WO2024251121A1 - 一种鳗鱼养殖废水的净化循环利用方法及应用 - Google Patents

一种鳗鱼养殖废水的净化循环利用方法及应用 Download PDF

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WO2024251121A1
WO2024251121A1 PCT/CN2024/097343 CN2024097343W WO2024251121A1 WO 2024251121 A1 WO2024251121 A1 WO 2024251121A1 CN 2024097343 W CN2024097343 W CN 2024097343W WO 2024251121 A1 WO2024251121 A1 WO 2024251121A1
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water
eel
breeding wastewater
recycling
eel breeding
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French (fr)
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孔玲芬
黄全佳
阮鲤萍
刁心刚
黄雅娟
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Haoyu Xiamen Environment Protection Co Ltd
Xiamen Environmental Monitoring Station
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Haoyu Xiamen Environment Protection Co Ltd
Xiamen Environmental Monitoring Station
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F7/00—Aeration of stretches of water

Definitions

  • the invention belongs to the technical field of water resource recycling and environmental protection, and in particular relates to a purification and recycling method for eel breeding wastewater and its application.
  • Eel (Anguillidae) belongs to the order Anguilliformes, which is also known as eel, white eel, white eel, river eel, etc., including Asian eel, Japanese eel, bicolor eel, American eel (South American eel and North American eel) and European eel.
  • Eel is rich in high-quality protein and various amino acids and vitamins required by the human body, and contains high content of fish oil. It has high nutritional value and tastes fresh, so it has extremely high economic value for breeding.
  • Eel farming wastewater contains high concentrations of pollutants such as ammonia nitrogen, total nitrogen, total phosphorus and COD Cr . If it is not treated and directly discharged into the environment, it will lead to excessive concentrations of COD Cr , BOD 5 , nitrogen and phosphorus in natural water bodies such as rivers and lakes, as well as eutrophication of water bodies. Therefore, eel farming wastewater must be purified.
  • the concentrations of major pollutants in the discharged wastewater also vary greatly. For example, during the growth process, the bicolor eel eats less bait every day, and the feces it discharges are also less.
  • the ammonia nitrogen, total nitrogen, total phosphorus and COD Cr in the discharged wastewater are all low.
  • the ammonia nitrogen in the discharged wastewater is ⁇ 2mg/L, the total nitrogen is ⁇ 5mg/L, the total phosphorus is ⁇ 3.0mg/L and the COD is ⁇ 30mg/L; the American eel grows faster, and during the growth process, it eats more bait every day, and the feces it discharges are also more.
  • the ammonia nitrogen, total nitrogen, total phosphorus and COD Cr in the discharged wastewater are all high.
  • the ammonia nitrogen in the wastewater is ⁇ 7mg/L
  • the total nitrogen is ⁇ 20mg/L
  • the total phosphorus is ⁇ 3.5mg/L
  • the COD Cr is ⁇ 50mg/L.
  • the concentration of major pollutants in eel farming wastewater is also related to the growth period of eels. In the young and middle-aged period, due to fast growth, eating more and discharging more, the concentrations of major pollutants such as ammonia nitrogen, total nitrogen, total phosphorus and COD Cr in the wastewater are also higher.
  • the concentrations of major pollutants such as ammonia nitrogen, total nitrogen, total phosphorus and COD Cr in the wastewater in winter and summer also show a situation of low concentration in winter and high concentration in summer.
  • the concentration of major pollutants in eel farming wastewater is also closely related to the breeding mode and drainage method.
  • the treatment of eel farming wastewater mainly focuses on the treatment of COD Cr , BOD 5 , ammonia nitrogen and total phosphorus in the wastewater.
  • the main methods include multiple oxidation ponds in series with phosphorus removal agent precipitation, biochemical method, artificial wetland method, and a combination of oxidation ponds and precipitation methods.
  • the purpose of the present invention is to adapt to eel breeding wastewater with different pollution conditions, realize the purification and recycling of eel breeding wastewater, and provide a purification and recycling method and application of eel breeding wastewater.
  • a fiber rotary disc machine with a corresponding filter aperture can be selected for filtration according to the turbidity degree of the eel breeding wastewater.
  • the conventional filter aperture of the fiber rotary disc machine is 5 ⁇ 20 ⁇ m, and specifically can be 5 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m or any value therebetween.
  • the volume ratio of clean water and concentrated water obtained in the filtration diversion is regulated to achieve preliminary regulation of the pollution degree of clean water and concentrated water, which is beneficial to subsequent treatment.
  • the volume ratio of the clean water obtained can be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90% or any value therebetween
  • the volume ratio of the concentrated water obtained can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or any value therebetween.
  • the clean water is treated in a split and combined manner, and the clean water of the first part is first subjected to catalytic electrolysis denitrification, so that the ammonia nitrogen in the water is oxidized to nitrate by the hydroxyl radicals generated by electrolysis during the electrolysis process, and the nitrate is reduced to nitrogen gas by the hydrogen atoms generated by electrolysis, and at the same time, the hydrogen ions, hydroxyl radicals and sodium hypochlorite in the water can react with the ammonia nitrogen and nitrate in the second part to oxidize the ammonia nitrogen in the water to nitrogen gas and reduce the nitrate nitrogen to nitrogen gas.
  • the volume ratio of the first part and the second part can be adaptively adjusted according to the pollution condition of the clean water, which has better adaptability.
  • the standard potential of NH 3 /N 2 is -3.1, which is much lower than the standard potential of H + /H 2 , which is 0. Therefore, the hydroxyl radicals produced by electrolysis first react with ammonia to form nitrates. At the same time, nitrates react with hydrogen atoms produced by electrolysis to form nitrogen.
  • catalytic electrolysis oxidizes organic phosphorus and polyphosphorus in the wastewater into phosphate.
  • clean water treated by catalytic electrolytic denitrification and aeration is discharged into a biological activation pool, and the water body is mixed with a bacterial and algae culture solution for biological activation, and cultured at 20-35°C for 18-36 hours to rebuild the balance of the water body's microecology and restore the activity of the water body.
  • the temperature and time required for bioactivation can be determined according to the conditions of the water body.
  • the temperature of bioactivation can be 20°C, 21°C, 23°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 32°C, 34°C, 35°C or any value therebetween, and the time can be 18h, 20h, 21h, 23h, 25h, 27h, 28h, 30h, 32h, 34h, 36h or any value therebetween.
  • the microorganisms contained in the bacteria and algae culture solution are selected as microorganisms that are beneficial to the growth of eels, and specifically can be but not limited to photosynthetic bacteria, chlorella, diatoms, spirulina and Bacillus subtilis, used alone or in combination, and the water body is restored to activity by the large-scale reproduction of photosynthetic bacteria, chlorella, diatoms, spirulina and/or Bacillus subtilis.
  • the active substances such as subtilisin, polymyxin, nystatin, gramicidin, etc.
  • Bacillus subtilis produced during the proliferation of Bacillus subtilis have a significant inhibitory effect on pathogenic bacteria, and can stimulate the growth and development of eel immune organs, activate T and B lymphocytes, increase the level of immunoglobulins and antibodies, enhance cellular immunity and humoral immunity, and improve group immunity.
  • Bacillus subtilis can also synthesize VB1 , VB2 , VB6 and nicotinic acid and other B vitamins, and improve the activity of interferon and macrophages in eels; more specifically, the bacterial cell density in the bacteria and algae culture solution is 107 ⁇ 1010 /L.
  • the amount of bacteria and algae culture solution added is 1 ⁇ 5 ⁇ (v/v), that is, 1 ⁇ 5mL of bacteria and algae culture solution is added to 1L of the water sample to be bioactivated. At this time, the concentration of bacteria in the water sample is appropriate, which is conducive to subsequent cultivation and achieves an ideal bioactivation effect.
  • the amount of bacteria and algae culture solution added is 1 ⁇ (v/v), 2 ⁇ (v/v), 3 ⁇ (v/v), 4 ⁇ (v/v), 5 ⁇ (v/v) or any value therebetween.
  • step S3 in the treatment of concentrated water in step S3, flocculants and coagulants are first added to the concentrated water for flotation to remove 90-98% of phosphorus and 40-75% of COD Cr in the concentrated water.
  • the flocculant can be, but is not limited to, one or more of ferrous sulfate, ferrous chloride, basic aluminum chloride, calcium chloride, sodium polyacrylate, polyacrylamide, polystyrene sulfonate and polyethylene oxide; the addition amount is 5-200 mg/L, specifically 5 mg/L, 10 mg/L, 25 mg/L, 50 mg/L, 60 mg/L, 75 mg/L, 80 mg/L, 85 mg/L, 90 mg/L, 95 mg/L, 100 mg/L, 110 mg/L, 115 mg/L, 128 mg/L, 140 mg/L, 150 mg/L, 157 mg/L, 180 mg/L, 190 mg/L, 200 mg/L or any value therebetween.
  • the coagulant aid may be, but is not limited to, polyacrylamide; its addition amount is 0.1-20 mg/L, specifically 0.1 mg/L, 0.5 mg/L, 0.8 mg/L, 1.0 mg/L, 1.5 mg/L, 2.0 mg/L, 5.0 mg/L, 8 mg/L, 10 mg/L, 15 mg/L, 20 mg/L or any value therebetween.
  • the treatment method provided in the present invention also includes the treatment of sludge: collecting the sludge from sedimentation, anaerobic treatment and flotation sludge removal, performing gravity separation and filter pressing to obtain dewatered sludge and filtered water, and the filtered water can enter the concentrated water treatment process and be discharged after purification.
  • the present invention also provides the application of the above eel breeding wastewater purification and recycling method in the treatment of eel breeding wastewater, which can achieve ideal treatment effects on breeding wastewater with different pollution conditions, and the effluent water quality is high, which can be recycled in eel breeding, and the treatment cost is low and the operation is simple, and it has good application prospects.
  • Embodiments of the present invention are described in detail below, and the examples of the embodiments are intended to be used to explain the present invention, but should not be construed as limiting the present invention.
  • specific techniques or conditions are not specified, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not specified for reagents or instruments used, they are all conventional products that can be obtained commercially.
  • This embodiment is used to illustrate the purification and recycling method of eel breeding wastewater with a production volume of 3,000 tons/day.
  • the method specifically includes the following steps:
  • the eel farming wastewater is discharged into the sedimentation tank for sedimentation and anaerobic reaction at 25-35°C for 8 hours.
  • solid particles such as feces and residual feed in the eel farming wastewater are removed by sedimentation.
  • the carbon-containing organic matter in the eel farming wastewater is oxidized into CO2 and the organic phosphorus is converted into phosphate through the action of anaerobic microorganisms in the sedimentation tank.
  • the eel farming wastewater that has undergone sedimentation and anaerobic treatment overflows from the sedimentation tank to a fiber rotary disc filter with a filtration pore size of 15 ⁇ m for filtration and diversion.
  • the resulting clean water accounts for 80% of the total effluent volume, and the concentrated water accounts for 20% of the total effluent volume.
  • Catalytic electrolytic denitrification A portion of the clean water obtained by filtering the fiber rotary disc enters the catalytic electrolyzer at a flow rate of 100m3 /h, and catalytic electrolytic denitrification is carried out under the conditions of voltage of 62V and current of 850A;
  • the sludge from the sedimentation tank and the flotation device enters the plate and frame filter press for filtration and dehydration to obtain dehydrated sludge and sludge filtered water, which enters the flotation device for treatment together with concentrated water.
  • the water quality indicators of the inlet and outlet water in each treatment step of this embodiment are shown in Table 1.
  • the wastewater is separated into two paths, one is clean water and the other is concentrated water; the clean water is treated with catalytic electrolytic denitrification, aeration and biological activation, and the effluent COD Cr ⁇ 30mg/L, ammonia nitrogen ⁇ 0.5mg/L, total nitrogen ⁇ 3mg/L and total phosphorus nitrogen ⁇ 0.2mg/L, which can be recycled to the breeding pond for reuse; and the concentrated water is treated with flotation, microfiltration and catalytic electrolytic denitrification, and the effluent COD Cr ⁇ 40mg/L, ammonia nitrogen ⁇ 1.0mg/L, total nitrogen ⁇ 3mg/L and total phosphorus ⁇ 0.5mg/L, which meets the discharge standard.
  • This embodiment is used to illustrate the purification and recycling method of eel breeding wastewater with a production volume of 10,000 tons/day, which specifically includes the following steps:
  • the eel farming wastewater is discharged into the sedimentation tank for sedimentation and anaerobic reaction at 25-35°C for 8 hours.
  • solid particles such as feces and residual feed in the eel farming wastewater are removed by sedimentation.
  • the carbon-containing organic matter in the eel farming wastewater is oxidized into CO2 and the organic phosphorus is converted into phosphate through the action of anaerobic microorganisms in the sedimentation tank.
  • the eel farming wastewater that has undergone sedimentation and anaerobic treatment overflows from the sedimentation tank into a fiber rotary disc filter with a filtration pore size of 10 ⁇ m.
  • the clean water obtained by filtration accounts for 90% of the total effluent volume, and the concentrated water accounts for 10% of the total effluent volume.
  • Catalytic electrolytic denitrification A portion of the clean water obtained by filtering the fiber rotary disc enters the catalytic electrolyzer at a flow rate of 375m3 /h, and catalytic electrolytic denitrification is carried out under the conditions of voltage of 62V and current of 5600A;
  • (1) Flotation The concentrated water obtained by fiber disc filtration enters the flotation device, and 50 mg/L of ferrous sulfate, 50 mg/L of polyethylene oxide and 20 mg/L of polyacrylamide are added to remove phosphorus and organic compounds in the concentrated water by flotation.
  • Catalytic electrolysis denitrification The solution obtained through microfiltration enters the catalytic electrolyzer at a flow rate of 25m3 /h, and catalytic electrolysis denitrification is carried out under the conditions of voltage of 62V and current of 350A. The solution after catalytic electrolysis denitrification enters the gas separation tower, and the nitrogen is discharged from the gas separation tower and meets the emission standards.
  • the sludge from the sedimentation tank and the flotation device enters the plate and frame filter press for filtration and dehydration to obtain dehydrated sludge and sludge filtered water, which enters the flotation device for treatment together with concentrated water.
  • the water quality indicators of the inlet and outlet water in each treatment step of this embodiment are shown in Table 2.
  • the wastewater is separated into two paths, one is clean water and the other is concentrated water; the clean water is treated with catalytic electrolytic denitrification, aeration and biological activation, and the effluent COD Cr ⁇ 40mg/L, ammonia nitrogen ⁇ 0.5mg/L, total nitrogen ⁇ 3mg/L and total phosphorus ⁇ 0.2mg/L, which can be recycled to the breeding pond for reuse; and the concentrated water is treated with flotation, microfiltration and catalytic electrolytic denitrification, and the effluent COD Cr ⁇ 40mg/L, ammonia nitrogen ⁇ 1.0mg/L, total nitrogen ⁇ 3mg/L and total phosphorus ⁇ 0.5mg/L, which meets the discharge standard.
  • This embodiment is used to illustrate the purification and recycling method of eel breeding wastewater with a production volume of 1000 tons/day, which specifically includes the following steps:
  • the eel farming wastewater is discharged into the sedimentation tank for sedimentation and anaerobic reaction at 25-35°C for 8 hours.
  • solid particles such as feces and residual feed in the eel farming wastewater are removed by sedimentation.
  • the carbon-containing organic matter in the eel farming wastewater is oxidized into CO2 and the organic phosphorus is converted into phosphate through the action of anaerobic microorganisms in the sedimentation tank.
  • the eel farming wastewater that has undergone sedimentation and anaerobic treatment is overflowed from the sedimentation tank into a fiber rotary disc filter with a filtration pore size of 20 ⁇ m.
  • the clean water obtained by filtration accounts for 95% of the total effluent volume, and the concentrated water accounts for 5% of the total effluent volume.
  • Catalytic electrolytic denitrification A portion of the clean water obtained by filtering the fiber rotary disc enters the catalytic electrolyzer at a flow rate of 42m3 /h, and catalytic electrolytic denitrification is carried out under the conditions of voltage of 670V and current of 1000A;
  • (1) Flotation The concentrated water obtained by fiber disc filtration enters the flotation device, and 50 mg/L of ferrous sulfate and 10 mg/L of polyacrylamide are added to remove phosphorus and organic compounds in the concentrated water by flotation.
  • Catalytic electrolysis denitrification The solution obtained through microfiltration enters the catalytic electrolyzer at a flow rate of 10m3 /h, and catalytic electrolysis denitrification is carried out under the conditions of voltage of 65V and current of 320A. The solution after catalytic electrolysis denitrification enters the gas separation tower, and the nitrogen is discharged from the gas separation tower and meets the emission standards.
  • the sludge from the sedimentation tank and the flotation device enters the plate and frame filter press for filtration and dehydration to obtain dehydrated sludge and sludge filtered water, which enters the flotation device for treatment together with concentrated water.
  • the water quality indicators of the inlet and outlet water in each treatment step of this embodiment are shown in Table 3.
  • the wastewater is separated into two paths, one is clean water and the other is concentrated water; the clean water is treated with catalytic electrolytic denitrification, aeration and biological activation, and the effluent COD Cr ⁇ 40mg/L, ammonia nitrogen ⁇ 0.5mg/L, total nitrogen ⁇ 3mg/L and total phosphorus ⁇ 0.2mg/L, which can be recycled to the breeding pond for reuse; and the concentrated water is treated with flotation, microfiltration and catalytic electrolytic denitrification, and the effluent COD Cr ⁇ 40mg/L, ammonia nitrogen ⁇ 1.0mg/L, total nitrogen ⁇ 3mg/L and total phosphorus ⁇ 0.5mg/L, which meets the discharge standard.

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Abstract

本发明属于水资源循环利用和环保的技术领域，公开了一种鳗鱼养殖废水的净化循环利用方法及应用。一种鳗鱼养殖废水的净化循环利用方法具体为：对鳗鱼养殖废水进行沉淀和厌氧处理以及过滤分流处理，获得清水和浓水；将清水分为第一部分和第二部分，对第一部分进行催化电解脱氮后与第二部分进行混合进行曝气和生物活化得到可循环出水；采用絮凝剂和助凝剂加入浓水并进行气浮除渣、微滤和催化电解脱氮得到达标出水。本发明提供的方法能够适应不同污染情况的鳗鱼养殖废水，得到水质良好和达到排放标准的出水，可实现鳗鱼养殖废水的循环利用以及无污染排放，且工艺简单、处理成本低，具有良好的实际应用前景。

Description

一种鳗鱼养殖废水的净化循环利用方法及应用 技术领域
本发明属于水资源循环利用和环保的技术领域，尤其涉及一种鳗鱼养殖废水的净化循环利用方法及应用。
 背景技术
鳗鱼（Anguillidae）属于鳗鲡目，其又称为鳗鲡、白鳗、白鳝、河鳗等，具体包括有亚洲鳗、日本鳗、双色鳗、美洲鳗（南美鳗和北美鳗）和欧鳗等品种。鳗鱼含有丰富的优质蛋白和人体所需的各类氨基酸和维生素，且含有高含量的鱼油，营养价值高且口感鲜嫩，因此具有极高的养殖经济价值。
由于鳗鱼养殖过程中需要定时排除陈水和补充新水，因此会产生大量的鳗鱼养殖废水，而鳗鱼养殖废水中含有较高浓度的氨氮、总氮、总磷和COD Cr等污染物，如果不经处理，直接排放至环境，会导致河流、湖泊等自然水体的COD Cr、BOD 5、氮、磷浓度超标以及水体富营养化等问题，因此必须对鳗鱼养殖污水进行净化处理。
由于不同品种的鳗鱼因生长速度不一样，吃的饵料数量也不一样，排放的废水中主要污染物浓度也有较大差异。比如，双色鳗在生长过程中，每日吃的饵料较少，其排出的粪便也就较少，排放废水中的氨氮、总氮、总磷和COD Cr都较低，其排放废水中的氨氮≤2mg/L、总氮≤5mg/L、总磷≤3.0mg/L和COD≤30mg/L ；美洲鳗生长较快，在生长过程中，每日吃的饵料较多，其排出的粪便也就较多，排放废水中的氨氮、总氮、总磷和COD Cr都较高，其废水中氨氮≤7mg/L、总氮≤20mg/L、总磷≤3.5mg/L和COD Cr≤50mg/L。除上述外，鳗鱼养殖废水中主要污染物的浓度还与鳗鱼的生长期有关，青壮年期，因生长快，吃的多，排放的也多，废水中主要污染物氨氮、总氮、总磷和COD Cr的浓度也较高。同时，即使同一种、同一池鳗鱼，冬季和夏季废水废水中的氨氮、总氮、总磷和COD Cr等主要污染物的浓度也呈现出冬季浓度低，夏季浓度高的状况。另外，鳗鱼养殖废水主要污染物浓度还与养殖模式、排水方式有很大的关系。
目前，鳗鱼养殖废水处理主要是对废水中的COD Cr、BOD 5、氨氮以及总磷进行处理，主要方法有多个氧化塘串联加除磷剂沉淀的方法、生化法、人工湿地法、氧化塘与沉淀法组合法等。但是，多个氧化塘串联加除磷剂沉淀的方法出水的COD Cr、BOD 5、氨氮和总氮等污染物指标多数难以达到排放标准，仍会给周围环境带来较大污染；而采用生化法或人工湿地对鳗鱼养殖废水进行处理时，由于鳗鱼养殖废水中的COD Cr和BOD 5较低且碳氮磷比例严重失调，在运行需要不断添加碳源，处理成本高，运行效果差；而采用氧化塘与沉淀法组合去除鳗鱼养殖废水中的总磷和总氮时，需要不断投加混凝剂，处理过程中投加量高达120～300g/m 3，会产生大量的污泥，不仅除磷效果差，而且成本高达0.6元/m 3以上。因此，随着鳗鱼养殖业的迅速发展，急需一种经济实用且能实现鳗鱼养殖废水净化和循环再利用的处理方法。
发明内容
本发明的目的是为了适应不同污染情况的鳗鱼养殖废水，实现对鳗鱼养殖废水的净化及循环利用，提供了一种鳗鱼养殖废水的净化循环利用方法及应用。
第一方面，本发明提供的鳗鱼养殖废水的净化循环利用方法采用以下的技术方案：
一种鳗鱼养殖废水的净化循环利用方法，具体包括以下步骤：
S1、鳗鱼养殖废水的前处理：对鳗鱼养殖废水进行沉淀和厌氧处理，除去水中粪便、残余饲料等固体颗粒物以及将鳗鱼养殖废水中的含碳有机化合物氧化成CO 2和有机磷转化为磷酸根，得到粗处理水样；对所述粗处理水样进行过滤分流，获得清水和浓水；
S2、清水的处理：所述清水分为第一部分和第二部分，对所述第一部分进行催化电解脱氮，后与所述第二部分进行混合进行曝气和生物活化，得到可循环出水；
S3、浓水的处理：所述浓水依次进行气浮、微滤和催化电解脱氮，得到达标出水。
在一些具体的实施方式中，所述S1中，沉淀和厌氧处理的温度为15~35℃，时间为3~5h。
在一些具体的实施方式中，所述S1中，过滤分流为：采用过滤孔径为5~20µm的纤维转盘过滤机对所述粗处理水样进行过滤得到清水和浓水。
在一些具体的实施方式中，所述清水的体积占比为80~90%，所述浓水的体积占比为10~20%。
在一些具体的实施方式中，所述S2中，生物活化为：取菌藻培养液与经过曝气的清水混合，于20~35℃下培养18~36h。
在一些具体的实施方式中，所述菌藻培养液包括光合细菌、小球藻、硅藻、螺旋藻和枯草芽孢杆菌中的至少两种。
在一些具体的实施方式中，所述菌藻培养液中菌藻密度为10 7~10 10个/L。
在一些具体的实施方式中，所述菌藻培养液的添加量为1~5‰(v/v)。
在一些具体的实施方式中，该方法还包括步骤S4，所述S4中，将所述沉淀和厌氧处理以及气浮除渣中产生的污泥进行重力分离和压滤得到脱水污泥。
第二方面，本发明还提供了以上鳗鱼养殖废水的净化循环利用方法在鳗鱼养殖废水处理中的应用。
 附图说明
图1为本发明中实施例1提供的鳗鱼养殖废水的处理方法的流程图。
 具体实施方式
为了实现对不同污染程度的鳗鱼养殖废水的净化以及循环利用，发明人经过广泛且深入的研究，做出了以下的方案。
本发明中提供的鳗鱼养殖废水的净化循环利用方法包括对鳗鱼养殖废水的前处理获得清水和浓水；一方面，在进行清水净化处理时，将清水分成两部分，一部分进行催化电解脱氮，而另一部分与经过催化电解脱氮的清水混合后直接进行曝气和生物活化处理，得到的出水可供鳗鱼养殖使用，实现对鳗鱼养殖废水的循环利用；另一方面，对浓水进行气浮、微滤和催化电解脱氮，出水符合排放标准。
本发明中，首先对鳗鱼养殖过程中产生的鳗鱼养殖废水进行沉淀和厌氧处理，具体为：将鳗鱼养殖废水排放至处于厌氧条件下的沉淀池中，鳗鱼养殖废水中粪便和残余饲料等固体在重力的作用下发生沉降，同时在沉淀池中厌氧微生物的作用下，将污水中的有机含碳化合物氧化成二氧化碳、有机氮化合物水解成氨氮、硝酸根反硝化成氮气以及将有机含磷化合物氧化分解成磷酸根，得到的粗处理水样以进行后续的处理。
本发明中对于沉淀和厌氧处理的条件不做明确的限定，即在常规条件下即可进行沉淀和厌氧处理；在一些具体的实施方式中，沉淀和厌氧处理的温度为15~35℃，更加具体的可以是15℃、18℃、20℃、22℃、25℃、26℃、27℃、28℃、29℃、30℃、31℃、32℃、33℃、34℃、35℃或它们之间的任意值；时间为3~5h，更加具体的可以是3h、3.5h、4h、4.5h、5h或它们之间的任意值。
本发明中，粗处理水样溢流至过滤分流装置中进行过滤分流，获得污染程度不同的清水和浓水，过滤分流中所使用的装置并不做限制，现有技术中可实现过滤分流效果的装置即可。在一些具体的实施方式中，过滤分流装置选择为纤维转盘过滤机，通过纤维转盘机过滤，将水体中指环虫及虫卵、车轮虫及虫卵和小瓜虫及虫卵等鱼类主要害虫过滤得到清水，并采用少量清水进行反洗得到浓水。
其中，可根据鳗鱼养殖废水的浑浊程度选择相对应过滤孔径的纤维转盘机进行过滤，纤维转盘机常规的过滤孔径为5~20µm，具体的可以是5µm、8µm、9µm、10µm、12µm、15µm、16µm、17µm、18µm、19µm、20µm或它们之间的任意值。
在一些具体的实施方式中，调控过滤分流中获得的清水和浓水的体积占比，实现对清水和浓水污染程度的初步调控，有利于后续处理的进行，所获得清水的体积占比具体可以是80%、81%、82%、83%、84%、85%、86%、87%、88%、89%、90%或它们之间的任意值，所获得浓水的体积占比具体可以是10%、11%、12%、13%、14%、15%、16%、17%、18%、19%、20%或它们之间的任意值。
本发明中，清水采用分流和合并的方式进行处理，先对第一部分的清水进行催化电解脱氮，使水中的氨氮在电解过程中被电解产生的羟基氧化为硝酸根，硝酸根被电解产生和氢原子还原为氮气，同时水中的氢离子、羟基自由基和次氯酸钠可以与第二部分中的氨氮和硝酸根进行反应进行反应，将水中的氨氮氧化为氮气、将硝态氮还原成氮气。优选地，可根据清水的污染情况适应性地调整第一部分和第二部分的体积比，具有更加良好的适应性。
本发明中，清水的处理和无水的处理中催化电解脱氮中均涉及以下具体的反应：
1、催化电解脱氮的主反应之一：H 2O→H·+OH·，
因废水中有氨存在，NH 3/N 2的标准电位为-3.1，远低于H +/H 2的标准电位0，因此，电解产生的羟基自由基首先与氨反应，生成硝酸根。同时，硝酸根与电解产生的氢原子反应，生成氮气。
NH 3+9OH·→NO 3 -+6H 2O ，6H·+2NO 3 -→N 2↑+3H 2O。
2、催化电解脱氮的主要反应之二：
NH 4 ++NaClO→NH 2Cl+H 2O+Na +（一氯胺），
NH 2Cl+NaClO→NHCl 2+H 2O+Na +（二氯胺），
2NH 2Cl+NaClO→N 2↑+3HCl+H 2O+Na +（脱氮主反应一），
总反应式：2NH 4 ++3NaClO→N 2↑+3HCl+H 2O+3Na +。
去除氨氮的同时，催化电解将废水中的有机磷和多聚磷氧化为磷酸根。
本发明中，将经过催化电解脱氮和曝气处理的清水排入生物活化池中，并使得水体与菌藻培养液混合进行生物活化，于20~35℃下培养18~36h，重建水体微生态的平衡，使水体恢复活性。
生物活化所采用的温度和所需的时间根据水体的情况可以确定，在一些具体的实施方式中，生物活化的温度可以是20℃、21℃、23℃、25℃、26℃、27℃、28℃、29℃、30℃、32℃、34℃、35℃或它们之间的任意值，时间可以是18h、20h、21h、23h、25h、27h、28h、30h、32h、34h、36h或它们之间的任意值。
本发明中，菌藻培养液中所含有的微生物选择为有利于鳗鱼生长的微生物，具体可以是但不限制于光合细菌、小球藻、硅藻、螺旋藻和枯草芽孢杆菌单独使用或组合使用，通过光合菌、小球藻、硅藻、螺旋藻培和/或枯草芽孢杆菌的大量繁殖使水体恢复活性。其中，枯草芽孢杆菌增殖过程产生的枯草菌素、多粘菌素、制霉菌素、短杆菌肽等活性物质，对致病菌有明显的抑制作用，且能刺激鳗鱼免疫器官的生长发育，激活T、B淋巴细胞，提高免疫球蛋白和抗体水平，增强细胞免疫和体液免疫功能，提高群体免疫力，枯草芽孢杆菌还能合成VB 1、VB 2、VB 6和烟酸等多种B族维生素，提高鳗鱼体内干扰素和巨噬细胞的活性；更加具体的，菌藻培养液中菌体密度为10 7~10 10个/L。
在一些具体的实施方式中，菌藻培养液的添加量为1~5‰(v/v)，即往1L的待生物活化水样中加入1~5mL的菌藻培养液，此时水样中菌体浓度适宜，有利于后续的培养，实现理想的生物活化效果，菌藻培养液的添加量1‰(v/v)、2‰(v/v)、3‰(v/v)、4‰(v/v)、5‰(v/v)或它们之间的任意值。
本发明中，在步骤S3浓水的处理中，首先往浓水中加入絮凝剂和助凝剂进行气浮，去除浓水中90~98%的磷和40~75%的COD Cr。
在一些具体的实施方式中，絮凝剂具体可以是但不限制于硫酸亚铁、氯化亚铁、碱式氯化铝、氯化钙、聚丙烯酸钠、聚丙烯酰胺、聚苯乙烯磺酸盐和聚氧化乙烯中的一种或多种；其添加量为5~200mg/L，具体为5mg/L、10mg/L、25mg/L、50mg/L、60mg/L、75mg/L、80mg/L、85mg/L、90mg/L、95mg/L、100mg/L、110mg/L、115mg/L、128mg/L、140mg/L、150mg/L、157mg/L、180mg/L、190mg/L、200mg/L或它们之间的任意值。
在一些具体的实施方式中，助凝剂具体可以是但不限制于聚丙烯酰胺；其添加量为0.1~20mg/L，具体为0.1mg/L、0.5mg/L、0.8mg/L、1.0mg/L、1.5mg/L、2.0mg/L、5.0mg/L、8mg/L、10mg/L、15mg/L、20mg/L或它们之间的任意值。
在沉淀和厌氧处理以及气浮除渣中会产生一定量的污泥，因此，本发明中提供的处理办法还包括对污泥的处理：收集沉淀和厌氧处理以及气浮除渣的污泥，进行重力分离和压滤得到脱水污泥和滤水，该滤水可进入到浓水的处理工艺中经净化后排出。
本发明还提供了以上鳗鱼养殖废水的净化循环利用方法在鳗鱼养殖废水处理中的应用，对不同污染情况的养殖废水均能实现理想的处理效果，出水水质高，可进入鳗鱼养殖中循环使用，且处理的成本低、操作简单，具有良好的应用前景。
下面详细描述本发明的实施例，所述实施例的示例旨在用于解释本发明，而不能理解为对本发明的限制。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例
本实施例用以说明产生量为3000吨/日的鳗鱼养殖废水的净化循环利用方法，参照图1，该方法具体包括以下步骤：
1、鳗鱼养殖废水的沉淀和厌氧处理
将鳗鱼养殖废水排入沉淀池中，于25~35℃下进行沉淀和厌氧反应8h；一方面通过沉淀除去鳗鱼养殖废水中粪便和残余饲料等固体颗粒物，另一方面通过沉淀池中厌氧微生物的作用将鳗鱼养殖废水中的含碳有机物氧化成CO 2和将有机磷转化为磷酸根。
2、过滤分流
将经过沉淀和厌氧处理的鳗鱼养殖废水从沉淀池溢流至过滤孔径为15µm的纤维转盘过滤机中进行过滤分流，得到的清水占总出水体积的80%，浓水占总出水体积的20%。
3、清水的处理
（1）催化电解脱氮：经过纤维转盘过滤得到的一部分清水以100m 3/h的流速进入催化电解机中，在电压为62V和电流为850A的条件进行催化电解脱氮；
（2）曝气：经过催化电解脱氮的清水进入气体分离塔，经气体分离塔排出氮气后进入曝气池，同时，将纤维转盘过滤得到的另一部分清水直接泵入曝气池，在曝气池中经过催化电解脱氮后的清水与过滤分流得到的另一部分清水混合后进行曝气12h；
（3）生物活化：经过曝气的清水流入生物活化池，按照5‰(v/v)的用量加入菌体密度为10 7个/L的菌藻培养液，于25℃下培菌18h，使菌藻培养液中的光合菌、小球藻、硅藻、螺旋藻培和枯草芽孢杆菌在活化池中大量繁殖使清水恢复活性，继续投入鳗鱼养殖中循环使用。
3、浓水的处理
（1）气浮：经过纤维转盘过滤得到的浓水进入气浮装置，并按照50mg/L的用量加入硫酸亚铁和10mg/L的用量加入聚丙烯酰胺，进行气浮除渣去除浓水中的磷和有机化合物；
（2）微滤：经过气浮后得到的溶液进入微滤机中，通过微滤机去除水中微小的固体颗粒；
（3）催化电解脱氮：经过微滤得到的溶液以25m 3/h的流速进入催化电解机中，在电压为62V和电流为350A的条件进行催化电解脱氮，经过催化电解脱氮的溶液进入气体分离塔，经气体分离塔排出氮气后达标排放。
4、污泥的处理
沉淀池和气浮装置的污泥进入板框压滤机机中进行压滤脱水，得到脱水污泥和污泥滤水，该污泥滤水进入气浮装置与浓水一同处理。
本实施例中各处理步骤中进出水的水质指标如表1所示。鳗鱼养殖废水经过沉淀池沉淀和纤维转盘过滤后将废水分离成两路，一路为清水，另一路为浓水；清水经催化电解脱氮、曝气和生物活化等处理后的出水COD Cr≤30mg/L、氨氮≤0.5mg/L、总氮≤3mg/L和总磷氮≤0.2mg/L，可循环至养殖池中再次利用；而浓水经过气浮、微滤和催化电解脱氮等处理后的出水COD Cr≤40mg/L、氨氮≤1.0mg/L、总氮≤3mg/L和总磷≤0.5mg/L，达到排放标准。
表1. 进出水的水质指标（单位：mg/L）
实施例2.
本实施例用以说明产生量为10000吨/日的鳗鱼养殖废水的净化循环利用方法，具体包括以下步骤：
1、鳗鱼养殖废水的沉淀和厌氧处理
将鳗鱼养殖废水排入沉淀池中，于25~35℃下进行沉淀和厌氧反应8h；一方面通过沉淀除去鳗鱼养殖废水中粪便和残余饲料等固体颗粒物，另一方面通过沉淀池中厌氧微生物的作用将鳗鱼养殖废水中的含碳有机物氧化成CO 2和将有机磷转化为磷酸根。
2、过滤分流
将经过沉淀和厌氧处理的鳗鱼养殖废水从沉淀池溢流至过滤孔径为10µm的纤维转盘过滤机中，过滤得到的清水占总出水体积的90%，浓水占总出水体积的10%。
3、清水的处理
（1）催化电解脱氮：经过纤维转盘过滤得到的一部分清水以375m 3/h的流速进入催化电解机中，在电压为62V和电流为5600A的条件进行催化电解脱氮；
（2）曝气：经过催化电解脱氮的清水进入气体分离塔，经气体分离塔排出氮气后进入曝气池，同时，将纤维转盘过滤得到的另一部分清水直接泵入曝气池，在曝气池中经过催化电解脱氮后的清水与过滤分流得到的另一部分清水混合后进行曝气12h；
（3）生物活化：经过曝气的清水流入生物活化池，按照3‰(v/v)的用量加入菌体密度为10 10个/L的菌藻培养液，于30℃下培菌28h，使菌藻培养液中的光合菌、小球藻、硅藻、螺旋藻培和枯草芽孢杆菌在活化池中大量繁殖使清水恢复活性，继续投入鳗鱼养殖中循环使用。
3、浓水的处理
（1）气浮：经过纤维转盘过滤得到的浓水进入气浮装置，并按照50mg/L的用量加入硫酸亚铁、50mg/L的用量加入聚氧化乙烯和20mg/L的用量加入聚丙烯酰胺，进行气浮除渣去除浓水中的磷和有机化合物；
（2）微滤：经过气浮后得到的溶液进入微滤机中，通过微滤机去除水中微小的固体颗粒；
（3）催化电解脱氮：经过微滤得到的溶液以25m 3/h的流速进入催化电解机中，在电压为62V和电流为350A的条件进行催化电解脱氮，经过催化电解脱氮的溶液进入气体分离塔，经气体分离塔排出氮气后达标排放。
4、污泥的处理
沉淀池和气浮装置的污泥进入板框压滤机机中进行压滤脱水，得到脱水污泥和污泥滤水，该污泥滤水进入气浮装置与浓水一同处理。
本实施例中各处理步骤中进出水的水质指标如表2所示。鳗鱼养殖废水经过沉淀池沉淀和纤维转盘过滤后将废水分离成两路，一路为清水，另一路为浓水；清水经催化电解脱氮、曝气和生物活化等处理后的出水COD Cr≤40mg/L、氨氮≤0.5mg/L和、总氮≤3mg/L和总磷≤0.2mg/L，可循环至养殖池中再次利用；而浓水经过气浮、微滤和催化电解脱氮等处理后的出水COD Cr≤40mg/L、氨氮≤1.0mg/L、总氮≤3mg/L和总磷≤0.5mg/L，达到排放标准。
表2. 进出水的水质指标（单位：mg/L）
实施例3.
本实施例用以说明产生量为1000吨/日的鳗鱼养殖废水的净化循环利用方法，具体包括以下步骤：
1、鳗鱼养殖废水的沉淀和厌氧处理
将鳗鱼养殖废水排入沉淀池中，于25~35℃下进行沉淀和厌氧反应8h；一方面通过沉淀除去鳗鱼养殖废水中粪便和残余饲料等固体颗粒物，另一方面通过沉淀池中厌氧微生物的作用将鳗鱼养殖废水中的含碳有机物氧化成CO 2和将有机磷转化为磷酸根。
2、过滤分流
将经过沉淀和厌氧处理的鳗鱼养殖废水从沉淀池溢流至过滤孔径为20µm的纤维转盘过滤机中，过滤得到的清水占总出水体积的95%，浓水占总出水体积的5%。
3、清水的处理
（1）催化电解脱氮：经过纤维转盘过滤得到的一部分清水以42m 3/h的流速进入催化电解机中，在电压为670V和电流为1000A的条件进行催化电解脱氮；
（2）曝气：经过催化电解脱氮的清水进入气体分离塔，经气体分离塔排出氮气后进入曝气池，同时，将纤维转盘过滤得到的另一部分清水直接泵入曝气池，在曝气池中经过催化电解脱氮后的清水与过滤分流得到的另一部分清水混合后进行曝气12h；
（3）生物活化：经过曝气的清水流入生物活化池，按照1‰(v/v)的用量加入菌体密度为10 8个/L的菌藻培养液，于35℃下培菌18h，使菌藻培养液中的光合菌、小球藻、硅藻、螺旋藻培和枯草芽孢杆菌在活化池中大量繁殖使清水恢复活性，继续投入鳗鱼养殖中循环使用。
3、浓水的处理
（1）气浮：经过纤维转盘过滤得到的浓水进入气浮装置，并按照50mg/L的用量加入硫酸亚铁和10mg/L的用量加入聚丙烯酰胺，进行气浮除渣去除浓水中的磷和有机化合物；
（2）微滤：经过气浮后得到的溶液进入微滤机中，通过微滤机去除水中微小的固体颗粒；
（3）催化电解脱氮：经过微滤得到的溶液以10m 3/h的流速进入催化电解机中，在电压为65V和电流为320A的条件进行催化电解脱氮，经过催化电解脱氮的溶液进入气体分离塔，经气体分离塔排出氮气后达标排放。
4、污泥的处理
沉淀池和气浮装置的污泥进入板框压滤机机中进行压滤脱水，得到脱水污泥和污泥滤水，该污泥滤水进入气浮装置与浓水一同处理。
本实施例中各处理步骤中进出水的水质指标如表3所示。鳗鱼养殖废水经过沉淀池沉淀和纤维转盘过滤后将废水分离成两路，一路为清水，另一路为浓水；清水经催化电解脱氮、曝气和生物活化等处理后的出水COD Cr≤40mg/L、氨氮≤0.5mg/L、总氮≤3mg/L和总磷≤0.2mg/L，可循环至养殖池中再次利用；而浓水经过气浮、微滤和催化电解脱氮等处理后的出水COD Cr≤40mg/L、氨氮≤1.0mg/L、总氮≤3mg/L和总磷≤0.5mg/L，达到排放标准。
表3. 进出水的水质指标（单位：mg/L）
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (10)

  1. 一种鳗鱼养殖废水的净化循环利用方法，其特征在于，该方法包括以下步骤：
    S1、鳗鱼养殖废水的前处理：对鳗鱼养殖废水进行沉淀和厌氧处理，除去水中粪便、残余饲料等固体颗粒物以及将鳗鱼养殖废水中的含碳有机化合物氧化成CO 2和有机磷转化为磷酸根，得到粗处理水样；对所述粗处理水样进行过滤分流，获得清水和浓水；
    S2、清水的处理：所述清水分为第一部分和第二部分，对所述第一部分进行催化电解脱氮，后与所述第二部分进行混合进行曝气和生物活化，得到可循环出水；
    S3、浓水的处理：所述浓水依次进行气浮、微滤和催化电解脱氮，得到达标出水。
  2. 根据权利要求1所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述S1中，沉淀和厌氧处理的温度为15~35℃，时间为3~5h。
  3. 根据权利要求1所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述S1中，过滤分流为：采用过滤孔径为5~20µm的纤维转盘过滤机对所述粗处理水样进行过滤得到清水和浓水。
  4. 根据权利要求3所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述清水的体积占比为80~90%，所述浓水的体积占比为10~20%。
  5. 根据权利要求1所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述S2中，生物活化为：取菌藻培养液与经过曝气的清水混合，于20~35℃下培养18~36h。
  6. 根据权利要求5所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述菌藻培养液包括光合细菌、小球藻、硅藻、螺旋藻和枯草芽孢杆菌中的至少两种。
  7. 根据权利要求5所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述菌藻培养液中菌藻密度为10 7~10 10个/mL。
  8. 根据权利要求5所述的鳗鱼养殖废水的净化循环利用方法，其特征在于，所述菌藻培养液的添加量为1~5‰(v/v)。
  9. 根据权利要求1所述的鳗鱼养殖废水的净化循环利用方法， 其特征在于，该方法还包括步骤S4，所述S4中，将所述沉淀和厌氧处理以及气浮除渣中产生的污泥进行重力分离和压滤得到脱水污泥。
  10. 权利要求1~9任一所述的鳗鱼养殖废水的净化循环利用方法在鳗鱼养殖废水处理中的应用。
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