WO2020192536A1 - Method for efficiently treating nitrogen-containing wastewater based on dnra-anammox immobilized pellets - Google Patents

Method for efficiently treating nitrogen-containing wastewater based on dnra-anammox immobilized pellets Download PDF

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WO2020192536A1
WO2020192536A1 PCT/CN2020/080098 CN2020080098W WO2020192536A1 WO 2020192536 A1 WO2020192536 A1 WO 2020192536A1 CN 2020080098 W CN2020080098 W CN 2020080098W WO 2020192536 A1 WO2020192536 A1 WO 2020192536A1
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dnra
anammox
bacteria
water
containing wastewater
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Chinese (zh)
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倪寿清
李倩霞
董颖
占金华
崔兆杰
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山东大学
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/28Anaerobic digestion processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia

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  • the invention relates to a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets, and belongs to the technical field of sewage treatment.
  • the traditional biological denitrification process is built around the nitrification-denitrification pathway.
  • the process is complex and difficult to run, produces a large amount of excess sludge, and has a high operating cost.
  • the Anammox process has developed rapidly due to its short process flow, simple operation, low cost, and no N 2 O generation, and has broad development prospects.
  • ANAMMOX directly with ammonia to nitrite nitrogen into the process, the reaction is: NH 4 + + 1.32NO 2 - + 0.066HCO 3 - + 0.13H + ⁇ 1.02N 2 + 0.26NO 3 - + 0.066CH 2 O 0.5 N 0.15 +2.03H 2 O. Due to the formation of nitrate nitrogen in the product, theoretically, the total nitrogen removal rate will be limited. Therefore, it needs to be combined with other processes to improve the total nitrogen removal rate.
  • the DNRA process can consume the nitrate generated by the anammox process and reduce it to ammonium nitrogen, which can also be converted into nitrogen by anammox.
  • the theoretical reaction is: 0.74NH 4 + + 1.32NO 2 - + 0.13H + + 0.52CH 2 O ⁇ 1.02N 2 + 0.066CH 2 O 0.5 N 0.15 + 1.77H 2 O + 0.454HCO 3 -.
  • the theoretical maximum total nitrogen removal rate is 99%. This shows that the coupling of DNRA and Anammox process can improve the total nitrogen removal rate.
  • the traditional coupling process directly inoculates the sludge rich in different bacterial species for sewage treatment.
  • the nitrate dissimilation reduces to ammonium bacteria and anammox bacteria that grow slowly, are sensitive to environmental elements, start slowly, and free bacteria are easy in the water environment. Loss and poor adaptability of bacteria, therefore, it is of great significance and significance to choose suitable carriers to embed and fix nitrate dissimilation and reduction into ammonium bacteria and anammox bacteria to reduce sludge loss and slow down the negative impact of environmental factors on microorganisms.
  • the present invention provides a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets.
  • the DNRA-Anammox immobilized pellets are made of polyvinyl alcohol, sodium alginate and gelatinized starch.
  • the co-polymerization product is the carrier, and the immobilized pellets formed by embedding DNRA and Anammox bacteria.
  • the retention rate of DNRA and Anammox bacteria is good, and it is not easy to lose.
  • the shape is spherical, the strength and toughness are significantly improved, and it is more resistant to water erosion.
  • DNRA-Anammox immobilized beads couple anammox and DNRA together, maintain a high biomass concentration and biological activity during the treatment process, and reduce dissolved oxygen The impact on the system, enhance the stability of the system operation, thereby increasing the total nitrogen removal rate of the system.
  • DNRA bacteria i.e. organic-electron donor, NO 3- is an electron acceptor, which is eventually converted to through NO 2- NH 4+, reaction is NO 3 - ⁇ NO 2 - ⁇ NH 4 + .
  • ANAMMOX (Anammox): The ammonia and nitrite nitrogen into the process, the reaction is: NH 4 + + 1.32NO 2 - + 0.066HCO 3 - + 0.13H + ⁇ 1.02N 2 + 0.26NO 3 - +0.066CH 2 O 0.5 N 0.15 +2.03H 2 O.
  • a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets includes the following steps:
  • DNRA-Anammox immobilized pellets are activated and cultured at 25°C-30°C for one week to obtain activated DNRA-Anammox immobilized pellets, and DNRA-Anammox immobilized pellets are added to the submerged anaerobic bioreactor in;
  • the DNRA-Anammox immobilized pellets are formed by embedding DNRA bacteria and Anammox bacteria with cross-linked polymer products of polyvinyl alcohol, sodium alginate, gelatinized starch and polyurethane as carriers.
  • DNRA-Anammox immobilized pellets are prepared as follows:
  • the mass percentage of polyvinyl alcohol in the mixed solution 1 is 8-20%, and the mass percentage of sodium alginate is 0.5-1.5%.
  • the polyvinyl alcohol is polyvinyl alcohol with a degree of polymerization of 1600-1800 and a degree of alcoholysis> 99%.
  • the mass volume ratio of soluble starch to water is 1: (40-60), unit: g/mL.
  • the solid content of the water-based polyurethane emulsion is 20%-40%, and the mass fraction of the water-based polyurethane in the gel liquid is 0.1%-1.2%;
  • the volume ratio of liquid 1 is 1: (10-30).
  • the DNRA bacterial sludge is obtained by anaerobic sludge reduction by nitrate dissimilative reduction to ammonium bacteria enrichment culture and washing, and the water content of the DNRA bacterial sludge is 60-90wt%.
  • Nitrate dissimilation reduction to ammonium bacteria enrichment culture reference Research on the environmental distribution and enrichment culture of dissimilation nitrate reducing bacteria (DNRA), Bu Cuina, "Shandong University” 2018, deionization for cleaning the sludge after enrichment culture After washing with water, centrifuge at 8000 rpm for 10 min to remove the supernatant.
  • DNRA dissimilation nitrate reducing bacteria
  • the Anammox bacterial sludge is obtained by anaerobic ammonia oxidizing bacteria enrichment culture and cleaning, and the water content of the Anammox bacterial sludge is 60-70 wt%.
  • the enrichment culture of anammox bacteria is carried out according to the prior art.
  • the sludge after washing for enrichment culture is washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant.
  • the mass-volume ratio of the DNRA-Anammox mixed bacterial sludge to the gel liquid is 1: (3-8), unit: g/mL.
  • step (1.5) the mass fraction of boric acid in the coagulation liquid is 3%-5%, and the mass percentage of calcium chloride is 2%-6%.
  • the activation is to place the DNRA-Anammox immobilized pellets in activated water at 25°C-30°C for a week of activation and culture
  • the activated water composition is as follows: ammonium bicarbonate 190mg/L, phosphoric acid Potassium dihydrogen 25mg/L, magnesium sulfate 200mg/L, calcium chloride 300mg/L, glucose 12.2mg/L, trace element solution 1mL/L; the composition of the trace element solution is: ethylenediaminetetraacetic acid 20.0g/ L, zinc sulfate 0.43g/L, manganese chloride 0.99g/L, cobalt chloride 0.24g/L, nickel chloride 0.19g/L, copper sulfate 0.25g/L, sodium selenate 0.21g/L, molybdic acid Sodium 0.22g/L, boric acid 0.014g/L.
  • the filling rate of the activated DNRA-Anammox immobilized pellets in the reactor is preferably 15%-25% of the reactor volume.
  • the present invention has the following advantages:
  • the present invention uses polyvinyl alcohol, sodium alginate, gelatinized starch and polyurethane cross-linked polymer products as carriers to embed DNRA bacteria and Anammox bacteria.
  • the embedded immobilized microorganisms have high biomass concentration and are resistant to environmental toxicity. Strong, reusable and other advantages, can make DNRA bacteria and Anammox bacteria maintain a higher bacterial concentration and biological activity in the system, thereby improving the total nitrogen removal rate of the system.
  • Both DNRA bacteria and Anammox bacteria are anaerobic bacteria.
  • the DNRA-Anammox immobilized pellets hinder the mass transfer of dissolved oxygen, so that the DNRA bacteria and Anammox bacteria in the DNRA-Anammox immobilized pellets are not susceptible to the influence of dissolved oxygen, which enhances the system
  • the stability of the system can achieve joint denitrification and improve the total nitrogen removal rate of the system.
  • the DNRA-Anammox immobilized pellets of the present invention are not easy to cause sludge loss, and the obtained DNRA-Anammox immobilized pellets hinder the mass transfer of dissolved oxygen, thereby maintaining the anaerobic environment inside the DNRA-Anammox immobilized pellets, Can make the system run stably for a long time.
  • the DNRA-Anammox immobilized pellets of the present invention use soluble starch with swelling properties as a carrier, so that the bacterial sludge is attached between the porous soluble starch, avoiding the DNRA-Anammox immobilized pellets from being damaged due to excessive network pores. The embedded bacteria are partially lost and the utilization rate is low.
  • the DNRA-Anammox immobilized pellets of the present invention are dispersed independently, are not easy to bond together, have high toughness, are more resistant to hydraulic erosion, and have a long service life.
  • Figure 1 is an appearance photograph of DNRA-Anammox immobilized pellets prepared in Example 1 of the present invention.
  • Figure 2 is a schematic diagram of the structure of a submerged anaerobic bioreactor.
  • the submerged anaerobic bioreactor includes a reaction barrel.
  • a sealing cover is arranged on the top of the reaction barrel.
  • a water inlet 3, an air outlet 4 and a water outlet 6 are provided through the sealing cover.
  • the water inlet 3 is connected with a water inlet pump through a water inlet pipe. 2 and the reservoir 1, the outlet 6 is connected with the outlet pump 10 and the outlet pool 11 through the outlet pipe.
  • the bottom of the reaction barrel is filled with DNRA-Anammox immobilized beads 8, and the bottom of the reaction barrel is also equipped with a magnetic stirrer 9.
  • An aeration head is arranged in the reaction tank body, the aeration head is connected to the aeration tube 5, and extends through the sealing cover to the reaction tank body and a level gauge 7 is also provided.
  • a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets includes the following steps:
  • the anaerobic sludge is reduced to ammonium bacteria enrichment culture by nitrate dissimilation, and then washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant to obtain highly active DNRA bacterial sludge.
  • the anaerobic sludge is enriched and cultured with anammox bacteria, then washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant to obtain highly active Anammox bacterial sludge;
  • DNRA bacteria mud and Anammox bacteria mud in a mass ratio of 1:1 to obtain DNRA-Anammox mixed bacteria mud.
  • DNRA-Anammox mixed bacteria mud Take 30g of DNRA-Anammox mixed bacteria mud and 100ml of the gel solution cooled to room temperature and mix well to obtain a mixture of bacteria gum liquid;
  • DNRA-Anammox immobilized pellets Place the DNRA-Anammox immobilized pellets in activated water at 26°C for activation and culture for one week, so that the microorganisms inside the DNRA-Anammox immobilized pellets are fully recovered, and the activated DNRA-Anammox immobilized pellets are obtained.
  • DNRA-Anammox immobilized pellets were added to the submerged anaerobic bioreactor at a volume filling rate of 20%, and the effective volume of the reactor was 6L, as shown in Figure 2;
  • Water is fed into the reactor through the water inlet pump. In order to make the reactor water evenly distributed, it can fully contact with the DNRA-Anammox immobilized pellets.
  • a magnetic stirrer is installed at the bottom of the anaerobic reactor;
  • An aeration head is installed in the reactor to aerate nitrogen to maintain the anaerobic environment in the reactor.
  • a liquid level controller is installed in the reactor to adjust the effluent water, so that the reactor can maintain the balance of inlet and outlet water, and realize the efficient removal of nitrogen in the sewage. .
  • the appearance photo of the DNRA-Anammox immobilized pellets prepared in this example is shown in FIG. 1.

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Abstract

The present invention relates to a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets. The DNRA-Anammox immobilized pellets are formed by embedding DNRA bacteria and Anammox bacteria with a cross-linked polymerization product of polyvinyl alcohol, sodium alginate, and gelatinized starch as a carrier. The immobilized pellets used in the method of the present invention have the advantages of high biomass concentration, strong environmental toxicity resistance, recycling, and the like, and high bacterial concentration and bio-activity of the DNRA bacteria and Anammox bacteria in a system can be maintained, so that the total nitrogen removal rate of the system is increased. Both the DNRA bacteria and the Anammox bacteria are anaerobic bacteria, the DNRA-Anammox immobilized pellets block mass transfer of dissolved oxygen, so that the DNRA bacteria and Anammox bacteria in the DNRA-Anammox immobilized pellets are not easily affected by the dissolved oxygen, the stability of the system is enhanced, combined nitrogen removal is realized, and the total nitrogen removal rate of the system is increased.

Description

一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法Method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets 技术领域Technical field
本发明涉及一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法,属于污水处理技术领域。The invention relates to a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets, and belongs to the technical field of sewage treatment.
背景技术Background technique
随着时代的进步,人们生活水平不断提高,过量的氮素被人为地排放到环境中而造成氮素污染。近年发布的《中国环境状况公告》显示,氮素污染是造成我国水体污染的主要原因之一。对含氮废水进行脱氮处理一直是污水处理的研究热点,而生物脱氮途径是最为经济有效的方法。With the progress of the times, people's living standards continue to improve, and excessive nitrogen is artificially discharged into the environment, causing nitrogen pollution. The "Announcement on the State of the Environment in China" issued in recent years shows that nitrogen pollution is one of the main causes of water pollution in my country. Denitrification treatment of nitrogen-containing wastewater has always been a research hotspot in sewage treatment, and biological denitrification is the most economical and effective method.
传统的生物脱氮工艺是围绕硝化-反硝化途径进行构建,该工艺操作复杂不易运行,产生大量剩余污泥,且运行成本较高。近年来厌氧氨氧化(Anammox)工艺凭借其工艺流程短、操作简单、成本低、无N 2O生成等优点发展迅速,具有广阔的发展前景。厌氧氨氧化是直接将氨氮与亚硝氮转化为氮气的工艺,其反应式为:NH 4 ++1.32NO 2 -+0.066HCO 3 -+0.13H +→1.02N 2+0.26NO 3 -+0.066CH 2O 0.5N 0.15+2.03H 2O。由于其产物中会生成硝氮,从理论上来讲,其总氮去除率会受到限制。因此需要与其他工艺相结合以提高总氮去除率。 The traditional biological denitrification process is built around the nitrification-denitrification pathway. The process is complex and difficult to run, produces a large amount of excess sludge, and has a high operating cost. In recent years, the Anammox process has developed rapidly due to its short process flow, simple operation, low cost, and no N 2 O generation, and has broad development prospects. ANAMMOX directly with ammonia to nitrite nitrogen into the process, the reaction is: NH 4 + + 1.32NO 2 - + 0.066HCO 3 - + 0.13H + → 1.02N 2 + 0.26NO 3 - + 0.066CH 2 O 0.5 N 0.15 +2.03H 2 O. Due to the formation of nitrate nitrogen in the product, theoretically, the total nitrogen removal rate will be limited. Therefore, it needs to be combined with other processes to improve the total nitrogen removal rate.
近年来,硝酸盐异化还原为铵(DNRA)过程日益受到关注,该过程是将硝态氮逐步还原为氨氮,反应过程为NO 3 -→NO 2 -→NH 4 +。但是该过程将氮素保留在水体中,因而不能单独作为脱氮技术推广应用。在海洋、河口、稻田、红树林、城市水系等多种自然生态系统沉积物中均发现了厌氧氨氧化菌与DNRA菌共存,说明其在氮循环中具有重要作用。现在研究普遍认为在厌氧氨氧化耦合DNRA是海洋氮气的主要贡献者。并且,DNRA过程可以消耗厌氧氨氧化过程产生的硝氮还原为铵氮,氨氮亦可以被厌氧氨氧化转化为氮气。其理论反应式为:0.74NH 4 ++1.32NO 2 -+0.13H ++0.52CH 2O→1.02N 2+0.066CH 2O 0.5N 0.15+1.77H 2O+0.454HCO 3 -。理论最大总氮去除率为99%。由此可见DNRA与Anammox工艺的耦合可以提高总氮去除率。 In recent years, reduction of ammonium nitrate dissimilation (DNRA) growing concern during the process is the gradual reduction of nitrate to ammonia, the reaction of NO 3 - → NO 2 - → NH 4 +. However, this process retains nitrogen in the water body, so it cannot be promoted and applied as a denitrification technology alone. The coexistence of anammox bacteria and DNRA bacteria have been found in the sediments of various natural ecosystems such as oceans, estuaries, rice fields, mangroves, and urban water systems, indicating that they play an important role in the nitrogen cycle. The current research generally believes that DNRA coupled with anammox is the main contributor to ocean nitrogen. In addition, the DNRA process can consume the nitrate generated by the anammox process and reduce it to ammonium nitrogen, which can also be converted into nitrogen by anammox. The theoretical reaction is: 0.74NH 4 + + 1.32NO 2 - + 0.13H + + 0.52CH 2 O → 1.02N 2 + 0.066CH 2 O 0.5 N 0.15 + 1.77H 2 O + 0.454HCO 3 -. The theoretical maximum total nitrogen removal rate is 99%. This shows that the coupling of DNRA and Anammox process can improve the total nitrogen removal rate.
传统的耦合工艺直接接种富含不同菌种的污泥进行污水处理,硝酸盐异化还原为铵菌与厌氧氨氧化菌生长缓慢、对环境要素敏感、启动缓慢,游离的菌在水环境中容易流失、菌体 适应能力差,因此,选择合适的载体包埋固定硝酸盐异化还原为铵菌与厌氧氨氧化菌以减少污泥流失,减缓环境因素对微生物的消极影响,是极有意义且新颖的探索,并具有较大的经济效益。The traditional coupling process directly inoculates the sludge rich in different bacterial species for sewage treatment. The nitrate dissimilation reduces to ammonium bacteria and anammox bacteria that grow slowly, are sensitive to environmental elements, start slowly, and free bacteria are easy in the water environment. Loss and poor adaptability of bacteria, therefore, it is of great significance and significance to choose suitable carriers to embed and fix nitrate dissimilation and reduction into ammonium bacteria and anammox bacteria to reduce sludge loss and slow down the negative impact of environmental factors on microorganisms. Innovative exploration, and has greater economic benefits.
目前有报道以聚乙烯醇和海藻酸钠作为包埋剂,含有氯化钙与硼酸的水溶液为交联剂,通过交联剂对包埋剂固化将微生物包埋固化,得到具有多孔隙结构的凝胶小球,但是这种凝胶小球在实际应用中发现存在以下问题:(1)凝胶小球的网络孔隙过大,菌容易从凝胶小球的网络孔隙中泄露出来,导致被包埋的菌部分流失,利用率低,(2)凝胶小球强度和韧性较低,受到水力剪切容易软化变形,使用寿命大大减少。At present, it has been reported that polyvinyl alcohol and sodium alginate are used as embedding agents, and an aqueous solution containing calcium chloride and boric acid is used as a cross-linking agent. The embedding agent is solidified by the cross-linking agent to embed and solidify microorganisms to obtain a porous structure. However, the following problems have been found in the actual application of this kind of gel beads: (1) The network pores of the gel beads are too large, and bacteria are easy to leak from the network pores of the gel beads, resulting in entrapment The buried bacteria are partially lost, and the utilization rate is low. (2) The gel beads have low strength and toughness, and are easily softened and deformed by hydraulic shear, and their service life is greatly reduced.
发明内容Summary of the invention
针对现有技术的不足,本发明提供一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法,DNRA-Anammox固定化小球是以聚乙烯醇、海藻酸钠和糊化淀粉的交联聚合产物为载体,包埋DNRA菌和Anammox菌而形成的固定化小球,DNRA菌和Anammox菌保持率好,不容易流失,同时形状为球形,强度和韧性明显提高,更耐水力冲刷,使用寿命长,更利于菌的生长及富集,DNRA-Anammox固定化小球将厌氧氨氧化与DNRA耦合在一起,在处理过程中维持较高的生物量浓度和生物活性,并减弱溶解氧对系统的影响,增强系统运行的稳定性,从而提高系统的总氮去除率。In view of the shortcomings of the prior art, the present invention provides a method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets. The DNRA-Anammox immobilized pellets are made of polyvinyl alcohol, sodium alginate and gelatinized starch. The co-polymerization product is the carrier, and the immobilized pellets formed by embedding DNRA and Anammox bacteria. The retention rate of DNRA and Anammox bacteria is good, and it is not easy to lose. At the same time, the shape is spherical, the strength and toughness are significantly improved, and it is more resistant to water erosion. Long service life, more conducive to the growth and enrichment of bacteria, DNRA-Anammox immobilized beads couple anammox and DNRA together, maintain a high biomass concentration and biological activity during the treatment process, and reduce dissolved oxygen The impact on the system, enhance the stability of the system operation, thereby increasing the total nitrogen removal rate of the system.
术语说明:Term description:
硝酸盐异化还原为铵(DNRA):即DNRA菌以有机物为电子供体,NO 3-为电子受体,将其经过NO 2-最终转化为NH 4+,反应式为NO 3 -→NO 2 -→NH 4 +Dissimilatory nitrate reduction to ammonium (DNRA): DNRA bacteria i.e. organic-electron donor, NO 3- is an electron acceptor, which is eventually converted to through NO 2- NH 4+, reaction is NO 3 - → NO 2 - →NH 4 + .
厌氧氨氧化(Anammox):将氨氮与亚硝氮转化为氮气的工艺,其反应式为:NH 4 ++1.32NO 2 -+0.066HCO 3 -+0.13H +→1.02N 2+0.26NO 3 -+0.066CH 2O 0.5N 0.15+2.03H 2O。 ANAMMOX (Anammox): The ammonia and nitrite nitrogen into the process, the reaction is: NH 4 + + 1.32NO 2 - + 0.066HCO 3 - + 0.13H + → 1.02N 2 + 0.26NO 3 - +0.066CH 2 O 0.5 N 0.15 +2.03H 2 O.
为了达到上述目的,本发明是通过以下方案来实现:In order to achieve the above objective, the present invention is achieved through the following solutions:
一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法,包括步骤如下:A method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets includes the following steps:
(1)将DNRA-Anammox固定化小球在25℃-30℃下活化培养一周,得活化DNRA-Anammox固定化小球,将DNRA-Anammox固定化小球投加至浸没式厌氧生物反应器中;(1) DNRA-Anammox immobilized pellets are activated and cultured at 25℃-30℃ for one week to obtain activated DNRA-Anammox immobilized pellets, and DNRA-Anammox immobilized pellets are added to the submerged anaerobic bioreactor in;
(2)从反应器的底部利用蠕动泵通入待处理废水,调整进水流速,调整温度及pH,同时进行曝氮气及磁力搅拌,维持厌氧环境;实现对污水中的氮素的高效脱除;(2) Use a peristaltic pump to pass the wastewater to be treated from the bottom of the reactor, adjust the water flow rate, adjust the temperature and pH, and carry out nitrogen aeration and magnetic stirring at the same time to maintain an anaerobic environment; to achieve efficient removal of nitrogen in the sewage except;
所述的DNRA-Anammox固定化小球是以聚乙烯醇、海藻酸钠、糊化淀粉和聚氨酯的交联聚合产物为载体,包埋DNRA菌和Anammox菌而形成的固定化小球。The DNRA-Anammox immobilized pellets are formed by embedding DNRA bacteria and Anammox bacteria with cross-linked polymer products of polyvinyl alcohol, sodium alginate, gelatinized starch and polyurethane as carriers.
根据本发明优选的,DNRA-Anammox固定化小球是按如下方法制备得到的:According to the present invention, preferably, DNRA-Anammox immobilized pellets are prepared as follows:
(1.1)将聚乙烯醇、海藻酸钠依次加入水中并分别加热搅拌溶解混合均匀,得到混合液1;(1.1) Add polyvinyl alcohol and sodium alginate to water in sequence and heat and stir to dissolve and mix uniformly to obtain mixed solution 1;
(1.2)将可溶性淀粉加入水中加热糊化,之后冷却至70~80℃,得混合液2;(1.2) Add soluble starch to water and heat to gelatinize, and then cool to 70~80℃ to obtain mixture 2;
(1.3)将水性聚氨酯乳液、混合液2依次加入混合液1中混合,得凝胶液;(1.3) Add the water-based polyurethane emulsion and the mixed solution 2 to the mixed solution 1 and mix to obtain a gel solution;
(1.4)将凝胶液冷却到室温后,将DNRA菌泥与Anammox菌泥按质量比1:1的比例混合后,得到DNRA-Anammox混合菌泥,将混合菌泥加入冷却后的凝胶液中,混合均匀后得到菌胶混合液;(1.4) After cooling the gel liquid to room temperature, mix DNRA and Anammox bacteria in a mass ratio of 1:1 to obtain DNRA-Anammox mixed bacteria. Add the mixed bacteria to the cooled gel liquid After mixing evenly, the fungus gum mixture is obtained;
(1.5)取硼酸和氯化钙溶于水中,制备含有硼酸和氯化钙混合溶液,即为凝固液;(1.5) Dissolve boric acid and calcium chloride in water to prepare a mixed solution containing boric acid and calcium chloride, which is the coagulation liquid;
(1.6)将菌胶混合液在搅拌条件下滴加至凝固液中进行凝固成形,然后静置使其充分交联,得到DNRA-Anammox固定化小球。(1.6) Add the fungal gum mixture dropwise to the coagulation solution under stirring conditions for coagulation and shape, and then stand to make it fully crosslinked to obtain DNRA-Anammox immobilized pellets.
根据本发明优选的,步骤(1.1)中,混合液1中聚乙烯醇的质量百分含量为8-20%,海藻酸钠的质量百分含量为0.5-1.5%。According to the present invention, preferably, in step (1.1), the mass percentage of polyvinyl alcohol in the mixed solution 1 is 8-20%, and the mass percentage of sodium alginate is 0.5-1.5%.
根据本发明优选的,步骤(1.1)中,聚乙烯醇为聚合度为1600-1800、醇解度>99%的聚乙烯醇。Preferably according to the present invention, in step (1.1), the polyvinyl alcohol is polyvinyl alcohol with a degree of polymerization of 1600-1800 and a degree of alcoholysis> 99%.
根据本发明优选的,步骤(1.2)中,可溶性淀粉与水的质量体积比为:1:(40-60),单位:g/mL。According to the present invention, preferably, in step (1.2), the mass volume ratio of soluble starch to water is 1: (40-60), unit: g/mL.
根据本发明优选的,步骤(1.3)中,所述水性聚氨酯乳液的固含量为20%-40%,水性聚氨酯在凝胶液中的的质量分数为0.1%-1.2%;混合液2与混合液1的体积比为:1:(10-30)。According to the present invention, preferably, in step (1.3), the solid content of the water-based polyurethane emulsion is 20%-40%, and the mass fraction of the water-based polyurethane in the gel liquid is 0.1%-1.2%; The volume ratio of liquid 1 is 1: (10-30).
根据本发明优选的,步骤(1.4)中,DNRA菌泥为厌氧污泥经硝酸盐异化还原为铵菌富集培养、清洗后得到,DNRA菌泥的含水量为60-90wt%。According to the present invention, preferably, in step (1.4), the DNRA bacterial sludge is obtained by anaerobic sludge reduction by nitrate dissimilative reduction to ammonium bacteria enrichment culture and washing, and the water content of the DNRA bacterial sludge is 60-90wt%.
硝酸盐异化还原为铵菌富集培养参照:异化硝酸盐还原菌(DNRA)的环境分布及富集培养研究,卜翠娜,《山东大学》2018年,清洗为富集培养后的污泥用去离子水洗净后在8000rpm下离心10min,去除上清液。Nitrate dissimilation reduction to ammonium bacteria enrichment culture reference: Research on the environmental distribution and enrichment culture of dissimilation nitrate reducing bacteria (DNRA), Bu Cuina, "Shandong University" 2018, deionization for cleaning the sludge after enrichment culture After washing with water, centrifuge at 8000 rpm for 10 min to remove the supernatant.
根据本发明优选的,步骤(1.4)中,Anammox菌泥为厌氧污泥经厌氧氨氧化菌富集培养、清洗后得到,Anammox菌泥的含水量为60-70wt%。According to the present invention, preferably, in step (1.4), the Anammox bacterial sludge is obtained by anaerobic ammonia oxidizing bacteria enrichment culture and cleaning, and the water content of the Anammox bacterial sludge is 60-70 wt%.
厌氧氨氧化菌富集培养按现有技术进行,清洗为富集培养后的污泥用去离子水洗净后在8000rpm下离心10min,去除上清液。The enrichment culture of anammox bacteria is carried out according to the prior art. The sludge after washing for enrichment culture is washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant.
根据本发明优选的,步骤(1.4)中,DNRA-Anammox混合菌泥与凝胶液的质量体积比为:1:(3-8),单位:g/mL。Preferably, according to the present invention, in step (1.4), the mass-volume ratio of the DNRA-Anammox mixed bacterial sludge to the gel liquid is 1: (3-8), unit: g/mL.
根据本发明优选的,步骤(1.5)中,所述凝固液中硼酸的质量分数为3%-5%,氯化钙的质量百分含量为2%-6%。According to the present invention, in step (1.5), the mass fraction of boric acid in the coagulation liquid is 3%-5%, and the mass percentage of calcium chloride is 2%-6%.
根据本发明优选的,所述的活化为将DNRA-Anammox固定化小球置于活化水中在25℃-30℃下活化培养一周,所述的活化水组成如下:碳酸氢铵190mg/L,磷酸二氢钾25mg/L,硫酸镁200mg/L,氯化钙300mg/L,葡萄糖12.2mg/L,微量元素溶液1mL/L;所述微量元素溶液组成成分为:乙二胺四乙酸20.0g/L,硫酸锌0.43g/L,氯化锰0.99g/L,氯化钴0.24g/L,氯化镍0.19g/L,硫酸铜0.25g/L,硒酸钠0.21g/L,钼酸钠0.22g/L,硼酸0.014g/L。Preferably, according to the present invention, the activation is to place the DNRA-Anammox immobilized pellets in activated water at 25°C-30°C for a week of activation and culture, and the activated water composition is as follows: ammonium bicarbonate 190mg/L, phosphoric acid Potassium dihydrogen 25mg/L, magnesium sulfate 200mg/L, calcium chloride 300mg/L, glucose 12.2mg/L, trace element solution 1mL/L; the composition of the trace element solution is: ethylenediaminetetraacetic acid 20.0g/ L, zinc sulfate 0.43g/L, manganese chloride 0.99g/L, cobalt chloride 0.24g/L, nickel chloride 0.19g/L, copper sulfate 0.25g/L, sodium selenate 0.21g/L, molybdic acid Sodium 0.22g/L, boric acid 0.014g/L.
根据本发明优选的,活化DNRA-Anammox固定化小球在反应器中的填充率为反应器容积的15%-25%。According to the present invention, the filling rate of the activated DNRA-Anammox immobilized pellets in the reactor is preferably 15%-25% of the reactor volume.
本发明与现有技术相比具有以下优点:Compared with the prior art, the present invention has the following advantages:
1、本发明以聚乙烯醇、海藻酸钠、糊化淀粉和聚氨酯的交联聚合产物为载体,将DNRA菌和Anammox菌进行包埋,包埋固定化微生物具有生物量浓度高、抗环境毒性强、可反复利用等优点,可以使DNRA菌与Anammox菌在系统内维持较高的细菌浓度和生物活性,从而提高系统的总氮去除率。DNRA菌与Anammox菌均为厌氧菌,DNRA-Anammox固定化小球使得溶解氧传质受阻,使DNRA-Anammox固定化小球中的DNRA菌与Anammox菌不易受到溶解氧的影响,增强该系统的稳定性,实现联合脱氮并提高系统的总氮去除率。1. The present invention uses polyvinyl alcohol, sodium alginate, gelatinized starch and polyurethane cross-linked polymer products as carriers to embed DNRA bacteria and Anammox bacteria. The embedded immobilized microorganisms have high biomass concentration and are resistant to environmental toxicity. Strong, reusable and other advantages, can make DNRA bacteria and Anammox bacteria maintain a higher bacterial concentration and biological activity in the system, thereby improving the total nitrogen removal rate of the system. Both DNRA bacteria and Anammox bacteria are anaerobic bacteria. The DNRA-Anammox immobilized pellets hinder the mass transfer of dissolved oxygen, so that the DNRA bacteria and Anammox bacteria in the DNRA-Anammox immobilized pellets are not susceptible to the influence of dissolved oxygen, which enhances the system The stability of the system can achieve joint denitrification and improve the total nitrogen removal rate of the system.
2、本发明的DNRA-Anammox固定化小球不易造成污泥的流失,且得到的DNRA-Anammox固定化小球对溶解氧传质受阻,从而维持DNRA-Anammox固定化小球内部厌氧环境,可使系统长时间稳定运行。2. The DNRA-Anammox immobilized pellets of the present invention are not easy to cause sludge loss, and the obtained DNRA-Anammox immobilized pellets hinder the mass transfer of dissolved oxygen, thereby maintaining the anaerobic environment inside the DNRA-Anammox immobilized pellets, Can make the system run stably for a long time.
3、本发明的DNRA-Anammox固定化小球将具有溶胀性能的可溶性淀粉作为载体,使菌泥附着在多孔的可溶性淀粉之间,避免了DNRA-Anammox固定化小球因网络孔隙过大导致被包埋的菌部分流失,利用率低。3. The DNRA-Anammox immobilized pellets of the present invention use soluble starch with swelling properties as a carrier, so that the bacterial sludge is attached between the porous soluble starch, avoiding the DNRA-Anammox immobilized pellets from being damaged due to excessive network pores. The embedded bacteria are partially lost and the utilization rate is low.
4、本发明的DNRA-Anammox固定化小球独立分散,不容易粘结在一起,韧性大,更耐水力冲刷,使用寿命长。4. The DNRA-Anammox immobilized pellets of the present invention are dispersed independently, are not easy to bond together, have high toughness, are more resistant to hydraulic erosion, and have a long service life.
附图说明Description of the drawings
图1是本发明实施例1制备的DNRA-Anammox固定化小球的外观照片。Figure 1 is an appearance photograph of DNRA-Anammox immobilized pellets prepared in Example 1 of the present invention.
图2是浸没式厌氧生物反应器的结构示意图。Figure 2 is a schematic diagram of the structure of a submerged anaerobic bioreactor.
图2中:1、储水池 2、进水泵 3、进水口 4、出气口 5、曝气管 6、出水口 7、液位计 8、DNRA-Anammox固定化小球 9、磁力搅拌器 10、出水泵 11、出水池。In Figure 2: 1. Reservoir 2. Water inlet pump 3. Water inlet 4. Air outlet 5. Aeration pipe 6. Water outlet 7. Liquid level gauge 8. DNRA-Anammox immobilized ball 9. Magnetic stirrer 10. Outlet pump 11. Outlet pool.
具体实施方式:detailed description:
下面将结合实施例对本发明做进一步具体的描述,但本发明大的实施方式不限于此。The present invention will be further specifically described below in conjunction with examples, but the large implementation of the present invention is not limited to this.
浸没式厌氧生物反应器包括反应桶体,反应桶体的顶部设置有密封盖,贯穿密封盖设置有进水口3、出气口4和出水口6,进水口3通过进水管路连接有进水泵2和储水池1,出水口6通过出水管路连接有出水泵10和出水池11,反应桶体的底部填充有DNRA-Anammox固定化小球8,反应桶体的底部还设置有磁力搅拌器9,在反应桶体内设置有曝气头,曝气头连接曝气管5,贯穿密封盖延伸至反应桶体内还设有液位计7。The submerged anaerobic bioreactor includes a reaction barrel. A sealing cover is arranged on the top of the reaction barrel. A water inlet 3, an air outlet 4 and a water outlet 6 are provided through the sealing cover. The water inlet 3 is connected with a water inlet pump through a water inlet pipe. 2 and the reservoir 1, the outlet 6 is connected with the outlet pump 10 and the outlet pool 11 through the outlet pipe. The bottom of the reaction barrel is filled with DNRA-Anammox immobilized beads 8, and the bottom of the reaction barrel is also equipped with a magnetic stirrer 9. An aeration head is arranged in the reaction tank body, the aeration head is connected to the aeration tube 5, and extends through the sealing cover to the reaction tank body and a level gauge 7 is also provided.
实施例1:Example 1:
一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法,包括步骤如下:A method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets includes the following steps:
(1)将聚乙烯醇、海藻酸钠依次加入水中并分别加热搅拌溶解混合均匀,得到混合液1,混合液1中聚乙烯醇的质量百分含量为16%,海藻酸钠的质量百分含量为1.2%,聚乙烯醇为聚合度为1600-1800、醇解度>99%的聚乙烯醇(1) Add polyvinyl alcohol and sodium alginate to water in turn and heat and stir to dissolve and mix uniformly to obtain mixed solution 1. The mass percentage of polyvinyl alcohol in mixed solution 1 is 16%, and the mass percentage of sodium alginate The content is 1.2%, polyvinyl alcohol is polyvinyl alcohol with a degree of polymerization of 1600-1800 and a degree of alcoholysis >99%
(2)将可溶性淀粉加入水中加热糊化,之后冷却至70~80℃,得混合液2,可溶性淀粉与水的质量体积比为:1:33,单位:g/mL;(2) Add soluble starch to water for heating and gelatinization, and then cool to 70-80°C to obtain mixture 2. The mass volume ratio of soluble starch to water is 1:33, unit: g/mL;
(3)将固含量为30%的水性聚氨酯乳液、混合液2依次加入混合液1中混合,得凝胶液,水性聚氨酯在凝胶液中的的质量分数为0.6%;混合液2与混合液1的体积比为:1:25,单位:g/mL;(3) Add the water-based polyurethane emulsion with a solid content of 30% and the mixed liquid 2 to the mixed liquid 1 in turn to obtain a gel liquid. The mass fraction of the water-based polyurethane in the gel liquid is 0.6%; the mixed liquid 2 and the mixed liquid The volume ratio of liquid 1 is 1:25, unit: g/mL;
(4)厌氧污泥经硝酸盐异化还原为铵菌富集培养,然后用去离子水洗净后在8000rpm下离心10min,去除上清液,得到活性高的DNRA菌泥,(4) The anaerobic sludge is reduced to ammonium bacteria enrichment culture by nitrate dissimilation, and then washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant to obtain highly active DNRA bacterial sludge.
厌氧污泥经厌氧氨氧化菌富集培养,然后用去离子水洗净后在8000rpm下离心10min,去除上清液,得到活性高的Anammox菌泥;The anaerobic sludge is enriched and cultured with anammox bacteria, then washed with deionized water and centrifuged at 8000 rpm for 10 minutes to remove the supernatant to obtain highly active Anammox bacterial sludge;
将DNRA菌泥与Anammox菌泥按质量比1:1的比例混合均匀,得到DNRA-Anammox混合菌泥,取30gDNRA-Anammox混合菌泥与100ml冷却到室温的凝胶液混合均匀,得到菌 胶混合液;Mix the DNRA bacteria mud and Anammox bacteria mud in a mass ratio of 1:1 to obtain DNRA-Anammox mixed bacteria mud. Take 30g of DNRA-Anammox mixed bacteria mud and 100ml of the gel solution cooled to room temperature and mix well to obtain a mixture of bacteria gum liquid;
(5)取硼酸和氯化钙溶于水中,制备含有硼酸和氯化钙混合溶液,即为凝固液;所述凝固液中硼酸的质量分数为4%,氯化钙的质量百分含量为3%;(5) Dissolve boric acid and calcium chloride in water to prepare a mixed solution containing boric acid and calcium chloride, which is the coagulation liquid; the mass fraction of boric acid in the coagulation liquid is 4%, and the mass percentage of calcium chloride is 3%;
(6)将菌胶混合液在搅拌条件下滴加至凝固液中进行凝固成形,然后静置使其充分交联,得到DNRA-Anammox固定化小球。(6) Add the fungus gum mixture dropwise to the coagulation solution under stirring conditions for coagulation and shape, and then stand for full cross-linking to obtain DNRA-Anammox immobilized pellets.
(7)将DNRA-Anammox固定化小球在26℃下置于活化水中活化培养一周,使DNRA-Anammox固定化小球内部的微生物得到充分的恢复,得活化DNRA-Anammox固定化小球,将DNRA-Anammox固定化小球按体积填充率20%投加至浸没式厌氧生物反应器中,反应器的有效容积为6L,如图2所示;(7) Place the DNRA-Anammox immobilized pellets in activated water at 26°C for activation and culture for one week, so that the microorganisms inside the DNRA-Anammox immobilized pellets are fully recovered, and the activated DNRA-Anammox immobilized pellets are obtained. DNRA-Anammox immobilized pellets were added to the submerged anaerobic bioreactor at a volume filling rate of 20%, and the effective volume of the reactor was 6L, as shown in Figure 2;
(8)通过进水泵向反应器内进水,为了使反应器进水布水均匀,能够与DNRA-Anammox固定化小球充分接触,在厌氧反应器底部设置磁力搅拌器;在厌氧反应器内设置曝气头,曝氮气以维持反应器内的厌氧环境,反应器内安装液位控制器调节出水,使反应器内维持进出水平衡,实现对污水中的氮素的高效脱除。(8) Water is fed into the reactor through the water inlet pump. In order to make the reactor water evenly distributed, it can fully contact with the DNRA-Anammox immobilized pellets. A magnetic stirrer is installed at the bottom of the anaerobic reactor; An aeration head is installed in the reactor to aerate nitrogen to maintain the anaerobic environment in the reactor. A liquid level controller is installed in the reactor to adjust the effluent water, so that the reactor can maintain the balance of inlet and outlet water, and realize the efficient removal of nitrogen in the sewage. .
本实施例制得的DNRA-Anammox固定化小球外观照片如图1所示。The appearance photo of the DNRA-Anammox immobilized pellets prepared in this example is shown in FIG. 1.

Claims (10)

  1. 一种基于DNRA-Anammox固定化小球高效处理含氮废水的方法,包括步骤如下:A method for efficiently treating nitrogen-containing wastewater based on DNRA-Anammox immobilized pellets includes the following steps:
    (1)将DNRA-Anammox固定化小球在25℃-30℃下活化培养一周,得活化DNRA-Anammox固定化小球,将DNRA-Anammox固定化小球投加至浸没式厌氧生物反应器中;(1) DNRA-Anammox immobilized pellets are activated and cultured at 25℃-30℃ for one week to obtain activated DNRA-Anammox immobilized pellets, and DNRA-Anammox immobilized pellets are added to the submerged anaerobic bioreactor in;
    (2)从反应器的底部利用蠕动泵通入待处理废水,调整进水流速,调整温度及pH,同时进行曝氮气及磁力搅拌,维持厌氧环境;实现对污水中的氮素的高效脱除;(2) Use a peristaltic pump to pass the wastewater to be treated from the bottom of the reactor, adjust the water flow rate, adjust the temperature and pH, and carry out nitrogen aeration and magnetic stirring at the same time to maintain an anaerobic environment; to achieve efficient removal of nitrogen in the sewage except;
    所述的DNRA-Anammox固定化小球是以聚乙烯醇、海藻酸钠、糊化淀粉和聚氨酯的交联聚合产物为载体,包埋DNRA菌和Anammox菌而形成的固定化小球。The DNRA-Anammox immobilized pellets are formed by embedding DNRA bacteria and Anammox bacteria with cross-linked polymer products of polyvinyl alcohol, sodium alginate, gelatinized starch and polyurethane as carriers.
  2. 根据权利要求1所述的高效处理含氮废水的方法,其特征在于,DNRA-Anammox固定化小球是按如下方法制备得到的:The method for efficiently treating nitrogen-containing wastewater according to claim 1, wherein the DNRA-Anammox immobilized pellets are prepared as follows:
    (1.1)将聚乙烯醇、海藻酸钠依次加入水中并分别加热搅拌溶解混合均匀,得到混合液1;(1.1) Add polyvinyl alcohol and sodium alginate to water in sequence and heat and stir to dissolve and mix uniformly to obtain mixed solution 1;
    (1.2)将可溶性淀粉加入水中加热糊化,之后冷却至70~80℃,得混合液2;(1.2) Add soluble starch to water and heat to gelatinize, and then cool to 70~80℃ to obtain mixture 2;
    (1.3)将水性聚氨酯乳液、混合液2依次加入混合液1中混合,得凝胶液;(1.3) Add the water-based polyurethane emulsion and the mixed solution 2 to the mixed solution 1 and mix to obtain a gel solution;
    (1.4)将凝胶液冷却到室温后,将DNRA菌泥与Anammox菌泥按质量比1:1的比例混合后,得到DNRA-Anammox混合菌泥,将混合菌泥加入冷却后的凝胶液中,混合均匀后得到菌胶混合液;(1.4) After cooling the gel liquid to room temperature, mix DNRA and Anammox bacteria in a mass ratio of 1:1 to obtain DNRA-Anammox mixed bacteria. Add the mixed bacteria to the cooled gel liquid After mixing evenly, the fungus gum mixture is obtained;
    (1.5)取硼酸和氯化钙溶于水中,制备含有硼酸和氯化钙混合溶液,即为凝固液;(1.5) Dissolve boric acid and calcium chloride in water to prepare a mixed solution containing boric acid and calcium chloride, which is the coagulation liquid;
    (1.6)将菌胶混合液在搅拌条件下滴加至凝固液中进行凝固成形,然后静置使其充分交联,得到DNRA-Anammox固定化小球。(1.6) Add the fungal gum mixture dropwise to the coagulation solution under stirring conditions for coagulation and shape, and then stand to make it fully crosslinked to obtain DNRA-Anammox immobilized pellets.
  3. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,步骤(1.1)中,混合液1中聚乙烯醇的质量百分含量为8-20%,海藻酸钠的质量百分含量为0.5-1.5%。The method for efficiently treating nitrogen-containing wastewater according to claim 2, wherein in step (1.1), the mass percentage of polyvinyl alcohol in the mixed solution 1 is 8-20%, and the mass percentage of sodium alginate The content is 0.5-1.5%.
  4. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,步骤(1.1)中,聚乙烯醇为聚合度为1600-1800、醇解度>99%的聚乙烯醇。The method for efficiently treating nitrogen-containing wastewater according to claim 2, wherein in step (1.1), the polyvinyl alcohol is polyvinyl alcohol with a degree of polymerization of 1600-1800 and a degree of alcoholysis> 99%.
  5. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,步骤(1.2)中,可溶性淀粉与水的质量体积比为:1:(40-60),单位:g/mL。The method for efficiently treating nitrogen-containing wastewater according to claim 2, characterized in that, in step (1.2), the mass volume ratio of soluble starch to water is 1: (40-60), unit: g/mL.
  6. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,步骤(1.3)中,所 述水性聚氨酯乳液的固含量为20%-40%,水性聚氨酯在凝胶液中的的质量分数为0.1%-1.2%;混合液2与混合液1的体积比为:1:(10-30)。The method for efficiently treating nitrogen-containing wastewater according to claim 2, wherein in step (1.3), the solid content of the aqueous polyurethane emulsion is 20%-40%, and the mass of the aqueous polyurethane in the gel liquid The fraction is 0.1%-1.2%; the volume ratio of the mixed solution 2 to the mixed solution 1 is 1: (10-30).
  7. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,DNRA菌泥为厌氧污泥经硝酸盐异化还原为铵菌富集培养、清洗后得到,DNRA菌泥的含水量为60-90wt%,Anammox菌泥为厌氧污泥经厌氧氨氧化菌富集培养、清洗后得到,Anammox菌泥的含水量为60-70wt%。The method for high-efficiency treatment of nitrogen-containing wastewater according to claim 2, characterized in that the DNRA bacterial sludge is obtained by anaerobic sludge after nitrate dissimilative reduction to ammonium bacteria enrichment culture and cleaning, and the water content of the DNRA bacterial sludge is 60-90wt%, Anammox bacterial sludge is obtained by anaerobic ammonia oxidizing bacteria enrichment culture and cleaning, and the water content of Anammox bacterial sludge is 60-70wt%.
  8. 根据权利要求2所述的高效处理含氮废水的方法,其特征在于,步骤(1.4)中,DNRA-Anammox混合菌泥与凝胶液的质量体积比为:1:(3-8),单位:g/mL;步骤(1.5)中,所述凝固液中硼酸的质量分数为3%-5%,氯化钙的质量百分含量为2%-6%。The method for efficiently treating nitrogen-containing wastewater according to claim 2, wherein in step (1.4), the mass-volume ratio of DNRA-Anammox mixed bacterial mud and gel liquid is 1: (3-8), unit : G/mL; in step (1.5), the mass fraction of boric acid in the coagulation liquid is 3%-5%, and the mass percentage of calcium chloride is 2%-6%.
  9. 根据权利要求1所述的高效处理含氮废水的方法,其特征在于,所述的活化为将DNRA-Anammox固定化小球置于活化水中在25℃-30℃下活化培养一周,所述的活化水组成如下:碳酸氢铵190mg/L,磷酸二氢钾25mg/L,硫酸镁200mg/L,氯化钙300mg/L,葡萄糖12.2mg/L,微量元素溶液1mL/L;所述微量元素溶液组成成分为:乙二胺四乙酸20.0g/L,硫酸锌0.43g/L,氯化锰0.99g/L,氯化钴0.24g/L,氯化镍0.19g/L,硫酸铜0.25g/L,硒酸钠0.21g/L,钼酸钠0.22g/L,硼酸0.014g/L。The method for high-efficiency treatment of nitrogen-containing wastewater according to claim 1, characterized in that the activation is to place the DNRA-Anammox immobilized pellets in activated water and activate and culture for one week at 25°C-30°C. The composition of activated water is as follows: ammonium bicarbonate 190mg/L, potassium dihydrogen phosphate 25mg/L, magnesium sulfate 200mg/L, calcium chloride 300mg/L, glucose 12.2mg/L, trace element solution 1mL/L; the trace elements The composition of the solution is: ethylenediaminetetraacetic acid 20.0g/L, zinc sulfate 0.43g/L, manganese chloride 0.99g/L, cobalt chloride 0.24g/L, nickel chloride 0.19g/L, copper sulfate 0.25g /L, sodium selenate 0.21g/L, sodium molybdate 0.22g/L, boric acid 0.014g/L.
  10. 根据权利要求1所述的高效处理含氮废水的方法,其特征在于,活化DNRA-Anammox固定化小球在反应器中的填充率为反应器容积的15%-25%。The method for efficiently treating nitrogen-containing wastewater according to claim 1, wherein the filling rate of the activated DNRA-Anammox immobilized pellets in the reactor is 15%-25% of the volume of the reactor.
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