CN1261370C - Oxidative coagulation aid method for combined treatment of drinking water source with ozone and potassium permanganate - Google Patents
Oxidative coagulation aid method for combined treatment of drinking water source with ozone and potassium permanganate Download PDFInfo
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技术领域：本发明涉及一种给水处理方法。Technical field: the present invention relates to a water treatment method.
背景技术：由于受污水排放和农田径流等因素的影响，饮用水源污染不断加重，水体富营养化，藻类过量繁殖，现行的常规给水处理工艺难以保障饮用水水质。预氯化是常采用的预氧化方法，可强化藻类的去除，然而，高浓度的氯与水中有机物作用会产生对人体有害的氯化副产物。虽然管网中的余氯可在一定程度上限制管网中的细菌生长，但在有机营养基质浓度较高时，细菌仍会再度繁殖，并附着生长在管壁上形成生物膜，增加水中细菌总数，况且有些细菌危害性更大，从一定程度上影响自来水的微生物安全性。水厂的实际运行结果也证明了存在这些问题。用预臭氧化取代预氯化已经被发达国家应用于水厂中。臭氧预氧化可用于脱色、除臭、控制氯化消毒副产物、强化去除藻类和藻毒素、助凝和助滤等。大量文献表明，目前国内外对臭氧预氧化的作用机理还不很清晰，有人认为臭氧预氧化可提高混凝效果，而有人认为臭氧预氧化不起助凝作用甚至对混凝有副作用。预臭氧化的效果受很多因素影响，如原水有机物浓度、硬度、臭氧投量、预氧化及混凝条件等。臭氧投量是影响预氧化效果的主要因素，据报道，臭氧投量较低时，预氧化助凝效果显著，但臭氧投量过高，使水中有机物极性增加，会对混凝有副作用。此外，臭氧化会增加水的可生化性，增加水中有机营养基质的含量，具体表现为水的生物可同化有机碳(AOC)和可生物降解的溶解性有机碳(BDOC)浓度升高，影响程度也与原水水质、臭氧化条件有关。Background technology: Due to the influence of factors such as sewage discharge and farmland runoff, the pollution of drinking water sources continues to increase, the water body becomes eutrophic, and algae grow excessively. The current conventional water supply treatment process is difficult to guarantee the quality of drinking water. Pre-chlorination is a commonly used pre-oxidation method, which can strengthen the removal of algae. However, the interaction of high concentrations of chlorine with organic matter in water will produce chlorination by-products that are harmful to humans. Although the residual chlorine in the pipe network can limit the growth of bacteria in the pipe network to a certain extent, when the concentration of the organic nutrient substrate is high, the bacteria will still multiply again, and attach and grow on the pipe wall to form a biofilm, increasing the number of bacteria in the water. The total number, and some bacteria are more harmful, which affects the microbial safety of tap water to a certain extent. The actual operation results of the water plant also proved the existence of these problems. Replacing pre-chlorination with pre-ozonation has been applied in water plants in developed countries. Ozone pre-oxidation can be used for decolorization, deodorization, control of chlorination disinfection by-products, enhanced removal of algae and algal toxins, coagulation aid and filter aid, etc. A large number of literatures show that the mechanism of ozone pre-oxidation at home and abroad is not very clear at present. Some people think that ozone pre-oxidation can improve the coagulation effect, while others think that ozone pre-oxidation has no effect on coagulation and even has side effects on coagulation. The effect of pre-ozonation is affected by many factors, such as the concentration of organic matter in raw water, hardness, ozone dosage, pre-oxidation and coagulation conditions, etc. The dosage of ozone is the main factor affecting the effect of pre-oxidation. According to reports, when the dosage of ozone is low, the effect of pre-oxidation and coagulation is significant. However, if the dosage of ozone is too high, the polarity of organic matter in water will increase, which will have side effects on coagulation. In addition, ozonation will increase the biodegradability of water and increase the content of organic nutrient substrates in water, which is manifested in the increase of the concentration of bioassimilable organic carbon (AOC) and biodegradable dissolved organic carbon (BDOC) in water, affecting The degree is also related to the raw water quality and ozonation conditions.
发明内容：本发明就是为了弥补臭氧单独氧化的缺点，提高处理效果，从而保障饮用水的水质安全，本发明的方法是在原水中投加臭氧和高锰酸钾两种氧化剂，臭氧投加量为0.1～3mg/l，高锰酸钾的投加量为0.1～1.5mg/l，两种氧化剂的投加时间差在5分钟之内，还可以用高锰酸钾与以下任意一种或几种药剂的混合物作为氧化剂代替单一的高锰酸钾：硫酸铝、三氯化铝、三氯化铁、聚合硫酸铝、聚合氯化铝、聚合铁、活化硅酸、聚硅酸铁、聚硅酸铝、沸石、氧化镁、氧化钙、氢氧化钙、粉末活性炭、氯化钙、高铁酸钾、硫酸铁、次氯酸钙、次氯酸钠、硫酸亚铁、氢氧化钠、氢氧化钾、碳酸氢钠、聚丙烯酰胺、膨润土、高岭土、硅藻土。本发明在预臭氧之前或之后投加适量的高锰酸盐(本发明中的高锰酸盐指的是单独高锰酸钾或高锰酸钾与以下任意一种或几种药剂的混合物：聚合铝、硫酸铝、三氯化铝、三氯化铁、聚合硫酸铝、聚合氯化铝、聚合铁、活化硅酸、聚硅酸铁、聚硅酸铝、沸石、氧化镁、氧化钙、氢氧化钙、粉末活性炭、氯化钙、高铁酸钾、硫酸铁、次氯酸钙、次氯酸钠、硫酸亚铁、氢氧化钠、氢氧化钾、碳酸氢钠、聚丙烯酰胺、非离子有机高分子、阴离子有机高分子、阳离子有机高分子、膨润土、高岭土、硅藻土)，利用高锰酸盐来强化或催化臭氧氧化，提高对水中微污染物的去除效果，同时高锰酸盐本身的助凝作用也可以提高混凝效果。本发明的优点在于：臭氧与高锰酸钾或含有高锰酸钾的复合药剂联合预氧化，两者之间产生协同氧化和催化氧化作用，从而提高臭氧的氧化能力，强化对水中微污染物的去除、水中嗅味的去除、强化水中藻类去除、提高助凝效果，两者联用可降低或避免单纯投加臭氧产生的副作用，提高综合除污染效率，保障饮用水水质安全。高锰酸盐在反应过程中形成的中间态的锰和新生态的锰氧化物对臭氧氧化具有催化作用，能够强化臭氧的除污染效果。本发明与单独臭氧化相比，对藻类、有机物、氮类、消毒副产物前质等污染物的去除率都分别可以提高10％以上。用臭氧和高锰酸盐复合预氧化强化混凝，后续投加混凝剂进行混凝，各种不同类型的混凝剂均有明显的助凝作用。高锰酸盐的投加不需要增加很多构筑物和设备，对新建水厂和现有水厂的改造都是简单易行的。本发明能够节省混凝剂以及臭氧的投加量，不但可以降低制水成本，而且可避免由于臭氧过量投加产生的副作用，在经济上和技术上都是可行的，具有良好的推广应用价值。Summary of the invention: The present invention is to make up for the shortcomings of ozone alone oxidation, improve the treatment effect, thereby ensuring the water quality safety of drinking water. The method of the present invention is to add two kinds of oxidants, ozone and potassium permanganate, to the raw water, and the dosage of ozone is 0.1 ~ 3mg/l, the dosage of potassium permanganate is 0.1 ~ 1.5mg/l, the time difference between the two oxidants is within 5 minutes, and potassium permanganate can also be used with any one or more of the following A mixture of agents as an oxidant instead of a single potassium permanganate: aluminum sulfate, aluminum trichloride, ferric chloride, polyaluminum sulfate, polyaluminum chloride, polyferric, activated silicic acid, polysilicate iron, polysilicate Aluminum, zeolite, magnesium oxide, calcium oxide, calcium hydroxide, powdered activated carbon, calcium chloride, potassium ferrate, ferric sulfate, calcium hypochlorite, sodium hypochlorite, ferrous sulfate, sodium hydroxide, potassium hydroxide, sodium bicarbonate , polyacrylamide, bentonite, kaolin, diatomaceous earth. The present invention adds an appropriate amount of permanganate before or after pre-ozone (permanganate in the present invention refers to the mixture of potassium permanganate alone or potassium permanganate and any one or more of the following medicaments: Polyaluminum, aluminum sulfate, aluminum trichloride, ferric chloride, polyaluminum sulfate, polyaluminum chloride, polyferric, activated silicic acid, polyferric silicate, polyaluminum silicate, zeolite, magnesium oxide, calcium oxide, Calcium hydroxide, powdered activated carbon, calcium chloride, potassium ferrate, ferric sulfate, calcium hypochlorite, sodium hypochlorite, ferrous sulfate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, polyacrylamide, non-ionic organic polymer , anionic organic polymers, cationic organic polymers, bentonite, kaolin, diatomaceous earth), use permanganate to strengthen or catalyze ozone oxidation, improve the removal effect of micro-pollutants in water, and permanganate itself helps Coagulation can also improve the coagulation effect. The advantages of the present invention are: ozone and potassium permanganate or the compound agent containing potassium permanganate are combined for pre-oxidation, and synergistic oxidation and catalytic oxidation are produced between the two, thereby improving the oxidation ability of ozone and strengthening the treatment of micro-pollutants in water The removal of ozone, the removal of odor in water, the strengthening of algae removal in water, and the improvement of coagulation aid effect, the combination of the two can reduce or avoid the side effects of simply adding ozone, improve the comprehensive decontamination efficiency, and ensure the safety of drinking water quality. The intermediate state manganese and new ecological manganese oxides formed by permanganate during the reaction can catalyze the oxidation of ozone, which can strengthen the decontamination effect of ozone. Compared with the single ozonation, the present invention can increase the removal rates of algae, organic matter, nitrogen, disinfection by-product precursors and other pollutants by more than 10%. Ozone and permanganate composite pre-oxidation is used to strengthen coagulation, and coagulants are added for subsequent coagulation. Various types of coagulants have obvious coagulation-assisting effects. The addition of permanganate does not need to add a lot of structures and equipment, and the transformation of new water plants and existing water plants is simple and easy. The invention can save the dosage of coagulant and ozone, not only can reduce the cost of water production, but also can avoid the side effects caused by excessive dosage of ozone, is economically and technically feasible, and has good popularization and application value .
具体实施方式一：针对本发明进行了实验室阶段的小试研究：试验采用六联搅拌器进行研究，臭氧投加量在0.1～3mg/l，高锰酸钾投加量在0.1～1.5mg/l。两者之间的剂量比是通过大量试验验证所得，在本实施方式中两种氧化剂同时投加到原水中。试验结果表明，两种氧化剂之间的联用可以达到良好的处理效果，对有机物的去除率可以提高10～20％，浊度可以降低到1NTU左右。Specific embodiment 1: Carry out the small-scale test research of laboratory stage for the present invention: the experiment adopts six joint agitator to carry out research, and the dosage of ozone is 0.1～3mg/l, and the dosage of potassium permanganate is 0.1～1.5mg /l. The dose ratio between the two is verified through a large number of experiments. In this embodiment, the two oxidants are added to the raw water at the same time. The test results show that the combined use of the two oxidants can achieve a good treatment effect, the removal rate of organic matter can be increased by 10-20%, and the turbidity can be reduced to about 1NTU.
具体实施方式二：本实施方式与具体实施方式一的不同之处在于，高锰酸钾在投加臭氧之后的5分钟时投加，其它与具体实施方式一相同。Specific embodiment two: the difference between this embodiment and specific embodiment one is that potassium permanganate is added 5 minutes after ozone is added, and others are the same as specific embodiment one.
具体实施方式三：本实施方式与具体实施方式一的不同之处在于，臭氧在投加高锰酸钾之后的3分钟投加，其它与具体实施方式一相同。Embodiment 3: The difference between this embodiment and Embodiment 1 is that ozone is added 3 minutes after potassium permanganate is added, and the others are the same as Embodiment 1.
具体实施方式四：本实施方式根据生产性试验研究结果。一种氧化剂为高锰酸钾与以下任意一种或几种药剂的混合物作为氧化剂：聚合铝、硫酸铝、三氯化铝、三氯化铁、聚合硫酸铝、聚合氯化铝、聚合铁、活化硅酸、聚硅酸铁、聚硅酸铝、沸石、氧化镁、氧化钙、氢氧化钙、粉末活性炭、氯化钙、高铁酸钾、硫酸铁、次氯酸钙、次氯酸钠、硫酸亚铁、氢氧化钠、氢氧化钾、碳酸氢钠、聚丙烯酰胺、非离子有机高分子、阴离子有机高分子、阳离子有机高分子、膨润土、高岭土、硅藻土，高锰酸盐选择投加在了臭氧氧化之后。即经过臭氧氧化后的出水再投加前述氧化剂进行强化氧化和协同氧化，氧化时间为1min，然后投加混凝剂聚合氯化铝。Specific implementation mode 4: This implementation mode is based on the research results of the productivity test. An oxidizing agent is a mixture of potassium permanganate and any one or more of the following agents: polyaluminum, aluminum sulfate, aluminum trichloride, ferric chloride, polyaluminum sulfate, polyaluminum chloride, polyferric, Activated silicic acid, iron polysilicate, aluminum polysilicate, zeolite, magnesium oxide, calcium oxide, calcium hydroxide, powdered activated carbon, calcium chloride, potassium ferrate, ferric sulfate, calcium hypochlorite, sodium hypochlorite, ferrous sulfate , sodium hydroxide, potassium hydroxide, sodium bicarbonate, polyacrylamide, non-ionic organic polymers, anionic organic polymers, cationic organic polymers, bentonite, kaolin, diatomaceous earth, and permanganate are added to the after ozone oxidation. That is, the effluent after ozone oxidation is added with the aforementioned oxidant for enhanced oxidation and coordinated oxidation. The oxidation time is 1 min, and then the coagulant polyaluminum chloride is added.
对浊度的去除结果表明，随着高锰酸盐投量的增加，沉后水浊度也逐渐降低。到高锰酸盐投加量达到0.6mg/l时，去除效果最好，出水浊度保持在1.0NTU左右。臭氧投量在0.8～1.0mg/l时，出水浊度最低。从1.0mg/l之后再增加臭氧的量，却随着投量的增加出水效果逐渐变差。The results of turbidity removal showed that with the increase of permanganate dosage, the turbidity of sinking water gradually decreased. When the dosage of permanganate reaches 0.6mg/l, the removal effect is the best, and the turbidity of the effluent remains at about 1.0NTU. When the dosage of ozone is 0.8-1.0mg/l, the turbidity of the effluent is the lowest. After increasing the amount of ozone from 1.0 mg/l, the water outlet effect gradually becomes worse with the increase of the dosage.
对有机物的去除结果表明，在预氧化后和沉后水阶段，它们的处理效果相差不大，但在滤后水阶段，高锰酸盐的投加可以将有机物的去除率提高10％左右。臭氧投加量的变化并没有使CODMn的去除呈现有规律性的变化，反而是在0.5mg/L时达到最佳的去除率，可以达50％。The results of the removal of organic matter show that the treatment effects are not much different in the post-oxidation and sinking water stages, but in the filtered water stage, the addition of permanganate can increase the removal rate of organic matter by about 10%. The change of ozone dosing amount did not make the removal of COD Mn change regularly, but reached the best removal rate at 0.5mg/L, which could reach 50%.
对藻类的观测结果表明，对于不同处理情况而言，在预氧化阶段，随着高锰酸盐投加量的增加，去除率也逐渐升高，可以由单纯的预臭氧的20％升高到两者联用的50％左右。之后在不同的处理阶段，也能提高10％左右。The observation results of algae show that for different treatment conditions, in the pre-oxidation stage, with the increase of permanganate dosage, the removal rate also gradually increases, which can be increased from 20% of simple pre-ozone to About 50% of the combined use of the two. After that, in different processing stages, it can also increase by about 10%.
在预氧化出水阶段，不同处理情况下都表现出氨氮增加的趋势，而单独预臭氧增加的趋势较为明显，到了沉后水阶段，预臭氧仍然继续增加，而投加高锰酸盐的情况氨氮却呈下降趋势。到滤后阶段，都有明显的下降，去除率可达到20～30％。这表明高锰酸盐的投加可以提高氨氮的去除率，而单独臭氧化却不能达到这一效果。In the pre-oxidation effluent stage, different treatments showed a trend of increasing ammonia nitrogen, while the trend of increasing pre-ozone alone was more obvious. But a downward trend. In the post-filtration stage, there is a significant decline, and the removal rate can reach 20-30%. This indicated that the addition of permanganate could increase the removal rate of ammonia nitrogen, but ozonation alone could not achieve this effect.
预氧化后，亚硝酸盐的去除率非常高，单独预臭氧可以达到50％左右的去除率，而投加高锰酸盐后，去除率都有所升高，分别可以进一步提高10～20％。After pre-oxidation, the removal rate of nitrite is very high, the removal rate of pre-ozone alone can reach about 50%, and after adding permanganate, the removal rate has increased, and can be further increased by 10-20% respectively .
生产运行和实验结果均得出如下主要结论：高锰酸盐预氧化和臭氧的联合使用可以在不同方面提高处理水水质，不同处理指标都可以分别提高10％以上；在一定的臭氧投加量条件下，较高的高锰酸盐投加量可以达到较好的处理效果；高锰酸盐投加量不变，改变臭氧的投量，结果并不是随着臭氧投加量越高，处理结果越好，反而是较低的臭氧投加量较好；在投加高锰酸盐的情况下，臭氧投加量控制在0.5～1.0mg/l时可以达到较好的处理效果，而高锰酸盐的投加量可以在0.2～0.6mg/l范围内变化；高锰酸盐的投加可以节省混凝剂和臭氧的投加量，从而节省了制水成本，综合考虑，投加高锰酸盐可以至少节省成本1分/立方水。Both the production operation and the experimental results have drawn the following main conclusions: the combined use of permanganate pre-oxidation and ozone can improve the quality of treated water in different aspects, and different treatment indicators can be increased by more than 10% respectively; Under certain conditions, a higher dosage of permanganate can achieve a better treatment effect; the dosage of permanganate remains unchanged, but the dosage of ozone is changed. The result is not that the higher the dosage of ozone, the treatment The better the result, the lower the dosage of ozone is better; in the case of adding permanganate, the better treatment effect can be achieved when the dosage of ozone is controlled at 0.5-1.0mg/l, while the dosage of high The dosage of manganate can be changed within the range of 0.2-0.6mg/l; the dosage of permanganate can save the dosage of coagulant and ozone, thus saving the cost of water production. Permanganate can save at least 1 cent/cubic water.
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2004
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