CN102225793A - Method for removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water synchronously - Google Patents
Method for removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water synchronously Download PDFInfo
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Abstract
A method for removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water synchronously. The invention relates to a method for removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water synchronously. Through the invention, the technical problems that nitrogen in three forms can not be removed synchronously through the existing method removing ammonia nitrogen, nitrogen nitrate and nitrogen nitrite in water and the existing method is complex in operation and can produce a secondary pollution thus can not be utilized in drinking water treatment are solved. In the invention, water needing to be treated is subjected to a PH adjusting process and a dissolved oxygen control process, and then is radiated by ultraviolet light with a wavelength in the range of 150 to 260 nm. The method can remove ammonia nitrogen, nitrogen nitrate and nitrogen nitrite synchronously without multistage removal, expensive oxidizing agents and catalysts, no secondary pollution and no subsequent process, and show the characteristics of safety, convenience, economy and high efficiency while removing nitrogen in three forms. Therefore, the method can be utilized for treatments of underground water, drinking water, water discharged from sewage treatment plants, industrial water and domestic water, and the remediation of natural water body.
Description
Technical field
The present invention relates to remove the method for ammonia nitrogen in the water, nitrate nitrogen and nitrite nitrogen.
Background technology
Ammonia nitrogen extensively exists in the liquid effluent of trade effluent, and the extensive chemical fertilizer that uses also can cause the pollution of area source of ammonia nitrogen in the agricultural.Ammonia nitrogen in the water body can cause the eutrophication in lake and river, and water body natural ecological environment and aquaculture are produced harm.Simultaneously, ammonia nitrogen also can burn into blocking pipe and watering equipment, and ammonia nitrogen in high density can react with water treatment sterilizing agent chlorine, and the consumption of aqueous disinfectant is increased greatly, and produces the disgusting flavor of smelling.Composition such as ammonia nitrogen can change into nitrite nitrogen, nitrate nitrogen under certain condition in the water, influences drinking-water quality safety, and HUMAN HEALTH is caused serious harm, brings out methemoglobinemia and produces carcinogenic nitrosamine.According to China's drinking water sanitary standard in 2006, the safe level of ammonia nitrogen is that 0.5mg/L, nitrate are 10mg/L in the tap water.Therefore, be necessary very much ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in the water this " three nitrogen " are removed.
At present, the removal method to " three nitrogen " mainly contains biological denitrificaion method, air stripping method, ion exchange method, catalytic oxidation, break point chlorination, chemical reduction method etc.Though existing method can both be carried out removal to a certain degree to " three nitrogen ", the whole bag of tricks all has certain drawback.
The biological denitrificaion method is under various microbial processs, and series reaction such as process is nitrated, denitrification are converted into nitrogen with the ammonia nitrogen in the waste water, thereby reach the purpose of waste water treatment.Its main drawback is: floor space is big, and oxygen requirement is big, and some objectionable impurities such as heavy metal ion etc. have restraining effect to microorganism, needs to remove before the biological process carrying out." three nitrogen " removed simultaneously in the water needs multilevel processing technology, and the method complexity is not suitable in the tap water.
Air stripping method is to add enough alkali in system, and the ammonia nitrogen in the water is existed with the unionized attitude, utilizes air that ammonia nitrogen is blown out.Its deficiency is: blow-off method easily makes the packing layer fouling, influences the operation of equipment; When water temperature was hanged down, stripping efficient was low; After finishing, stripping also need adjust back waste water ph.In addition, still contain little ammonia in the waste water after stripping is handled, usually can not qualified discharge, so blow-off method usually is used as the pretreatment process of high-concentration ammonia nitrogenous wastewater, method complexity.This method can not be used for the removal of nitrate and nitrite, also is not suitable for using in tap water.
Ion exchange method is to remove the method for " three nitrogen " in the waste water by ion being had the adsorbing material of very strong selection.Its main drawback is when handling high-concentration ammonia nitrogenous wastewater, and regeneration, backwash are frequent, also need carry out pre-treatment to former water, and the processing cost height, the regenerated liquid of generation must be handled, and can cause secondary pollution.In addition, the removal of negatively charged ion (nitrite anions and nitrate radical), positively charged ion (ammonium radical ion) will be handled operational management complexity, method complexity with resin of different nature.
Catalytic oxidation is meant and utilizes catalyzer and oxygenant coupling, produces the free radical of strong oxidizing property, and organism in the water and ammonia selective oxidation are resolved into CO
2, N
2And H
2Innoxious substances such as O reach the purpose of purification.Its main drawback is: need to add a large amount of oxygenants, the recovery of catalyzer is run off and is utilized to wait again and has some problems, and the method complexity influences the stability of this technology.It can only realize the removal of ammonia nitrogen and nitrite in the water, can not remove nitrate.
Break point chlorination is meant and feeds finite concentration chlorine in waste water, realizes the removal of ammonia nitrogen.Its main drawback is: the use of liquid chlorine and storage are to the security requirement height; The water that produces need add alkali neutralization, processing cost height; Residual chlorine, by product chloramines and chlorination organism can cause secondary pollution; Can not remove nitrate in this process, the method complexity.
Chemical reduction method is to utilize certain reductive agent that nitrate and nitrite are converted into the method for nitrogen, also can realize catalytic reduction by adding catalyzer.When it is mainly not enough: can only remove nitrate and nitrite, but can not realize the removal of ammonia nitrogen.In addition, the reductive agent of adding also needs to carry out the removal processing of ammonia nitrogen.
In addition, the ultraviolet treatment technology, as a kind of emerging water technology, safe, efficient, simple to operate, be used for sterilizing process on a large scale, be to utilize UV-light control pollutent such as bromate in the Chinese patent of CN 201567248U as publication number, but handle also do not have bibliographical information both at home and abroad for the ultraviolet of " three nitrogen " in the water.
Summary of the invention
The present invention will solve the technical problem that the method complicated operation of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the existing removal water can't be removed, may produce secondary pollution synchronously to " three nitrogen ", can't be applied to drinking water treatment, and the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water is provided.
The method of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen is in a kind of synchronous removal water of the present invention: the pH value with staying water is adjusted to 3～11 earlier, dissolved oxygen content is adjusted to 0.1mg/L～40mg/L, and then is the treatment with ultraviolet light of 150nm～260nm with wavelength.
It is the UV-light illumination of 150nm～260nm that the present invention selects wavelength for use, realizes the synchronous removal of ammonia nitrogen, nitrate nitrogen, nitrite nitrogen.Be under the irradiation of UV-light of 150nm～260nm at wavelength, nitrate ion
And nitrite ion
After absorbing UV-light, by stable ground state transition to unsettled excited state
Transition of electron takes place and photodissociation, its reaction equation is as follows:
Simultaneously, under the uviolizing of 150nm～260nm, water molecules is decomposed and produces hydrogen atom (H), hydrated electron
And hydroxyl radical free radical materials such as (HO), wherein hydroxyl radical free radical has very strong oxidisability, the ammonia nitrogen in the water can be oxidized to nitrite nitrogen and nitrate nitrogen; And hydrogen atom in the water (H) and hydrated electron have very strong reducing property, can further nitrate nitrogen in the water and nitrite nitrogen be removed.
HO·+NH
3→H
2O+NH
2·→…→N
2
(NO
2)·
2-+H
2O→NO·+2HO
-→…→N
2O
And through reactions such as a series of free radicals, " three nitrogen " in the water is free of contamination N by eventual degradation finally
2And N
2O gas, and the denitrogenation processing of realization water body.
In sum, the principle of removing " three nitrogen " in the water with the ultraviolet lighting method is that the removal of ammonia nitrogen is to utilize the strong oxidizing property of the hydroxyl radical free radical that produces synchronously in the system under the UV-irradiation that it is removed; And the removal of nitrate and nitrite, be to be undertaken by two kinds of different approach, the one, utilize them in ultraviolet spectral range, to have absorptivity to carry out direct photodissociation, the 2nd, the free radical that the hydrogen atom that produces synchronously when utilizing UV-light photodissociation system, power and water etc. have strong reducing property carries out indirect photodissociation removal.
The method of ammonia nitrogen, nitrate and nitrite in a kind of synchronous removal water of the present invention has the following advantages: removing " three nitrogen " does not need multistage removal; Do not need expensive oxygenant and catalyzer; Do not need to be easy to generate the sorbent materials such as gac of secondary pollution; Can utilize the ultraviolet wave spectrum light source of common, inexpensive; Can remove " three nitrogen " in the water fast, method of the present invention be a kind of safe, convenient, economical, efficiently, do not produce the method for secondary pollution, can be used for the water treatment that of sewage work, to effectively reduce the emission concentration of " three nitrogen " in the sewage; Can be used for the processing of urban drinking water, under the prerequisite of not introducing secondary pollution, remove in the former water of tap water " three nitrogen "; Also can be used for the reparation of natural water, the processing of process water and domestic water; Reactor design easily satisfies the needs of various different water bodys, comes into operation as early as possible; Economical operation, convenient management can ensure water quality safety.
Method of the present invention not only can be removed ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the water body synchronously, for containing a kind of in ammonia nitrogen, nitrate nitrogen and the nitrite nitrogen or wherein two kinds water body is suitable equally.
Description of drawings
Fig. 1 is the clearance graph of relation in time of nitrate ion in the staying water of embodiment 23, nitrite ion and total nitrogen.
Embodiment
Embodiment one: the method for ammonia nitrogen, nitrate and nitrite is in a kind of synchronous removal water of present embodiment: earlier the pH value of staying water is adjusted to 3～11, dissolved oxygen content is adjusted to 0.1mg/L～40mg/L, and then is the treatment with ultraviolet light of 150nm～260nm with wavelength.
To select wavelength for use be the UV-light illumination of 150nm～260nm to the method for ammonia nitrogen, nitrate nitrogen, nitrite nitrogen in the synchronous removal water of present embodiment, realizes that ammonia nitrogen, nitrate nitrogen, nitrite nitrogen remove synchronously.Have the following advantages: removing " three nitrogen " does not need multistage removal; Do not need expensive oxygenant and catalyzer; Do not need to be easy to generate the sorbent materials such as gac of secondary pollution; Can utilize the ultraviolet wave spectrum light source of common, inexpensive; Can remove " three nitrogen " in the water fast, method of the present invention be a kind of safe, convenient, economical, efficiently, do not produce the method for secondary pollution.
Embodiment two: what present embodiment and embodiment one were different is: the pH value of staying water is adjusted to 4～10.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is:: the pH value of staying water is adjusted to 8.Other is identical with embodiment one.
Embodiment four: what present embodiment was different with one of embodiment one to three is.The dissolved oxygen content of staying water is 0.2mg/L～8.2mg/L.Other is identical with embodiment one or two.
When oxygen in water content is 0.2mg/L～8.2mg/L, can keeps reducing environments by in system, feeding nitrogen, hydrogen or rare gas element such as argon gas etc., thereby improve the efficient that nitrate and nitrite are removed in reduction.
Embodiment five: what present embodiment was different with one of embodiment one to three is: the dissolved oxygen content of staying water is 1mg/L.Other is identical with one of embodiment one to three.
Embodiment six: what present embodiment was different with one of embodiment one to three is: the dissolved oxygen content of staying water is 8.5mg/L～40mg/L.Other is identical with one of embodiment one to three.
Present embodiment can increase dissolved oxygen by the mode that blasts air or oxygen in system, when oxygen in water content is 8.5mg/L～40mg/L, reaches the purpose of oxidation efficiency of the ammonia nitrogen of raising system.
Embodiment seven: what present embodiment was different with one of embodiment one to three is: the dissolved oxygen content of staying water is 20mg/L.Other is identical with one of embodiment one to three.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: described UV-light excites a kind of or wherein several generation in ultraviolet lamp, xenon lamp and the halogen lamp by low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, amalgam ultraviolet lamp, quasi-molecule.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: staying water is meant underground water, tap water, sewage disposal plant effluent, process water or domestic water.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different with one of embodiment one to nine is: described treatment with ultraviolet light is immersion irradiation or the irradiation of irradiation formula.Other is identical with one of embodiment one to nine.
Embodiment 11: what present embodiment was different with one of embodiment one to ten is: the time of treatment with ultraviolet light is 0.1min～100min, and UV-light dosage is 15 joules/liter～90000 joules/liter.Other is identical with one of embodiment one to ten.
Embodiment 12: what present embodiment was different with one of embodiment one to 11 is: the time of UV-irradiation is 30min, and UV-light dosage is 9000 joules/liter.Other is identical with one of embodiment one to 11.
Embodiment 13: what present embodiment was different with one of embodiment one to 11 is: the flow pattern of staying water is circulation batch type, complete hybrid or continuously streamed.Other is identical with one of embodiment one to 11.
Embodiment 14: what present embodiment was different with one of embodiment one to 13 is: the staying water wavelength is the treatment with ultraviolet light of 160nm～220nm.Other is identical with one of embodiment one to 13.
Embodiment 15: what present embodiment was different with one of embodiment one to 13 is: the staying water wavelength is the treatment with ultraviolet light of 185nm.Other is identical with one of embodiment one to 13.
Embodiment 16: present embodiment with specifically be embodiment one to 15 different be: the nitrogen of staying water is inorganic ammonia nitrogen and organic ammonia nitrogen.Other is identical with one of embodiment one to 15.
Embodiment 17: what present embodiment was different with one of embodiment one to 16 is: the nitrogen of staying water is nitrate nitrogen.Other is identical with one of embodiment one to 16.
Nitrogen in the staying water of present embodiment is that nitrate nitrogen is a kind of, by the processing of present embodiment, nitrate nitrogen is removed.
Embodiment 18: what present embodiment was different with one of embodiment one to 17 is: the nitrogen of staying water is nitrite nitrogen.Other is identical with one of embodiment one to 17.
Nitrogen in the staying water of present embodiment is that nitrite nitrogen is a kind of, by the processing of present embodiment, nitrite nitrogen is removed.
Embodiment 19: what present embodiment was different with one of embodiment one to 18 is: the nitrogen of staying water is ammonia nitrogen and nitrate nitrogen.Other is identical with one of embodiment one to 18.
Nitrogen in the staying water of present embodiment is two kinds of ammonia nitrogen and nitrate nitrogens, by the processing of present embodiment, ammonia nitrogen and nitrate nitrogen is removed synchronously.
Embodiment 20: what present embodiment was different with one of embodiment one to 19 is: the nitrogen of staying water is ammonia nitrogen and nitrite nitrogen.Other is identical with one of embodiment one to 19.
Nitrogen in the staying water of present embodiment is two kinds of ammonia nitrogen and nitrite nitrogens, by the processing of present embodiment, ammonia nitrogen and nitrite nitrogen is removed synchronously.
Embodiment 21: what present embodiment was different with one of embodiment one to 20 is: the nitrogen of staying water is nitrate nitrogen and nitrite nitrogen.Other is identical with one of embodiment one to 20.
Nitrogen in the staying water of present embodiment is two kinds of nitrate nitrogen and nitrite nitrogens, by the processing of present embodiment, nitrate nitrogen and nitrite nitrogen is removed synchronously.
Embodiment 22: what present embodiment was different with one of embodiment one to 21 is: the nitrogen in the staying water is ammonia nitrogen, nitrate nitrogen and nitrite nitrogen.Other is identical with one of embodiment one to 21.
Nitrogen in the staying water in the present embodiment is ammonia nitrogen, nitrate nitrogen and nitrite nitrogen, by the processing of present embodiment, ammonia nitrogen, nitrate nitrogen and nitrite nitrogen is removed synchronously.
Embodiment 23: the method for ammonia nitrogen, nitrate and nitrite is in a kind of synchronous removal water of present embodiment: earlier the pH value of staying water is adjusted to 10, dissolved oxygen content is adjusted to 1mg/L, and then be the treatment with ultraviolet light of 170nm～260nm with wavelength, temperature is 25 ℃ during processing, UV-light is that the low pressure mercury lamp of 10W sends by power, at the nested silica tube of low pressure mercury lamp outer wall, be positioned over the cylindrical reactor axle center, be immersed in the staying water.
The volume of the staying water of present embodiment is 800mL, and the concentration of ammonia nitrogen is 0.9mg/L (in nitrogen) in the staying water, and nitrate concentration is that 3.1mg/L is (with NO
3 -Meter), nitrite concentration is that 2.3mg/L is (with NO
2 -Meter).
Pick up counting during from UV-irradiation, and nitrate ion in the detection staying water, the concentration of nitrite ion and total nitrogen, the nitrate ion that obtains, the clearance of nitrite ion and total nitrogen relation curve in time as shown in Figure 1, a is the clearance relation curve in time of nitrate ion among the figure, b is the clearance relation curve in time of nitrite ion, c is the clearance relation curve in time of total nitrogen, as can be seen from Figure 1, after ultraviolet is handled 10min, the clearance of total nitrogen is near 50%, the nitrate removal rate is about 74%, and the nitrite clearance is about 20%; Behind the 20min, nitrogen removal rate reaches 90%, and the nitrate removal rate can reach 96%, and the nitrite clearance can reach 84%.Present method has good effect of removing for " three nitrogen ".As seen, more stable always for the removal speed of total nitrogen, efficient is higher.
Claims (7)
1. method of removing synchronously ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in the water, it is characterized in that the method for removing ammonia nitrogen in the water, nitrate nitrogen and nitrite nitrogen synchronously is: earlier the pH value of staying water is adjusted to 3～11, dissolved oxygen content is adjusted to 0.1mg/L～40mg/L, and then is the treatment with ultraviolet light of 150nm～260nm with wavelength.
2. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water according to claim 1 is characterized in that the pH value of staying water is adjusted to 4～10.
3. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water according to claim 1 and 2, the dissolved oxygen content that it is characterized in that staying water is 0.2mg/L～8.2mg/L.
4. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water according to claim 1 and 2 is characterized in that described UV-light excites a kind of or wherein several generation in ultraviolet lamp, xenon lamp and the halogen lamp by low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, amalgam ultraviolet lamp, quasi-molecule.
5. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen is characterized in that staying water is meant underground water, tap water, sewage disposal plant effluent, process water or domestic water in a kind of synchronous removal water according to claim 1 and 2.
6. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water according to claim 1 and 2 is characterized in that described treatment with ultraviolet light is immersion irradiation or the irradiation of irradiation formula.
7. the method for ammonia nitrogen, nitrate nitrogen and nitrite nitrogen in a kind of synchronous removal water according to claim 1 and 2, the time that it is characterized in that treatment with ultraviolet light is 0.1min～100min, UV-light dosage is 15 joules/liter～90000 joules/liter.
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| CN103787448A (en) * | 2014-02-20 | 2014-05-14 | 南京大学 | Denitrification method combining denitrification agent and ultraviolet light |
| CN104828900A (en) * | 2015-06-05 | 2015-08-12 | 广西大学 | Method for using photocatalytic reduction to treat waste water containing nitroimidazole antibiotics |
| CN107640802A (en) * | 2016-07-21 | 2018-01-30 | 杭州中兵环保股份有限公司 | The device and method of denitrogenation of water is circulated in Ozone flue gas desulfurization and denitrification cleaning system |
| CN107973323A (en) * | 2017-12-06 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method for oxidation of desulphurization denitration waste liquid Nitrite ion |
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| CN103787448A (en) * | 2014-02-20 | 2014-05-14 | 南京大学 | Denitrification method combining denitrification agent and ultraviolet light |
| CN104828900A (en) * | 2015-06-05 | 2015-08-12 | 广西大学 | Method for using photocatalytic reduction to treat waste water containing nitroimidazole antibiotics |
| CN107640802A (en) * | 2016-07-21 | 2018-01-30 | 杭州中兵环保股份有限公司 | The device and method of denitrogenation of water is circulated in Ozone flue gas desulfurization and denitrification cleaning system |
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| CN108911320A (en) * | 2018-06-06 | 2018-11-30 | 东南大学 | A kind of nitrite decomposing processor and method |
| CN108975504A (en) * | 2018-07-31 | 2018-12-11 | 苏州科技大学 | The method that bismuthic acid copper-fullerene photochemical catalyst removes nitrite and ammonia nitrogen simultaneously |
| CN108975505B (en) * | 2018-07-31 | 2021-08-06 | 苏州科技大学 | Sewage treatment method for simultaneously removing nitrite and ammonia nitrogen |
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| CN108975506B (en) * | 2018-07-31 | 2021-08-06 | 苏州科技大学 | Method for removing nitrite and ammonia nitrogen by zinc ferrite-activated carbon photocatalysis |
| CN108975502B (en) * | 2018-07-31 | 2021-08-06 | 苏州科技大学 | Method for removing nitrite and ammonia nitrogen in sewage simultaneously by photocatalysis |
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