CN1170780C - Method and reactor for eliminating nitate and nitrogen from drinking water - Google Patents
Method and reactor for eliminating nitate and nitrogen from drinking water Download PDFInfo
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- CN1170780C CN1170780C CNB001298518A CN00129851A CN1170780C CN 1170780 C CN1170780 C CN 1170780C CN B001298518 A CNB001298518 A CN B001298518A CN 00129851 A CN00129851 A CN 00129851A CN 1170780 C CN1170780 C CN 1170780C
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- denitrification
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- denitrification device
- heterotrophic
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Abstract
The present invention provides a method for eliminating nitrate and nitrogen from drinking water, which makes the heterotroph denitrification of extra nutrient sources and electrochemical autotrophy denitrification combined. The present invention also provides a reactor which eliminates the nitrate nitrogen in water, the reactor comprises a heterotrophic denitrification device of a fixed bed and a denitrification device of electrochemical autotrophy, and the two devices are connected in series. The nitrate-bearing drinking water which is processed by the method of the present invention and the reactor has more than 98% of denitrification efficiency, the content of the processed nitrite nitrogen in water is lower than 0.01 mg/l, and secondary pollution does not exist.
Description
Invention field
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 biological fixed-bed heterotrophic denitrification process that organic matter provides nutrition source and electrochemistry of will adding is produced the autotrophic denitrification process of hydrogen and combined and remove the method for nitrate nitrogen in the tap water, and in same reactor, realize the optimization of two kinds of processes and integrated.
Invention field
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 be with some organic matter as nutrition source, organism commonly used comprises methyl alcohol, ethanol and acetic acid etc.The advantage of this method is, optionally removes nitrate, is translated into harmless nitrogen, and no waste liquid produces, and processing costs is low.Shortcoming mainly is when organic matrix is not enough, has the nitrite accumulation phenomenon in the water outlet; And when organic matrix was excessive, the residual organic substrate in reaction back had secondary pollution to water outlet, either way required 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 denitrifying efficient is lower simultaneously.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 falling property 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.The main drawback that this method is compared with the heterotrophic denitrification method is that denitrification speed is slow, unit volume reactor for treatment ability is less.
Summary of the invention
The objective of the invention is: overcome the defective of existing method, the advantage of comprehensive utilization heterotrophism 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 that two kinds of processes of heterotrophic denitrification and electrochemistry product hydrogen autotrophic denitrification that will add nutrition source combine, and make heterotrophic denitrification device and electrochemical autotrophic denitrification device with series system work: after adding organic matters such as methyl alcohol in shortage, ethanol, formic acid, acetate in the former water, carrying out heterotrophic denitrification handles, remove the nitrate of the overwhelming majority, enter the electrochemical autotrophic denitrification device that the source of supporting is provided by electrolytic hydrogen production then, remove residual nitric acid salt, nitrite and organic radical thing.
The essential structure of reactor of the present invention as shown in Figure 1.Reactor is taked two sections placed in-line modes up and down, if current adopt the decline streaming, then the heterotrophic denitrification device of reactor is descending at last, electrochemical autotrophic denitrification device; If current adopt the rising streaming, then the heterotrophic denitrification device down, the electrochemical autotrophic denitrification device 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 1 is made of electrochemical autotrophic denitrification device 2 and fixed bed heterotrophic denitrification device 3 two portions, and the shared volume of electrochemical autotrophic denitrification device and the shared volume ratio of heterotrophic denitrification device of reactor are 1: 1-1: 5.The anode 4 of electrochemical autotrophic denitrification device 2 can adopt graphite cake, carbon fiber sheet, metallic nickel, metal titanium, titanium-ruthenium etc., preferred graphite cake; Negative electrode 5 can adopt stainless steel plate, iron plate, aluminium sheet, graphite cake, carbon fiber sheet, metallic nickel, metal titanium, titanium-ruthenium etc., preferred stainless steel plate.Each electrode adopts parallel being arranged in parallel, and polar plate spacing is 0.5-5cm, can guarantee can not be short-circuited phenomenon by make the measure of electrode fixed in reactor.Anode and negative electrode are connected to the positive pole and the negative pole of silicon commutating power supply 8 by lead 6 and 7.Heterotrophic denitrification device 3 suitable static bed biomembrane reactors of reactor, with the solid particulate 9 of particle diameter 1.8～4.0mm as filled media, as hard coal, activated carbon, quartz sand, zeolite etc., preferred hard coal and activated carbon.Contain NO
3 -Pending water 10 after adding organic matters such as methyl alcohol 11 or ethanol, formic acid, acetate, enter reactor by water transfer pump 12 and inlet valve 13.Water after the processing is discharged by water outlet 15.The nitrogen that produces in denitrification process is discharged by vapor pipe 16.In the time of need carrying out back flushing to fixed bed, provide institute's water by backwashing water valve 14.
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 32 ℃ in the process of medium biofilm, when being 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 13, open water transfer pump 12 then, add methyl alcohol 11, pending water 10 upwards enters electrochemical autotrophic denitrification device 2 by the fixed biologically bed heterotrophic denitrification device 3 of particulate materials such as filling hard coal, after water reaches certain water level, discharge from water outlet 15, this moment opening power 8, and adjustment voltage and current, reactor enters system's operation, and week post-reactor water outlet promptly obtains good and stable denitrification effect.When need carry out back flushing to the heterotrophic denitrification device fixed bed of reactor, stop organic the adding and water transfer pump 12 operations, close inlet valve 13, open backwashing water valve 14, adjusting backwash water flow carries out the cleaning of 5-20min.After back flushing is finished, valve-off 14, restarting systems.
Characteristics of the present invention are:
1. with heterotrophic denitrification and autotrophic denitrification integrated use, make two kinds of denitrification denitrification process integrated in a reactor;
2. based on heterotrophic denitrification, bring into play the fireballing advantage of heterotrophic denitrification as far as possible, and can regulate the dosage of organic substrate according to the situation of processed water;
3. when the water inlet nitrate concentration fluctuation occurs and makes organic substrate in shortage, the denitrifying capacity that utilizes the electrochemical autotrophic denitrification device of reactor to be had remedies this part deficiency;
4. when the fluctuation of water inlet nitrate concentration made organic substrate excessive, the oxidation capacity of utilizing electrochemical autotrophic denitrification device anode to be had was carried out oxidation removal to residual organic substrate;
5. because based on the heterotrophic denitrification process, power consumption reduces greatly;
6. not remaining organic pollutants of water outlet and nitrite, non-secondary pollution.
Brief Description Of Drawings
Fig. 1 represents reactor of the present invention.
Embodiment:
Example 1 adds granularity 1.8～2.0mm in volume is the reactor casing of 28L hard coal is a filling medium, and the medium charge volume is 15L; The upper strata is the electrochemical autotrophic denitrification device, and volume is 13L (containing the electrode area occupied).Processed former water is prepared by saltpetre, and the concentration of nitrate nitrogen is 40mg/l in the water.Carrying out denitration under the following conditions handles:
Electrode anode: graphite cake, 60 * 350 * 180mm, 22
Negative electrode: stainless steel plate, 10 * 350 * 180mm, 23
Interelectrode distance: 0.5cm
Strength of current: 0.7mA
Current density: 0.03mA/cm
2
Voltage: 1.8v
The maximum denitrification load of electrochemical autotrophic denitrification device: 0.0728g NO
3 --N/h.
Water inlet humidity: 24 ℃
Water inlet dissolved oxygen: 0.5mg/L
Flow: 17L/h
Current efficiency: 115%
The C of heterotrophic denitrification device: N (mg/mg): 2.7
It is as shown in table 1 to handle back water quality.
Water quality after table 1 embodiment 1 handles
NO
3 --N NO
2 -NO
3 --N removes electric current imitates methyl alcohol
(mg/L) (mg/L) rate (%) rate (%) is (mg/L)
Handle preceding 40 0 292
Handle back 0.1＜0.01 99.8 110 0.93mg/L
Example 2 adds granularity 1.8～2.0mm in volume is the reactor casing of 28L hard coal is a filling medium, and the medium charge volume is 15L; The upper strata is the electrochemical autotrophic denitrification device, and volume is 13L (containing the electrode area occupied).Processed former water is prepared by saltpetre, and the concentration of nitrate nitrogen is 40mg/l in the water.Carrying out denitration under the following conditions handles:
Electrode anode: graphite cake, 60 * 350 * 180mm, 22
Negative electrode: stainless steel plate, 10 * 350 * 180mm, 23
Interelectrode distance: 0.5cm
Strength of current: 0.7mA
Current density: 0.03mA/cm
2
Voltage: 1.8v
The maximum denitrification load of electrochemical autotrophic denitrification device: 0.0728g NO
3 --N/h.
Water inlet humidity: 24 ℃
Water inlet dissolved oxygen: 0.5mg/L
Flow: 17L/h
Current efficiency: 115%
The C of heterotrophic denitrification device: N (mg/mg): 2.9
It is as shown in table 2 to handle back water quality.
Water quality after table 2 embodiment 1 handles
NO
3 --N NO
2 -NO
3 --N removes electric current imitates methyl alcohol
(mg/L) (mg/L) rate (%) rate (%) is (mg/L)
Handle preceding 40 0 292
Handle back 0.04＜0.005 99.9 113 1.24
Claims (7)
1, a kind of method that removes nitrate nitrogen in the tap water, it is characterized in that, the two kinds of processes of heterotroph denitrification and electrochemical autotrophic denitrification that add nutrition source are combined, wherein, the heterotroph denitrification carries out as the heterotrophic denitrification nutrition source by adding methyl alcohol, ethanol, formic acid, acetate, and electrochemical autotrophic denitrification is to be undertaken by the nutrition source that electrolytic hydrogen production provides.
2, in accordance with the method for claim 1, wherein, heterotrophic denitrification is that to adopt hard coal, activated carbon, quartz sand or zeolite be that the fixed bed of filler carries out.
3, in accordance with the method for claim 1, 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.
4, a kind of reactor that removes nitrate nitrogen in the water, it is characterized in that, it comprises fixed bed heterotrophic denitrification device and electrochemical autotrophic denitrification device, heterotrophic denitrification device and electrochemical autotrophic denitrification device are taked two sections placed in-line modes up and down, and the shared volume of electrochemical autotrophic denitrification device and the shared volume ratio of heterotrophic denitrification device of reactor are 1: 1---and 1: 5.
5. according to the described reactor of claim 4, it is characterized in that, the heterotrophic denitrification device down, the electrochemical autotrophic denitrification device is last.
According to the described reactor of claim 4, it is characterized in that 6, the filler of the fixed bed of heterotrophic denitrification is hard coal, activated carbon, quartz sand or zeolite.
7, according to the described reactor of claim 4, it is characterized in that, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001298518A CN1170780C (en) | 2000-10-20 | 2000-10-20 | Method and reactor for eliminating nitate and nitrogen from drinking water |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001298518A CN1170780C (en) | 2000-10-20 | 2000-10-20 | Method and reactor for eliminating nitate and nitrogen from drinking water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1349934A CN1349934A (en) | 2002-05-22 |
| CN1170780C true CN1170780C (en) | 2004-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001298518A Expired - Fee Related CN1170780C (en) | 2000-10-20 | 2000-10-20 | Method and reactor for eliminating nitate and nitrogen from drinking water |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI449674B (en) * | 2004-12-14 | 2014-08-21 | Kurita Water Ind Ltd | Drainage treatment device and treatment method |
| 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 |
| CN102923854B (en) * | 2012-11-06 | 2014-03-12 | 沈阳建筑大学 | Method regarding wood chips as carbon source and for removing nitrate in underground water by using solid-phase heterotrophy and sulfur autotrophic integrated denitrification |
| CN102992544B (en) * | 2012-11-27 | 2014-03-12 | 中国科学院沈阳应用生态研究所 | Method and device for double-sectional treatment of nitrate-polluted drinking water through modified activated sludge |
| CN103359894B (en) * | 2013-08-06 | 2014-10-15 | 山东建筑大学 | Groundwater microbial denitrification system |
| CN105347625A (en) * | 2015-11-20 | 2016-02-24 | 中国地质大学（北京） | Method for removing nitrate in underground water and reactor |
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- 2000-10-20 CN CNB001298518A patent/CN1170780C/en not_active Expired - Fee Related
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