to solve the above technical problems, the technical solution adopted by the utility model is: a combined treatment device for COD in PCB wastewater, which includes the following components in turn: an iron-carbon pool, the top of which is provided with a water inlet and an automatic pH adjustment device to adjust the water inlet. It is acidic, and its bottom is equipped with an aeration system; the Fenton pool, its water inlet is equipped with an automatic dosing device, hydrogen peroxide is added, and its bottom is equipped with an aeration system; the coagulation tank, its water inlet is equipped with an automatic pH adjustment The device adjusts the water to be alkaline, and the water inlet is also equipped with an automatic dosing device to add coagulant; the sedimentation tank has a mud discharge port at the bottom.
进一步地,所述沉淀池内设有斜板。 Further, a sloping plate is provided in the sedimentation tank.
进一步地,所述混凝池内设有搅拌装置。 Further, a stirring device is provided in the coagulation tank.
与现有技术相比,有益效果是: Compared with the prior art, the beneficial effect is:
1、本装置处理高浓度有机废水所需时间短,处理效果好。污水从进入本装置到流出的平均时间约为8h,处理时间短,因此抗冲击能力强。铁碳微电解和芬顿高级氧化均可降解大分子有机物,之后再经过混凝沉淀,有机物去除率高,出水清澈,水质良好。 1. The device takes a short time to treat high-concentration organic wastewater and has a good treatment effect. The average time from entering the device to flowing out of the sewage is about 8 hours, and the treatment time is short, so the impact resistance is strong. Both iron-carbon micro-electrolysis and Fenton advanced oxidation can degrade macromolecular organic matter, and then undergo coagulation and sedimentation. The removal rate of organic matter is high, the effluent is clear, and the water quality is good.
2、本装置自动化程度高,方便运行管理。由于本装置设有自动加药系统,pH自动调节系统,曝气系统,因此在进水稳定的情况下,可以实现全部的自动化流程,只需注意定期排泥及添加铁炭填料即可,运行管理非常方便。 2. The device has a high degree of automation and is convenient for operation and management. Since the device is equipped with an automatic dosing system, an automatic pH adjustment system, and an aeration system, the entire automatic process can be realized under the condition of stable water intake, and only need to pay attention to regular sludge discharge and adding iron-carbon fillers to run. Management is very convenient.
3、因铁碳池反应所需的pH较低,在1~2之间,而芬顿池反应所需的pH为2~3之间,且经过铁碳微电解反应后溶液的pH会略有升高,大约为2~3,因此对芬顿池无需调节pH,可方便安装和运行。 3. Because the pH required for the iron-carbon pool reaction is low, between 1 and 2, while the pH required for the Fenton pool reaction is between 2 and 3, and the pH of the solution will be slightly lower after the iron-carbon micro-electrolysis reaction. There is an increase, about 2~3, so there is no need to adjust the pH of the Fenton pool, which is convenient for installation and operation.
4、因铁碳微电解反应会产生大量的亚铁离子,随水流进入芬顿池,可提供芬顿反应所需的亚铁离子,因此芬顿池无需外在添加含亚铁的物质,便于操作且节约成本。 4. Because the iron-carbon micro-electrolysis reaction will produce a large amount of ferrous ions, which will enter the Fenton cell with the water flow, which can provide the ferrous ions required by the Fenton reaction. Therefore, the Fenton cell does not need to add ferrous substances externally, which is convenient operation and cost savings.
5、铁碳池和芬顿池均有曝气系统,使溶液含氧量在1.5~2mg/L,既可以促进铁碳池的电极反应,又可以促进芬顿池的氧化反应,同时还可以起到搅拌混合的作用,以使溶液混合均匀,反应彻底。 5. Both the iron-carbon pool and the Fenton pool have an aeration system, so that the oxygen content of the solution is 1.5~2mg/L, which can not only promote the electrode reaction of the iron-carbon pool, but also promote the oxidation reaction of the Fenton pool. It plays the role of stirring and mixing, so that the solution is mixed evenly and the reaction is thorough.
6、铁碳微电解反应可以去除重金属离子,而且可以氧化分解许多难降解的大分子有机物,芬顿反应可以生成氧化能力极强的·O游离基,与有机物质发生氧化反应,使其碳链断裂,最后的生成的物质为二氧化碳和水,从而较彻底地处理难降解有机物,两种方法的联用可以相互促进,最终达到高效去除难降解污染物的效果。 6. The iron-carbon micro-electrolysis reaction can remove heavy metal ions, and can oxidize and decompose many macromolecular organic substances that are difficult to degrade. The final substances produced are carbon dioxide and water, so that the refractory organic matter can be treated more thoroughly. The combination of the two methods can promote each other, and finally achieve the effect of efficiently removing refractory pollutants.
附图说明 Description of drawings
图1是本实用新型的结构示意图; Fig. 1 is the structural representation of the utility model;
图2是本实用新型的优选实施例的结构示意图; Fig. 2 is the structural representation of the preferred embodiment of the utility model;
其中:1,铁碳池;2,芬顿池;3,混凝池;4,沉淀池;5,铁碳填料;6,曝气系统;7,PH自动调节装置一;8,PH自动调节装置二;9,自动加药装置一;10,自动加药装置二;11,搅拌装置;12,斜板。 Among them: 1, iron-carbon tank; 2, Fenton tank; 3, coagulation tank; 4, sedimentation tank; 5, iron-carbon filler; 6, aeration system; 7, PH automatic adjustment device 1; 8, PH automatic adjustment Device two; 9, automatic dosing device one; 10, automatic dosing device two; 11, stirring device; 12, inclined plate.
具体实施方式 Detailed ways
附图1和附图2为本实用新型的优选实施例,主要包括四部分:铁碳池1、芬顿池2、混凝池3和沉淀池4。其中铁碳池1中装有新型铁炭填料5,其入口在池顶端,入口处装有pH自动调节装置一7,以保证入水pH为酸性且稳定,底端装有曝气系统6以提供氧气促进反应;芬顿池2入水口设有自动加药装置一9,投加双氧水,其底部设有曝气系统6以促进反应;混凝池3入口装有pH自动调节装置二8以调节水为碱性便于絮凝沉淀,还设有自动加药装置二10,投加混凝剂,且内部有搅拌装置11,利于絮体的形成和凝聚;沉淀池4内设有斜板12,以提高泥水分离效果,最终清水由上端溢流口排出,污泥经由底部排泥口定期排出。
Accompanying drawing 1 and accompanying drawing 2 are the preferred embodiment of the present utility model, mainly comprise four parts: iron-carbon pond 1, Fenton pond 2, coagulation pond 3 and sedimentation pond 4. Wherein iron-carbon pool 1 is equipped with novel iron-
本实用新型的工作过程如下:废水经由水泵抽入铁碳池1,从顶端入口处进入系统,通过pH自动调节装置一7调节入水pH在1~2之间,铁炭填料5与废水发生微电解反应,降解其中的污染物及重金属离子,停留时间大约为40~50min,由曝气系统6曝气以提供适量的氧气,加强微电解效果。之后进入芬顿池2,因铁碳微电解反应后pH略有升高而芬顿池适宜pH恰为2~3,因此芬顿池无需调节pH,又因铁碳池1会带入足够的亚铁离子,因此芬顿池2无需投加亚铁离子,只需投加适量双氧水,停留时间约为2h,曝气以促进氧化反应且保证混合均匀,通过芬顿高级氧化进一步去除剩余的难降解有机物。之后进入混凝池3,通过pH自动调节装置二8将pH调节至8~9之间,水中的亚铁和三价铁离子沉淀形成絮体,再投加混凝剂使小絮体聚集团结形成大絮体,之后进入斜板式沉淀池4沉淀,泥水分离效果良好,上部清水经溢流口流出,检测达标后排放,污泥由底部排泥口排出。
The working process of the utility model is as follows: the waste water is pumped into the iron-carbon pool 1 through the water pump, and enters the system from the top entrance, and the pH of the water is adjusted between 1 and 2 through the pH automatic adjustment device 7, and the iron-
其中,铁碳微电解工艺的电解材料一般采用铸铁屑和活性炭或焦炭,当材料浸没在酸性废水中时,发生内部和外部两方面的电解反应。一方面铸铁中含有微量的碳化铁,碳化铁和纯铁存在明显的氧化还原电势差,这样在铸铁屑内部就形成了许多细微的原电池,纯铁作为原电池的阳极,碳化铁作为原电池的阴极;此外,铸铁屑和其周围的炭粉又形成了较大的原电池,因此利用微电解进行废水处理的过程实际上是内部和外部双重电解的过程,或者称之为存在微观和宏观的原电池反应,同时电化学腐蚀又引发了一系列连带协同作用,故铁炭微电解法是絮凝、吸附、架桥、卷扫、共沉、电沉积、电化学还原等多种作用综合效应的结果。其电极反应如下: Among them, the electrolytic materials of the iron-carbon micro-electrolysis process generally use cast iron chips and activated carbon or coke. When the materials are immersed in acidic wastewater, both internal and external electrolytic reactions occur. On the one hand, cast iron contains a small amount of iron carbide, and there is an obvious redox potential difference between iron carbide and pure iron, so many tiny primary batteries are formed inside the cast iron filings, pure iron is used as the anode of the primary battery, and iron carbide is used as the primary battery Cathode; in addition, cast iron scraps and carbon powder around it form a larger primary battery, so the process of using micro-electrolysis for wastewater treatment is actually a process of internal and external double electrolysis, or called micro and macro The reaction of the original battery, and at the same time, the electrochemical corrosion has triggered a series of joint and synergistic effects. Therefore, the iron-carbon micro-electrolysis method is a combination of various effects such as flocculation, adsorption, bridging, sweeping, co-precipitation, electrodeposition, and electrochemical reduction. result. Its electrode reaction is as follows:
阳极: Fe-2e-→Fe2+ E(Fe/Fe2+)=-0.44V Anode: Fe-2e-→Fe2+ E(Fe/Fe2+)=-0.44V
阴极: 中性或碱性条件下:O2+2H2O+4e-→4OH- E(O2/OH-)=0.40V cathode: Under neutral or alkaline conditions: O2+2H2O+4e-→4OH- E (O2/OH-)=0.40V
酸性条件下:2H++2e-→2[H]→H2 E(H+/H2)=0V Under acidic conditions: 2H++2e-→2[H]→H2 E(H+/H2)=0V
酸性富氧条件下:4H++O2+4e-→2H2O E(O2)=1.23V Under acidic oxygen-enriched conditions: 4H++O2+4e-→2H2O E(O2)=1.23V
可以看出,在酸性富氧条件下,电位差最大,腐蚀反应最快,即处理效果最好。因此本实用新型铁碳池需控制pH为酸性,且曝气以提供氧气促进微电解反应。 It can be seen that under acidic oxygen-enriched conditions, the potential difference is the largest and the corrosion reaction is the fastest, that is, the treatment effect is the best. Therefore, the iron-carbon pool of the utility model needs to control the pH to be acidic, and aerate to provide oxygen to promote the micro-electrolysis reaction.
Fenton试剂氧化法在工业废水处理方面,对难于生物降解或一般化学氧化处理解决不了的物质有独到的优点。其作用机理为: Fenton's reagent oxidation method has unique advantages in the treatment of industrial wastewater for substances that are difficult to biodegrade or cannot be solved by general chemical oxidation treatment. Its mechanism of action is:
Fe2+与过氧化氢反应很快,生成氧化能力极强的·O游离基,与有机物质发生氧化反应,使其碳链断裂,最后的生成的物质为二氧化碳和水,从而达到较彻底地处理有机污水的目的。大剂量的Fenton试剂可使酚的聚合物进一步转化成CO2,从而达到净化废水的目的。对于芳香族化合物来说,·OH可以破坏芳香环,形成脂肪族化合物,从而消除芳香族化合物的生物毒性,改善废水的生物降解性能。 对于染料,·OH可以直接攻击发色基团,打开染料发色官能团的不饱和键,使染料氧化分解,同时达到对废水进行脱色和降低COD的目的。 此外,对于某些水溶性有机物(如带磺酸基团的萘系有机物),·OH可与其发生反应,改变其电子云密度和结构,降低其水溶性,有利于采用混凝或吸附的方法对其进行去除。 Fe 2+ reacts with hydrogen peroxide very quickly to generate O free radicals with strong oxidizing ability, which oxidize with organic substances to break the carbon chain, and the final substances are carbon dioxide and water, so as to achieve a more thorough The purpose of treating organic sewage. A large dose of Fenton's reagent can further convert the phenolic polymer into CO2, thereby achieving the purpose of purifying wastewater. For aromatic compounds, OH can destroy aromatic rings to form aliphatic compounds, thereby eliminating the biological toxicity of aromatic compounds and improving the biodegradability of wastewater. For dyes, OH can directly attack the chromophoric group, open the unsaturated bond of the dye chromogenic functional group, oxidatively decompose the dye, and at the same time achieve the purpose of decolorizing the wastewater and reducing COD. In addition, for some water-soluble organic compounds (such as naphthalene-based organic compounds with sulfonic acid groups), OH can react with it, change its electron cloud density and structure, and reduce its water solubility, which is conducive to the use of coagulation or adsorption methods Remove it.
两者联用借助铁炭微电解氧化和芬顿自由基氧化共同作用,使废水中难降解的有机物分解氧化,生成二氧化碳、水及其他无机物。 The combination of the two uses iron-carbon micro-electrolytic oxidation and Fenton free radical oxidation to decompose and oxidize refractory organic matter in wastewater to generate carbon dioxide, water and other inorganic substances.
下面介绍两个实例: Two examples are described below:
实例一:某PCB厂的有机废水,经其酸化池酸化后进入此装置,入水颜色呈蓝绿色,pH约为1~2,所含金属离子主要为铜离子,COD约为2500~3000 mg/L。废水经由水泵抽取至铁碳池1,流量为3m3/h。由于废水已经酸化,因此pH调节装置一7主要用于监测铁碳池内液体pH稳定且符合要求。曝气系统6曝气以向池内提供空气,使溶液含氧量在1.5~2mg/L,促进铁碳微电解反应,通过反应,铜离子等金属离子可被置换而脱离废水,大分子有机物等污染物亦可被反应和降解一部分,同时产生亚铁离子,pH略有升高,停留时间约为40~50min。之后流入芬顿池2,因pH和亚铁离子无需调节而由铁碳池1提供即可,因此加药装置一9只需投加双氧水即可,在此实施例中,投加量为167mL/min 50%H2O2,由曝气系统6曝气以保证混合均匀,通过芬顿高级氧化反应,废水中剩余的污染物会被降解,COD大大降低,停留时间约为2h。之后进入混凝池3,入口由pH调节装置二8自动调节pH为8~9,因此水中所含的铁离子和亚铁离子会形成絮体,再在入口投加10ppm的混凝剂PAM,投加量为208mL/min,以促进小絮体凝聚成大絮体,池中的搅拌装置11通过搅拌促进混凝效果,停留时间大约为1h。最后流入沉淀池4,斜板12可提升泥水分离效果,污泥蓄积在底部,由底部排泥口排出,清水由上部溢流口流出,出水COD较低,透明无色无味。选取几组测试结果,见下表。
Example 1: The organic wastewater of a PCB factory enters the device after being acidified by its acidification tank. The color of the water is blue-green, the pH is about 1~2, the metal ions contained are mainly copper ions, and the COD is about 2500~3000 mg/ L. The waste water is pumped to the iron-carbon pool 1 with a flow rate of 3m 3 /h. Because the waste water has been acidified, the pH adjustment device-7 is mainly used to monitor that the pH of the liquid in the iron-carbon pool is stable and meets the requirements. The aeration system 6 aerates to provide air into the pool, so that the oxygen content of the solution is 1.5~2mg/L, and promotes the iron-carbon micro-electrolysis reaction. Through the reaction, metal ions such as copper ions can be replaced and separated from waste water, macromolecular organic matter, etc. Pollutants can also be reacted and partially degraded, and ferrous ions are produced at the same time, the pH is slightly increased, and the residence time is about 40~50min. Then it flows into the Fenton pool 2, and it can be provided by the iron-carbon pool 1 because pH and ferrous ions do not need to be adjusted. Therefore, the dosing device-9 only needs to add hydrogen peroxide. In this embodiment, the dosage is 167mL /min 50%H2O2, aeration by the aeration system 6 to ensure uniform mixing, through the Fenton advanced oxidation reaction, the remaining pollutants in the wastewater will be degraded, COD is greatly reduced, and the residence time is about 2h. After entering the coagulation tank 3, the pH at the entrance is automatically adjusted to 8~9 by the pH adjustment device 28, so the ferric ions and ferrous ions contained in the water will form flocs, and then add 10ppm coagulant PAM at the entrance, The dosage is 208mL/min to promote the coagulation of small flocs into large flocs. The stirring device 11 in the pool promotes the coagulation effect by stirring, and the residence time is about 1h. Finally, it flows into the sedimentation tank 4. The sloping
表1 实例一测试数据 Table 1 Example 1 test data
实例二:某PCB厂经处理后的水,入水颜色透明无异味,pH约为7~8,COD约为300~400 mg/L。废水经由水泵抽取至铁碳池1,流量为3m3/h。由pH调节装置一7自动调节入水pH在1~2之间,曝气系统6曝气以向池内提供空气,促进铁碳微电解反应,通过反应,金属离子可被置换而脱离废水,大分子有机物等污染物亦可被反应和降解一部分,同时产生亚铁离子,pH略有升高,停留时间约为40~50min。之后流入芬顿池2,因pH和亚铁离子无需调节而由铁碳池1提供即可,因此加药装置一9只需投加双氧水即可,在此实施例中,投加量为104mL/min 50%H2O2,由曝气系统6曝气以保证混合均匀,通过芬顿高级氧化反应,废水中剩余的污染物会被降解,COD大大降低,停留时间约为2h。之后进入混凝池3,入口由pH调节装置二8自动调节pH为8~9,因此水中所含的铁离子和亚铁离子会形成絮体,再在入口投加10ppm的混凝剂PAM,投加量为208mL/min,以促进小絮体凝聚成大絮体,池中的搅拌装置11通过搅拌促进混凝效果,停留时间大约为1h。最后流入沉淀池4,斜板12可提升泥水分离效果,污泥蓄积在底部,由底部排泥口排出,清水由上部溢流口流出,出水COD较低,透明无色无味。选取几组测试结果,见下表。
Example 2: The treated water of a PCB factory is transparent and odorless, the pH is about 7~8, and the COD is about 300~400 mg/L. The waste water is pumped to the iron-carbon pool 1 with a flow rate of 3m 3 /h. The pH of the incoming water is automatically adjusted between 1 and 2 by the pH adjustment device 7, and the aeration system 6 aerates to provide air into the pool to promote the iron-carbon micro-electrolysis reaction. Through the reaction, metal ions can be replaced and separated from wastewater, macromolecules Pollutants such as organic matter can also be reacted and partially degraded, and ferrous ions are produced at the same time, the pH is slightly increased, and the residence time is about 40~50min. Afterwards, it flows into the Fenton pool 2, and is provided by the iron-carbon pool 1 because pH and ferrous ions do not need to be adjusted. Therefore, the dosing device-9 only needs to add hydrogen peroxide. In this embodiment, the dosage is 104mL /min 50%H 2 O 2 , aeration by the aeration system 6 to ensure uniform mixing, through the Fenton advanced oxidation reaction, the remaining pollutants in the wastewater will be degraded, COD is greatly reduced, and the residence time is about 2h. After entering the coagulation tank 3, the pH at the entrance is automatically adjusted to 8~9 by the pH adjustment device 28, so the ferric ions and ferrous ions contained in the water will form flocs, and then add 10ppm coagulant PAM at the entrance, The dosage is 208mL/min to promote the coagulation of small flocs into large flocs. The stirring device 11 in the pool promotes the coagulation effect by stirring, and the residence time is about 1h. Finally, it flows into the sedimentation tank 4. The
表2 实例二测试数据 Table 2 Test data of instance 2
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