[go: up one dir, main page]

CN105271514A - Biological nitrogen removal method based on anaerobic Feammox and application thereof - Google Patents

Biological nitrogen removal method based on anaerobic Feammox and application thereof Download PDF

Info

Publication number
CN105271514A
CN105271514A CN201510775812.8A CN201510775812A CN105271514A CN 105271514 A CN105271514 A CN 105271514A CN 201510775812 A CN201510775812 A CN 201510775812A CN 105271514 A CN105271514 A CN 105271514A
Authority
CN
China
Prior art keywords
sewage
solution
reactor
anaerobic
feammox
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510775812.8A
Other languages
Chinese (zh)
Other versions
CN105271514B (en
Inventor
张代钧
姚宗豹
李玉莲
万新宇
何强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CN201510775812.8A priority Critical patent/CN105271514B/en
Publication of CN105271514A publication Critical patent/CN105271514A/en
Application granted granted Critical
Publication of CN105271514B publication Critical patent/CN105271514B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treatment Of Sludge (AREA)

Abstract

本发明公开了一种基于厌氧铁氧化氨的生物脱氮方法,包括如下步骤:在厌氧反应器中加入含有Feammox微生物的污泥,将含氨污水通入反应器中,利用Fe(III)NTA氧化污水中的NH4 +生成NO2 -,再进行脱氮处理,具体步骤为:一、培养富集Feammox微生物:1)污泥预处理,2)Feammox微生物的培养;二、利用Feammox微生物处理污水中的NH4 +:1)污水预处理,2)利用Feammox微生物进行污水处理;三、将前述厌氧Feammox处理后收集到的液体进行脱氮处理。该方法具有更低的能耗、更少的碳源需求、更少的温室气体排放、更少的NO3 -产生等优势,投资和运行费用少,应用前景广阔。The invention discloses a biological denitrification method based on anaerobic iron oxidation of ammonia, comprising the following steps: adding sludge containing Feammox microorganisms to an anaerobic reactor, passing ammonia-containing sewage into the reactor, and using Fe(III ) NTA oxidizes NH 4 + in sewage to generate NO 2 - , and then performs denitrification treatment. The specific steps are: 1. Cultivate and enrich Feammox microorganisms: 1) Sludge pretreatment, 2) Feammox microorganism cultivation; 2. Use Feammox Microbial treatment of NH 4 + in sewage: 1) sewage pretreatment, 2) sewage treatment using Feammox microorganisms; 3, denitrification of the liquid collected after the aforementioned anaerobic Feammox treatment. The method has the advantages of lower energy consumption, less demand for carbon sources, less greenhouse gas emissions, less NO 3 - generation, low investment and operating costs, and broad application prospects.

Description

基于厌氧铁氧化氨的生物脱氮方法及其应用Biological denitrification method based on anaerobic iron oxidation of ammonia and its application

技术领域technical field

本发明属于污水处理技术领域,具体涉及一种利用厌氧铁氧化氨处理污水中氨的方法及其在污水脱氮中的应用。The invention belongs to the technical field of sewage treatment, and in particular relates to a method for treating ammonia in sewage by using anaerobic iron to oxidize ammonia and its application in sewage denitrification.

背景技术Background technique

目前在污水处理中能够实现NH4 +氧化的微生物过程主要为好氧氨氧化以及厌氧氨氧化。传统的好氧氨氧化过程虽然已经在污水处理中广泛应用,但是该工艺需要从外部通入氧气才能够实验NH4 +的氧化,同时在好氧氨氧化体系中存在氧气和产物NO2 -,因此体系中通常会存在亚硝酸盐氧化菌将NO2 -氧化为NO3 -,然后在经过反硝化过程才能够将NO3 -还原为N2实现NH4 +的去除,因此传统的硝化反硝化工艺需要外加O2、有机物,同时污泥产量高。虽然厌氧氨氧化过程能够在厌氧条件下将NH4 +氧化,但是需要提供NO2 -来实现NH4 +的氧化,因此该工艺需要和好氧氨氧化过程结合在一起才能实现NH4 +的氧化。At present, the microbial processes that can realize NH 4 + oxidation in sewage treatment are mainly aerobic ammonium oxidation and anaerobic ammonium oxidation. Although the traditional aerobic ammonium oxidation process has been widely used in sewage treatment, this process needs oxygen from the outside to be able to experiment with the oxidation of NH 4 + . At the same time, there are oxygen and product NO 2 - in the aerobic ammonium oxidation system. Therefore, there are usually nitrite oxidizing bacteria in the system to oxidize NO 2 - to NO 3 - , and then after the denitrification process, NO 3 - can be reduced to N 2 to achieve the removal of NH 4 + , so the traditional nitrification and denitrification The process needs to add O 2 and organic matter, and at the same time, the sludge output is high. Although the anaerobic ammonium oxidation process can oxidize NH 4 + under anaerobic conditions, it needs to provide NO 2 - to realize the oxidation of NH 4 + , so this process needs to be combined with the aerobic ammonium oxidation process to realize NH 4 + Oxidation.

铁是过渡金属的一种,其是地壳含量第二高的金属元素。Fe与C、O、N、S的氧化还原反应驱动着全球的生物化学循环。微生物异化Fe(Ⅲ)还原是一个重要的生物及地球化学过程,不仅对铁的分布以及矿物学形态产生影响,而且因为微生物异化Fe(Ⅲ)还原过程耦联了有机物的氧化降解,已逐渐应用于生物冶金、重金属(铀,铬,砷等)污染环境的生物修复以及石化类有机污水的生物降解。Fe在含N物质的化学和微生物氧化还原过程中也起到一定的作用,包括温室气体N2O的产生。自然界中可进行Fe(Ⅲ)铁还原的微生物从古细菌到细菌种类繁多。然而,目前微生物Fe(Ⅲ)还原的生物化学性能仍是较新的研究领域。Iron is a type of transition metal, which is the second most abundant metallic element in the earth's crust. Redox reactions of Fe with C, O, N, and S drive global biochemical cycles. Fe(Ⅲ) reduction by microbial dissimilation is an important biological and geochemical process, which not only affects the distribution and mineralogy of iron, but also has been gradually applied because the reduction process of microbial dissimilation Fe(Ⅲ) is coupled with the oxidative degradation of organic matter. It is used in biometallurgy, bioremediation of heavy metal (uranium, chromium, arsenic, etc.) polluted environment and biodegradation of petrochemical organic sewage. Fe also plays a role in the chemical and microbial redox processes of N-containing species, including the production of the greenhouse gas N2O . There are a wide variety of microorganisms that can reduce Fe(III) iron in nature, ranging from archaea to bacteria. However, the biochemical properties of microbial Fe(III) reduction are still a relatively new field of research.

目前研究发现在稻田、沉积物、淡水生态系统等环境中普遍存在能够实现在厌氧条件下依赖Fe(III)氧化NH4+的现象,该现象被称为Feammox(铁氧化氨),发现Feammox现象的文献如:1)河流沉积物中:Clement等(Ammoniumoxidationcoupledtodissimilatoryreductionofironunderanaerobicconditionsinwetlandsoils,2005);2)湿地生态系统:Shrestha等.(OxidationofAmmoniumtoNitriteUnderIron-ReducingConditionsinWetlandSoilsLaboratory,FieldDemonstrations,andPush-PullRateDetermination,2009);3)山地土壤:Yang等(Nitrogenlossfromsoilthroughanaerobicammoniumoxidationcoupledtoironreduction,2012);4)河岸草地:HuangandJaffe等(Characterizationofincubationexperimentsanddevelopmentofanenrichmentculturecapableofammoniumoxidationunderiron-reducingconditions,2015);5)厌氧消化污泥:Sawayama等(Possibilityofanoxicferricammoniumoxidation.JournalofBioscienceandBioengineering,2006);6)稻田土壤:Ding等.(NitrogenLossthroughAnaerobicAmmoniumOxidationCoupledtoIronReductionfromPaddySoilsinaChronosequence,2014);7)淡水湖泊沉积物:Melton等(Microbialiron(II)oxidationinlittoralfreshwaterlakesediment:thepotentialforcompetitionbetweenphototrophicvs.nitrate-reducingiron(II)-oxidizers,2012)。现有研究认为Feammox反应原理如下Current studies have found that in rice fields, sediments, freshwater ecosystems and other environments, the phenomenon of relying on Fe(III) to oxidize NH4+ under anaerobic conditions is ubiquitous. This phenomenon is called Feammox (iron oxidation ammonia).文献如:1)河流沉积物中:Clement等(Ammoniumoxidationcoupledtodissimilatoryreductionofironunderanaerobicconditionsinwetlandsoils,2005);2)湿地生态系统:Shrestha等.(OxidationofAmmoniumtoNitriteUnderIron-ReducingConditionsinWetlandSoilsLaboratory,FieldDemonstrations,andPush-PullRateDetermination,2009);3)山地土壤:Yang等(Nitrogenlossfromsoilthroughanaerobicammoniumoxidationcoupledtoironreduction ,2012);4)河岸草地:HuangandJaffe等(Characterizationofincubationexperimentsanddevelopmentofanenrichmentculturecapableofammoniumoxidationunderiron-reducingconditions,2015);5)厌氧消化污泥:Sawayama等(Possibilityofanoxicferricammoniumoxidation.JournalofBioscienceandBioengineering,2006);6)稻田土壤:Ding等.(NitrogenLossthroughAnaerobicAmmoniumOxidationCoupledtoIronReductionfromPaddySoilsinaChronosequence,2014) ; 7) Freshwater lake sediment: Melton et al (Microbialiron (II) oxidation in littoral fresh water lake sediment: the potential for competition between phototrophic vs. rs, 2012). Existing studies believe that the Feammox reaction principle is as follows

美国普林斯顿大学的Jaffé等在河岸草地的土壤中发现了Feammox细菌,能够实现Feammox,他们从现场取土壤样品,在实验室中利用厌氧反应器通过外加水铁矿或针铁矿经过180天富集培养了Feammox细菌,但是由于水铁矿或针铁矿中铁的溶解性很低,生物可利用性差,富集效果并不十分理想。Jaffé of Princeton University in the United States found Feammox bacteria in the soil of riverbank grasslands, which can realize Feammox. They took soil samples from the site and used anaerobic reactors in the laboratory to pass ferrihydrite or goethite through 180 days. Feammox bacteria were cultured, but because of the low solubility and poor bioavailability of iron in ferrihydrite or goethite, the enrichment effect is not very ideal.

Feammox微生物能够在厌氧条件下将NH4 +氧化为NO2 -,将该过程与污水处理系统中的厌氧氨氧化(Anammox)工艺结合起来,就能够实现在厌氧条件下将NH4 +转化为N2的过程,相对于传统的硝化-反硝化工艺,该耦合工艺将具有更低的能耗、更少的碳源需求、更少的温室气体排放(如N2O)、更少的NO3 -产生和更低的污泥产量等优势。因此这个反应在污水处理方面具有广泛的应用前景。Feammox microorganisms can oxidize NH 4 + to NO 2 - under anaerobic conditions. Combining this process with the anaerobic ammonium oxidation (Anammox) process in sewage treatment systems, it is possible to achieve NH 4 + under anaerobic conditions. Compared with the traditional nitrification-denitrification process, this coupled process will have lower energy consumption, less carbon source demand, less greenhouse gas emissions (such as N 2 O ) , less The advantages of NO 3 -production and lower sludge production. Therefore, this reaction has broad application prospects in sewage treatment.

虽然铁在地表环境、沉积物中含量很高,但中性条件下Fe(Ⅲ)的溶解度只有10-9mol,大多数情况下蓄水层中Fe(Ⅲ)都是以不可溶解、难溶解的铁氧化物形态存在。这就限制了Fe–ammox微生物的大量存在,因此通过提升生物可利用性Fe(Ⅲ)的含量,能够有效的促进Fe–ammox过程,例如通过在NTA(氨三乙酸)、EDTA(乙二胺四乙酸)和多磷酸盐等螯合剂的作用下形成可溶性螯合铁,并通过扩散作用被输送到微生物表面,从而提升Feammox过程。Although the content of iron in the surface environment and sediments is very high, the solubility of Fe(Ⅲ) is only 10 -9 mol under neutral conditions. In most cases, Fe(Ⅲ) in the aquifer is insoluble in the form of iron oxides. This limits the abundance of Fe-ammox microorganisms, so by increasing the content of bioavailable Fe(III), the Fe-ammox process can be effectively promoted, for example, by adding NTA (nitrilotriacetic acid), EDTA (ethylenediamine Soluble chelated iron is formed under the action of chelating agents such as tetraacetic acid) and polyphosphate, and is transported to the surface of microorganisms by diffusion, thereby enhancing the Feammox process.

发明内容Contents of the invention

本发明的目的在于提供一种能耗低、投资和运行费用少,应用前景广阔的基于厌氧铁氧化氨的生物脱氮方法。The purpose of the present invention is to provide a biological denitrification method based on anaerobic iron ammonia oxidation with low energy consumption, low investment and operating costs and broad application prospects.

本发明的技术方案如下:一种基于厌氧铁氧化氨的生物脱氮方法,包括如下步骤:在厌氧反应器中加入含有Feammox微生物的污泥,将含氨污水通入反应器中,利用Fe(III)NTA氧化污水中的NH4 +生成NO2 -,再进行脱氮处理,具体步骤如下:The technical scheme of the present invention is as follows: a kind of biological denitrification method based on anaerobic ferric ammonium oxidation comprises the following steps: adding the sludge containing Feammox microorganism in the anaerobic reactor, passing ammonia-containing sewage into the reactor, utilizing Fe(III)NTA oxidizes NH 4 + in sewage to generate NO 2 - , and then performs denitrification treatment. The specific steps are as follows:

一、培养富集Feammox微生物1. Cultivate and enrich Feammox microorganisms

1)污泥预处理:将含有Feammox微生物的种源污泥用培养液混合得到泥水混合物,所述培养液由营养液和微量元素溶液混匀而得,其组成配比为每升营养液中加入1.0~1.5mL微量元素溶液;所述营养液中含有0.16~0.20mMFe(III)NTA、2.00~2.30mMNH4 +和矿物质;1) Sludge pretreatment: mix the provenance sludge containing Feammox microorganisms with a culture solution to obtain a mud-water mixture, and the culture solution is obtained by mixing a nutrient solution and a trace element solution, and the composition ratio is as follows: Add 1.0-1.5mL trace element solution; the nutrient solution contains 0.16-0.20mM Fe(III)NTA, 2.00-2.30mM NH 4 + and minerals;

2)Feammox微生物的培养:将前述泥水混合物接入厌氧反应器中,先曝N2至泥水混合物中溶解氧为0mg/L,然后开始运行反应器,加入所述泥水混合物一半体积的前述培养液运行180~240min,然后停止运行沉淀15~25min、沉淀后排出上清液,排出量与加入的培养液体积相同,至此完成一个处理周期;重新在反应器内加入与排出液体积相同体积的培养液,开始一个新的处理周期,如此循环完成多个运行周期;反应器的运行温度为30~35℃,反应器中的泥水混合物pH控制在7.0~8.0;每天一次从反应器中排出反应后的泥水混合物总体积的十五分之一丢弃,然后重新补入与丢弃液体积相同体积的新培养液;共运行70~110天;2) Cultivation of Feammox microorganisms: Connect the aforementioned mud-water mixture into an anaerobic reactor, first expose to N2 until the dissolved oxygen in the mud-water mixture is 0mg/L, then start the reactor, add half the volume of the mud-water mixture for the aforementioned cultivation The solution runs for 180-240 minutes, then stops running for 15-25 minutes, and discharges the supernatant after precipitation. The discharge volume is the same as the volume of the added culture solution. At this point, a treatment cycle is completed; Culture liquid, start a new treatment cycle, and complete multiple operation cycles in this way; the operating temperature of the reactor is 30-35°C, and the pH of the mud-water mixture in the reactor is controlled at 7.0-8.0; the reaction is discharged from the reactor once a day One-fifteenth of the total volume of the final mud-water mixture is discarded, and then refilled with a new culture solution of the same volume as the discarded solution; a total of 70 to 110 days of operation;

二、利用Feammox微生物处理污水中的NH4 + 2. Using Feammox microorganisms to treat NH 4 + in sewage

1)污水预处理:在待处理含氨污水中加入0.16~0.20mMFe(III)NTA、矿物质溶解混匀得到混合液,再按每升混合液加入1.0~1.5mL微量元素溶液的比例加入微量元素溶液混合得到污水预处理液;1) Sewage pretreatment: Add 0.16-0.20mMFe(III)NTA to the ammonia-containing sewage to be treated, dissolve and mix the minerals to obtain a mixed solution, and then add trace elements at a rate of 1.0-1.5mL of trace element solution per liter of the mixed solution The element solution is mixed to obtain the sewage pretreatment liquid;

2)将前述富集培养Feammox微生物后得到的泥水混合物排掉一半体积的液体后加进厌氧反应器中进行污水处理:在反应器中加入与反应器内泥水混合物相同体积的前述污水预处理液运行180~240min、然后停止运行沉淀15~25min、沉淀后排出与加入的污水预处理液相同体积的溶液并收集该液体,至此完成一个处理周期;重新在反应器内加入与与排出体积相同体积的污水预处理液,开始一个新的处理周期,如此循环即可持续地进行污水处理;反应器的运行温度为30~35℃,反应器中的泥水混合物pH控制在7.0~8.0;每天一次从反应器内排出反应后的泥水混合物总体积的十五分之一丢弃,然后重新补入与排出液相同体积的污水预处理液;至此完成了将污水中的NH4 +转化为NO2 -的过程;2) Drain half of the volume of the mud-water mixture obtained after enriching and cultivating Feammox microorganisms, and then add it to the anaerobic reactor for sewage treatment: add the same volume of the mud-water mixture in the reactor as the aforementioned sewage pretreatment The solution runs for 180-240 minutes, then stops to settle for 15-25 minutes, discharges the solution with the same volume as the sewage pretreatment solution added after the precipitation and collects the liquid, and completes a treatment cycle; Volume of sewage pretreatment liquid, start a new treatment cycle, so that the sewage treatment can be carried out continuously; the operating temperature of the reactor is 30-35 ℃, and the pH of the mud-water mixture in the reactor is controlled at 7.0-8.0; once a day Discard one-fifteenth of the total volume of the reacted mud-water mixture from the reactor, and then replenish the same volume of sewage pretreatment liquid as the effluent; so far, the conversion of NH 4 + in sewage into NO 2 - the process of;

三、将前述厌氧Feammox处理后收集到的液体进行脱氮处理。3. The liquid collected after the aforementioned anaerobic Feammox treatment is subjected to denitrification treatment.

作为优选地,所述营养液中的Fe(III)NTA的浓度为0.18mM、NH4 +的浓度为2.15mM,所述污水预处理液中的Fe(III)NTA的浓度为0.18mM。Preferably, the concentration of Fe(III)NTA in the nutrient solution is 0.18mM, the concentration of NH 4 + is 2.15mM, and the concentration of Fe(III)NTA in the sewage pretreatment solution is 0.18mM.

作为优选地,所述的Fe(III)NTA由Fe2(SO4)3和NTA按1:1的摩尔比配得,所述的NH4 +来源于硫酸铵或氯化铵。Preferably, the Fe(III)NTA is prepared from Fe 2 (SO 4 ) 3 and NTA at a molar ratio of 1:1, and the NH 4 + is derived from ammonium sulfate or ammonium chloride.

在上述技术方案中,所述营养液和所述污水预处理液中包含的矿物质组分及配比均为:NaH2PO40.04~0.06g/L、CaCl2·2H2O0.2~0.4g/L、MgSO4·7H2O0.2~0.4g/L、KHCO31.0~1.5g/L、FeSO40.0060~0.0065g/L、EDTA0.0060~0.0065g/L;所述的微量元素溶液包括如下浓度的组分:EDTA13~17g/L、H3BO40.010~0.016g/L、MnCl2·4H2O0.90~1.10g/L、CuSO4·5H2O0.20~0.30g/L、ZnSO4·7H2O0.35~0.50g/L、NiCl2·6H2O0.15~.025g/L、Na2SeO4·10H2O0.15~0.26g/L、Na2MoO4·2H2O0.17~0.27g/L、Na2WO4·2H2O0.03~0.07g/L。In the above technical solution, the mineral components and ratios contained in the nutrient solution and the sewage pretreatment solution are: NaH 2 PO 4 0.04~0.06g/L, CaCl 2 ·2H 2 O0.2~ 0.4g/L, MgSO 4 ·7H 2 O 0.2~0.4g/L, KHCO 3 1.0~1.5g/L, FeSO 4 0.0060~0.0065g/L, EDTA0.0060~0.0065g/L; The element solution includes components with the following concentrations: EDTA13 ~17g/L, H3BO40.010 ~0.016g/L, MnCl2 · 4H2O0.90 ~1.10g/L, CuSO4 · 5H2O0.20 ~0.30 g/L, ZnSO 4 ·7H 2 O 0.35~0.50g/L, NiCl 2 ·6H 2 O0.15~.025g/L, Na 2 SeO 4 ·10H 2 O0.15~0.26g/L, Na 2 MoO 4 ·2H 2 O 0.17-0.27g/L, Na 2 WO 4 ·2H 2 O 0.03-0.07g/L.

作为优选地,所述营养液和所述污水预处理液中包含的矿物质组分及配比均为:NaH2PO40.05g/L、CaCl2·2H2O0.3g/L、MgSO4·7H2O0.3g/L、KHCO31.25g/L、FeSO40.00625g/L、EDTA0.00625g/L;所述微量元素溶液包括如下浓度的组分:EDTA15g/L、H3BO40.014g/L、MnCl2·4H2O0.99g/L、CuSO4·5H2O0.25g/L、ZnSO4·7H2O0.43g/L、NiCl2·6H2O0.19g/L、Na2SeO4·10H2O0.21g/L、Na2MoO4·2H2O0.22g/L、Na2WO4·2H2O0.05g/L。Preferably, the mineral components and ratios contained in the nutrient solution and the sewage pretreatment solution are: NaH 2 PO 4 0.05g/L, CaCl 2 ·2H 2 O 0.3g/L, MgSO 4 7H 2 O 0.3g/L, KHCO 3 1.25g/L, FeSO 4 0.00625g/L, EDTA 0.00625g/L; the trace element solution includes the following components: EDTA 15g/L, H 3 BO 4 0.014 g/L, MnCl 2 4H 2 O 0.99g/L, CuSO 4 5H 2 O 0.25g/L, ZnSO 4 7H 2 O 0.43g/L, NiCl 2 6H 2 O 0.19g/L, Na 2 SeO 4 ·10H 2 O 0.21 g/L, Na 2 MoO 4 ·2H 2 O 0.22 g/L, Na 2 WO 4 ·2H 2 O 0.05 g/L.

作为优选地,所述将厌氧Feammox处理后收集到的液体进行脱氮处理的方法为厌氧氨氧化工艺处理,将溶液中的NO2 -转化为N2Preferably, the method of denitrifying the liquid collected after anaerobic Feammox treatment is anaerobic ammonium oxidation process, which converts NO 2 in the solution into N 2 .

在上述技术方案中,所述厌氧反应器是SBR反应器或者UASB反应器或者EGSB反应器。In the above technical scheme, the anaerobic reactor is an SBR reactor or a UASB reactor or an EGSB reactor.

作为优选地,所述微量元素溶液加入量为:每升营养液中加入1.25mL微量元素溶液,污水预处理时每升混合液加入1.25mL微量元素溶液。Preferably, the added amount of the trace element solution is: 1.25mL trace element solution is added to every liter of nutrient solution, and 1.25mL trace element solution is added to every liter of mixed solution during sewage pretreatment.

作为优选地,反应器中的运行温度为30~32℃,反应器中的泥水混合物pH控制在7.0~7.5。Preferably, the operating temperature in the reactor is 30-32° C., and the pH of the mud-water mixture in the reactor is controlled at 7.0-7.5.

本方法的原理为厌氧条件下利用Feammox微生物将污水中的NH4 +氧化为NO2 -,结合现有的NO2 -脱氮处理工艺,即可实现将污水中的NH4 +转化为N2从而实现污水脱氮处理。The principle of this method is to use Feammox microorganisms to oxidize NH 4 + in sewage to NO 2 - under anaerobic conditions. Combined with the existing NO 2 - denitrification treatment process, NH 4 + in sewage can be converted into N 2 So as to realize the denitrification treatment of sewage.

本发明的另一目的在于提供上述基于厌氧铁氧化氨的生物脱氮方法在污水脱氮处理中的应用。Another object of the present invention is to provide the application of the above-mentioned biological denitrification method based on anaerobic iron ammonia oxidation in sewage denitrification treatment.

本发明的有益效果是:相比传统的好氧氨氧化或者厌氧氨氧化两种工艺,本发明方法能够在厌氧条件下将NH4 +氧化为NO2 -,后续仅需要结合现有成熟的厌氧氨氧化(Anammox)工艺就可以实现NH4 +的去除,这两个工艺过程都是厌氧过程,条件容易控制,免去了好氧处理工艺中需要的O2,节省了成本;相对于传统的硝化-反硝化工艺,该耦合工艺具有更低的能耗、更少的碳源需求、更少的温室气体排放(如N2O)、更少的NO3 -产生等优势。该方法能耗低、投资和运行费用少,具有很好的应用前景。The beneficial effects of the present invention are: compared with the traditional aerobic ammonium oxidation or anaerobic ammonium oxidation, the method of the present invention can oxidize NH 4 + to NO 2 - under anaerobic conditions. The advanced Anammox process can realize the removal of NH 4 + . These two processes are anaerobic processes, and the conditions are easy to control, eliminating the need for O 2 in the aerobic treatment process and saving costs; Compared with the traditional nitrification-denitrification process, this coupled process has the advantages of lower energy consumption, less carbon source demand, less greenhouse gas emissions (such as N 2 O), and less NO 3 -production . The method has low energy consumption, low investment and operation costs, and has good application prospects.

附图说明Description of drawings

图1是本发明实施例中在SBR反应器中Fe(III)NTA氧化NH4 +的工艺流程图;其中,1SBR反应器、2中空夹层、3水浴进口、4水浴出口、5水浴泵、6水浴锅、7进水泵、8进水箱、9出水泵、10出水箱、11pH计、12在线溶解氧分析仪、13磁力搅拌器、14出气孔。Fig. 1 is in the embodiment of the present invention in the SBR reactor Fe (III) NTA oxidation process flow chart of NH 4 + ; Wherein, 1 SBR reactor, 2 hollow interlayers, 3 water bath inlets, 4 water bath outlets, 5 water bath pumps, 6 Water bath, 7 water inlet pump, 8 water inlet tank, 9 water outlet pump, 10 water outlet tank, 11pH meter, 12 online dissolved oxygen analyzer, 13 magnetic stirrer, 14 air outlet.

具体实施方式detailed description

以下结合技术方案和附图详细叙述本发明的具体实施方式,但本发明不仅仅局限于如下实施实例。The specific implementation manners of the present invention will be described in detail below in conjunction with the technical solutions and accompanying drawings, but the present invention is not limited to the following examples.

在实验室内利用图1中的总反应体积为3L的SBR反应器进行本发明方法的Fe(III)NTA氧化NH4 +,种源污泥取自重庆大学资环学院水处理实验室铁氧化氨(Feammox)污泥种源(来源于重庆污水处理厂的二沉池污泥)。具体操作步骤如下:In the laboratory, the SBR reactor with a total reaction volume of 3L in Figure 1 is used to carry out the Fe(III)NTA oxidation of NH 4 + in the method of the present invention. Ammonia (Feammox) sludge provenance (from the secondary sedimentation tank sludge of Chongqing Wastewater Treatment Plant). The specific operation steps are as follows:

一、培养富集Feammox微生物1. Cultivate and enrich Feammox microorganisms

(1)污泥预处理:取1000ml的前述种源污泥,在连续曝氮气条件下用培养液冲洗污泥3-5次后,用培养液定容至2L得到处理后的泥水混合物。所述培养液由营养液和微量元素溶液混匀而得,其组成配比为每升营养液中加入1.25mL微量元素溶液。(1) Sludge pretreatment: Take 1000ml of the aforementioned provenance sludge, wash the sludge with culture medium for 3-5 times under continuous nitrogen aeration, and then use the culture medium to make the volume to 2L to obtain the treated mud-water mixture. The culture solution is obtained by mixing the nutrient solution and the trace element solution, and its composition ratio is to add 1.25mL of the trace element solution to each liter of the nutrient solution.

每升营养液中各组分含量为:Fe2(SO4)30.036克、(NH4)2SO40.14克或者NH4Cl0.113克、NTA0.034克、NaH2PO40.05g、CaCl2·2H2O0.3g、MgSO4·7H2O0.3g、KHCO31.25g、FeSO40.00625g、EDTA0.00625g。The content of each component in each liter of nutrient solution is: Fe 2 (SO 4 ) 3 0.036 grams, (NH 4 ) 2 SO 4 0.14 grams or NH 4 Cl 0.113 grams, NTA 0.034 grams, NaH 2 PO 4 0.05 grams, CaCl 2 ·2H 2 O 0.3g, MgSO 4 ·7H 2 O 0.3g, KHCO 3 1.25g, FeSO 4 0.00625g, EDTA 0.00625g.

每升微量元素溶液中各组分含量在:EDTA15g、H3BO40.014g、MnCl2·4H2O0.99g、CuSO4·5H2O0.25g、ZnSO4·7H2O0.43g、NiCl2·6H2O0.19g、Na2SeO4·10H2O0.21g、Na2MoO4·2H2O0.22g、Na2WO4·2H2O0.050g。The content of each component in each liter of trace element solution is: EDTA15g , H3BO40.014g , MnCl2 · 4H2O0.99g , CuSO4 · 5H2O0.25g , ZnSO4 · 7H2O0.43g , NiCl2 0.19 g of 6H 2 O, 0.21 g of Na 2 SeO 4 .10H 2 O, 0.22 g of Na 2 MoO 4 .2H 2 O, and 0.050 g of Na 2 WO 4 .2H 2 O.

(2)Feammox微生物的培养:将前述得到的2L的泥水混合物接入SBR反应器1中进行菌种培养,配制好的培养液储存在进水箱8内,先曝N2至溶解氧为0mg/L,然后开始运行SBR反应器1,一个运行周期为240min,搅拌状态下运行210min(在开头的12min内由进水泵7从进水箱8内泵出1L培养液进入SBR反应器1内)、运行210min后停止搅拌沉淀18min、然后出水12min(由出水泵9从SBR反应器1内泵出1L反应后的泥水混合物至出水箱10),至此完成一个处理周期。接着由进水泵7从进水箱8内重新泵出1L培养液进入SBR反应器1内,开始一个新的处理周期,如此循环完成多个运行周期。反应器的运行温度为30~32℃,反应器中的泥水混合物pH控制在7.0~7.5,磁力搅拌器搅拌速度为100~200rpm。每天一次从SBR反应器1内排出200ml反应后的泥水混合物丢弃,然后加入200ml新培养液。共运行90天(多次实验证明运行70~110天均能实现本发明目的),使污泥中的Feammox微生物得到富集,得到的污泥即可用于污水中NH4 +的氧化。也可用其它反应器或者其它设备进行污泥中Feammox微生物的接种和培养。富集Feammox微生物后的污泥的保存方法为:取富集好的污泥,用所述的培养液在连续曝N2的情况下洗三次,将洗过之后的污泥储存在不透光厌氧玻璃瓶中,加入0.5L厌氧培养液并密封,放置在4℃的冰箱中保存可作为种源污泥使用(通常可以保存6个月)。(2) Cultivation of Feammox microorganisms: put the 2L mud-water mixture obtained above into the SBR reactor 1 for strain cultivation, the prepared culture solution is stored in the water inlet tank 8 , and first exposed to N until the dissolved oxygen is 0mg /L, then start to run SBR reactor 1, a cycle of operation is 240min, and run for 210min under agitation (in the first 12min, 1L culture solution is pumped out from the water inlet tank 8 by the inlet pump 7 into the SBR reactor 1) 1. After running for 210 minutes, stop stirring and settling for 18 minutes, then discharge water for 12 minutes (1L of the reacted mud-water mixture is pumped out from the SBR reactor 1 by the discharge pump 9 to the discharge tank 10), so far a treatment cycle is completed. Then, 1L of culture solution is pumped out from the water inlet tank 8 again by the water inlet pump 7 into the SBR reactor 1, and a new treatment cycle is started, and multiple operation cycles are completed in this way. The operating temperature of the reactor is 30-32° C., the pH of the mud-water mixture in the reactor is controlled at 7.0-7.5, and the stirring speed of the magnetic stirrer is 100-200 rpm. Once a day, 200ml of the reacted mud-water mixture was discharged from the SBR reactor 1 and discarded, and then 200ml of new culture solution was added. A total of 90 days of operation (multiple experiments have proved that the purpose of the present invention can be achieved by running for 70-110 days), so that the Feammox microorganisms in the sludge can be enriched, and the obtained sludge can be used for the oxidation of NH 4 + in sewage. Other reactors or other equipment can also be used to inoculate and cultivate Feammox microorganisms in sludge. The preservation method of the sludge enriched with Feammox microorganisms is as follows: take the enriched sludge, wash it three times with the culture solution under the condition of continuous exposure to N 2 , and store the washed sludge in a light-proof In an anaerobic glass bottle, add 0.5L of anaerobic culture solution and seal it, and store it in a refrigerator at 4°C for use as provenance sludge (usually it can be stored for 6 months).

二、利用Feammox微生物处理污水中的NH4 + 2. Using Feammox microorganisms to treat NH 4 + in sewage

本步骤仍旧在图1所示的SBR反应器1中进行Feammox微生物处理污水中的NH4 +。如果是在其它设备中进行的Feammox微生物的培养富集,将富集培养Feammox微生物后得到的污泥接入要进行污水处理的厌氧反应器中即可。In this step, the Feammox microbial treatment of NH 4 + in sewage is still carried out in the SBR reactor 1 shown in FIG. 1 . If the culture and enrichment of Feammox microorganisms is carried out in other equipment, the sludge obtained after the enrichment and cultivation of Feammox microorganisms can be connected to the anaerobic reactor for sewage treatment.

(1)污水预处理:在含有2.15mMNH4 +的待处理污水中加入如下配比的如下组分得到污水预处理液:每升污水中加入Fe2(SO4)30.036克、NTA0.034克、NaH2PO40.05g、CaCl2·2H2O0.3g、MgSO4·7H2O0.3g、KHCO31.25g、FeSO40.00625g、EDTA0.00625g溶解混匀,然后在溶液中加入前述的1.25mL微量元素溶液混合;将污水预处理液储存在SBR反应器1中的进水箱8内(如果是用的前述用于培养Feammox微生物的同一个SBR反应器,将原进水箱8内的培养液排出换为污水预处理液即可),在进水箱8中曝N2至污水中的溶解氧为0mg/L,达到厌氧条件。(1) Sewage pretreatment: Add the following components in the following ratio to the sewage to be treated containing 2.15mMNH 4 + to obtain a sewage pretreatment liquid: add Fe 2 (SO 4 ) 3 0.036 grams, NTA0.034 per liter of sewage gram, NaH 2 PO 4 0.05g, CaCl 2 2H 2 O 0.3g, MgSO 4 7H 2 O 0.3g, KHCO 3 1.25g, FeSO 4 0.00625g, EDTA 0.00625g, dissolve and mix well, then add the aforementioned 1.25mL trace element solution mixed; the sewage pretreatment liquid is stored in the water inlet tank 8 in the SBR reactor 1 (if the same SBR reactor used for cultivating Feammox microorganisms mentioned above is used, the original water inlet tank 8 The culture solution in the tank is discharged and replaced with the sewage pretreatment solution), and N is exposed in the water inlet tank 8. The dissolved oxygen in the sewage is 0 mg/L to reach the anaerobic condition.

(2)从前述富集培养Feammox微生物后的SBR反应器1中在曝N2的情况下排出1L液体,然后开始进行污水处理:污水处理时SBR反应器1的每个运行周期为240min,搅拌状态下运行210min(在开头的12min内由进水泵7从进水箱8内泵出1L污水预处理液进入SBR反应器1内)、运行210min后停止搅拌沉淀18min、出水12min(由出水泵9从SBR反应器1内泵出1L处理后的污水至出水箱10);至此完成一个处理周期。接着由进水泵7从进水箱8内重新泵出1L污水预处理液进入SBR反应器1内,开始一个新的处理周期,如此循环即可持续地进行污水处理。反应器的运行温度为30~32℃,反应器中的泥水混合物pH控制在7.0~7.5,磁力搅拌器搅拌速度为100~200rpm。每天一次从SBR反应器1内排出200ml反应后的泥水混合物丢弃,然后加入200ml前述的污水预处理液。(2) discharge 1L of liquid from the SBR reactor 1 after the aforementioned enrichment and cultivation of Feammox microorganisms under the condition of exposure to N 2 , and then start to carry out sewage treatment: each operating cycle of SBR reactor 1 during sewage treatment is 240min, stirring running for 210 minutes under normal conditions (in the first 12 minutes, 1L of sewage pretreatment liquid is pumped out from the water inlet tank 8 by the water inlet pump 7 into the SBR reactor 1), after running for 210 minutes, the stirring and sedimentation are stopped for 18 minutes, and the water is discharged for 12 minutes (by the water outlet pump 9 1L of treated sewage is pumped out from the SBR reactor 1 to the outlet tank 10); thus far, a treatment cycle is completed. Next, the water inlet pump 7 pumps out 1L of sewage pretreatment liquid from the water inlet tank 8 again into the SBR reactor 1 to start a new treatment cycle, so that the sewage can be treated continuously in this cycle. The operating temperature of the reactor is 30-32° C., the pH of the mud-water mixture in the reactor is controlled at 7.0-7.5, and the stirring speed of the magnetic stirrer is 100-200 rpm. Once a day, 200ml of the reacted mud-water mixture is discharged from the SBR reactor 1 and discarded, and then 200ml of the aforementioned sewage pretreatment solution is added.

在污水处理过程中测定了NH4 +的氧化效果,实验连续运行4h,待处理的污水中的NH4 +为2.15mM,在连续4h的测试中,NH4 +的平均氧化速率为156.16mgN/(L·d),出水箱10中收集到的处理后的水中的NO2 -的平均累积速率亦为156.16mgN/(L·d)。The oxidation effect of NH 4 + was measured during the sewage treatment process. The experiment ran continuously for 4 hours, and the NH 4 + in the sewage to be treated was 2.15mM. During the continuous 4-hour test, the average oxidation rate of NH 4 + was 156.16mgN/ (L·d), the average accumulation rate of NO 2 in the treated water collected in the outlet tank 10 is also 156.16 mgN/(L·d).

三、厌氧Feammox处理后的污水进行厌氧氨氧化处理3. Anaerobic ammonium oxidation treatment of sewage after anaerobic Feammox treatment

将前述厌氧铁氧化氨处理后出水箱10中收集到的出水进行厌氧氨氧化处理,厌氧氨氧化工艺是现有很成熟的工艺,在此不赘述。通过厌氧氨氧化工艺将水中的NO2 -转化为N2,实现污水中NH4 +的厌氧去除。The effluent collected in the effluent tank 10 after the aforementioned anaerobic iron ammonium oxidation treatment is subjected to anaerobic ammonium oxidation treatment. The anaerobic ammonium oxidation process is a very mature process at present and will not be described in detail here. The NO 2 - in the water is converted into N 2 through the anaerobic ammonium oxidation process, and the anaerobic removal of NH 4 + in the sewage is realized.

经过实验,本发明方法中所述的营养液、污水预处理液、微量元素溶液中各组分配比在以下范围也都能实现本发明方法:所述的营养液和污水预处理液中包含的矿物质组分:NaH2PO40.04~0.06g/L、CaCl2·2H2O0.2~0.4g/L、MgSO4·7H2O0.2~0.4g/L、KHCO31.0~1.5g/L、FeSO40.0060~0.0065g/L、EDTA0.0060~0.0065g/L;所述的营养液中Fe2(SO4)30.032~0.04克、(NH4)2SO40.13~0.15克或者NH4Cl0.11~0.12克、NTA0.03~0.034克;所述的污水预处理液中Fe2(SO4)30.032~0.04克、NTA0.03~0.034克;所述的微量元素溶液包括如下浓度的组分:EDTA13~17g/L、H3BO40.010~0.016g/L、MnCl2·4H2O0.90~1.10g/L、CuSO4·5H2O0.20~0.30g/L、ZnSO4·7H2O0.35~0.50g/L、NiCl2·6H2O0.15~.025g/L、Na2SeO4·10H2O0.15~0.26g/L、Na2MoO4·2H2O0.17~0.27g/L、Na2WO4·2H2O0.03~0.07g/L;Through experimentation, in the nutrient solution described in the inventive method, sewage pretreatment liquid, the distribution ratio of each component in the trace element solution also can realize the inventive method in the following scope: described nutrient solution and sewage pretreatment liquid comprise Mineral components: NaH 2 PO 4 0.04~0.06g/L, CaCl 2 2H 2 O 0.2~0.4g/L, MgSO 4 7H 2 O 0.2~0.4g/L, KHCO 3 1.0~1.5g /L, FeSO 4 0.0060~0.0065g/L, EDTA 0.0060~0.0065g/L; Fe 2 (SO 4 ) 3 0.032~0.04g, (NH 4 ) 2 SO 4 0.13~0.15g in the nutrient solution Or 0.11-0.12 grams of NH 4 Cl, 0.03-0.034 grams of NTA; 0.032-0.04 grams of Fe 2 (SO 4 ) 3 and 0.03-0.034 grams of NTA in the sewage pretreatment solution; the trace element solution Contains the following components: EDTA13 ~17g/L, H3BO40.010 ~0.016g/L, MnCl2 · 4H2O0.90 ~1.10g/L, CuSO4 · 5H2O0.20 ~0.30g/L L, ZnSO 4 7H 2 O 0.35~0.50g/L, NiCl 2 6H 2 O 0.15~.025g/L, Na 2 SeO 4 10H 2 O 0.15~0.26g/L, Na 2 MoO 4 2H 2 O 0.17~0.27g/L, Na 2 WO 4 2H 2 O0.03~0.07g/L;

本发明方法实现了将污水中的NH4 +在厌氧厌氧条件下转化为NO2 -,将该过程与污水处理系统中的厌氧氨氧化工艺结合起来,实现在厌氧条件下将NH4 +最终转化为N2的过程,相对于传统的硝化-反硝化工艺,该耦合工艺将具有更低的能耗、更少的碳源需求、更少的温室气体排放(如N2O)、更少的NO3 -产生等优势。The method of the invention realizes the conversion of NH 4 + in sewage into NO 2 - under anaerobic and anaerobic conditions, and combines this process with the anaerobic ammonium oxidation process in the sewage treatment system to realize the conversion of NH under anaerobic conditions. 4 + final conversion into N2 , compared with the traditional nitrification-denitrification process, this coupled process will have lower energy consumption, less carbon source demand, and less greenhouse gas emissions (such as N2O ) , less NO 3 -production and other advantages.

Claims (10)

1.一种基于厌氧铁氧化氨的生物脱氮方法,其特征在于,包括如下步骤:在厌氧反应器中加入含有Feammox微生物的污泥,将含氨污水通入反应器中,利用Fe(III)NTA氧化污水中的NH4 +生成NO2 -,再进行脱氮处理,具体步骤如下:1. A biological denitrification method based on anaerobic iron ammonia oxidation, it is characterized in that, comprises the steps: in anaerobic reactor, add the sludge that contains Feammox microorganism, ammoniacal sewage is passed in reactor, utilizes Feammox (III) NTA oxidizes NH 4 + in sewage to generate NO 2 - , and then performs denitrification treatment. The specific steps are as follows: 一、培养富集Feammox微生物1. Cultivate and enrich Feammox microorganisms 1)污泥预处理:将含有Feammox微生物的种源污泥用培养液混合得到泥水混合物,所述培养液由营养液和微量元素溶液混匀而得,其组成配比为每升营养液中加入1.0~1.5mL微量元素溶液;所述营养液中含有0.16~0.20mMFe(III)NTA、2.00~2.30mMNH4 +和矿物质;1) Sludge pretreatment: mix the provenance sludge containing Feammox microorganisms with a culture solution to obtain a mud-water mixture, and the culture solution is obtained by mixing a nutrient solution and a trace element solution, and the composition ratio is as follows: Add 1.0-1.5mL trace element solution; the nutrient solution contains 0.16-0.20mM Fe(III)NTA, 2.00-2.30mM NH 4 + and minerals; 2)Feammox微生物的培养:将前述泥水混合物接入厌氧反应器中,先曝N2至泥水混合物中溶解氧为0mg/L,然后开始运行反应器,加入所述泥水混合物一半体积的前述培养液运行180~240min,然后停止运行沉淀15~25min、沉淀后排出上清液,排出量与加入的培养液体积相同,至此完成一个处理周期;重新在反应器内加入与排出液体积相同体积的培养液,开始一个新的处理周期,如此循环完成多个运行周期;反应器的运行温度为30~35℃,反应器中的泥水混合物pH控制在7.0~8.0;每天一次从反应器中排出反应后的泥水混合物总体积的十五分之一丢弃,然后重新补入与丢弃液体积相同体积的新培养液;共运行70~110天;2) Cultivation of Feammox microorganisms: Connect the aforementioned mud-water mixture into an anaerobic reactor, first expose to N2 until the dissolved oxygen in the mud-water mixture is 0mg/L, then start the reactor, add half the volume of the mud-water mixture for the aforementioned cultivation The solution runs for 180-240 minutes, then stops running for 15-25 minutes, and discharges the supernatant after precipitation. The discharge volume is the same as the volume of the added culture solution. At this point, a treatment cycle is completed; Culture liquid, start a new treatment cycle, and complete multiple operation cycles in this way; the operating temperature of the reactor is 30-35°C, and the pH of the mud-water mixture in the reactor is controlled at 7.0-8.0; the reaction is discharged from the reactor once a day One-fifteenth of the total volume of the final mud-water mixture is discarded, and then refilled with a new culture solution of the same volume as the discarded solution; a total of 70 to 110 days of operation; 二、利用Feammox微生物处理污水中的NH4 + 2. Using Feammox microorganisms to treat NH 4 + in sewage 1)污水预处理:在待处理含氨污水中加入0.16~0.20mMFe(III)NTA、矿物质溶解混匀得到混合液,再按每升混合液加入1.0~1.5mL微量元素溶液的比例加入微量元素溶液混合得到污水预处理液;1) Sewage pretreatment: Add 0.16-0.20mMFe(III)NTA to the ammonia-containing sewage to be treated, dissolve and mix the minerals to obtain a mixed solution, and then add trace elements at a rate of 1.0-1.5mL of trace element solution per liter of the mixed solution The element solution is mixed to obtain the sewage pretreatment liquid; 2)将前述富集培养Feammox微生物后得到的泥水混合物排掉一半体积的液体后加进厌氧反应器中进行污水处理:在反应器中加入与反应器内泥水混合物相同体积的前述污水预处理液运行180~240min、然后停止运行沉淀15~25min、沉淀后排出与加入的污水预处理液相同体积的溶液并收集该液体,至此完成一个处理周期;重新在反应器内加入与与排出体积相同体积的污水预处理液,开始一个新的处理周期,如此循环即可持续地进行污水处理;反应器的运行温度为30~35℃,反应器中的泥水混合物pH控制在7.0~8.0;每天一次从反应器内排出反应后的泥水混合物总体积的十五分之一丢弃,然后重新补入与排出液相同体积的污水预处理液;至此完成了将污水中的NH4 +转化为NO2-的过程;2) Drain half of the volume of the mud-water mixture obtained after enriching and cultivating Feammox microorganisms, and then add it to the anaerobic reactor for sewage treatment: add the same volume of the mud-water mixture in the reactor as the aforementioned sewage pretreatment The solution runs for 180-240 minutes, then stops to settle for 15-25 minutes, discharges the solution with the same volume as the sewage pretreatment solution added after the precipitation and collects the liquid, and completes a treatment cycle; Volume of sewage pretreatment liquid, start a new treatment cycle, so that the sewage treatment can be carried out continuously; the operating temperature of the reactor is 30-35 ℃, and the pH of the mud-water mixture in the reactor is controlled at 7.0-8.0; once a day Discard one-fifteenth of the total volume of the reacted mud-water mixture from the reactor, and then refill the same volume of sewage pretreatment liquid as the effluent; so far, the conversion of NH 4 + in sewage into NO 2- the process of; 三、将前述厌氧Feammox处理后收集到的液体进行脱氮处理。3. The liquid collected after the aforementioned anaerobic Feammox treatment is subjected to denitrification treatment. 2.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述营养液中的Fe(III)NTA的浓度为0.18mM、NH4 +的浓度为2.15mM,所述污水预处理液中的Fe(III)NTA的浓度为0.18mM。2. The biological denitrification method based on anaerobic iron ammonia oxidation as claimed in claim 1, wherein the concentration of Fe(III)NTA in the nutrient solution is 0.18mM, and the concentration of NH 4 + is 2.15mM , the concentration of Fe(III)NTA in the sewage pretreatment liquid is 0.18mM. 3.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述的Fe(III)NTA由Fe2(SO4)3和NTA按1:1的摩尔比配得,所述的NH4 +来源于硫酸铵或氯化铵。3. the biological denitrification method based on anaerobic iron ammonia oxidation as claimed in claim 1, is characterized in that, described Fe (III) NTA is by Fe 2 (SO 4 ) 3 and NTA by the molar ratio of 1:1 Yes, the NH 4 + is derived from ammonium sulfate or ammonium chloride. 4.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述营养液和所述污水预处理液中包含的矿物质组分及配比均为:NaH2PO40.04~0.06g/L、CaCl2·2H2O0.2~0.4g/L、MgSO4·7H2O0.2~0.4g/L、KHCO31.0~1.5g/L、FeSO40.0060~0.0065g/L、EDTA0.0060~0.0065g/L;所述的微量元素溶液包括如下浓度的组分:EDTA13~17g/L、H3BO40.010~0.016g/L、MnCl2·4H2O0.90~1.10g/L、CuSO4·5H2O0.20~0.30g/L、ZnSO4·7H2O0.35~0.50g/L、NiCl2·6H2O0.15~.025g/L、Na2SeO4·10H2O0.15~0.26g/L、Na2MoO4·2H2O0.17~0.27g/L、Na2WO4·2H2O0.03~0.07g/L。4. The biological denitrification method based on anaerobic iron ammonium oxidation as claimed in claim 1, wherein the mineral components and proportions contained in the nutrient solution and the sewage pretreatment solution are: NaH 2 PO 4 0.04~0.06g/L, CaCl 2 2H 2 O 0.2~0.4g/L, MgSO 4 7H 2 O 0.2~0.4g/L, KHCO 3 1.0~1.5g/L, FeSO 4 0.0060 ~0.0065g/L, EDTA0.0060~0.0065g/L; the trace element solution includes the following components: EDTA13~17g/L, H 3 BO 4 0.010~0.016g/L, MnCl 2 ·4H 2 O0.90~1.10g/L, CuSO 4 5H 2 O0.20~0.30g/L, ZnSO 4 7H 2 O0.35~0.50g/L, NiCl 2 6H 2 O0.15~.025g/L , Na 2 SeO 4 ·10H 2 O 0.15-0.26 g/L, Na 2 MoO 4 ·2H 2 O 0.17-0.27 g/L, Na 2 WO 4 ·2H 2 O 0.03-0.07 g/L. 5.如权利要求4所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述营养液和所述污水预处理液中包含的矿物质组分及配比均为:NaH2PO40.05g/L、CaCl2·2H2O0.3g/L、MgSO4·7H2O0.3g/L、KHCO31.25g/L、FeSO40.00625g/L、EDTA0.00625g/L;所述微量元素溶液包括如下浓度的组分:EDTA15g/L、H3BO40.014g/L、MnCl2·4H2O0.99g/L、CuSO4·5H2O0.25g/L、ZnSO4·7H2O0.43g/L、NiCl2·6H2O0.19g/L、Na2SeO4·10H2O0.21g/L、Na2MoO4·2H2O0.22g/L、Na2WO4·2H2O0.05g/L。5. The biological denitrification method based on anaerobic iron ammonium oxidation as claimed in claim 4, characterized in that, the mineral components and proportions contained in the nutrient solution and the sewage pretreatment solution are: NaH 2 PO 4 0.05g/L, CaCl 2 2H 2 O 0.3g/L, MgSO 4 7H 2 O 0.3g/L, KHCO 3 1.25g/L, FeSO 4 0.00625g/L, EDTA 0.00625g/L; The trace element solution includes components at the following concentrations: EDTA 15g/L, H 3 BO 4 0.014g/L, MnCl 2 4H 2 O 0.99g/L, CuSO 4 5H 2 O 0.25g/L, ZnSO 4 . 7H 2 O 0.43g/L, NiCl 2 6H 2 O 0.19g/L, Na 2 SeO 4 10H 2 O 0.21g/L, Na 2 MoO 4 2H 2 O 0.22g/L, Na 2 WO 4 2H 2 O 0.05g/L. 6.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述将厌氧Feammox处理后收集到的液体进行脱氮处理的方法为厌氧氨氧化工艺处理,将溶液中的NO2 -转化为N26. the biological denitrification method based on anaerobic iron ammonium oxidation as claimed in claim 1, is characterized in that, the method that the liquid collected after the anaerobic Feammox treatment is carried out denitrification treatment is anaerobic ammonium oxidation process treatment , to convert NO 2 - in the solution into N 2 . 7.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述厌氧反应器是SBR反应器或者UASB反应器或者EGSB反应器。7. The biological denitrification method based on anaerobic iron ammonia oxidation as claimed in claim 1, wherein the anaerobic reactor is an SBR reactor or a UASB reactor or an EGSB reactor. 8.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,所述微量元素溶液加入量为:每升营养液中加入1.25mL微量元素溶液,污水预处理时每升混合液加入1.25mL微量元素溶液。8. The biological denitrification method based on anaerobic ferric ammonium oxidation as claimed in claim 1, characterized in that, the added amount of said trace element solution is: add 1.25mL trace element solution in every liter of nutrient solution, during sewage pretreatment Add 1.25mL trace element solution per liter of mixed solution. 9.如权利要求1所述的基于厌氧铁氧化氨的生物脱氮方法,其特征在于,反应器中的运行温度为30~32℃,反应器中的泥水混合物pH控制在7.0~7.5。9 . The biological denitrification method based on anaerobic ferric ammonium oxidation as claimed in claim 1 , wherein the operating temperature in the reactor is 30-32° C., and the pH of the mud-water mixture in the reactor is controlled at 7.0-7.5. 10.如权利要求1至8项中任一项所述的基于厌氧铁氧化氨的生物脱氮方法在污水脱氮处理中的应用。10. Application of the biological denitrification method based on anaerobic iron ammonia oxidation in sewage denitrification treatment as described in any one of claims 1 to 8.
CN201510775812.8A 2015-11-13 2015-11-13 Biological denitrification method and its application based on anaerobic ferrite oxidization ammonia Active CN105271514B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510775812.8A CN105271514B (en) 2015-11-13 2015-11-13 Biological denitrification method and its application based on anaerobic ferrite oxidization ammonia

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510775812.8A CN105271514B (en) 2015-11-13 2015-11-13 Biological denitrification method and its application based on anaerobic ferrite oxidization ammonia

Publications (2)

Publication Number Publication Date
CN105271514A true CN105271514A (en) 2016-01-27
CN105271514B CN105271514B (en) 2018-03-23

Family

ID=55141452

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510775812.8A Active CN105271514B (en) 2015-11-13 2015-11-13 Biological denitrification method and its application based on anaerobic ferrite oxidization ammonia

Country Status (1)

Country Link
CN (1) CN105271514B (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105923764A (en) * 2016-06-27 2016-09-07 南京大学 Method for quickly starting anaerobic ammonia oxidation technology by manganese dioxide
CN105948280A (en) * 2016-07-22 2016-09-21 中国环境科学研究院 Anaerobic biological oxidation water pollution remediation method using Fe3+ in hematite as electron acceptor
CN107555616A (en) * 2017-10-31 2018-01-09 苏州科技大学 A kind of method that ammonia nitrogen and nitrate nitrogen synchronously remove in water body
WO2018011242A1 (en) * 2016-07-14 2018-01-18 Basf Se Fermentation medium comprising chelating agent
CN107973496A (en) * 2017-12-29 2018-05-01 中国科学院南京地理与湖泊研究所 The apparatus and method that ammonia anaerobic oxidation is realized based on up-flow fixed bed reactors
CN107973495A (en) * 2017-12-29 2018-05-01 中国科学院南京地理与湖泊研究所 The apparatus and method that multistage up-flow surface water body nitrogen and organic matter synchronously remove
CN109650536A (en) * 2019-01-03 2019-04-19 大连理工大学 Ammonia nitrogen anaerobic in-situ treatment device and method based on iron circulation driving
CN111943444A (en) * 2020-08-19 2020-11-17 苏州科技大学 A sewage treatment device and method for strengthening the autotrophic denitrification and simultaneous phosphorus recovery of municipal sewage
CN112777736A (en) * 2020-12-16 2021-05-11 中海油天津化工研究设计院有限公司 Anaerobic nitrification method
CN112897835A (en) * 2021-02-23 2021-06-04 沈阳建筑大学 Preparation device and domestication method for domesticating anaerobic digestion sludge into Feammox functional sludge
CN113087143A (en) * 2021-04-19 2021-07-09 北京交通大学 Domestication method of iron metabolism coupling anaerobic ammonia oxidation sludge, and treatment method and system of ammonia nitrogen wastewater
CN113415910A (en) * 2021-06-04 2021-09-21 北京工业大学 Device and method for denitrification coupling anaerobic ammonium oxidation biological nitrogen and phosphorus removal in iron ammonium oxidation enhanced AAO process
CN113912179A (en) * 2021-10-15 2022-01-11 北京工业大学 Rapid culture method for anaerobic ferric salt oxidized ammonia nitrogen and synchronous denitrification sludge
US20220032349A1 (en) * 2018-09-27 2022-02-03 The Trustees Of Princeton University Feammox activity in bioelectrochemical reactors
CN115124142A (en) * 2022-07-28 2022-09-30 兰州资源环境职业技术大学 Device for removing nitrogen in sewage by utilizing ferric ammonium oxidation and denitrification process
CN116040787A (en) * 2023-01-12 2023-05-02 郑州轻工业大学 A bioelectrochemical constructed wetland system and its application
CN116218640A (en) * 2023-02-28 2023-06-06 乐山师范学院 A device for acclimating concentrated sludge into Feammox flora

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008279433A (en) * 2007-04-13 2008-11-20 National Institute Of Advanced Industrial & Technology Anaerobic ammonia oxidation treatment method and apparatus
CN103803703A (en) * 2014-02-25 2014-05-21 合肥工业大学 Method for simultaneously removing phosphorous and nitrogen through synergistic effect of nanoscale-iron and microbes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008279433A (en) * 2007-04-13 2008-11-20 National Institute Of Advanced Industrial & Technology Anaerobic ammonia oxidation treatment method and apparatus
CN103803703A (en) * 2014-02-25 2014-05-21 合肥工业大学 Method for simultaneously removing phosphorous and nitrogen through synergistic effect of nanoscale-iron and microbes

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SAWAYAMA, S: "Possibility of anoxic ferric ammonium oxidation", 《JOURNAL OF BIOSCIENCE AND BIOENGINEERING》 *
冯娟娟: "活性污泥异化铁还原协同脱氮除磷研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *
刘福鑫: "厌氧氨氧化微生物利用不同电子受体的可行性研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105923764A (en) * 2016-06-27 2016-09-07 南京大学 Method for quickly starting anaerobic ammonia oxidation technology by manganese dioxide
WO2018011242A1 (en) * 2016-07-14 2018-01-18 Basf Se Fermentation medium comprising chelating agent
CN105948280A (en) * 2016-07-22 2016-09-21 中国环境科学研究院 Anaerobic biological oxidation water pollution remediation method using Fe3+ in hematite as electron acceptor
CN107555616B (en) * 2017-10-31 2020-05-12 苏州科技大学 Method for synchronously removing ammonia nitrogen and nitrate nitrogen in water body
CN107555616A (en) * 2017-10-31 2018-01-09 苏州科技大学 A kind of method that ammonia nitrogen and nitrate nitrogen synchronously remove in water body
CN107973496A (en) * 2017-12-29 2018-05-01 中国科学院南京地理与湖泊研究所 The apparatus and method that ammonia anaerobic oxidation is realized based on up-flow fixed bed reactors
CN107973495A (en) * 2017-12-29 2018-05-01 中国科学院南京地理与湖泊研究所 The apparatus and method that multistage up-flow surface water body nitrogen and organic matter synchronously remove
US11807563B2 (en) * 2018-09-27 2023-11-07 The Trustees Of Princeton University Feammox activity in bioelectrochemical reactors
US20220032349A1 (en) * 2018-09-27 2022-02-03 The Trustees Of Princeton University Feammox activity in bioelectrochemical reactors
CN109650536A (en) * 2019-01-03 2019-04-19 大连理工大学 Ammonia nitrogen anaerobic in-situ treatment device and method based on iron circulation driving
CN111943444A (en) * 2020-08-19 2020-11-17 苏州科技大学 A sewage treatment device and method for strengthening the autotrophic denitrification and simultaneous phosphorus recovery of municipal sewage
CN111943444B (en) * 2020-08-19 2021-11-23 苏州科技大学 Sewage treatment device and method for enhancing municipal sewage autotrophic nitrogen removal and synchronous phosphorus recovery
CN112777736A (en) * 2020-12-16 2021-05-11 中海油天津化工研究设计院有限公司 Anaerobic nitrification method
CN112897835A (en) * 2021-02-23 2021-06-04 沈阳建筑大学 Preparation device and domestication method for domesticating anaerobic digestion sludge into Feammox functional sludge
CN112897835B (en) * 2021-02-23 2023-08-25 沈阳建筑大学 Preparation device and domestication method for domesticating anaerobic digested sludge into Feamox functional sludge
CN113087143A (en) * 2021-04-19 2021-07-09 北京交通大学 Domestication method of iron metabolism coupling anaerobic ammonia oxidation sludge, and treatment method and system of ammonia nitrogen wastewater
CN113415910A (en) * 2021-06-04 2021-09-21 北京工业大学 Device and method for denitrification coupling anaerobic ammonium oxidation biological nitrogen and phosphorus removal in iron ammonium oxidation enhanced AAO process
CN113415910B (en) * 2021-06-04 2023-01-13 北京工业大学 A device and method for short-range denitrification coupling anaerobic ammonium oxidation biological nitrogen and phosphorus removal in iron ammonium oxidation enhanced AAO process
CN113912179B (en) * 2021-10-15 2023-09-29 北京工业大学 A rapid culture method for anaerobic iron salt oxidation of ammonia nitrogen and simultaneous denitrification of sludge
CN113912179A (en) * 2021-10-15 2022-01-11 北京工业大学 Rapid culture method for anaerobic ferric salt oxidized ammonia nitrogen and synchronous denitrification sludge
CN115124142A (en) * 2022-07-28 2022-09-30 兰州资源环境职业技术大学 Device for removing nitrogen in sewage by utilizing ferric ammonium oxidation and denitrification process
CN115124142B (en) * 2022-07-28 2024-06-07 兰州资源环境职业技术大学 Device for removing nitrogen in sewage by using ferric ammonium oxidation and denitrification process
CN116040787A (en) * 2023-01-12 2023-05-02 郑州轻工业大学 A bioelectrochemical constructed wetland system and its application
CN116040787B (en) * 2023-01-12 2023-08-08 郑州轻工业大学 Bioelectrochemistry constructed wetland system and application thereof
CN116218640A (en) * 2023-02-28 2023-06-06 乐山师范学院 A device for acclimating concentrated sludge into Feammox flora

Also Published As

Publication number Publication date
CN105271514B (en) 2018-03-23

Similar Documents

Publication Publication Date Title
CN105271514B (en) Biological denitrification method and its application based on anaerobic ferrite oxidization ammonia
US20250136486A1 (en) Device and method for realizing advanced nitrogen removal of domestic sewage via two stage partical nitrification-anammox coupled with sulfer antotrophic denitrification
CN104310580B (en) Part denitrification series connection autotrophic denitrification realizes the apparatus and method of nitrate wastewater and city sewage deep denitrogenation
Li et al. Enhancing the nitrogen removal efficiency of a new autotrophic biological nitrogen-removal process based on the iron cycle: Feasibility, progress, and existing problems
CN106830573A (en) Low energy consumption municipal sewage denitrogenation method based on the capture of reinforcing carbon with Anammox
CN105152323A (en) Method for oxidation treatment of nitric oxide by combining complexing absorption with anaerobic ammonium and application of method
Ma et al. Simultaneous removal of COD and NH4+-N from domestic sewage by a single-stage up-flow anaerobic biological filter based on Feammox
CN108623012A (en) A kind of iron ion fortified Anammox denitrification process
CN110228908A (en) Utilize the sewage water treatment method of A/O-SBR and the combined denitrification dephosphorization of sulphur autotrophic denitrification
CN102795739A (en) Device and method for comprehensively treating acidic sulfate organic waste water based on biological desulfurization
CN108101310B (en) Device and method for treating desulfurization and denitrification wastewater of thermal power plant
CN106045056A (en) Method for treating zinc pyrithione production wastewater by sulfate reducing bacteria
CN102502950A (en) Method for improving activity of nitrification function microorganisms in activated sludge by directly adding Fe ions
Zhang et al. A novel iron-mediated nitrogen removal technology of ammonium oxidation coupled to nitrate/nitrite reduction: Recent advances
Wang et al. Enhanced nitrogen removal driven by S/Fe2+ cycle in a novel hybrid constructed wetland
CN110029075A (en) A kind of culture medium and the preparation method and application thereof using activated sludge fast enriching anaerobic ammonia oxidizing bacteria
CN110092482A (en) A method of realizing that synchronous PND-DNRA handles carbon containing, nitrogen waste water based on immobilized spherule
CN101289247A (en) Single-stage aerobic biological denitrification operation method of sequencing batch reactor
CN1189462A (en) Tech. for treatment of waste water containing cyanogen by hydrogen peroxide oxidation process
Xia et al. The humic substance analogue antraquinone-2, 6-disulfonate (AQDS) enhanced zero-valent iron based autotrophic denitrification: Performances and mechanisms
CN107055816A (en) A kind of quick, method of a large amount of enrichment nitrifiers and application
Zhang et al. CH4 control and nitrogen removal from constructed wetlands by plant combination
CN116715351A (en) Based on Fe 2+ And Fe (Fe) 3+ Circularly driven sewage biological denitrification method
CN103241916B (en) Method for realizing maximal accumulation of nitrite in sludge fermentation coupling denitrification process
CN205419926U (en) Low energy consumption enhanced nitrogen removal phosphorus removal device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant