CN115677043A - A New Technology for Efficient Nitrogen Removal of Low Salt and Low C/N Wastewater - Google Patents
A New Technology for Efficient Nitrogen Removal of Low Salt and Low C/N Wastewater Download PDFInfo
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Abstract
本发明提供一种对低盐低C/N废水高效脱氮的新技术,属于生物脱氮技术领域,通过生物挂膜法快速启动硫自养反硝化反应器,通入人工配制废水,在废水中加入少量的葡萄糖后,体系能够很好的适应人工配制废水,微生物生长迅速,脱氮效果良好。相比常规的异养反硝化工艺既节约了碳源,减少污泥排放和二次污染,还形成良好的硫自养/异养协同反硝化作用系统;在设定HRT为4h的时候,对30mg/L的硝态氮去除效果可以达到96%,体系稳定高效;在加入2g/L的低盐条件下,体系并无抑制作用,正常高效运行;该技术成本低廉,操作简便,脱氮效果显著,可以大规模应用。
The invention provides a new technology for high-efficiency denitrification of low-salt and low-C/N wastewater, which belongs to the technical field of biological denitrification. The sulfur autotrophic denitrification reactor is quickly started by the biological film-hanging method, and artificially prepared wastewater is fed into the wastewater. After adding a small amount of glucose, the system can well adapt to artificially prepared wastewater, the microorganisms grow rapidly, and the denitrification effect is good. Compared with the conventional heterotrophic denitrification process, it not only saves carbon sources, reduces sludge discharge and secondary pollution, but also forms a good sulfur autotrophic/heterotrophic synergistic denitrification system; when the HRT is set to 4h, the The removal effect of 30mg/L nitrate nitrogen can reach 96%, and the system is stable and efficient; under the condition of adding 2g/L of low salt, the system has no inhibitory effect and operates normally and efficiently; Significantly, it can be applied on a large scale.
Description
技术领域technical field
本发明涉及生物脱氮技术领域,尤其涉及一种对低盐低C/N废水高效脱氮的新技术。The invention relates to the technical field of biological denitrification, in particular to a new technology for efficient denitrification of low-salt and low-C/N wastewater.
背景技术Background technique
传统生物脱氮工艺采用硝化和反硝化工艺,存在污泥产量高,需外加碳源和运行成本高等缺点。硫自养反硝化的原理是一些无机化能营养型、光能营养型的硫氧化细菌可在缺氧或厌氧条件下利用还原态硫(S0、S2-、S2O3 2-等)作为电子供体,通过对还原态硫进行氧化获取能量,同时以硝酸盐为电子受体,将其还原为氮气,利用无机碳(如CO3 2-、HCO3 -)合成细胞,从而实现自养反硝化过程。硫自养反硝技术具有无需添加外部碳源和污泥产量低等优点。The traditional biological denitrification process adopts nitrification and denitrification process, which has the disadvantages of high sludge output, additional carbon source and high operating cost. The principle of sulfur autotrophic denitrification is that some inorganic chemotrophic and phototrophic sulfur-oxidizing bacteria can use reduced sulfur (S 0 , S 2- , S 2 O 3 2- etc.) as an electron donor, obtain energy by oxidizing reduced sulfur, and use nitrate as an electron acceptor to reduce it to nitrogen, and use inorganic carbon (such as CO 3 2- , HCO 3 - ) to synthesize cells, thereby Realize autotrophic denitrification process. Sulfur autotrophic denitrification technology has the advantages of no need to add external carbon sources and low sludge production.
元素硫(S0)作为地球上硫循环中的中心中间体,相比于其他硫中间体(如硫化物、硫代硫酸盐和硫酸盐)具有一些优势:(1)是地球上丰富的资源;(2)具有多功能性,允许氧化和还原;(3)固态时,储存更安全,运输成本低。因此,在过去几十年中,已经广泛报道利用S0还原和氧化特性来处理废水。应用包括S0驱动的自养反硝化(S0AD),是由一些S0氧化菌(S0OB)来介导的。并且在常见的还原态硫中,硫化物会抑制水生微生物的活性,硫代硫酸盐的制备复杂,而单质硫具有无毒、不溶于水和经济有效等特点,有较好的应用前景。Elemental sulfur (S 0 ), as a central intermediate in the sulfur cycle on Earth, has several advantages over other sulfur intermediates such as sulfide, thiosulfate, and sulfate: (1) It is an abundant resource on Earth ; (2) multifunctionality, allowing oxidation and reduction; (3) in the solid state, storage is safer and transportation costs are low. Therefore, exploiting the reducing and oxidizing properties of S0 to treat wastewater has been widely reported in the past decades. Applications include S 0 driven autotrophic denitrification (S 0 AD), mediated by some S 0 oxidizing bacteria (S 0 OB). And in the common reduced sulfur, sulfide can inhibit the activity of aquatic microorganisms, and the preparation of thiosulfate is complicated, while elemental sulfur is non-toxic, insoluble in water, economical and effective, and has a good application prospect.
目前以单质硫作为电子供体的硫自养反硝化技术已被大量应用,但是反应有着启动时间慢、稳定性不高、脱氮效率不理想、耐盐性一般等缺点。因此,开发出一项快速启动、稳定性好、脱氮效果优良、耐盐的体系是硫自养反硝化技术研究的重点,需要一种对低盐低C/N废水高效脱氮的新技术。At present, the sulfur autotrophic denitrification technology using elemental sulfur as the electron donor has been widely used, but the reaction has the disadvantages of slow start-up time, low stability, unsatisfactory denitrification efficiency, and general salt tolerance. Therefore, the development of a system with quick start, good stability, excellent denitrification effect and salt tolerance is the focus of sulfur autotrophic denitrification technology research, and a new technology for efficient denitrification of low-salt and low C/N wastewater is needed .
发明内容Contents of the invention
本发明的目的在于提供一种对低盐低C/N废水高效脱氮的新技术,解决现有启动时间慢、稳定性不高、脱氮效率不理想、耐盐性一般的技术问题。本发明通过生物挂膜法启动反应器,通入人工配水,形成良好的自养/异养协同反硝化作用系统,在HRT为4h时,对30mg/L硝态氮的去除效果可以达到96%,在2%低盐条件下,体系并无抑制作用,正常高效运行;具有快速启动、耐低盐、脱氮效果优异、体系稳定的特点。The purpose of the present invention is to provide a new technology for high-efficiency denitrification of low-salt and low-C/N wastewater to solve the existing technical problems of slow start-up time, low stability, unsatisfactory denitrification efficiency and general salt tolerance. In the present invention, the reactor is started by the biofilm-hanging method, and artificial water distribution is introduced to form a good autotrophic/heterotrophic synergistic denitrification system. When the HRT is 4h, the removal effect of 30mg/L nitrate nitrogen can reach 96%. , Under the condition of 2% low salt, the system has no inhibitory effect, and operates normally and efficiently; it has the characteristics of quick start, low salt resistance, excellent denitrification effect, and stable system.
为了实现上述目的,本发明采用的技术方案如下:In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
一种对低盐低C/N废水高效脱氮的新技术,包括以下步骤:A new technology for efficient denitrification of low-salt and low C/N wastewater, comprising the following steps:
(1)反应器的选用:选用圆柱形升流式反硝化生物反应器,反应器的材质为有机玻璃,反应器的内径为8.6cm,反应器的外径为9.6cm,反应器的高度为90cm,反应器的有效容积为4L,反应器内设置有填料和人工配制废水,填料的高度为22.5cm,水的容积为2.2L;(1) Selection of the reactor: select a cylindrical upflow denitrification bioreactor, the material of the reactor is plexiglass, the inner diameter of the reactor is 8.6cm, the outer diameter of the reactor is 9.6cm, and the height of the reactor is 90cm, the effective volume of the reactor is 4L, the reactor is equipped with packing and artificially prepared waste water, the height of the packing is 22.5cm, and the volume of water is 2.2L;
(2)反应器的启动:采用生物挂膜法启动反应器,通过监测反应器内出水水质及反应器的运行效果来探究反应器启动情况,反应器启动污泥取自生活污水活性污泥,通过每天检测出水NO3 -,NO2 -,TN等指标的浓度,连续一周测定NO3 -、TN的去除效果达到90%以上,并且无NO2 -积累,能看到有明显的生物膜附着,表明反应器启动成功;(2) Start-up of the reactor: The reactor is started by the bio-filming method, and the reactor start-up situation is explored by monitoring the effluent water quality in the reactor and the operation effect of the reactor. The reactor start-up sludge is taken from domestic sewage activated sludge, By detecting the concentration of NO 3 - , NO 2 - , TN and other indicators in the water every day, the removal effect of NO 3 - and TN has been determined to be over 90% for one week, and there is no accumulation of NO 2 - , and obvious biofilm adhesion can be seen , indicating that the reactor started successfully;
(3)反应器的稳定运行阶段:反应器稳定运行阶段进水采用人工配制废水,废水配方为:每1L自来水,加入0.033g葡萄糖、0.182g硝酸钠、0.0045g磷酸二氢钾和微量元素营养液1mL/L,在0-5天设定HRT为10h,5-10天设定HRT为7h,10-25天设定HRT为4h,在HRT为4h期间,对NO3 -、TN去除效果可达95%,并且无NO2 -、NH4 +积累,实现了快速启动,系统稳定运行;(3) Stable operation stage of the reactor: In the stable operation stage of the reactor, artificially prepared wastewater is used for the influent water. The wastewater formula is: for every 1L of tap water, add 0.033g of glucose, 0.182g of sodium nitrate, 0.0045g of potassium dihydrogen phosphate and trace element nutrients 1mL/L, set the HRT to 10h on the 0-5 day, set the HRT to 7h on the 5-10 day, set the HRT to 4h on the 10-25 day, during the HRT of 4h, the removal effect on NO 3 - and TN It can reach 95%, and there is no accumulation of NO 2 - and NH 4 + , which realizes quick startup and stable operation of the system;
(4)在稳定运行15天后,向配水中加入2g/L的NaCl,观察硫自养/异养协同体系在低盐条件下是否对脱氮效率有抑制,结果表明低盐对于本反应体系并无影响,体系正常运行,对NO3 -N、TN去除效率达到96%。(4) After 15 days of stable operation, add 2g/L NaCl to the distribution water to observe whether the sulfur autotrophic/heterotrophic synergistic system can inhibit the denitrification efficiency under low-salt conditions. The results show that low-salt has no effect on the reaction system. No effect, the system operates normally, and the removal efficiency of NO 3 -N and TN reaches 96%.
进一步地,在步骤(1)中,反应器内的填料为硫磺和石灰石颗粒,硫磺和石灰石颗粒的体积比为1:1,硫磺的粒径为3-4mm,石灰石颗粒的粒径为2-3mm。Further, in step (1), the filler in the reactor is sulfur and limestone particles, the volume ratio of sulfur and limestone particles is 1:1, the particle diameter of sulfur is 3-4mm, and the particle diameter of limestone particles is 2- 3mm.
进一步地,在步骤(2)中,驯化废水的指标浓度为:NO3 --N=20mg/L,NO2 --N=9mg/L,NH4 +-N=3mg/L,TN=30mg/L,COD=30mg/L,pH值为7.5。Further, in step (2), the index concentration of domesticated wastewater is: NO 3 − -N=20 mg/L, NO 2 − -N=9 mg/L, NH 4 + -N=3 mg/L, TN=30 mg /L, COD=30mg/L, pH value is 7.5.
进一步地,在步骤(2)中,反应器启动用水量为:0-7天HRT为10h,7-15天HRT为7h。Further, in step (2), the starting water consumption of the reactor is: 0-7 days HRT is 10 h, and 7-15 days HRT is 7 h.
进一步地,在步骤(3)中,废水水质的指标浓度为:COD=30±2mg/L,PO4 3-=1±0.2mg/L,NO3 -=30±1mg/L,pH值为7.0-7.2。Further, in step (3), the index concentration of wastewater quality is: COD=30±2mg/L, PO 4 3− =1±0.2mg/L, NO 3 − =30±1mg/L, and the pH value is 7.0-7.2.
本发明由于采用了上述技术方案,具有以下有益效果:The present invention has the following beneficial effects due to the adoption of the above technical solution:
本发明通过生物挂膜法启动反应器,通入人工配水,形成良好的自养/异养协同反硝化作用系统,在HRT为4h时,对各种氮素的去除效果可以达到96%,在2%低盐条件下,体系并无抑制作用,正常高效运行;具有快速启动、耐低盐、脱氮效果优异、体系稳定的特点。In the present invention, the reactor is started by the biofilm-hanging method, and artificial water distribution is introduced to form a good autotrophic/heterotrophic synergistic denitrification system. When the HRT is 4h, the removal effect of various nitrogen can reach 96%. Under 2% low-salt conditions, the system has no inhibitory effect and operates normally and efficiently; it has the characteristics of fast start-up, low-salt resistance, excellent denitrification effect, and stable system.
附图说明Description of drawings
图1是本发明启动与稳定运行氮素指标变化图;Fig. 1 is the change figure of the nitrogen index of start-up and stable operation of the present invention;
图2是本发明稳定运行阶段pH和COD变化图;Fig. 2 is a pH and COD change figure in the stable operation stage of the present invention;
图3是本发明稳定运行阶段出水SO4 2-浓度;Fig. 3 is the effluent SO 4 2- concentration in the stable operation stage of the present invention;
图4是本发明2g/L NaCl阶段(HRT=4h)氮素浓度的变化图;Fig. 4 is the change diagram of nitrogen concentration in the 2g/L NaCl stage (HRT=4h) of the present invention;
图5是本发明2g/L NaCl阶段(HRT=4h)COD浓度和pH值的变化图;Fig. 5 is the change figure of COD concentration and pH value of 2g/L NaCl stage (HRT=4h) of the present invention;
图6是本发明2g/L NaCl阶段(HRT=4h)出水硫酸根浓度的变化图。Fig. 6 is a graph showing the variation of sulfate concentration in effluent in the 2g/L NaCl stage (HRT=4h) of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案及优点更加清楚明白,以下参照附图并举出优选实施例,对本发明进一步详细说明。然而,需要说明的是,说明书中列出的许多细节仅仅是为了使读者对本发明的一个或多个方面有一个透彻的理解,即便没有这些特定的细节也可以实现本发明的这些方面。In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be described in further detail below with reference to the accompanying drawings and preferred embodiments. However, it should be noted that many of the details listed in the specification are only for readers to have a thorough understanding of one or more aspects of the present invention, and these aspects of the present invention can be implemented even without these specific details.
如图1-2所示,一种对低盐低C/N废水高效脱氮的新技术,包括以下步骤:包括以下步骤:As shown in Figure 1-2, a new technology for efficient denitrification of low-salt and low-C/N wastewater includes the following steps: including the following steps:
(1)反应器的选用:选用圆柱形升流式反硝化生物反应器,反应器的材质为有机玻璃,反应器的内径为8.6cm,反应器的外径为9.6cm,反应器的高度为90cm,反应器的有效容积为4L,反应器内设置有填料和人工配制废水,填料的高度为22.5cm,水的容积为2.2L;反应器内的填料为硫磺和石灰石颗粒,硫磺和石灰石颗粒的体积比为1:1,硫磺的粒径为3-4mm,石灰石颗粒的粒径为2-3mm;采用上流式进水运行方式,粒径越小填料的比表面积越大,微生物可以附着在硫磺和石灰石填料上,同时通过消耗硫磺产生能量,一部分来实现脱氮的过程,一部分用于细菌自身生长。(1) Selection of the reactor: select a cylindrical upflow denitrification bioreactor, the material of the reactor is plexiglass, the inner diameter of the reactor is 8.6cm, the outer diameter of the reactor is 9.6cm, and the height of the reactor is 90cm, the effective volume of the reactor is 4L, the reactor is equipped with packing and artificially prepared waste water, the height of the packing is 22.5cm, and the volume of water is 2.2L; the packing in the reactor is sulfur and limestone particles, sulfur and limestone particles The volume ratio of the sulfur is 1:1, the particle size of the sulfur is 3-4mm, and the particle size of the limestone particles is 2-3mm; using the upflow water inlet operation mode, the smaller the particle size is, the larger the specific surface area of the filler is, and the microorganisms can attach to it. Sulfur and limestone fillers consume sulfur to generate energy, part of which is used for the process of denitrification, and part of which is used for the growth of bacteria themselves.
(2)反应器的启动:采用生物挂膜法启动反应器,通过监测反应器内出水水质及反应器的运行效果来探究反应器启动情况,反应器启动污泥取自生活污水活性污泥,通过每天检测出水NO3 -,NO2 -,TN等指标的浓度,连续一周测定NO3 -、TN的去除效果达到90%以上,并且无NO2 -积累,能看到有明显的生物膜附着,表明反应器启动成功;驯化废水的指标浓度为:NO3 --N=20mg/L,NO2 --N=9mg/L,NH4 +-N=3mg/L,TN=30mg/L,COD=30mg/L,pH值为7.5;反应器启动用水量为:0-7天HRT为10h,7-15天HRT为7h;接种废水中含有大量各种微生物,可以缩短微生物的培养和驯化时间。(2) Start-up of the reactor: The reactor is started by the bio-filming method, and the reactor start-up situation is explored by monitoring the effluent water quality in the reactor and the operation effect of the reactor. The reactor start-up sludge is taken from domestic sewage activated sludge, By detecting the concentration of NO 3 - , NO 2 - , TN and other indicators in the water every day, the removal effect of NO 3 - and TN has been determined to be over 90% for one week, and there is no accumulation of NO 2 - , and obvious biofilm adhesion can be seen , indicating that the reactor was started successfully; the index concentration of domesticated wastewater is: NO 3 - -N=20mg/L, NO 2 - -N=9mg/L, NH 4 + -N=3mg/L, TN=30mg/L, COD=30mg/L, pH value is 7.5; the water consumption for reactor start-up is: 0-7 days HRT is 10h, 7-15 days HRT is 7h; inoculation wastewater contains a large number of various microorganisms, which can shorten the cultivation and domestication of microorganisms time.
(3)反应器的稳定运行阶段:反应器稳定运行阶段进水采用人工配制废水,废水配方为:每1L自来水,加入0.033g葡萄糖、0.182g硝酸钠、0.0045g磷酸二氢钾和微量元素营养液1mL/L,在0-5天设定HRT为10h,5-10天设定HRT为7h,10-25天设定HRT为4h,在HRT为4h期间,对NO3 -、TN去除效果可达95%,并且无NO2 -、NH4 +积累,实现了快速启动,系统稳定运行;废水水质的指标浓度为:COD=30±2mg/L,PO4 3-=1±0.2mg/L,NO3 -=30±1mg/L,pH值为7.0-7.2。在加入了葡萄糖有机碳源后,体系能够很好的适应人工配水,微生物生长迅速,脱氮效果良好,相比常规的异养反硝化工艺节约了碳源,减少污泥排放和二次污染,还形成良好的硫自养/异养协同反硝化作用系统;硫自养反硝化与异养反硝化耦合优势在于:①可减少碱度的投加,降低成本;②在碳源强化下,异养反硝化反应承担部分NO3 --N负荷,不仅有效提高了反硝化效率,同时也保证了出水有机物含量较低。(3) Stable operation stage of the reactor: In the stable operation stage of the reactor, artificially prepared wastewater is used for the influent water. The wastewater formula is: for every 1L of tap water, add 0.033g of glucose, 0.182g of sodium nitrate, 0.0045g of potassium dihydrogen phosphate and trace element nutrients 1mL/L, set the HRT to 10h on the 0-5 day, set the HRT to 7h on the 5-10 day, set the HRT to 4h on the 10-25 day, during the HRT of 4h, the removal effect on NO 3 - and TN It can reach 95%, and there is no accumulation of NO 2 - and NH 4 + , which realizes rapid startup and stable operation of the system; the index concentration of wastewater quality is: COD=30±2mg/L, PO 4 3- =1±0.2mg/ L, NO 3 − =30±1 mg/L, pH value is 7.0-7.2. After adding glucose organic carbon source, the system can well adapt to artificial water distribution, rapid microbial growth, and good denitrification effect. Compared with conventional heterotrophic denitrification process, it saves carbon source, reduces sludge discharge and secondary pollution, A good sulfur autotrophic/heterotrophic synergistic denitrification system has also been formed; the advantages of coupling sulfur autotrophic denitrification and heterotrophic denitrification are: ① It can reduce the addition of alkalinity and reduce costs; ② Under the strengthening of carbon sources, heterotrophic denitrification The denitrification reaction bears part of the NO 3 - -N load, which not only effectively improves the denitrification efficiency, but also ensures that the content of organic matter in the effluent is low.
(4)在稳定运行15天后,向配水中加入2g/L的NaCl,观察硫自养/异养协同体系在低盐条件下是否对脱氮效率有抑制,结果表明低盐对于本反应体系并无影响,体系正常运行,对NO3 -N、TN去除效果可达96%。(4) After 15 days of stable operation, add 2g/L NaCl to the distribution water to observe whether the sulfur autotrophic/heterotrophic synergistic system can inhibit the denitrification efficiency under low-salt conditions. The results show that low-salt has no effect on the reaction system. No effect, the system operates normally, and the removal effect of NO 3 -N and TN can reach 96%.
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be It is regarded as the protection scope of the present invention.
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