CN109437394A - A method of short distance nitration is controlled using combined depressant - Google Patents
A method of short distance nitration is controlled using combined depressant Download PDFInfo
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- CN109437394A CN109437394A CN201811372714.XA CN201811372714A CN109437394A CN 109437394 A CN109437394 A CN 109437394A CN 201811372714 A CN201811372714 A CN 201811372714A CN 109437394 A CN109437394 A CN 109437394A
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- hydrazine
- short distance
- distance nitration
- formic acid
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1263—Sequencing batch reactors [SBR]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Hydrology & Water Resources (AREA)
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The invention belongs to sewage water treatment method technical fields, more particularly to a kind of method using combined depressant control short distance nitration, in stable SBR or MBBR, repeat to add in the way of formic acid, hydrazine, hydrazine, other conditions are constant, stablize and realize short distance nitration.Method nitrosoation rate provided by the invention is 92% or more, and ammonia nitrogen removal frank is 98% or more.
Description
Technical field
The invention belongs to sewage water treatment method technical fields, and in particular to a kind of to control short distance nitration using combined depressant
Method.
Background technique
With the fast development of China's economy and science and technology, shortage of water resources, water environment pollution problem become increasingly conspicuous.Water pollution
Problem has become one of most important restraining factors of China's socio-economic development, and ammonia and nitrogen pollution problem is even more the most important thing,
Through causing the great attention of national and local governments.
Short-cut nitrification and denitrification denitrification process is the new biological nitrogen removal technology just to have grown up in recent years, which produces
Mud amount is few, compact efficient and energy saving, has had been more and more widely used.The method that short distance nitration uses is realized at present
It is mostly the control parameters such as dissolved oxygen and pH, reaction rate is low, and short distance nitration is unstable, influences the popularization and application of short distance nitration.
Summary of the invention
In order to solve the above technical problem, the present invention provides it is a kind of using combined depressant control short distance nitration method,
By addition formic acid and hydrazine, quick, stable short distance nitration can be realized.
The invention is realized in this way a method of short distance nitration is controlled using combined depressant, stable
It in SBR or MBBR, repeats to add in the way of formic acid, hydrazine, hydrazine, other conditions are constant, stablize and realize short distance nitration.
Further, in stable SBR or MBBR, according to adding formic acid, add hydrazine, again every two days every two days
Add the mode of hydrazine, repetition adds, repeat twice between mutually every two days, other conditions are constant, stablize and realize short distance nitration.
Further, the dosage of formic acid is 0.25mL/L, and the dosage of hydrazine is 7.5mg/L.
Further, it carries out 8 days in the method, stablizes and realize short distance nitration.
Further, the time that adds of formic acid and hydrazine is fixed on the same time for adding the same day.
Compared with the prior art, the advantages of the present invention are as follows: the nitrosoation rates of this method 92% or more, ammonia nitrogen removal frank
98% or more, and also have the advantage that
1. realizing short distance nitration by adding combined depressant (formic acid and hydrazine), controlled without harsh environment condition；
2. a pair influent ammonium concentration does not have excessive demand, ammonia nitrogen removal frank is higher；
3. inhibitor residual is not detected in water outlet, adding the combined depressant does not influence effluent quality.
Detailed description of the invention
Fig. 1 is formic acid comparison schematic diagram in conjunction with protease；
Fig. 2 is the influence of formic acid and hydrazine to ammonia nitrogen；
Fig. 3 is the influence of formic acid and hydrazine to water outlet nitrite nitrogen and nitrate nitrogen；
Fig. 4 is the influence of formic acid and hydrazine to nitrite accumulation rate.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not used to
Limit the present invention.
Traditional biological denitrification process realizes that denitrogenation of waste water is that ammonia undergoes complete nitrification and denitrification process to turn ammonia finally
Become gaseous nitrogen to remove from system.And it is electron acceptor to realize denitrogenation that short distance nitration denitrogenation, which is cultured water, i.e., by ammonia nitrogen
Then oxidation control carries out denitrification in Nitrification Stage.The key of short-cut nitrification and denitrification is to control nitrifying process in NO2 -
Stage, i.e. NO2 -Without being oxidized to NO3 -, and denitrification is carried out directly as the final hydrogen acceptor of electronics.Short-cut nitrification and denitrification is not
It needs to undergo the step for forming nitrate, reduces the demand to substrate and oxygen, reduce operating cost.
NO is substituted to the research of nitration reaction inhibiting effect and external addition hydrazine when volatile fatty acid is as carbon source2 -
It is oxidized to NO3 -It is that the electronics that approach consumes anaerobic ammonia oxidizing bacteria anabolism is supplemented research shows that formic acid, hydrazine conduct
It is feasible for controlling analysis in the inhibitor principle of short distance nitration, but there has been no researchs, therefore the present invention uses MOE molecule mould first
Work done in the manner of a certain author guidance, analyzing formic acid and hydrazine influences AOB and NOB key enzyme activity, explores formic acid and hydrazine and controls short distance nitration
Feasibility.
AOB ammona monooxygenase (AMO) and AOB azanol oxidoreducing enzyme (HAO) are almost the key enzyme of all AOB, are dominated
The metabolic process of entire bacterium, Nir-Cu are the key enzymes of denitrifying bacterium, have dominated the metabolic process of denitrifying bacterium, can be from
Their x-ray crystal structure is obtained in the PDB database of RCSB.NXR is the key enzyme of NOB, but the crystalline substance of its X-ray at present
Body structure does not obtain also, because β subunit is its principal functional structure, so the present invention simulates its β by Swiss-model
Structure.
From formic acid it is known that formic acid and AMO, HAO, Nir are tied in 2D the and 3D structure in conjunction with AMO, HAO, NXR, Nir
The quantity for closing key will be more than NXR, this shows that stability of the formic acid in conjunction with AMO, HAO, Nir is higher than NXR, in addition, of the invention
Have chosen the feelings of associative key when formic acid is docked with these four enzymes the most securely (in conjunction with distance recently, in conjunction with energy maximum absolute value)
Condition is compared, and analyzes power of the formic acid in conjunction with each enzyme with this, as shown in Figure 1.Formic acid and AOB are closed as seen from Figure 1
Key enzyme HAO is combined on Glu206 (glutamic acid), has the shortest distanceWith -7.6 kcal/mol of maximum combined energy, with
AMO on Leu110 (leucine) with- 4.1kcal/mol is combined；With NOB key enzyme NXR in Lle281 (different bright ammonia
Acid) on- 2.3kcal/mol is combined；With denitrifying bacterium key enzyme Nir-Cu on His60 (histidine) with- 3.7kcal/mol is combined.Therefore, degree of strength of each enzyme in conjunction with formic acid successively should be HAO > AMO > Nir >
NXR。
According to the MOE molecular simulation interpretation of result of formic acid and four kinds of enzymes, formic acid is small organic molecule, can be used as micro- life
The carbon source of object growth, hydroxyl thereon belong to active group, are easy and a variety of amino acid residues combine, therefore formic acid is easy and enzyme
It is decomposed in conjunction with and by it, provides energy for cellular activity, bacterium is promoted to increase.Therefore, in terms of analog angle, formic acid is to ammoxidation
Bacterium facilitation is most strong, followed by denitrifying bacterium, nitrite oxidizing bacteria.In the presence of having formic acid, ammonia oxidation bacteria and anti-
Nitrifier can gradually increase and become dominant bacteria.
AOB ammona monooxygenase (AMO), azanol oxidoreducing enzyme (HAO), NOB oxidoreducing enzyme (NXR β), denitrifying bacterium
Nitrite reductase (Nir-Cu) can not be docked with hydrazine, hydrazine can not replicate simultaneously itself far from protease
Suitable site is found on enzyme to combine.The reason of leading to such case may be because the N-N structure of hydrazine is relatively stable
Plane rigid structure, when being simulated, can not fold or allosteric become suitable shape docked with albumen.From this knot
Fruit, the present invention speculate hydrazine will not by with functional metabolism that bacterium is influenced and protein binding, then hydrazine is to short distance nitration
Influence may be only that the toxicity of hydrazine produces stronger inhibiting effect to NOB.
It can be seen that the promotion work for adding formic acid to AOB from the mechanism analysis for adding formic acid and hydrazine realization short distance nitration
It with the inhibiting effect being better than to NOB, adds hydrazine and inhibiting effect mainly is played to NOB, accordingly, it is considered to formic acid and hydrazine joint
Using can preferably realize short distance nitration.
By individually adding, determining formic acid is tested in the written instructions of formic acid and hydrazine and hydrazine controls the best of short distance nitration first
Dosage is respectively 0.25mL/L and 7.5mg/L.
Then the comparative test of different dosing methods has been carried out:
Five identical sbr reactor devices are run simultaneously, device 1, number LnZ0, using formic acid-formic acid-hydrazine dosing side
Formula (add formic acid, add formic acid again every two days, adding hydrazine every two days, repetition adds, repeat twice between mutually every two days)；Dress
2, number LnZ1 are set, (formic acid is added using formic acid-hydrazine dosing method, adds hydrazine every two days, repetition adds, and weighs twice
Between multiple mutually every two days)；Device 3, number LnZ11 (add formic acid, every two days using formic acid-hydrazine-hydrazine dosing method
The mode for adding hydrazine, adding hydrazine every two days again, repetition add, twice repeat between mutually every two days)；Device 4, number LnM,
Using the dosing method for adding a formic acid every three days；Device 5, number LnH, using the dosing side for every other day adding a hydrazine
Formula.It is affected since two kinds of inhibitor add simultaneously to ammoxidation, so not carrying out long-term influence experiment to this dosing method.
With reference to Fig. 2, Fig. 3 and Fig. 4, it can be seen that device LnZ1 and LnZ11 is substantially stable when experiment proceeds to the 8th day,
LnZ0 reaches longer the time required to stable operation, reaches stable operation to the 12nd day when side, in whole experiment process, LnZ1 and
LnZ11 influences less the removal of ammonia nitrogen, after stable, ammonia nitrogen of the ammonia nitrogen average removal rate in 98% or more, LnZ0
Removal rate is slightly below LnZ1 and LnZ11, is 96.6%.From the point of view of the value for comparing five device water outlet nitrite nitrogens and nitrate nitrogen, operation is steady
After fixed, LnZ0, LnZ1, LnZ11, LnzM and LnzH be averaged nitrite accumulation rate be respectively 83.6%, 88.6%, 92.4%,
79.8%, 72.1%, water outlet nitrate nitrogen average value is respectively 4.7mg/L, 3.34mg/L, 1.81mg/L, 5.72mg/L, 5.24mg/
L.Judging from the experimental results, short distance nitration effect is best when dosing method is formic acid-hydrazine-hydrazine.
Embodiment,
A method of short distance nitration being controlled using combined depressant, in stable SBR, according to same on the day of
One time, the mode for adding 0.25mL/L formic acid, adding 7.5mg/L hydrazine every two days, adding 7.5mg/L hydrazine every two days again,
Repetition add, twice repeat between mutually every two days, other conditions are constant, after proceeding to the 8th day realize short distance nitration stablize fortune
When row, average nitrosoation rate [NO2 --N/(NO2 --N+ NO3 -- N)] reach 92% or more.
Claims (5)
1. a kind of method using combined depressant control short distance nitration, which is characterized in that in stable SBR or MBBR
In, it repeats to add in the way of formic acid, hydrazine, hydrazine, other conditions are constant, stablize and realize short distance nitration.
2. the method according to claim 1 using combined depressant control short distance nitration, which is characterized in that steady in operation
In fixed SBR or MBBR, in the way of adding formic acid, adding hydrazine every two days, add hydrazine every two days again, repetition is added,
Between repeating twice mutually every two days, other conditions are constant, stablize and realize short distance nitration.
3. the method according to claim 2 using combined depressant control short distance nitration, which is characterized in that the throwing of formic acid
Dosage is 0.25mL/L, and the dosage of hydrazine is 7.5mg/L.
4. the method according to claim 3 using combined depressant control short distance nitration, which is characterized in that according to the party
Method carries out 8 days, stablizes and realizes short distance nitration.
5. according to any method using combined depressant control short distance nitration of claim 2-4, which is characterized in that first
The time that adds of acid and hydrazine is fixed on the same time for adding the same day.
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| CN201811372714.XA CN109437394B (en) | 2018-11-19 | 2018-11-19 | Method for controlling short-cut nitrification by using combined inhibitor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921819A (en) * | 2019-12-04 | 2020-03-27 | 沈阳师范大学 | Method for controlling short-cut nitrification and denitrification by using hydrazine |
| CN112811582A (en) * | 2021-02-23 | 2021-05-18 | 沈阳建筑大学 | Nitrosation SBR device for promoting short-cut nitrification by adding hydrazine and improved process |
| CN114314838A (en) * | 2022-01-06 | 2022-04-12 | 华东理工大学 | Formic acid inhibition type semi-shortcut nitrification coupled sulfenyl autotrophic nitrogen removal process device and method |
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| JPS58196890A (en) * | 1982-04-28 | 1983-11-16 | Hitachi Plant Eng & Constr Co Ltd | Biological dephosphorization of waste water |
| CN105000664A (en) * | 2014-04-16 | 2015-10-28 | 中国科学院生态环境研究中心 | Integrated shortcut nitrification-anaerobic ammonium oxidation process denitrogenation effect deterioration in-situ recovery method |
| CN105923752A (en) * | 2016-05-23 | 2016-09-07 | 沈阳师范大学 | Method for achieving shortcut nitrification by utilizing formic acid |
| CN107188307A (en) * | 2017-07-01 | 2017-09-22 | 清华大学 | A kind of Integral waste water nitrogen rejection facility and a kind of method of denitrogenation of waste water |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58196890A (en) * | 1982-04-28 | 1983-11-16 | Hitachi Plant Eng & Constr Co Ltd | Biological dephosphorization of waste water |
| CN105000664A (en) * | 2014-04-16 | 2015-10-28 | 中国科学院生态环境研究中心 | Integrated shortcut nitrification-anaerobic ammonium oxidation process denitrogenation effect deterioration in-situ recovery method |
| CN105923752A (en) * | 2016-05-23 | 2016-09-07 | 沈阳师范大学 | Method for achieving shortcut nitrification by utilizing formic acid |
| CN107188307A (en) * | 2017-07-01 | 2017-09-22 | 清华大学 | A kind of Integral waste water nitrogen rejection facility and a kind of method of denitrogenation of waste water |
Non-Patent Citations (1)
| Title |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921819A (en) * | 2019-12-04 | 2020-03-27 | 沈阳师范大学 | Method for controlling short-cut nitrification and denitrification by using hydrazine |
| CN112811582A (en) * | 2021-02-23 | 2021-05-18 | 沈阳建筑大学 | Nitrosation SBR device for promoting short-cut nitrification by adding hydrazine and improved process |
| CN114314838A (en) * | 2022-01-06 | 2022-04-12 | 华东理工大学 | Formic acid inhibition type semi-shortcut nitrification coupled sulfenyl autotrophic nitrogen removal process device and method |
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