CN103420480B - A kind of anaerobism molysite biological denitrification process - Google Patents
A kind of anaerobism molysite biological denitrification process Download PDFInfo
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- CN103420480B CN103420480B CN201310341091.0A CN201310341091A CN103420480B CN 103420480 B CN103420480 B CN 103420480B CN 201310341091 A CN201310341091 A CN 201310341091A CN 103420480 B CN103420480 B CN 103420480B
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Abstract
The invention discloses a kind of anaerobism molysite biological denitrification process.Using denitrifying bacteria enrichment culture thing as biological catalyst, under anaerobic, being electron acceptor(EA) with nitrate, take ferrous salt as electron donor, is N in same reactor by nitrate reduction
2, ferrous salt is oxidized to ferric iron.The mol ratio of nitrate and ferrous salt is 1.0 ~ 5.0, and temperature of reaction is 20 ~ 35 DEG C, and pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0d.Advantage of the present invention is: be 1) electron donor with ferrous salt, take nitrate as electron acceptor(EA), the treatment of wastes with processes of wastes against one another, realizes the removal of nitre nitrogen pollutant and the utilization of ferrous salt waste; 2) without the need to providing organism, the problem of carbon source relative deficiency in wastewater biological denitrificaion process is effectively alleviated; 3) the ferrous salt oxidation products ferric iron of high value is reclaimed; 4) is treatable nitrate and ferrous salt concentration up to 1500mg? N/L and 30000mg? Fe/L.
Description
Technical field
The present invention relates to a kind of anaerobism molysite biological denitrification process.
Background technology
After " control source reduces discharging " is implemented in the whole nation, waste water organic contamination is effectively administered, and nitrate pollution rises to main environmental problem.According to " national Environmental statistics publication ", national wastewater emission amount 617.3 hundred million tons in 2010, chemical oxygen demand (COD) (COD) quantity discharged 1238.1 ten thousand tons, ammonia nitrogen quantity discharged 120.3 ten thousand tons.According to another " China Environmental State Bulletin ", within 2010, in 26 states's control emphasis lake (reservoir), IV class to bad V class water body accounts for 77%, and slightly account for 54% to severe eutrophic water body, main contamination index is total nitrogen.Nitrate pollution controls to have 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 this kind of low C:N than wastewater treatment, conventional waste water denitrification process (nitrification-denitrification technique) is aobvious weak, this is because denitrification process needs electron donor, is usually provided by organism.Carbon source relative deficiency has become the significant 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
6about t.At present, though have research ferrous salt is applied to fertilizer and flocculation agent production etc., demand is limited, and the overwhelming majority is still banked up everywhere as waste material, not only wastes resource, and severe contamination Soil Surrounding and water body environment bad.The comprehensive utilization of ferrous salt is extremely urgent.
Nitric acid salt form anaerobic ferrite oxidization (Nitrate-dependentAnaerobicFerrousOxidation, NAFO) be the great discovery of environment and microorganism field, namely under anaerobic, some microorganisms can take ferrous salt as electron donor, are N by nitrate or nitrate reductase
2.But have no and be applied to field of waste water treatment.If nitrate can be reduced accordingly using ferrous salt as electron donor, not only effectively can alleviate the problem of carbon source relative deficiency in wastewater biological denitrificaion process, realize denitrogenation of waste water; And can ferrous salt be made full use of, 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, provides a kind of anaerobism molysite biological denitrification process.
Anaerobism molysite biological denitrification process is: under anaerobic, using denitrifying bacteria enrichment culture thing as biological catalyst, is electron acceptor(EA) with nitrate, take ferrous salt as electron donor, is N in same reactor by nitrate reduction
2, ferrous salt is oxidized to ferric iron; Nitrate concentration is 20 ~ 1500mgN/L, and the concentration of ferrous salt is 100 ~ 30000mgFe/L, and the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 5.0, and temperature of reaction is 20 ~ 35 DEG C, and pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0d.
Described ferrous salt and the mol ratio of nitrate concentration are preferably 1.0 ~ 3.0.Described anaerobic condition should to control in reaction solution dissolved oxygen at below 0.5mg/L.Described temperature of reaction is preferably 28 ~ 33 DEG C.Described pH value in reaction is preferably 7.5 ~ 8.5.Described hydraulic detention time is preferably 1.0 ~ 1.5d.
Advantage of the present invention is: 1) using denitrifying bacteria enrichment culture thing as biological catalyst, sustainable use; 2) be electron acceptor(EA) with nitrate, take ferrous salt as electron donor, the treatment of wastes with processes of wastes against one another, realizes the removal of nitre nitrogen pollutant and making full use of of ferrous salt waste; 2) without the need to providing organism, the problem of carbon source relative deficiency in wastewater biological denitrificaion process is effectively alleviated; 3) the ferrous salt oxidation products ferric iron of high value can be reclaimed, realize Sustainable development; 4) treatable nitrate concentration is up to 1500mg/L, ferrous salt concentration up to 30000mg/L, maximum speed of reaction 0.35kgN/ (m
3d) with 9.81kgFe/ (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, nitrate sections oxidizing bacteria mixed training thing is obtained with a certain proportion of nitrate and ferrous salt enrichment, by mixing with the ferrous salt solution of preparation containing nitre nitrogen waste water from nitrator, pump in molysite biological denitrification reactor, generate N
2and ferric iron.The technological condition controlled is: nitrate concentration is 20 ~ 1500mgN/L, ferrous salt concentration is 100 ~ 30000mgFe/L, the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 5.0, dissolved oxygen concentration is below 0.5mg/L, temperature of reaction is 20 ~ 35 DEG C, pH value is 7.0 ~ 9.0, and hydraulic detention time is 0.5 ~ 2.0d.Take temperature bright to the fortune that this technique is done, the treatable nitrate concentration of molysite biological denitrification process up to 1500mg/L, ferrous salt concentration up to 30000mg/L, maximum speed of reaction 0.35kgN/ (m
3d) with 9.81kgFe/ (m
3d).
Embodiment 1
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:2 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 800mgFe/L, and dissolved oxygen concentration is 0.4mg/L, and temperature of reaction is 32 DEG C, and initial pH value is 7.0, and hydraulic detention time is 0.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt clearance reach 95.97% and 96.22% respectively.
Embodiment 2
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:5 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 2000mgFe/L, and dissolved oxygen concentration is 0.3mg/L, and temperature of reaction is 30 DEG C, and initial pH value is 7.3, and hydraulic detention time is 0.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, the volume elimination capacity of nitrate and ferrous salt reaches 0.18kgN/ (m respectively
3d) with 2.60kgFe/ (m
3d).
Embodiment 3
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:2 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 800mgFe/L, and dissolved oxygen concentration is 0.4mg/L, and temperature of reaction is 28 DEG C, and initial pH value is 8.0, and hydraulic detention time is 0.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt removal speed reach 0.17kgN/ (m respectively
3d) with 1.58kgFe/ (m
3d).
Embodiment 4
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:3 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 1500mgN/L and 18000mgFe/L, and dissolved oxygen concentration is 0.2mg/L, and temperature of reaction is 29 DEG C, and initial pH value is 7.0, and hydraulic detention time is 1.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, the volume removal speed of nitrate and ferrous salt reaches 0.28kgN/ (m respectively
3d) with 4.96kgFe/ (m
3d).
Embodiment 5
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:5 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 1500mgN/L and 30000mgFe/L, and dissolved oxygen concentration is 0.5mg/L, and temperature of reaction is 29 DEG C, and initial pH value is 7.0, and hydraulic detention time is 2.0d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, the volume removal speed of nitrate and ferrous salt reaches 0.34kgN/ (m respectively
3d) with 7.92kgFe/ (m
3d).
Embodiment 6
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:2 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 800mgFe/L, and dissolved oxygen concentration is 0.3mg/L, and temperature of reaction is 20 DEG C, and initial pH value is 7.0, and hydraulic detention time is 0.5d.This technique can remove 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 molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:2 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 800mgFe/L, and dissolved oxygen concentration is 0.3mg/L, and temperature of reaction is 30 DEG C, and initial pH value is 9.0, and hydraulic detention time is 0.5d.This technique can remove 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 molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:2 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 800mgFe/L, and dissolved oxygen concentration is 0.3mg/L, and temperature of reaction is 35 DEG C, and initial pH value is 7.0, and hydraulic detention time is 0.5d.This technique can remove 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 molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:1 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 100mgN/L and 400mgFe/L, and dissolved oxygen concentration is 0.2mg/L, and temperature of reaction is 32 DEG C, and initial pH value is 7.1, and hydraulic detention time is 0.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, the volume elimination capacity of nitrate and ferrous salt reaches 0.20kgN/ (m respectively
3d) with 0.73kgFe/ (m
3d).
Embodiment 10
In molysite biological denitrification reactor, with denitrifying bacteria enrichment culture thing for biological catalyst, the simulated wastewater being 1:1.25 with the mol ratio of nitrate and ferrous salt concentration, runs molysite biological denitrification reactor.The technological condition controlled is: the concentration of nitrate and ferrous salt is respectively 20mgN/L and 100mgFe/L, and dissolved oxygen concentration is 0.3mg/L, and temperature of reaction is 31 DEG C, and initial pH value is 7.3, and hydraulic detention time is 0.5d.This technique can remove nitrate and ferrous salt simultaneously, and in water outlet, nitrate and ferrous salt removal speed reach 0.019kgN/ (m respectively
3d) with 0.195kgFe/ (m
3d).
Claims (1)
1. an anaerobism molysite biological denitrification process, is characterized in that: under anaerobic, and using denitrifying bacteria enrichment culture thing as biological catalyst, being electron acceptor(EA) with nitrate, take ferrous salt as electron donor, is N in same reactor by nitrate reduction
2, ferrous salt is oxidized to ferric iron, and nitrate concentration is 20 ~ 1500mgN/L, and the concentration of ferrous salt is 100 ~ 30000mgFe/L, and the mol ratio of ferrous salt and nitrate concentration is 1.0 ~ 3.0, and anaerobic condition should to control in reaction solution dissolved oxygen at below 0.5mg/L; Temperature of reaction is 28 ~ 33 DEG C, and pH value in reaction is 7.5 ~ 8.5, and hydraulic detention time is 1.0 ~ 1.5d.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693806B (en) * | 2013-12-06 | 2014-11-19 | 浙江大学 | Authigenic ferric salt chemical phosphorus removal-anaerobic ferrous oxidization biological denitrification integrated device |
| CN105600923B (en) * | 2015-11-15 | 2019-01-11 | 农业部沼气科学研究所 | The biological denitrification process of high ammonia-nitrogen wastewater |
| CN105645602B (en) * | 2016-03-30 | 2018-02-16 | 浙江大学 | A kind of strain gravity flow plus the efficient molysite denitrogenation reactor of formula and its 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 |
| JP6889586B2 (en) * | 2017-03-31 | 2021-06-18 | 住友重機械エンバイロメント株式会社 | Nitrification denitrification system and nitrification denitrification treatment method |
| 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 |
Citations (3)
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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 |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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