CN101805065A - Method for remediating pollution of nitrate nitrogen in underground water - Google Patents
Method for remediating pollution of nitrate nitrogen in underground water Download PDFInfo
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- CN101805065A CN101805065A CN201010144839A CN201010144839A CN101805065A CN 101805065 A CN101805065 A CN 101805065A CN 201010144839 A CN201010144839 A CN 201010144839A CN 201010144839 A CN201010144839 A CN 201010144839A CN 101805065 A CN101805065 A CN 101805065A
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Abstract
The invention relates to a method for remediating pollution of nitrate nitrogen in underground water, which mainly comprises the following steps: firstly, preparing Fe/Cu nanoparticles by liquid phase reduction step by step: under the protection of argon gas, reducing a FeSO4.7H2O solution with a KHB4 solution to prepare FeO nanoparticles, then introducing a CuSO4.5H2O solution into the FeO nanoparticles for continuously stirring for reacting, after reacting, washing the nano Fe/Cu solution with deoxidized and deionized water, and then, selecting the Fe/Cu nanoparticles by a magnetic method; secondly, introducing the deoxidized reaction solution into the prepared Fe/Cu nanoparticles for physically mixing simply; and finally, adding underground water containing nitrate nitrogen and sealing to carry out oscillating reaction. The method has high efficiency for remediating pollution of nitrate nitrogen in underground water, has simple required equipment and convenient operation, and provides a new way for remediating pollution of nitrate nitrogen in underground water with high efficiency and low cost.
Description
Technical field
The present invention relates to a kind of method of repairing pollution of nitrate nitrogen in underground water.Specifically utilize the denitrification of the chemical reduction effect of nanometer Fe/Cu and denitrifying bacteria (Alcaligenes eutrophus) to remove the method for nitrate nitrogen in underground water jointly.
Background technology
Nitrate nitrogen is mainly derived from resident living sewage and form garbage and dejection, chemical fertilizer, trade effluent, atmospheric nitrogen oxygen compound dried wet deposition and sewage irrigation etc.All closely related with the pollution of nitrate nitrogen in view of the generation of present human numerous disease, as cancer, methemoglobinemia, lymphoma or the like, therefore, the research of carrying out nitrate in groundwater nitrogen recovery technique more and more receives publicity.
The technology that is used at present the nitrate nitrogen reparation both at home and abroad mainly contains biological denitrification, ion-exchange, reverse osmosis and chemical reduction etc.; Wherein not only cost is high but also be difficult to reach the purpose of real removal pollutent for physico-chemical process such as ion-exchange and reverse osmosis, just to a certain extent, pollutent has been carried out simple phase transition or concentrates; Chemical reduction method mainly by adding reagent and pollutent reacts, although can reach the purpose of removing pollutent fully, easily causes secondary pollution.But the nitrate nitrogen in the work proof bimetal nano Fe/Cu fast restore underground water is arranged, but its product is mainly ammonia nitrogen, has only the smaller portions nitrate nitrogen to be converted into nitrogen.In addition, studies show that in a large number that the biological denitrification technology can perform well in the reparation of nitrate nitrogen in underground water, and it is lower that ammonia nitrogen generates ratio, but also exist many problems, such as, heterotrophic denitrification easily causes organic residual, causes that ground water aquifer stops up; And autotrophic denitrification adopts H usually
2As electron donor, but because H
2Inflammable and explosive characteristic makes that also difficulty increases in the operating process, and cost improves.This shows that above-mentioned multiple recovery technique is handled nitrate nitrogen in underground water if use separately, all has deficiency to a certain extent.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of repairing pollution of nitrate nitrogen in underground water is provided, this method is degrade nitrate nitrogen fast, and can make product ammonia nitrogen generation ratio reduce again, is a kind of low basis treatment process efficiently.
The present invention is achieved through the following technical solutions:
A kind of method of repairing pollution of nitrate nitrogen in underground water, this method may further comprise the steps:
(1) nanometer Fe
0The preparation of particle
With FeSO
47H
2O is dissolved in the ethanol-water system that PEG-4000 is a dispersion agent, feeds the argon gas deoxygenation, adds KBH then
4The aqueous solution, stir while dripping, drip and finish the back and continue stirring reaction 40～60min, obtain the nanometer Fe of black
0Solution; Select nanometer Fe with magnetic method
0Particle is used the deoxidation deionized water wash;
(2) preparation of nanometer Fe/Cu particle
With CuSO
45H
2The aqueous solution of O joins nanometer Fe
0In the particle, continue stirring reaction and prepare nanometer Fe/Cu particle;
(3) preparation of reaction solution
In denitrifying bacteria bacterium liquid and nutrient solution, add deionized water dilution preparation feedback liquid;
(4) preparation of reaction system
To import to preparation feedback system in nanometer Fe/Cu particle after the reaction solution deoxidation, the concentration of nanometer Fe/Cu particle is 0.4～0.7g/L;
(5) oscillatory reaction
Add the underground water contain nitrate nitrogen in reaction system, concentration is controlled at 30～70mg/L, and regulating pH is 6.5～8.6, and temperature is controlled at 30 ℃ and rotating speed and is controlled at 140～160rpm, seals and carries out oscillatory reaction.
And, described FeSO
47H
2O and PEG-4000 mass ratio are 1: 2～2: 1.
And in the described ethanol-water system, ethanol and water volume ratio are 1: 4～2: 5.
And, described FeSO
47H
2O and KBH
4Mol ratio is 1: 5～2: 5.
And the Cu charge capacity mass percent of described nanometer Fe/Cu particle is 1～20%.
And described denitrifying bacteria bacterium liquid, nutrient solution and deionized water volume ratio are 2: 1: 13～7: 2: 13, and the denitrifying bacteria bacterium is denitrifying bacteria bacterium liquid OD wherein
420Be 0.0027～0.0058.
Advantage of the present invention and beneficial effect are:
Technology required equipment of the present invention is simple, easy to operate, can remove the nitrate nitrogen in the underground water fast, and ammonia nitrogen generation ratio is lower, has received the treatment effect of low-cost high-efficiency.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is nitrate nitrogen effect comparison diagram in the present invention and other the independent technology removal water;
Fig. 3 is the generation situation of ammonia nitrogen behind the present invention and other independent technology removal nitrate nitrogens;
Fig. 4 removes nitrate nitrogen effect comparison diagram for the present invention under nanometer Fe/Cu different Cu charge capacity condition;
Fig. 5 generates situation for the present invention's ammonia nitrogen after removing nitrate nitrogen under nanometer Fe/Cu different Cu charge capacity condition;
Fig. 6 is nitrate nitrogen effect comparison diagram in the present invention and other United Technologies removal water;
Fig. 7 is the generation situation of ammonia nitrogen behind the present invention and other United Technologies removal nitrate nitrogens.
Embodiment
The present invention is described in further detail in conjunction with the accompanying drawings by following examples, but the technology contents that present embodiment is narrated is illustrative, rather than determinate, should not limit to protection scope of the present invention according to this.
A kind of method of repairing pollution of nitrate nitrogen in underground water, this method may further comprise the steps:
(1) nanometer Fe
0The preparation of particle
With FeSO
47H
2O is dissolved in the ethanol-water system that PEG-4000 is a dispersion agent, feeds the argon gas deoxygenation, adds KBH then
4The aqueous solution, stir while dripping, drip and finish the back and continue stirring reaction 40～60min, obtain the nanometer Fe of black
0Solution; Select nanometer Fe with magnetic method
0Particle is used the deoxidation deionized water wash;
(2) preparation of nanometer Fe/Cu particle
With CuSO
45H
2The aqueous solution of O joins nanometer Fe
0In the particle, continue stirring reaction and prepare nanometer Fe/Cu particle;
(3) preparation of reaction solution
In denitrifying bacteria bacterium liquid and nutrient solution, add deionized water dilution preparation feedback liquid;
(4) preparation of reaction system
To import to preparation feedback system in nanometer Fe/Cu particle after the reaction solution deoxidation, the concentration of nanometer Fe/Cu particle is 0.4～0.7g/L;
(5) oscillatory reaction
Add the underground water contain nitrate nitrogen in reaction system, regulating pH is 6.5～8.6, and temperature is controlled at 30 ℃ and rotating speed and is controlled at 140～160rpm, seals and carries out oscillatory reaction.
Described FeSO
47H
2O and PEG-4000 mass ratio are 1: 2～2: 1.
In the described ethanol-water system, ethanol and water volume ratio are 1: 4～2: 5.
Described FeSO
47H
2O and KBH
4Mol ratio is 1: 5～2: 5.
The Cu charge capacity mass percent of described nanometer Fe/Cu particle is 1～20%.
Described denitrifying bacteria bacterium liquid, nutrient solution and deionized water volume ratio are 2: 1～7: 2, wherein denitrifying bacteria bacterium liquid OD
420Be 0.0027～0.0058.
The nutrient solution composition is: 15.000g/L NaHCO
3, 3.036g/L NaNO
3, 0.975g/LKH
2PO
4, and trace element solution, wherein micro-component is: 0.52mg/L ZnCl
2, 1.90mg/LCoCl
26H
2O, 1.00mg/L MnSO
47H
2O, 0.24mg/L NiCl
26H
2O, 0.29mg/LCuCl
22H
2O, 0.36mg/L Na
2MoO
42H
2O and 0.30mg/L H
3BO
3
Embodiment 1:
Adopting present method is that the nitrate nitrogen of 30mg/L is removed to underground water concentration.Wherein prepare nanometer Fe/used FeSO of Cu particle
47H
2O and KBH
4Mol ratio be 1: 3, PEG-4000 and FeSO
47H
2The O mass ratio is 1: 2, and the alcohol-water volume ratio is 1: 4, and its stirring reaction time is 50min, and nanometer Fe/Cu particle dosage is 0.40g/L (the Cu charge capacity is 10%), adds denitrifying bacteria bacterium liquid (OD then
420=0.0027): nutrient solution: the volume ratio of deionized water is 5: 2: 13, carry out simple physical and mix, and sealing, regulator solution pH=8.6 carries out oscillatory reaction, and its temperature is controlled at 30 ℃, and rotating speed is 140rpm.Sampling regularly, analytical reaction thing NO
3 --N and product NH
4 +-N content over time.Analytical procedure is: NO
3 --N: ultraviolet spectrophotometry; NH
4 +-N: nessler reagent spectrophotometry.Analytical results as shown in Figures 2 and 3, therefrom nanometer Fe/Cu-denitrifying bacteria combination treatment technology obviously is better than treatment technology that their use separately as can be seen.
Embodiment 2:
Adopting present method is that the nitrate nitrogen of 50mg/L is removed to underground water concentration.Wherein prepare nanometer Fe/used FeSO of Cu particle
47H
2O and KBH
4Mol ratio be 1: 5, PEG-4000 and FeSO
47H
2The O mass ratio is 1: 1, and the alcohol-water volume ratio is 2: 5, and its stirring reaction time is 40min, and nanometer Fe/Cu particle dosage is 0.57g/L (a different Cu charge capacity), adds denitrifying bacteria bacterium liquid (OD then
420=0.0046): nutrient solution: the volume ratio of deionized water is 7: 2: 13, carry out simple physical and mix, and sealing, regulator solution pH=7.5 carries out oscillatory reaction, and its temperature is controlled at 30 ℃, and rotating speed is 150rpm.Sampling regularly, analytical reaction thing NO
3 --N and product NH
4 +-N content over time.Analytical procedure is: NO
3 --N: ultraviolet spectrophotometry; NH
4 +-N: nessler reagent spectrophotometry.Analytical results as shown in Figure 4 and Figure 5, therefrom 1%Cu charge capacity Fe/Cu-denitrifying bacteria system, 5%Cu charge capacity Fe/Cu-denitrifying bacteria system, 10%Cu charge capacity Fe/Cu-denitrifying bacteria system, 20%Cu charge capacity Fe/Cu-denitrifying bacteria system were removed nitrate nitrogen in 7 days, 8 days, 8 days and 9 days respectively fully as can be seen, and the ratio that generates ammonia nitrogen simultaneously is respectively 75%, 39%, 45% and 67%.
Embodiment 3:
Adopting present method is that the nitrate nitrogen of 70mg/L is removed to underground water concentration.Wherein prepare nanometer Fe/used FeSO of Cu particle
47H
2O and KBH
4Mol ratio be 2: 5, PEG-4000 and FeSO
47H
2The O mass ratio is 2: 1, and the alcohol-water volume ratio is 1: 3, and its stirring reaction time is 60min, and nanometer Fe/Cu particle dosage is 0.70g/L (the Cu charge capacity is 5%), and the Ni charge capacity is that nanometer Fe/Ni particle dosage of 5% is 0.70g/L, nanometer Fe
0The particle dosage is 0.70g/L.Add denitrifying bacteria bacterium liquid OD then
420=0.0053: nutrient solution: the volume ratio of deionized water is 2: 1: 13, carry out simple physical and mix, and sealing, regulator solution pH=6.5 carries out oscillatory reaction, and temperature is controlled at 30 ℃, rotating speed 160rpm.Sampling regularly, analytical reaction thing NO
3-N and product NH
4 +-N content over time.Analytical results is therefrom compared other two kinds of technology as shown in Figure 6 and Figure 7 as can be seen, and nanometer Fe/Cu-denitrifying bacteria United Technologies not only can be removed nitrate nitrogen fast, and ammonia nitrogen generation ratio is minimum.
Claims (6)
1. method of repairing pollution of nitrate nitrogen in underground water, it is characterized in that: this method may further comprise the steps:
(1) nanometer Fe
0The preparation of particle
With FeSO
47H
2O is dissolved in the ethanol-water system that PEG-4000 is a dispersion agent, feeds the argon gas deoxygenation, adds KBH then
4The aqueous solution, stir while dripping, drip and finish the back and continue stirring reaction 40～60min, obtain the nanometer Fe of black
0Solution; Select nanometer Fe with magnetic method
0Particle is used the deoxidation deionized water wash;
(2) preparation of nanometer Fe/Cu particle
With CuSO
45H
2The aqueous solution of O joins nanometer Fe
0In the particle, continue stirring reaction and prepare nanometer Fe/Cu particle;
(3) preparation of reaction solution
In denitrifying bacteria bacterium liquid and nutrient solution, add deionized water dilution preparation feedback liquid;
(4) preparation of reaction system
To import to preparation feedback system in nanometer Fe/Cu particle after the reaction solution deoxidation, the concentration of nanometer Fe/Cu particle is 0.4～0.7g/L;
(5) oscillatory reaction
Add the underground water contain nitrate nitrogen in reaction system, regulating pH is 6.5～8.6, and temperature is controlled at 30 ℃ and rotating speed and is controlled at 140～160rpm, seals and carries out oscillatory reaction.
2. the method for reparation pollution of nitrate nitrogen in underground water according to claim 1 is characterized in that: described FeSO
47H
2O and PEG-4000 mass ratio are 1: 2～2: 1.
3. the method for reparation pollution of nitrate nitrogen in underground water according to claim 1 is characterized in that: in the described ethanol-water system, ethanol and water volume ratio are 1: 4～2: 5.
4. the method for reparation pollution of nitrate nitrogen in underground water according to claim 1 is characterized in that: described FeSO
47H
2O and KBH
4Mol ratio is 1: 5～2: 5.
5. the method for reparation pollution of nitrate nitrogen in underground water according to claim 1 is characterized in that: the Cu charge capacity mass percent of described nanometer Fe/Cu particle is 1～20%.
6. the method for reparation pollution of nitrate nitrogen in underground water according to claim 1 is characterized in that: described denitrifying bacteria bacterium liquid, nutrient solution and deionized water volume ratio are 2: 1～7: 2, wherein denitrifying bacteria bacterium liquid OD
420Be 0.0027～0.0058.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962448A (en) * | 2012-10-31 | 2013-03-13 | 无锡南理工科技发展有限公司 | Method for preparing Fe-clad Cu composite nano- complex phase powder |
| CN102976464A (en) * | 2012-11-29 | 2013-03-20 | 常州大学 | Composite ammonia nitrogen removal agent and using method thereof |
| CN103755042A (en) * | 2014-02-13 | 2014-04-30 | 长江水利委员会长江科学院 | Preparation method and application of attapulgite/nano-iron composite material-microorganism coupled body |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
| CN105217741A (en) * | 2015-09-21 | 2016-01-06 | 清华大学 | A kind of Fe-Graphene high efficiency particulate removes the method for nitrate in groundwater |
| CN107523560A (en) * | 2017-09-05 | 2017-12-29 | 西安建筑科技大学 | Nitrate nitrogen removal fixation support and preparation method in Low Concentration Iron ion underground water |
| 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 |
| CN109937670A (en) * | 2019-04-08 | 2019-06-28 | 东华大学 | Water-fertilizer integral irrigation system based on sponge iron chemical denitrification |
-
2010
- 2010-04-13 CN CN201010144839A patent/CN101805065A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962448A (en) * | 2012-10-31 | 2013-03-13 | 无锡南理工科技发展有限公司 | Method for preparing Fe-clad Cu composite nano- complex phase powder |
| CN102976464A (en) * | 2012-11-29 | 2013-03-20 | 常州大学 | Composite ammonia nitrogen removal agent and using method thereof |
| CN102976464B (en) * | 2012-11-29 | 2014-08-13 | 常州大学 | Composite ammonia nitrogen removal agent and using method thereof |
| CN103755042A (en) * | 2014-02-13 | 2014-04-30 | 长江水利委员会长江科学院 | Preparation method and application of attapulgite/nano-iron composite material-microorganism coupled body |
| CN103755042B (en) * | 2014-02-13 | 2015-04-29 | 长江水利委员会长江科学院 | Preparation method and application of attapulgite/nano-iron composite material-microorganism coupled body |
| CN103964550A (en) * | 2014-05-24 | 2014-08-06 | 长安大学 | Method for removing nitrate nitrogen in water body |
| CN105217741A (en) * | 2015-09-21 | 2016-01-06 | 清华大学 | A kind of Fe-Graphene high efficiency particulate removes the method for nitrate in groundwater |
| CN107523560A (en) * | 2017-09-05 | 2017-12-29 | 西安建筑科技大学 | Nitrate nitrogen removal fixation support and preparation method in Low Concentration Iron ion underground water |
| CN107523560B (en) * | 2017-09-05 | 2020-07-14 | 西安建筑科技大学 | Immobilized carrier for removing nitrate nitrogen in low-concentration iron ion underground water and preparation 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 |
| CN109937670A (en) * | 2019-04-08 | 2019-06-28 | 东华大学 | Water-fertilizer integral irrigation system based on sponge iron chemical denitrification |
| CN109937670B (en) * | 2019-04-08 | 2022-03-22 | 东华大学 | Water and fertilizer integrated irrigation system based on sponge iron chemical denitrification |
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Application publication date: 20100818 |