CN117904095A - Method for fixing nitrifying bacteria by sodium alginate-polyurethane filler - Google Patents

Method for fixing nitrifying bacteria by sodium alginate-polyurethane filler Download PDF

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CN117904095A
CN117904095A CN202410102178.0A CN202410102178A CN117904095A CN 117904095 A CN117904095 A CN 117904095A CN 202410102178 A CN202410102178 A CN 202410102178A CN 117904095 A CN117904095 A CN 117904095A
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nitrifying bacteria
sodium alginate
polyurethane filler
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刘国华
袁俊莉
齐鲁
王洪臣
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Renmin University of China
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Abstract

本发明公开了一种海藻酸钠‑聚氨酯填料固定硝化细菌的方法,属于水处理技术领域。先将海藻酸钠与硝化细菌混合,再将聚氨酯填料加入海藻酸钠和硝化细菌的混合液中,充分搅拌均匀后,置于氯化钙溶液中进行交联固定。本发明的优点是利用海藻酸钠和多孔聚氨酯填料直接固定硝化细菌,避免传统污水生物脱氮过程通过延长活性污泥停留时间和水力停留时间来培养硝化细菌的缺陷,同时固定化后的硝化细菌载体具有高活性,可定向提高硝化速率,减小曝气池池容,为污水处理行业低碳高效脱氮提供技术支持。

The invention discloses a method for fixing nitrifying bacteria with sodium alginate-polyurethane filler, and belongs to the technical field of water treatment. Sodium alginate is first mixed with nitrifying bacteria, and then polyurethane filler is added to the mixed solution of sodium alginate and nitrifying bacteria, and after being fully stirred, it is placed in a calcium chloride solution for cross-linking and fixation. The advantage of the present invention is that nitrifying bacteria are directly fixed by using sodium alginate and porous polyurethane filler, avoiding the defect of cultivating nitrifying bacteria by prolonging the activated sludge retention time and hydraulic retention time in the traditional sewage biological denitrification process, and at the same time, the immobilized nitrifying bacteria carrier has high activity, which can directionally increase the nitrification rate and reduce the aeration tank capacity, providing technical support for low-carbon and high-efficiency denitrification in the sewage treatment industry.

Description

一种海藻酸钠-聚氨酯填料固定硝化细菌的方法A method for fixing nitrifying bacteria using sodium alginate-polyurethane filler

技术领域Technical Field

本发明属于水处理技术领域,尤其涉及一种海藻酸钠-聚氨酯填料固定硝化细菌的方法。The invention belongs to the technical field of water treatment, and in particular relates to a method for fixing nitrifying bacteria with sodium alginate-polyurethane filler.

背景技术Background technique

氮素过量排放是导致水体富营养化的关键因素之一。污水生物脱氮主要依靠微生物的硝化作用与反硝化作用,其中硝化反应是限速步骤。这是由于污水处理厂的活性污泥系统中硝化细菌增长速度慢、世代周期长,以及硝化细菌在活性污泥中数量少、占比小造成的。污水处理厂中硝化细菌的硝化速率较低,导致硝化过程需要较长的水力停留时间才能将氨氮完全去除,进而导致具有脱氮功能的污水处理设施的占地面积较大。在城市土地资源十分紧张的情况下,如果能够提高硝化细菌的硝化速率对于节约土地资源有重要意义。Excessive nitrogen discharge is one of the key factors leading to eutrophication of water bodies. Biological denitrification of sewage mainly relies on the nitrification and denitrification of microorganisms, among which nitrification reaction is the rate-limiting step. This is due to the slow growth rate and long generation cycle of nitrifying bacteria in the activated sludge system of the sewage treatment plant, as well as the small number and small proportion of nitrifying bacteria in the activated sludge. The nitrification rate of nitrifying bacteria in sewage treatment plants is low, resulting in a longer hydraulic retention time in the nitrification process to completely remove ammonia nitrogen, which in turn leads to a larger area occupied by sewage treatment facilities with denitrification functions. In the case of extremely tight urban land resources, it is of great significance to save land resources if the nitrification rate of nitrifying bacteria can be increased.

固定化微生物技术是依靠物理或者化学方法将微生物限制在一定空间区域内。该技术可以提高微生物在系统中的数量,减少微生物的流失,同时减弱外界因素对微生物的干扰。目前,固定化微生物技术最常见的固定方法为包埋法。包埋法使用的材料分为合成高分子有机物和天然高分子有机物两大类。其中聚乙烯醇是合成高分子有机物中最常见的载体之一,但是聚乙烯醇以及聚乙烯醇的交联剂硼酸均对微生物有毒害作用,会降低微生物的活性,同时聚乙烯醇作为固定化材料传质性能较差。海藻酸钠是天然高分子有机物中最常见的载体之一,与聚乙烯醇相比,海藻酸钠具有传质性能好和对微生物无毒无害的优势。此外,海藻酸钠在微生物固定化过程中与交联剂氯化钙的反应速度快,所需时间短,可以降低固定化过程使用时间。但是海藻酸钠的机械性能也较差,使用寿命短。Immobilized microbial technology relies on physical or chemical methods to restrict microorganisms to a certain spatial area. This technology can increase the number of microorganisms in the system, reduce the loss of microorganisms, and reduce the interference of external factors on microorganisms. At present, the most common fixation method for immobilized microorganism technology is the embedding method. The materials used in the embedding method are divided into two categories: synthetic high molecular organic matter and natural high molecular organic matter. Among them, polyvinyl alcohol is one of the most common carriers in synthetic high molecular organic matter, but polyvinyl alcohol and polyvinyl alcohol cross-linking agent boric acid are toxic to microorganisms and will reduce the activity of microorganisms. At the same time, polyvinyl alcohol as an immobilized material has poor mass transfer performance. Sodium alginate is one of the most common carriers in natural high molecular organic matter. Compared with polyvinyl alcohol, sodium alginate has the advantages of good mass transfer performance and non-toxicity to microorganisms. In addition, sodium alginate reacts quickly with the cross-linking agent calcium chloride during the microbial immobilization process, and the time required is short, which can reduce the use time of the immobilization process. However, the mechanical properties of sodium alginate are also poor and the service life is short.

因此,开发一种机械性能优良、使用寿命长、对微生物毒害作用小、传质性能好、制备过程简单且价格低廉,可以实现高效硝化作用的固定化微生物方法,对于污水处理生物脱氮缩短硝化过程的水力停留时间,节约污水处理设施设备占地面积有重要现实意义。Therefore, it is of great practical significance to develop an immobilized microorganism method with excellent mechanical properties, long service life, low toxicity to microorganisms, good mass transfer performance, simple preparation process and low price, which can achieve efficient nitrification, shorten the hydraulic retention time of the nitrification process for biological denitrification in sewage treatment, and save the floor space of sewage treatment facilities and equipment.

发明内容Summary of the invention

为实现上述目的,本发明提供了一种海藻酸钠-聚氨酯填料固定硝化细菌的方法,包括以下步骤:To achieve the above object, the present invention provides a method for fixing nitrifying bacteria using sodium alginate-polyurethane filler, comprising the following steps:

(1)将海藻酸钠制备成海藻酸钠水凝胶;(1) preparing sodium alginate into sodium alginate hydrogel;

(2)将液体硝化细菌菌剂离心,弃去上清液,将沉淀物加入所述海藻酸钠水凝胶中,搅拌均匀,制得硝化细菌水凝胶混合物;(2) centrifuging the liquid nitrifying bacteria agent, discarding the supernatant, adding the precipitate to the sodium alginate hydrogel, and stirring evenly to obtain a nitrifying bacteria hydrogel mixture;

(3)将聚氨酯填料加入所述硝化细菌水凝胶混合物中,搅拌,得到含海藻酸钠和硝化细菌混合液的聚氨酯填料(聚氨酯填料内部含有海藻酸钠和硝化细菌细菌混合液),加入氯化钙溶液中交联固定,交联固定完成后清洗即可。(3) adding a polyurethane filler into the nitrifying bacteria hydrogel mixture and stirring to obtain a polyurethane filler containing a mixture of sodium alginate and nitrifying bacteria (the polyurethane filler contains a mixture of sodium alginate and nitrifying bacteria), adding the filler into a calcium chloride solution for cross-linking and fixing, and washing after the cross-linking and fixing are completed.

本发明方法的优点是既降低了固定化过程中对细菌的伤害,又提高了细菌固定化载体的机械性能,同时将具有高硝化性能的硝化细菌固定于聚氨酯填料上,可定向提高硝化速率,缩短污水脱氮硝化过程的水力停留时间,为污水处理行业高效脱氮提供技术支持。The advantages of the method of the present invention are that it reduces the damage to bacteria during the immobilization process and improves the mechanical properties of the bacterial immobilization carrier. At the same time, nitrifying bacteria with high nitrification performance are fixed on the polyurethane filler, which can directionally increase the nitrification rate and shorten the hydraulic retention time of the sewage denitrification and nitrification process, providing technical support for efficient denitrification in the sewage treatment industry.

本发明的液体硝化细菌菌剂也可以换成粉末态硝化细菌菌剂,如果是粉末态的硝化细菌菌剂需先用纯净水溶解然后离心,如果是液体菌剂可直接离心。The liquid nitrifying bacteria agent of the present invention can also be replaced with a powdered nitrifying bacteria agent. If it is a powdered nitrifying bacteria agent, it needs to be dissolved in pure water and then centrifuged. If it is a liquid agent, it can be directly centrifuged.

进一步地,步骤(1)中,所述海藻酸钠水凝胶的制备方法如下:将海藻酸钠加入水中,加热搅拌充分溶解后,于室温静置冷却制得海藻酸钠水凝胶;更进一步地,所述海藻酸钠水凝胶的制备方法如下:将海藻酸钠加入装有纯净水的烧杯中加热搅拌,得到海藻酸钠溶液,于室温静置冷却,制得海藻酸钠水凝胶。Furthermore, in step (1), the preparation method of the sodium alginate hydrogel is as follows: sodium alginate is added to water, heated and stirred to fully dissolve, and then allowed to stand and cool at room temperature to obtain the sodium alginate hydrogel; further, the preparation method of the sodium alginate hydrogel is as follows: sodium alginate is added to a beaker filled with pure water, heated and stirred to obtain a sodium alginate solution, and then allowed to stand and cool at room temperature to obtain the sodium alginate hydrogel.

进一步地,步骤(1)中,海藻酸钠溶液的质量分数为1%。海藻酸钠水凝胶的制备方法优选为:将海藻酸钠加入装有纯净水的烧杯中加热搅拌1h,得到质量分数为1%的海藻酸钠溶液,于室温静置1h,制得海藻酸钠水凝胶。海藻酸钠溶液的质量分数会影响固定后的硝化细菌的硝化速率,本发明中限定的海藻酸钠溶液的质量分数是经过筛选后的适宜浓度。Furthermore, in step (1), the mass fraction of the sodium alginate solution is 1%. The method for preparing the sodium alginate hydrogel is preferably as follows: sodium alginate is added to a beaker filled with purified water, heated and stirred for 1 hour to obtain a sodium alginate solution with a mass fraction of 1%, and the solution is allowed to stand at room temperature for 1 hour to obtain the sodium alginate hydrogel. The mass fraction of the sodium alginate solution will affect the nitrification rate of the fixed nitrifying bacteria, and the mass fraction of the sodium alginate solution defined in the present invention is an appropriate concentration after screening.

进一步地,步骤(1)中,加热搅拌的温度为70℃,转速为120r/min。Furthermore, in step (1), the temperature of heating and stirring is 70° C. and the rotation speed is 120 r/min.

进一步地,步骤(2)中,所述液体硝化细菌菌剂中硝化细菌为优势菌,其相对丰度为28.39%。硝化细菌菌剂的混合液悬浮固体浓度为3.7g/L(“混合液悬浮固体浓度”表示菌剂中微生物的浓度)。更进一步地,所述液体硝化细菌菌剂中亚硝化单胞菌和亚硝化螺菌为优势菌,其相对丰度分别为27.96%和0.43%。Further, in step (2), the nitrifying bacteria in the liquid nitrifying bacteria agent are the dominant bacteria, and their relative abundance is 28.39%. The mixed liquid suspended solid concentration of the nitrifying bacteria agent is 3.7 g/L ("mixed liquid suspended solid concentration" represents the concentration of microorganisms in the agent). Further, Nitrosomonas and Nitrosospirillum are the dominant bacteria in the liquid nitrifying bacteria agent, and their relative abundances are 27.96% and 0.43%, respectively.

进一步地,步骤(2)中,以干重计,所述硝化细菌水凝胶混合物中硝化细菌菌剂的质量分数为0.37%。Furthermore, in step (2), the mass fraction of the nitrifying bacteria agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight.

进一步地,步骤(2)中,离心时的转速为6000r/min,优选离心10min。Furthermore, in step (2), the rotation speed during centrifugation is 6000 r/min, preferably centrifugation for 10 min.

进一步地,步骤(3)中,聚氨酯填料的规格为1×1×1cm,孔隙密度为20ppi。Furthermore, in step (3), the specification of the polyurethane filler is 1×1×1 cm, and the pore density is 20 ppi.

进一步地,步骤(3)中,交联固定的时间为2h,所述清洗为交联固定完成后用纯净水冲洗3遍。Furthermore, in step (3), the cross-linking fixation time is 2 hours, and the cleaning is to rinse with pure water 3 times after the cross-linking fixation is completed.

进一步地,步骤(3)中,氯化钙溶液的质量分数为2%。Furthermore, in step (3), the mass fraction of the calcium chloride solution is 2%.

与现有技术相比,本发明具有如下优点和技术效果:Compared with the prior art, the present invention has the following advantages and technical effects:

(1)本发明使用的固定化材料海藻酸钠为天然高分子有机物,固定化过程中对微生物无毒无害,且传质性能好,有利于提高微生物对污染物的处理效果。此外,海藻酸钠与交联剂氯化钙的反应速度快,使得固定化制备过程简单且快速;(1) The immobilization material sodium alginate used in the present invention is a natural high molecular organic matter, which is non-toxic and harmless to microorganisms during the immobilization process, and has good mass transfer performance, which is conducive to improving the treatment effect of microorganisms on pollutants. In addition, the reaction speed of sodium alginate and the cross-linking agent calcium chloride is fast, making the immobilization preparation process simple and fast;

(2)本发明使用的聚氨酯填料为海藻酸钠提供了优良的机械支撑,可以延长其使用寿命,将海藻酸钠-聚氨酯填料固定硝化细菌颗粒投加到反应器中可以稳定使用60d以上;(2) The polyurethane filler used in the present invention provides excellent mechanical support for sodium alginate, which can extend its service life. The sodium alginate-polyurethane filler fixed nitrifying bacteria particles added to the reactor can be stably used for more than 60 days;

(3)本发明固定的微生物中硝化细菌的数量多,占比高,海藻酸钠-聚氨酯填料固定硝化细菌的硝化速率能达到9.32mg/(g MLSS·h),将海藻酸钠-聚氨酯填料固定硝化细菌颗粒投加到反应器,反应器启动时间短,且在较短的水力停留时间下就能将氨氮完全氧化去除。(3) The number of nitrifying bacteria in the immobilized microorganisms of the present invention is large and the proportion is high. The nitrification rate of nitrifying bacteria fixed by sodium alginate-polyurethane filler can reach 9.32 mg/(g MLSS·h). When the nitrifying bacteria particles fixed by sodium alginate-polyurethane filler are added to the reactor, the reactor startup time is short, and the ammonia nitrogen can be completely oxidized and removed under a short hydraulic retention time.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

构成本发明的一部分的附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。在附图中:The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

图1为实施例1海藻酸钠-聚氨酯填料固定硝化细菌实物图;FIG1 is a physical picture of sodium alginate-polyurethane filler immobilizing nitrifying bacteria in Example 1;

图2为应用例1中反应器进水氨氮浓度为30mg/L的出水情况;FIG2 shows the effluent of the reactor in Application Example 1 with an influent ammonia nitrogen concentration of 30 mg/L;

图3为应用例1中反应器进水氨氮浓度为50mg/L的出水情况;FIG3 shows the effluent of the reactor in Application Example 1 with an influent ammonia nitrogen concentration of 50 mg/L;

图4为应用例1中反应器进水氨氮浓度为100mg/L的出水情况;FIG4 shows the effluent of the reactor in Application Example 1 when the ammonia nitrogen concentration in the inlet water is 100 mg/L;

图5为对比例1中聚乙烯醇-海藻酸钠固定硝化细菌对氨氮的处理效果;FIG5 shows the treatment effect of polyvinyl alcohol-sodium alginate immobilized nitrifying bacteria on ammonia nitrogen in Comparative Example 1;

图6为对比例1中聚乙烯醇-海藻酸钠固定硝化细菌颗粒形态变化。FIG. 6 shows the morphological changes of the polyvinyl alcohol-sodium alginate-immobilized nitrifying bacteria particles in Comparative Example 1.

具体实施方式Detailed ways

现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值,以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. The intermediate value in any stated value or stated range, and each smaller range between any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

本发明实施例中的液体硝化细菌菌剂购自上海普罗生物技术有限公司,其中亚硝化单胞菌(Nitrosomonas)和亚硝化螺菌(Nitrosospira)的相对丰度分别为27.96%和0.43%,硝化细菌菌剂的混合液悬浮固体浓度为3.7g/L。The liquid nitrifying bacteria agent in the embodiment of the present invention was purchased from Shanghai Pro Biotechnology Co., Ltd., wherein the relative abundances of Nitrosomonas and Nitrosospira were 27.96% and 0.43%, respectively, and the suspended solid concentration of the mixed liquid of the nitrifying bacteria agent was 3.7 g/L.

实施例1Example 1

(1)取20g海藻酸钠,加入2L的纯净水中,在70℃、120r/min的条件下加热搅拌1h,然后静置冷却1h,制得海藻酸钠水凝胶;(1) 20 g of sodium alginate was added to 2 L of pure water, heated and stirred at 70 ° C and 120 r/min for 1 h, and then allowed to stand and cool for 1 h to obtain a sodium alginate hydrogel;

(2)取2L的液体硝化细菌菌剂,离心(转速为6000r/min)10min,弃去上清液,将沉淀物倒入所述海藻酸钠水凝胶中,搅拌均匀,制得硝化细菌水凝胶混合物,以干重计,硝化细菌水凝胶混合物中硝化细菌菌剂的质量分数为0.37%;(2) taking 2 L of liquid nitrifying bacteria agent, centrifuging (at a speed of 6000 r/min) for 10 min, discarding the supernatant, pouring the precipitate into the sodium alginate hydrogel, and stirring evenly to obtain a nitrifying bacteria hydrogel mixture, wherein the mass fraction of the nitrifying bacteria agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight;

(3)将聚氨酯填料(规格为1×1×1cm,孔隙密度为20ppi)加入到所述硝化细菌水凝胶混合物中,不断搅拌使硝化细菌水凝胶充分渗入聚氨酯填料内部,然后将聚氨酯填料(内部含有海藻酸钠和硝化细菌混合液)加入10L的质量分数为2%的氯化钙溶液中,交联固定2h,交联完成后用纯净水冲洗3遍,即得到规格为1×1×1cm的海藻酸钠-聚氨酯填料固定硝化细菌颗粒,如图1所示。(3) Add the polyurethane filler (with a specification of 1×1×1 cm and a pore density of 20 ppi) to the nitrifying bacteria hydrogel mixture, and stir continuously to allow the nitrifying bacteria hydrogel to fully penetrate into the polyurethane filler. Then, add the polyurethane filler (containing a mixture of sodium alginate and nitrifying bacteria) into 10 L of a 2% calcium chloride solution, cross-link and fix for 2 h, and rinse with pure water 3 times after the cross-linking is completed to obtain sodium alginate-polyurethane filler-fixed nitrifying bacteria particles with a specification of 1×1×1 cm, as shown in FIG1 .

实施例2Example 2

(1)取1g海藻酸钠,加入100mL的装有纯净水的烧杯中,70℃加热搅拌1h,转速为120r/min,然后于室温下静置1h,制得海藻酸钠水凝胶;(1) 1 g of sodium alginate was added to a beaker containing 100 mL of purified water, heated and stirred at 70° C. for 1 h at a speed of 120 r/min, and then allowed to stand at room temperature for 1 h to obtain a sodium alginate hydrogel;

(2)取100mL的硝化细菌菌剂,离心(转速为6000r/min)10min,弃去上清液,将沉淀物倒入所述海藻酸钠水凝胶中,搅拌均匀,制得硝化细菌水凝胶混合物,以干重计,硝化细菌水凝胶混合物中硝化细菌菌剂的质量分数为0.37%;(2) taking 100 mL of nitrifying bacteria agent, centrifuging (at a speed of 6000 r/min) for 10 min, discarding the supernatant, pouring the precipitate into the sodium alginate hydrogel, and stirring evenly to obtain a nitrifying bacteria hydrogel mixture, wherein the mass fraction of the nitrifying bacteria agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight;

(3)将聚氨酯填料(规格为1×1×1cm,孔隙密度为20ppi)加入到所述硝化细菌水凝胶混合物中,不断搅拌使硝化细菌水凝胶充分渗入聚氨酯填料内部,然后将聚氨酯填料(内部含有海藻酸钠和硝化细菌混合液)加入500mL的质量分数为2%的氯化钙溶液中,交联固定2h,交联完成后用纯净水冲洗3遍,即得到规格为1×1×1cm的海藻酸钠-聚氨酯填料固定硝化细菌颗粒。(3) Adding a polyurethane filler (with a specification of 1×1×1 cm and a pore density of 20 ppi) to the nitrifying bacteria hydrogel mixture, stirring continuously to allow the nitrifying bacteria hydrogel to fully penetrate into the polyurethane filler, and then adding the polyurethane filler (containing a mixture of sodium alginate and nitrifying bacteria) to 500 mL of a 2% calcium chloride solution, cross-linking and fixing for 2 hours, and rinsing with pure water three times after the cross-linking is completed, to obtain sodium alginate-polyurethane filler-fixed nitrifying bacteria particles with a specification of 1×1×1 cm.

将步骤(3)制备的海藻酸钠-聚氨酯填料固定硝化细菌颗粒放入300mL的配置好的测试溶液中(测试溶液中各物质及物质浓度如下:NH4Cl:382mg/L,MgSO4·7H2O:4mg/L,KH2PO4:10mg/L,FeSO4·7H2O:4mg/L,MnCl2·4H2O:0.2mg/L,CuSO4·5H2O:0.2mg/L)向其中逐滴滴加饱和碳酸氢钠溶液,调节pH为7~8,维持溶液中溶解氧浓度为4mg/L,然后置于转速为200rpm,温度为25℃的恒温摇床中。置于摇床前取水样一次,计时为0h,然后每隔0.5h取水样一次,每次取样前充分混合均匀,连续取样6次,分别为0.5h、1h、1.5h、2h、2.5h、3h,每次取样量为5mL,取样后立即用0.45um滤膜过滤,密闭保留滤液,用于滤液中氨氮、亚硝氮、硝氮的测定。每次取样之后用饱和碳酸钠溶液将锥形瓶中溶液pH调节至7~8,然后置于恒温摇床中继续反应。滤液在进行测定前于4℃条件下保存。The sodium alginate-polyurethane filler-immobilized nitrifying bacteria particles prepared in step (3) were placed in 300 mL of the prepared test solution (the substances and substance concentrations in the test solution were as follows: NH 4 Cl: 382 mg/L, MgSO 4 ·7H 2 O: 4 mg/L, KH 2 PO 4 : 10 mg/L, FeSO 4 ·7H 2 O: 4 mg/L, MnCl 2 ·4H 2 O: 0.2 mg/L, CuSO 4 ·5H 2 O: 0.2 mg/L), saturated sodium bicarbonate solution was added dropwise thereto, the pH was adjusted to 7-8, the dissolved oxygen concentration in the solution was maintained at 4 mg/L, and then placed in a constant temperature shaker at a speed of 200 rpm and a temperature of 25°C. Take a water sample once before placing it in a shaker, the timing is 0h, and then take a water sample every 0.5h. Mix thoroughly before each sampling, and take samples 6 times in succession, respectively 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, each sampling volume is 5mL, filter with a 0.45um filter membrane immediately after sampling, and keep the filtrate in a sealed manner for the determination of ammonia nitrogen, nitrite nitrogen, and nitric nitrogen in the filtrate. After each sampling, adjust the pH of the solution in the conical flask to 7-8 with a saturated sodium carbonate solution, and then place it in a constant temperature shaker to continue the reaction. The filtrate is stored at 4°C before the determination.

以取样时间t(h)为横坐标,测试溶液中残留氨氮的氨氮质量浓度p(mg/L)为纵坐标(以N计)作图,对图中的数据点进行拟合(p=r·t+b),得到直线斜率的绝对值r,单位为mg NH4 +-N/(L·h)。硝化细菌菌剂的硝化速率P,单位为mg NH4 +-N/(g MLSS·h),按照下列公式计算:Plot the graph with sampling time t (h) as the horizontal axis and the residual ammonia nitrogen mass concentration p (mg/L) of the test solution as the vertical axis (in N), fit the data points in the graph (p = r·t+b), and obtain the absolute value r of the slope of the straight line in mg NH 4 + -N/(L·h). The nitrification rate P of the nitrifying bacteria agent in mg NH 4 + -N/(g MLSS·h) is calculated according to the following formula:

式中:M-硝化细菌菌剂的浓度,单位为mg/L,M=3761mg/L;Where: M-the concentration of nitrifying bacteria agent, the unit is mg/L, M=3761mg/L;

V1-固定硝化细菌菌剂的体积,单位为mL,V1=100mL;V 1 - volume of fixed nitrifying bacteria agent, in mL, V 1 = 100 mL;

V2-测试溶液体积,单位为mL,V2=300mL;V 2 - volume of test solution, in mL, V 2 = 300 mL;

r-样品测定实验拟合直线的斜率的绝对值,单位为mg NH4 +-N/(L·h)。r - the absolute value of the slope of the fitting straight line of the sample measurement experiment, in mg NH 4 + -N/(L·h).

通过上述计算方式得到海藻酸钠-聚氨酯填料固定硝化细菌的硝化速率能达到9.32mg/(gMLSS·h),该结果表明海藻酸钠-聚氨酯填料固定硝化细菌具备良好的硝化性能。Through the above calculation method, it is obtained that the nitrification rate of nitrifying bacteria fixed on sodium alginate-polyurethane filler can reach 9.32 mg/(gMLSS·h). This result shows that nitrifying bacteria fixed on sodium alginate-polyurethane filler have good nitrification performance.

应用例1对模拟废水的处理效果Application Example 1 Treatment effect on simulated wastewater

将实施例1得到的海藻酸钠-聚氨酯填料固定硝化细菌颗粒投加到反应器中,设置填充比(固定化颗粒与进水的体积比)为40%,反应器的直径为160mm,高度为320mm(高度与直径比为2),有效容积为6L,反应器材料为有机玻璃。The sodium alginate-polyurethane filler immobilized nitrifying bacteria particles obtained in Example 1 were added to the reactor, and the filling ratio (volume ratio of immobilized particles to influent water) was set to 40%. The diameter of the reactor was 160 mm, the height was 320 mm (height to diameter ratio was 2), the effective volume was 6 L, and the reactor material was plexiglass.

反应器进水为人工配水,反应器配备一个30L的进水桶,进水桶中配水组分为NH+ 4-N、KH2PO4(氮磷比为5)、CaCl2(111mg/L)、MgSO4(15mg/L)、FeSO4·7H2O(11.1mg/L)、NaCl(50mg/L),通过定时器调节水力停留时间,利用曝气泵和曝气头进行曝气,反应器中溶解氧浓度由气体流量计控制。The reactor inlet water is artificially distributed. The reactor is equipped with a 30L water inlet bucket. The water components in the water inlet bucket are NH + 4 -N, KH 2 PO 4 (nitrogen-phosphorus ratio of 5), CaCl 2 (111 mg/L), MgSO 4 (15 mg/L), FeSO 4 ·7H 2 O (11.1 mg/L), and NaCl (50 mg/L). The hydraulic retention time is adjusted by a timer, and aeration is carried out using an aeration pump and an aeration head. The dissolved oxygen concentration in the reactor is controlled by a gas flow meter.

反应器先后在进水氨氮浓度为30mg/L、50mg/L、100mg/L的条件下运行,温度设置为25℃,pH控制在7~8,溶解氧控制在4~5mg/L,每天监测出水中氨氮、亚硝氮、硝氮的变化情况。The reactor was operated under the conditions of influent ammonia nitrogen concentration of 30 mg/L, 50 mg/L and 100 mg/L, the temperature was set to 25°C, the pH was controlled at 7-8, the dissolved oxygen was controlled at 4-5 mg/L, and the changes of ammonia nitrogen, nitrite nitrogen and nitric nitrogen in the effluent were monitored every day.

由图2可见,反应器在启动的第1天,氨氮去除率能达到100%,这说明反应器运行效果良好,能实现快速启动,对于进水氨氮浓度为30mg/L的模拟废水,HRT为2h可以将氨氮完全去除;由图3可见,对于进水氨氮浓度为50mg/L的模拟废水,HRT为2h时氨氮去除率在90%~100%之间波动;由图4可见,对于进水氨氮浓度为100mg/L的模拟废水,延长HRT可以增强对氨氮的去除效果,当HRT为6h,氨氮的去除率可以达到80%以上。As can be seen from Figure 2, on the first day of startup, the ammonia nitrogen removal rate of the reactor can reach 100%, which shows that the reactor operates well and can achieve rapid startup. For the simulated wastewater with an inlet ammonia nitrogen concentration of 30 mg/L, the ammonia nitrogen can be completely removed at an HRT of 2h; as can be seen from Figure 3, for the simulated wastewater with an inlet ammonia nitrogen concentration of 50 mg/L, the ammonia nitrogen removal rate fluctuates between 90% and 100% when the HRT is 2h; as can be seen from Figure 4, for the simulated wastewater with an inlet ammonia nitrogen concentration of 100 mg/L, extending the HRT can enhance the removal effect of ammonia nitrogen. When the HRT is 6h, the ammonia nitrogen removal rate can reach more than 80%.

综上,基于本发明的海藻酸钠-聚氨酯填料固定硝化细菌颗粒搭建的反应器启动时间短,所需的水力停留时间短,氨氮的去除效果稳定且高效。此外,海藻酸钠-聚氨酯填料固定硝化细菌颗粒在使用60d后不仅依旧保持高效的硝化性能,同时也没有出现颗粒破碎的情况,颗粒的使用寿命长。In summary, the reactor built based on the sodium alginate-polyurethane filler fixed nitrifying bacteria particles of the present invention has a short startup time, a short required hydraulic retention time, and a stable and efficient removal effect of ammonia nitrogen. In addition, the sodium alginate-polyurethane filler fixed nitrifying bacteria particles not only maintain efficient nitrification performance after 60 days of use, but also do not break the particles, and the particles have a long service life.

应用例2对实际生活污水的处理效果Application Example 2: Treatment effect on actual domestic sewage

将实施例1得到的海藻酸钠-聚氨酯填料固定硝化细菌颗粒投加到反应器中,设置填充比(固定化颗粒与进水的体积比)为40%,反应器的直径为160mm,高度为320mm(高度与直径比为2),有效容积为6L,反应器材料为有机玻璃。The sodium alginate-polyurethane filler immobilized nitrifying bacteria particles obtained in Example 1 were added to the reactor, and the filling ratio (volume ratio of immobilized particles to influent water) was set to 40%. The diameter of the reactor was 160 mm, the height was 320 mm (height to diameter ratio was 2), the effective volume was 6 L, and the reactor material was plexiglass.

反应器进水为实际生活污水,进水氨氮浓度在60~90mg/L之间波动,反应器配备一个30L的进水桶,通过定时器调节水力停留时间,利用曝气泵和曝气头进行曝气,反应器中溶解氧浓度由流量计控制。The reactor inlet water is actual domestic sewage, and the inlet ammonia nitrogen concentration fluctuates between 60 and 90 mg/L. The reactor is equipped with a 30L inlet bucket. The hydraulic retention time is adjusted by a timer, and aeration is performed using an aeration pump and an aeration head. The dissolved oxygen concentration in the reactor is controlled by a flow meter.

反应器温度设置为25℃,溶解氧控制在4~5mg/L,每天监测出水中氨氮、亚硝氮、硝氮的变化情况。The reactor temperature was set at 25°C, the dissolved oxygen was controlled at 4-5 mg/L, and the changes in ammonia nitrogen, nitrite nitrogen, and nitrate nitrogen in the effluent were monitored every day.

反应器在水力停留时间为4h且进水氨氮浓度波动较大的情况,反应器运行稳,对氨氮的去除率能达到80%。这说明海藻酸钠-聚氨酯填料固定硝化细菌颗粒对实际生活污水的氨氮也具有高效处理能力。When the hydraulic retention time of the reactor is 4h and the concentration of ammonia nitrogen in the influent fluctuates greatly, the reactor operates stably and the removal rate of ammonia nitrogen can reach 80%. This shows that the sodium alginate-polyurethane filler fixed nitrifying bacteria particles also have a high efficiency in treating ammonia nitrogen in actual domestic sewage.

对比例1(无聚氨酯填料作为支撑)Comparative Example 1 (without polyurethane filler as support)

取200g聚乙烯醇,加入装有2L纯净水的烧杯中,浸泡24h后,将其放入恒温水浴锅中加热(70℃)2h,得到聚乙烯醇水凝胶,取16g海藻酸钠,加入聚乙烯醇水凝胶中,在70℃下加热搅拌1h,转速为120r/min,然后静置1h,制得聚乙烯醇-海藻酸钠水凝胶;Take 200g of polyvinyl alcohol, add it to a beaker filled with 2L of pure water, soak it for 24h, put it in a constant temperature water bath and heat it (70℃) for 2h to obtain polyvinyl alcohol hydrogel, take 16g of sodium alginate, add it to the polyvinyl alcohol hydrogel, heat and stir at 70℃ for 1h, the speed is 120r/min, and then stand for 1h to obtain polyvinyl alcohol-sodium alginate hydrogel;

取2L的硝化细菌菌剂,离心10min,取出弃上清液,将沉淀物倒入所述聚乙烯醇-海藻酸钠水凝胶中,搅拌均匀,制得硝化细菌水凝胶混合物;Take 2 L of nitrifying bacteria inoculum, centrifuge for 10 min, remove and discard the supernatant, pour the precipitate into the polyvinyl alcohol-sodium alginate hydrogel, stir evenly, and prepare a nitrifying bacteria hydrogel mixture;

将所述硝化细菌水凝胶混合物通过注射滴加到20L交联剂(交联剂由质量分数为4%的硼酸和质量分数为2%的氯化钙组成)中,交联固定16h,交联完成后用纯净水冲洗3遍,即得到聚乙烯醇-海藻酸钠固定硝化细菌颗粒;The nitrifying bacteria hydrogel mixture is added dropwise into 20 L of a cross-linking agent (the cross-linking agent is composed of 4% by mass boric acid and 2% by mass calcium chloride) by injection, cross-linked and fixed for 16 hours, and rinsed with pure water 3 times after the cross-linking is completed, so as to obtain polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles;

将聚乙烯醇-海藻酸钠固定硝化细菌颗粒投加到反应器中,设置填充比(固定化颗粒与进水的体积比)为40%,反应器的直径为160mm,高度为320mm(高度与直径比为2),有效容积为6L,反应器材料为有机玻璃。Polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles are added to the reactor, and the filling ratio (volume ratio of immobilized particles to influent water) is set to 40%. The diameter of the reactor is 160 mm, the height is 320 mm (height to diameter ratio is 2), the effective volume is 6 L, and the reactor material is plexiglass.

反应器进水为人工配水,反应器配备一个30L的进水桶,进水桶中配水组分为NH+ 4-N、KH2PO4(氮磷比为5)、CaCl2(111mg/L)、MgSO4(15mg/L)、FeSO4·7H2O(11.1mg/L)、NaCl(50mg/L),通过定时器调节水力停留时间,利用曝气泵和曝气头进行曝气,反应器中溶解氧浓度由流量计控制。The reactor inlet water is artificially distributed. The reactor is equipped with a 30L water inlet bucket. The water components in the water inlet bucket are NH + 4 -N, KH 2 PO 4 (nitrogen-phosphorus ratio of 5), CaCl 2 (111mg/L), MgSO 4 (15mg/L), FeSO 4 ·7H 2 O (11.1mg/L), and NaCl (50mg/L). The hydraulic retention time is adjusted by a timer, and aeration is carried out using an aeration pump and an aeration head. The dissolved oxygen concentration in the reactor is controlled by a flow meter.

温度设置为25℃,pH控制在7~8,溶解氧控制在4~5mg/L,水力停留时间为4h,每天监测出水中氨氮、亚硝氮、硝氮的变化情况。The temperature was set at 25°C, the pH was controlled at 7-8, the dissolved oxygen was controlled at 4-5 mg/L, the hydraulic retention time was 4 h, and the changes in ammonia nitrogen, nitrite nitrogen, and nitrate nitrogen in the effluent were monitored every day.

由图5可见,进水氨氮浓度为50mg/L,水力停留时间时间在4h情况下,基于聚乙烯醇-海藻酸钠固定硝化细菌颗粒搭建的反应器对氨氮的去除率在90%左右。但是,由图6可见,随着聚乙烯醇-海藻酸钠固定硝化细菌颗粒使用时间地增加,聚乙烯醇-海藻酸钠固定硝化细菌颗粒变软,并且出现溶解现象。As shown in Figure 5, when the influent ammonia nitrogen concentration is 50 mg/L and the hydraulic retention time is 4 hours, the removal rate of ammonia nitrogen by the reactor based on polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles is about 90%. However, as shown in Figure 6, as the use time of polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles increases, the polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles become soft and dissolve.

与聚乙烯醇-海藻酸钠固定硝化细菌颗粒相比,基于海藻酸钠-聚氨酯填料固定硝化细菌颗粒搭建的反应器在相同的水力停留时间下对氨氮的去除效果更好,且使用寿命更长。Compared with polyvinyl alcohol-sodium alginate fixed nitrifying bacteria particles, the reactor built based on sodium alginate-polyurethane filler fixed nitrifying bacteria particles has a better removal effect on ammonia nitrogen at the same hydraulic retention time and a longer service life.

以上,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求的保护范围为准。The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims (9)

1.一种海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,包括以下步骤:1. A method for fixing nitrifying bacteria using sodium alginate-polyurethane filler, characterized in that it comprises the following steps: (1)将海藻酸钠制备成海藻酸钠水凝胶;(1) preparing sodium alginate into sodium alginate hydrogel; (2)将液体硝化细菌菌剂离心,弃去上清液,将沉淀物加入所述海藻酸钠水凝胶中,搅拌均匀,制得硝化细菌水凝胶混合物;(2) centrifuging the liquid nitrifying bacteria agent, discarding the supernatant, adding the precipitate to the sodium alginate hydrogel, and stirring evenly to obtain a nitrifying bacteria hydrogel mixture; (3)将聚氨酯填料加入所述硝化细菌水凝胶混合物中搅拌,得到含海藻酸钠和硝化细菌混合液的聚氨酯填料,用氯化钙溶液交联固定,交联固定完成后清洗即可。(3) adding a polyurethane filler into the nitrifying bacteria hydrogel mixture and stirring to obtain a polyurethane filler containing a mixture of sodium alginate and nitrifying bacteria, cross-linking and fixing with a calcium chloride solution, and washing after the cross-linking and fixing is completed. 2.根据权利要求1所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(1)中,所述海藻酸钠水凝胶的制备方法如下:将海藻酸钠加入水中,加热搅拌,于室温静置冷却制得海藻酸钠水凝胶。2. The method for fixing nitrifying bacteria on sodium alginate-polyurethane filler according to claim 1, characterized in that in step (1), the preparation method of the sodium alginate hydrogel is as follows: sodium alginate is added to water, heated and stirred, and allowed to stand and cool at room temperature to obtain the sodium alginate hydrogel. 3.根据权利要求2所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(1)中,海藻酸钠溶液的质量分数为1%。3. The method for fixing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 2, characterized in that in step (1), the mass fraction of the sodium alginate solution is 1%. 4.根据权利要求2所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(1)中,加热搅拌的温度为70℃,转速为120r/min。4. The method for fixing nitrifying bacteria with sodium alginate-polyurethane filler according to claim 2, characterized in that in step (1), the temperature of heating and stirring is 70°C and the rotation speed is 120r/min. 5.根据权利要求1所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(2)中,所述液体硝化细菌菌剂中硝化细菌为优势菌,其相对丰度为28.39%。5. The method for fixing nitrifying bacteria with sodium alginate-polyurethane filler according to claim 1, characterized in that, in step (2), nitrifying bacteria are dominant bacteria in the liquid nitrifying bacteria agent, and their relative abundance is 28.39%. 6.根据权利要求5所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,所述液体硝化细菌菌剂中亚硝化单胞菌和亚硝化螺菌为优势菌,其相对丰度分别为27.96%和0.43%。6. The method for fixing nitrifying bacteria on sodium alginate-polyurethane filler according to claim 5, characterized in that Nitrosomonas and Nitrosospirillum are dominant bacteria in the liquid nitrifying bacteria agent, and their relative abundances are 27.96% and 0.43%, respectively. 7.根据权利要求1所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(2)中,以干重计,所述硝化细菌水凝胶混合物中硝化细菌菌剂的质量分数为0.37%。7. The method for fixing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 1, characterized in that, in step (2), the mass fraction of the nitrifying bacteria agent in the nitrifying bacteria hydrogel mixture is 0.37% based on dry weight. 8.根据权利要求1所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(2)中,离心时的转速为6000r/min。8. The method for fixing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 1, characterized in that in step (2), the rotation speed during centrifugation is 6000 r/min. 9.根据权利要求1所述的海藻酸钠-聚氨酯填料固定硝化细菌的方法,其特征在于,步骤(3)中,聚氨酯填料的规格为1×1×1cm,孔隙密度为20ppi。9. The method for fixing nitrifying bacteria using sodium alginate-polyurethane filler according to claim 1, characterized in that in step (3), the specification of the polyurethane filler is 1×1×1 cm, and the pore density is 20 ppi.
CN202410102178.0A 2024-01-24 2024-01-24 Method for fixing nitrifying bacteria by sodium alginate-polyurethane filler Pending CN117904095A (en)

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