CN1403389A - Integral electrochemical denitration method and reactor - Google Patents
Integral electrochemical denitration method and reactor Download PDFInfo
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- CN1403389A CN1403389A CN 01130845 CN01130845A CN1403389A CN 1403389 A CN1403389 A CN 1403389A CN 01130845 CN01130845 CN 01130845 CN 01130845 A CN01130845 A CN 01130845A CN 1403389 A CN1403389 A CN 1403389A
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Abstract
The present invention provides one kind of method of elimianting nitrate nitrogen from drinking water to combine two chemical processes of sulfuric autotrophic denitrification and electrochemical autotrophic denitrification. One reactor to eliminate nitrate nitrogen from water is also provided, and it includes sulfuric autotrophic denitrification unit and electrochemical autotrophic denitrifcation unit connected serially together. The present invention has a denitrification efficiency as high as 98% and the drinking water after treated by means of the method and reactor has nitrite nitrogen content lower than 0.01 mg/L and no secondary pollution.
Description
The present invention relates to a kind of method and reactor of removing nitrate nitrogen in the tap water, specifically be that a kind of autotrophic denitrification process that sulphur autotrophic denitrification process and electrochemistry are produced hydrogen combines and removes the method for nitrate nitrogen in the tap water, and in same reactor, realize the optimization of two kinds of processes and integrated.
Nitrate nitrogen mainly contains ion exchange method, membrane separation process, biological denitrification method etc. in the removal water.The biological denitrification method is because process is simple, efficient is higher, is considered to the most promising tap water method of denitration.Because tap water lacks nutrition source, when the nitrate of removing with the denitrification method in the water, need add the trophoplasm of capacity in some way.Therefore, biological denitrification is divided into heterotrophic denitrification and autotrophic denitrification because of the difference of the nutritive substance that provided again.The heterotrophic denitrification method requires to be purified by subsequent disposal.The autotrophic denitrification method mainly is to adopt sulphur or hydrogen as electron donor.Remove nitrate with sulphur as the autotrophy source is alternative, and cost is lower, economical convenient.But the greatest drawback of this method is a sulphur is oxidized to sulfate radical, causes the water outlet sulphate content to increase; And do not add lime carbonate and regulate, can cause water outlet H
+Raise, the pH value descends.Carry out autotrophic denitrification optionally removing in the water in the nitrate nitrogen with hydrogen as reductive agent, can protect no any secondary pollution, need not extra biopurification after the processing.But be easy to blast by the external source hydrogen supply, and the hydrogen cost is higher.Adopting electrolysis process to produce hydrogen for the autotrophic denitrification process provides nutrition source, is a kind of cleaning and effective means.Specifically be to be anode with the noble electrode, metals such as iron or aluminium are the electrolysis reactor that negative electrode is made a double oxygen, after water is by reactor and energising, just provide hydrogen for biological denitrification process.Simultaneously can be filled in electrolysis reactor, improve electrolytic efficiency.
The objective of the invention is: overcome the defective of existing method, the advantage of comprehensive utilization sulphur autotrophy and electrolytic hydrogen production autotrophic denitrification is set up a kind of denitration novel method of tap water safely and efficiently and integrated reactor.
Method of the present invention is sulphur autotrophic denitrification and electrochemistry to be produced two kinds of processes of hydrogen autotrophic denitrification combine, and make sulphur autotrophy section and electrochemical autotrophic section with one or more levels series system work: former water carries out the sulphur autotrophic denitrification to be handled, remove the suitably nitrate of part, by water outlet sulfate radical control ratio, enter the electrochemical autotrophic denitrification section that the source of supporting is provided by electrolytic hydrogen production then, remove a small amount of organic matter in residual nitric acid salt, nitrite and the former water.
The essential structure of reactor of the present invention as shown in drawings.Reactor is taked two sections placed in-line modes up and down, if current adopt the decline streaming, then the sulphur autotrophy section of reactor was descended in last, the electrochemical term; If current adopt the rising streaming, then sulphur autotrophy section down, the electrochemical term is last.Considering has gas (nitrogen, carbonic acid gas, hydrogen etc.) produces in the reaction, can discharge smoothly for making gas, should adopt the rising streaming.
Integrated Benitration reactor is made of electrification term autotrophic organism reactor I and fixed bed sulphur autotrophic organism reactor II two portions, and the shared volume of electrochemical autotrophic section of reactor and the shared volume ratio of sulphur autotrophy section are 1: 2-1: 5.
The anode 5 of electrification term I can adopt graphite rod, carbon fiber rod, metallic nickel, metal titanium, titanium-ruthenium etc., preferred graphite rod; Negative electrode 4 can adopt stainless steel cylinder, work durm, aluminum barrel, graphite tube, carbon fiber tube, metallic nickel, metal titanium, titanium-ruthenium etc., preferred stainless steel cylinder.Anode bar places central authorities, and negative electrode is close to reactor wall or negative electrode directly as reactor wall, and interpole gap is 1-5cm.Anode and negative electrode are connected to the positive pole and the negative pole of silicon commutating power supply 1 by lead 12 and 13.Can load particle diameter between electrode and be the particle 7 of 1.8～4.0mm and do filled media, as hard coal, gac.
Do the suitable static bed biomembrane reactor of sulphur autotrophy section II of reactor, with the solid particulate 8 of particle diameter 2.0～6.0mm as filled media, as sulphur simple substance particle or the sulphur particle alternate with lime carbonate.Contain NO
3 -Pending water 14 enter reactor by transferpump 11 and inlet valve 15.Water after the processing is discharged by water outlet 3.The nitrogen that produces in denitrification process is discharged by vapor pipe 2.In the time of need carrying out back flushing to fixed bed, provide institute's water by backwashing water valve 16.
Reactor assembly operating process of the present invention is as follows:
At first inoculate, culturing bacterium, and make the medium biofilm, in this stage, add organic matters such as competent methyl alcohol, ethanol, formic acid, acetate, temperature keeps 30 ℃ in the process of medium biofilm, is matrix with methyl alcohol, the ratio C of methyl alcohol and nitrate nitrogen: N (mg/mg)=3 is with K
2HPO
3And KH
2PO
3For the pH value in the pH buffer reagent guarantee system maintains about 7, and suitable trace element supplement.This process carry out after fortnight can be on the reactor lower part filler and upper electrode surface observe clearly biofilm phenomenon.Intake by reactor mode shown in the drawings subsequently: at first open inlet valve 15, open water transfer pump 11 then, processed water 14 upwards enters electrochemical autotrophic biological denitrification section I by sulphur autotrophic denitrification section II, after water reaches certain water level, discharge the voltage and current of opening power 8, and adjustment at this moment from water outlet 3, reactor enters system's operation, and fortnight post-reactor water outlet promptly obtains good and stable denitrification effect.When need carry out back flushing to the whole reactor fixed bed, stop water transfer pump 11 operations, close inlet valve 15, open backwashing water valve 16, regulate the backwash water flow, carry out the cleaning of 1-5min.After back flushing is finished, valve-off 16, restarting systems.
Characteristics of the present invention are:
1. with sulphur autotrophic denitrification and the integrated use of hydrogen autotrophic denitrification, make two kinds of denitrification denitrification process integrated in a reactor;
2. can carry out two sections or multistage combination according to water quality, can apply in a flexible way.
3. based on the sulphur autotrophic denitrification, bring into play the cheap easily advantage of row of sulphur autotrophic denitrification as far as possible, and can regulate the height of sulphur section, make the water outlet sulfate radical be lower than national standard according to the situation of processed water.
4. owing to the electrification term needs H
+, the H that sulphur autotrophy section produces
+Favourable electrochemical reaction, the lime carbonate of traditional sulphur section can reduce consumption or not add.
5. when fluctuation appears in the water inlet nitrate concentration, utilize the denitrifying capacity that the electrochemical term had of reactor that this part deficiency is remedied; Effluent quality is unaffected.
6. when water inlet contained organic substrate, the oxidation capacity of utilizing electrification term anode to be had was carried out oxidation removal to it;
7. because sulphur autotrophy section accounts for significant proportion, power consumption reduces greatly;
8. not remaining organic pollutants of water outlet and nitrite, non-secondary pollution.
Embodiment:
Example 1 adds granularity 3.0～4.0mm in volume is the reactor cylinder of 1.477L (the synthetic glass post of the long 355mm of internal diameter 7.28mm) sulphur simple substance and lime carbonate are filling medium, insert after the two mixes, and the medium charge volume is 0.848L; The upper strata is the electrification term, and volume is 0.515L (not containing the shared volume of electrode), does not have the filling material in the electrification term.Processed former water is prepared by SODIUMNITRATE, and the concentration of nitrate nitrogen is 30mg/L in the water.Carrying out denitration under the following conditions handles:
Electrode anode: carbon-point, diameter 25mm, long 140mm.
Negative electrode: stainless steel cylinder, internal diameter 72.8mm, long 160mm.
Interelectrode distance: 2.39cm
Strength of current: 3mA
Current density: 0.01mA/cm
2
Voltage: 1.9V
The maximum denitrification load of electrification term: 0.128g NO
3 --N/h.
Temperature: 30 ℃
Water inlet dissolved oxygen: 0.5mg/L
Hydraulic detention time: 4h
Current efficiency: 95.9% processing back water quality is as shown in table 1.
Water quality after table 1 embodiment 1 handles
Example 2 adds granularity 3.0～4.0mm in volume is the reactor cylinder of 1.469L (the synthetic glass post of the long 353mm of internal diameter 7.28mm) sulphur simple substance is filling medium, and the medium charge volume is 0.839L; The upper strata is the electrification term, and volume is 0.515L (not containing the shared volume of electrode); The electrification term there is not the filling material.Processed former water is prepared by saltpetre, and the concentration of nitrate nitrogen is 30mg/L in the water.Carrying out denitration under the following conditions handles:
Electrode anode: carbon-point, diameter 25mm, long 140mm.
Negative electrode: stainless steel cylinder, internal diameter 72.8mm, long 160mm.
Interelectrode distance: 2.39cm
Strength of current: 3.4mA
Current density: 0.011mA/cm
2
Voltage: 2.0V
The maximum denitrification load of electrification term: 0.506g NO
3 --N/h.
Temperature: 30 ℃
Water inlet dissolved oxygen: 0.5mg/L
Hydraulic detention time: 3.4h
Current efficiency: 98% processing back water quality is as shown in table 2.
Water quality after table 2 embodiment 2 handles
Claims (11)
1, a kind of method that removes nitrate nitrogen in the tap water is characterized in that, two kinds of processes of sulphur autotrophic denitrification and electrochemical autotrophic denitrification are combined.
2, in accordance with the method for claim 1, wherein, the sulphur autotrophic denitrification is to carry out denitrifying by elemental sulfur as electron donor.
3, in accordance with the method for claim 1, wherein, electrochemical autotrophic denitrification is to be undertaken by the nutrition source that electrolytic hydrogen production or three-diemsnional electrode product hydrogen provide.
4, in accordance with the method for claim 2, wherein, the sulphur autotrophic denitrification is that to adopt sulfur granules and lime carbonate be that the fixed bed of filler carries out.The two ratio of sulfur granules and lime carbonate is 3: 1～1: 0.
5, in accordance with the method for claim 3, wherein, electrochemical autotrophic denitrification is to adopt graphite cake, carbon fiber sheet, metallic nickel, metal titanium or titanium-ruthenium to make anode, and stainless steel plate, iron plate, aluminium sheet, graphite cake, carbon fiber sheet, metallic nickel, metal titanium or titanium-ruthenium do that the electrolyzer of negative electrode carries out.
6, in accordance with the method for claim 3, the electrolyzer of electrochemical autotrophic denitrification can be dosed the filler of hard coal, gac or the easy settled organism of other good conductivity between electrode.
7, a kind of reactor that removes nitrate nitrogen in the water is characterized in that, it comprises sulphur autotrophic denitrification device and electrochemical autotrophic denitrification device, and the two is cascaded or the two alternately is cascaded.
8. according to the described reactor of claim 7, it is characterized in that, sulphur autotrophic denitrification device down, electrochemistry denitrification device is last.Also can between two devices, replace simultaneously interspersed stream oriented device.
According to the described reactor of claim 7, it is characterized in that 9, the filler of the denitrifying fixed bed of sulphur is elemental sulfur and lime carbonate.The two ratio of sulfur granules and lime carbonate is 3: 1～1: 0.
10, according to the described reactor of claim 7, anode in the electrochemical autotrophic denitrification device is made by graphite cake, carbon fiber sheet, metallic nickel, metal titanium or titanium-ruthenium, and negative electrode is made by stainless steel plate, iron plate, aluminium sheet, graphite cake, carbon fiber sheet, metallic nickel, metal titanium or titanium-ruthenium.
11,, it is characterized in that the electrolyzer of electrochemical autotrophic denitrification can dose the filler of hard coal, gac or the easy settled organism of other good conductivity between electrode according to the described reactor of claim 7.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267763A (en) * | 2010-06-04 | 2011-12-07 | 国立成功大学 | Water-permeable electrochemical microbial reactive barrier and application method thereof |
| CN102126789B (en) * | 2010-01-18 | 2013-03-27 | 中国科学院沈阳应用生态研究所 | Method and device for removing nitrates from drinking water |
| CN101624226B (en) * | 2008-07-11 | 2013-05-08 | 中国科学院生态环境研究中心 | Method and reactor for removing nitrate through catalytic electrochemical biological hydrogen autotrophic denitrification |
| CN103183402A (en) * | 2013-04-21 | 2013-07-03 | 北京工业大学 | Reinforced nitrogen and phosphorus removal method suitable for reclaimed water with low carbon nitrogen ratio |
| CN103193301A (en) * | 2013-04-27 | 2013-07-10 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
| CN104829065A (en) * | 2015-05-19 | 2015-08-12 | 东华大学 | Device for intensifying artificial wetland integrating nitrification and denitrification by virtue of self-driven micro-electric field |
| CN105776759A (en) * | 2016-04-18 | 2016-07-20 | 浙江艾摩柯斯环境科技有限公司 | Alkalinity self-regulating efficient anaerobic iron oxidation denitrification reactor and method thereof |
| CN108499567A (en) * | 2018-04-04 | 2018-09-07 | 中国科学技术大学 | The restoring method of nitrate under a kind of normal temperature and pressure |
| CN110156146A (en) * | 2019-04-25 | 2019-08-23 | 青岛理工大学 | Biomembrane electrochemical reactor that is a kind of while removing nitrate nitrogen and micro-content organism in water removal |
| CN112607847A (en) * | 2020-11-19 | 2021-04-06 | 西北工业大学 | Sewage nitrogen and phosphorus removal treatment method, device and application |
| CN112794553A (en) * | 2020-12-22 | 2021-05-14 | 哈尔滨工创环保科技有限公司 | Device for treating coal pyrolysis wastewater through micro-electric field coupling sulfur autotrophic denitrification and method for treating coal pyrolysis wastewater by using device |
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| CN108946917B (en) * | 2018-06-21 | 2020-12-29 | 南京大学 | Enhanced sulfur autotrophic denitrification sewage deep denitrification device and method |
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2001
- 2001-08-27 CN CNB011308451A patent/CN1162356C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624226B (en) * | 2008-07-11 | 2013-05-08 | 中国科学院生态环境研究中心 | Method and reactor for removing nitrate through catalytic electrochemical biological hydrogen autotrophic denitrification |
| CN102126789B (en) * | 2010-01-18 | 2013-03-27 | 中国科学院沈阳应用生态研究所 | Method and device for removing nitrates from drinking water |
| CN102267763A (en) * | 2010-06-04 | 2011-12-07 | 国立成功大学 | Water-permeable electrochemical microbial reactive barrier and application method thereof |
| CN102267763B (en) * | 2010-06-04 | 2014-04-16 | 国立成功大学 | Water-permeable electrochemical microbial reactive barrier and application method thereof |
| CN103183402A (en) * | 2013-04-21 | 2013-07-03 | 北京工业大学 | Reinforced nitrogen and phosphorus removal method suitable for reclaimed water with low carbon nitrogen ratio |
| CN103183402B (en) * | 2013-04-21 | 2014-09-03 | 北京工业大学 | Reinforced nitrogen and phosphorus removal method suitable for reclaimed water with low carbon nitrogen ratio |
| CN103193301A (en) * | 2013-04-27 | 2013-07-10 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
| CN103193301B (en) * | 2013-04-27 | 2014-07-30 | 国电环境保护研究院 | Electrochemical reactor for processing nitrogenous organic wastewater, and application and processing method thereof |
| CN104829065A (en) * | 2015-05-19 | 2015-08-12 | 东华大学 | Device for intensifying artificial wetland integrating nitrification and denitrification by virtue of self-driven micro-electric field |
| CN104829065B (en) * | 2015-05-19 | 2016-11-02 | 东华大学 | The device of integration nitration denitrification self-driven electric microfield strengthened artificial wet land |
| CN105776759A (en) * | 2016-04-18 | 2016-07-20 | 浙江艾摩柯斯环境科技有限公司 | Alkalinity self-regulating efficient anaerobic iron oxidation denitrification reactor and method thereof |
| CN105776759B (en) * | 2016-04-18 | 2018-11-30 | 浙江艾摩柯斯环境科技有限公司 | The efficient anaerobic iron oxidation process denitrification reactor and its method of basicity Self-controlled |
| CN108499567A (en) * | 2018-04-04 | 2018-09-07 | 中国科学技术大学 | The restoring method of nitrate under a kind of normal temperature and pressure |
| CN108499567B (en) * | 2018-04-04 | 2020-06-26 | 中国科学技术大学 | Method for reducing nitrate at normal temperature and normal pressure |
| CN110156146A (en) * | 2019-04-25 | 2019-08-23 | 青岛理工大学 | Biomembrane electrochemical reactor that is a kind of while removing nitrate nitrogen and micro-content organism in water removal |
| CN110156146B (en) * | 2019-04-25 | 2021-09-07 | 青岛理工大学 | Biological membrane electrochemical reactor for simultaneously removing nitric acid nitrogen and trace organic matters in water |
| CN112607847A (en) * | 2020-11-19 | 2021-04-06 | 西北工业大学 | Sewage nitrogen and phosphorus removal treatment method, device and application |
| CN112794553A (en) * | 2020-12-22 | 2021-05-14 | 哈尔滨工创环保科技有限公司 | Device for treating coal pyrolysis wastewater through micro-electric field coupling sulfur autotrophic denitrification and method for treating coal pyrolysis wastewater by using device |
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