CN103420480A - Anaerobic molysite biological nitrogen removal process - Google Patents
Anaerobic molysite biological nitrogen removal process Download PDFInfo
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- CN103420480A CN103420480A CN2013103410910A CN201310341091A CN103420480A CN 103420480 A CN103420480 A CN 103420480A CN 2013103410910 A CN2013103410910 A CN 2013103410910A CN 201310341091 A CN201310341091 A CN 201310341091A CN 103420480 A CN103420480 A CN 103420480A
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Abstract
The invention discloses an anaerobic molysite biological nitrogen removal process which is characterized in that denitrifying bacterium enrichment culture is taken as a biocatalyst, under the anaerobic condition, nitrate is taken as an electron acceptor, ferrous salt is taken as an electron donor, the nitrate is reduced into N2 in the same reactor, and the ferrous salt is oxygenized into ferric iron, wherein the molar ratio of the nitrate to the ferrous salt is 1.0 to 5.0, the reaction temperature is 20 to 35 DEG C, the pH value is 7.0 to 9.0, and the hydraulic retention time is 0.5 to 2.0 d. The process has the following advantages: 1, ferrous salt is taken as the electron donor, nitrate is taken as the electron acceptor, and waste is treated with waste, so that the purposes of removing nitrate-nitrogen pollutant and utilizing ferrous salt waste can be achieved; 2, no organic matter is required, so that the problem that the carbon source is not enough relatively during waste water biological nitrogen removal can be relieved effectively; 3, ferric iron, which is a ferrous salt oxidation product and has high values, can be reclaimed; 4, the concentrations of nitrate and ferrous salt, which can be treated, can reach 1500 mgN/L and 30000 mgFe/L.
Description
Technical field
The present invention relates to a kind of anaerobism molysite biological denitrification process.
Background technology
After " reduction of discharging of control source " implemented in the whole nation, the waste water organic contamination is effectively administered, and nitrate pollution rises to main environmental problem.According to " national Environmental statistics communique ", within 2010, national wastewater emission amount is 617.3 hundred million tons, 1238.1 ten thousand tons of chemical oxygen demand (COD) (COD) quantity dischargeds, 120.3 ten thousand tons of ammonia nitrogen quantity dischargeds.According to another " China Environmental State Bulletin ", within 2010, in 26 states control emphasis lakes (reservoir), IV class to bad V class water body accounts for 77 %, slightly accounts for 54 % to the severe eutrophic water body, and main contamination index is total nitrogen.Nitrate pollution is controlled has become China's great environmental protection subject urgently to be resolved hurrily.
Wastewater biological denitrificaion is the important channel of control body eutrophication.After biological treatment (second-stage treatment), waste water COD concentration is substantially up to standard, but ammonia nitrogen concentration still exceeds standard.For the low C:N ratio wastewater of this class, process, traditional wastewater denitrification process (nitrated-denitrification process) is aobvious weak, and this is because denitrification process needs electron donor, usually by organism, is provided.The carbon source relative deficiency has become the great bottleneck factor of wastewater biological denitrificaion.
Ferrous salt (as ferrous sulfate) is the by product that titanium white production and iron and steel embathe liquid, and output is huge, expects the year two thousand twenty and will increase to 1 * 10
6The t left and right.At present, though have research ferrous salt is applied to fertilizer and flocculation agent production etc., demand is limited, the overwhelming majority is still banked up everywhere as waste material, not only wastes resource, and the severe contamination Soil Surrounding and water body environment bad.The comprehensive utilization of ferrous salt is extremely urgent.
Nitrate type anaerobism iron oxidation (Nitrate-dependent Anaerobic Ferrous Oxidation, NAFO) be the great discovery of environment and microorganism field, under anaerobic, some microorganisms can be take ferrous salt as electron donor, and nitrate or nitrite are reduced to N
2.Be applied to field of waste water treatment but have no.If the ferrous salt of usining accordingly reduces nitrate as electron donor, not only can effectively alleviate the problem of carbon source relative deficiency in the wastewater biological denitrificaion process, realize denitrogenation of waste water; And can take full advantage of ferrous salt, and reclaim the ferrous salt oxidation products ferric iron of high value, realize the treatment of wastes with processes of wastes against one another.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and a kind of anaerobism molysite biological denitrification process is provided.
Anaerobism molysite biological denitrification process is: under anaerobic, using denitrifying bacteria enrichment culture thing as biological catalyst, take nitrate as electron acceptor(EA), take ferrous salt as electron donor, be N by nitrate reduction in same reactor
2, ferrous salt is oxidized to ferric iron; Nitrate concentration is 20 ~ 1500 mg N/L, the concentration of ferrous salt is 100 ~ 30000 mg Fe/L, and the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 5.0, and temperature of reaction is 20 ~ 35 ℃, the pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0 d.
The mol ratio of described ferrous salt and nitrate concentration is preferably 1.0 ~ 3.0.Described anaerobic condition should be controlled in reaction solution dissolved oxygen below 0.5 mg/L.Described temperature of reaction is preferably 28 ~ 33 ℃.Described pH value in reaction is preferably 7.5 ~ 8.5.Described hydraulic detention time is preferably 1.0 ~ 1.5 d.
Advantage of the present invention is: 1) using denitrifying bacteria enrichment culture thing as biological catalyst, sustainable use; 2) take nitrate as electron acceptor(EA), take ferrous salt as electron donor, the treatment of wastes with processes of wastes against one another, realize the removal of nitre nitrogen pollutant and taking full advantage of of ferrous salt waste; 2) without organism is provided, effectively alleviate the problem of carbon source relative deficiency in the wastewater biological denitrificaion process; 3) can reclaim the ferrous salt oxidation products ferric iron of high value, realize Sustainable development; 4) treatable nitrate concentration is up to 1500 mg/L, and ferrous salt concentration is up to 30000 mg/L, maximum speed of reaction 0.35 kg N/ (m
3D) and 9.81 kg Fe/ (m
3D).
Embodiment
Biological respinse involved in the present invention is: 10Fe
2++ 10CO
3 2-+ 2NO
3 -+ 24H
2O → 10Fe (OH)
3+ N
2+ 10HCO
3 -+ 8H
+.Under anaerobic, using denitrifying bacteria enrichment culture thing as biological catalyst, obtain the mixed training of nitrate sections oxidizing bacteria thing with a certain proportion of nitrate and ferrous salt enrichment, to with the ferrous salt solution of preparation, mix from the nitre nitrogen waste water that contains of nitrator, pump in the molysite biological denitrification reactor, generate N
2And ferric iron.The technological condition of controlling is: nitrate concentration is 20 ~ 1500 mg N/L, ferrous salt concentration is 100 ~ 30000 mg Fe/L, the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 5.0, dissolved oxygen concentration is below 0.5 mg/L, temperature of reaction is 20 ~ 35 ℃, the pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0 d.The fortune that this technique is done is taken temperature bright, and the treatable nitrate concentration of molysite biological denitrification process is up to 1500 mg/L, and ferrous salt concentration is up to 30000 mg/L, maximum speed of reaction 0.35 kg N/ (m
3D) and 9.81 kg Fe/ (m
3D).
Embodiment 1
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 2, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 800 mg Fe/L, and dissolved oxygen concentration is 0.4 mg/L, and temperature of reaction is 32 ℃, and initial pH value is 7.0, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt clearance reach respectively 95.97 % and 96.22 %.
Embodiment 2
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 5, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 2000 mg Fe/L, and dissolved oxygen concentration is 0.3 mg/L, and temperature of reaction is 30 ℃, and initial pH value is 7.3, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the volume of nitrate and ferrous salt is removed to load and reached respectively 0.18 kg N/ (m
3D) and 2.60 kg Fe/ (m
3D).
Embodiment 3
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 2, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 800 mg Fe/L, and dissolved oxygen concentration is 0.4 mg/L, and temperature of reaction is 28 ℃, and initial pH value is 8.0, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt removal speed reach respectively 0.17 kg N/ (m
3D) and 1.58 kg Fe/ (m
3D).
Embodiment 4
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 3, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 1500 mg N/L and 18000 mg Fe/L, and dissolved oxygen concentration is 0.2 mg/L, and temperature of reaction is 29 ℃, and initial pH value is 7.0, and hydraulic detention time is 1.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the volume of nitrate and ferrous salt removal speed reaches respectively 0.28 kg N/ (m
3D) and 4.96 kg Fe/ (m
3D).
Embodiment 5
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 5, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 1500 mg N/L and 30000 mg Fe/L, and dissolved oxygen concentration is 0.5 mg/L, and temperature of reaction is 29 ℃, and initial pH value is 7.0, and hydraulic detention time is 2.0 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the volume of nitrate and ferrous salt removal speed reaches respectively 0.34 kg N/ (m
3D) and 7.92 kg Fe/ (m
3D).
Embodiment 6
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 2, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 800 mg Fe/L, and dissolved oxygen concentration is 0.3 mg/L, and temperature of reaction is 20 ℃, and initial pH value is 7.0, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the clearance of nitrate and ferrous salt is respectively 69.60 % and 84.27 %.
Embodiment 7
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 2, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 800 mg Fe/L, and dissolved oxygen concentration is 0.3 mg/L, and temperature of reaction is 30 ℃, and initial pH value is 9.0, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the clearance of nitrate and ferrous salt is respectively 73.11 % and 99.95 %.
Embodiment 8
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 2, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 800 mg Fe/L, and dissolved oxygen concentration is 0.3 mg/L, and temperature of reaction is 35 ℃, and initial pH value is 7.0, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the clearance of nitrate and ferrous salt is respectively 71.10 % and 94.12 %.
Embodiment 9
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 1, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 100 mg N/L and 400 mg Fe/L, and dissolved oxygen concentration is 0.2 mg/L, and temperature of reaction is 32 ℃, and initial pH value is 7.1, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, the volume of nitrate and ferrous salt is removed to load and reached respectively 0.20 kg N/ (m
3D) and 0.73 kg Fe/ (m
3D).
Embodiment 10
In the molysite biological denitrification reactor, the denitrifying bacteria enrichment culture thing of take is biological catalyst, the simulated wastewater that the mol ratio of nitrate and ferrous salt concentration of take is 1: 1.25, operation molysite biological denitrification reactor.The technological condition of controlling is: the concentration of nitrate and ferrous salt is respectively 20 mg N/L and 100 mg Fe/L, and dissolved oxygen concentration is 0.3 mg/L, and temperature of reaction is 31 ℃, and initial pH value is 7.3, and hydraulic detention time is 0.5 d.This technique can be removed nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt removal speed reach respectively 0.019 kg N/ (m
3D) and 0.195 kg Fe/ (m
3D).
Claims (6)
1. an anaerobism molysite biological denitrification process, it is characterized in that: under anaerobic, using denitrifying bacteria enrichment culture thing as biological catalyst, take nitrate as electron acceptor(EA), take ferrous salt as electron donor, be N by nitrate reduction in same reactor
2, ferrous salt is oxidized to ferric iron; Nitrate concentration is 20 ~ 1500 mg N/L, the concentration of ferrous salt is 100 ~ 30000 mg Fe/L, and the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 5.0, and temperature of reaction is 20 ~ 35 ℃, the pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0 d.
2. a kind of anaerobism molysite biological denitrification process according to claim 1, it is characterized in that: the mol ratio of described ferrous salt and nitrate concentration is 1.0 ~ 3.0.
3. a kind of anaerobism molysite biological denitrification process according to claim 1 is characterized in that: described anaerobic condition should be controlled in reaction solution dissolved oxygen below 0.5 mg/L.
4. a kind of anaerobism molysite biological denitrification process according to claim 1, it is characterized in that: described temperature of reaction is 28 ~ 33 ℃.
5. a kind of anaerobism molysite biological denitrification process according to claim 1, it is characterized in that: described pH value in reaction is 7.5 ~ 8.5.
6. a kind of anaerobism molysite biological denitrification process according to claim 1, it is characterized in that: described hydraulic detention time is 1.0 ~ 1.5 d.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103693806A (en) * | 2013-12-06 | 2014-04-02 | 浙江大学 | Authigenic ferric salt chemical phosphorus removal-anaerobic ferrous oxidization biological denitrification integrated device |
CN105600923A (en) * | 2015-11-15 | 2016-05-25 | 农业部沼气科学研究所 | Biological denitrification method of high ammonia-nitrogen wastewater |
CN105645602A (en) * | 2016-03-30 | 2016-06-08 | 浙江大学 | Automatic fed-batch type efficient iron salt denitrification reaction device and automatic fed-batch type efficient iron salt denitrification reaction method for bacteria |
CN105776530A (en) * | 2016-04-22 | 2016-07-20 | 浙江大学 | Self-shelling malysite denitrification reaction device and self-shelling method |
CN107601775A (en) * | 2017-10-20 | 2018-01-19 | 新乡市绿丰环保工程有限公司 | High COD, low CN ratios a kind of waste water treatment process |
CN107879427A (en) * | 2017-08-28 | 2018-04-06 | 北京石油化工学院 | A kind of denitrogenation method based on interior circulation micro-electrolysis reaction |
JP2018171550A (en) * | 2017-03-31 | 2018-11-08 | 住友重機械エンバイロメント株式会社 | Nitration denitrification system, and method for nitration denitrification treatment |
CN118324296A (en) * | 2024-01-31 | 2024-07-12 | 中国海洋大学 | Method for enhancing biological film activity and driving low-temperature low-carbon source to control nitrogen and reduce carbon |
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CN102531228A (en) * | 2011-11-08 | 2012-07-04 | 国家标准件产品质量监督检验中心 | Method for treating acidic wastewater containing iron |
CN103121758A (en) * | 2013-03-05 | 2013-05-29 | 中国科学院新疆生态与地理研究所 | Method for purifying arsenic and nitrate in sewage by anaerobic ferrite oxidization and denitrifying bacteria |
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US6019900A (en) * | 1998-08-03 | 2000-02-01 | The Regents Of The University Of California | Single stage denitrification anaerobic digestion |
CN102531228A (en) * | 2011-11-08 | 2012-07-04 | 国家标准件产品质量监督检验中心 | Method for treating acidic wastewater containing iron |
CN103121758A (en) * | 2013-03-05 | 2013-05-29 | 中国科学院新疆生态与地理研究所 | Method for purifying arsenic and nitrate in sewage by anaerobic ferrite oxidization and denitrifying bacteria |
Cited By (10)
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CN103693806A (en) * | 2013-12-06 | 2014-04-02 | 浙江大学 | Authigenic ferric salt chemical phosphorus removal-anaerobic ferrous oxidization biological denitrification integrated device |
CN105600923A (en) * | 2015-11-15 | 2016-05-25 | 农业部沼气科学研究所 | Biological denitrification method of high ammonia-nitrogen wastewater |
CN105645602A (en) * | 2016-03-30 | 2016-06-08 | 浙江大学 | Automatic fed-batch type efficient iron salt denitrification reaction device and automatic fed-batch type efficient iron salt denitrification reaction method for bacteria |
CN105776530A (en) * | 2016-04-22 | 2016-07-20 | 浙江大学 | Self-shelling malysite denitrification reaction device and self-shelling method |
CN105776530B (en) * | 2016-04-22 | 2018-05-29 | 浙江大学 | One kind is from shell molysite denitrogenation reactor and from shell method |
JP2018171550A (en) * | 2017-03-31 | 2018-11-08 | 住友重機械エンバイロメント株式会社 | Nitration denitrification system, and method for nitration denitrification treatment |
CN107879427A (en) * | 2017-08-28 | 2018-04-06 | 北京石油化工学院 | A kind of denitrogenation method based on interior circulation micro-electrolysis reaction |
CN107879427B (en) * | 2017-08-28 | 2021-02-19 | 北京石油化工学院 | Denitrification method based on internal circulation micro-electrolysis reaction |
CN107601775A (en) * | 2017-10-20 | 2018-01-19 | 新乡市绿丰环保工程有限公司 | High COD, low CN ratios a kind of waste water treatment process |
CN118324296A (en) * | 2024-01-31 | 2024-07-12 | 中国海洋大学 | Method for enhancing biological film activity and driving low-temperature low-carbon source to control nitrogen and reduce carbon |
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