CN108046426A - Reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process - Google Patents
Reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process Download PDFInfo
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- CN108046426A CN108046426A CN201810004264.2A CN201810004264A CN108046426A CN 108046426 A CN108046426 A CN 108046426A CN 201810004264 A CN201810004264 A CN 201810004264A CN 108046426 A CN108046426 A CN 108046426A
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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
- C02F3/28—Anaerobic digestion processes
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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
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Abstract
The method that nitrate nitrogen generates in anaerobic ammonium oxidation process is reduced the invention discloses a kind of, is as follows：The anaerobic ammonia oxidizing bacteria that nitrogen removal performance is stablized is taken to be seeded to reactor, is added in into reaction and contains certain density ammonia nitrogen (NH4 +) and nitrite (NO2 ‑) substrate reaction liquid, suitable Anammox intermediate product hydrazine (N is added in into reactor2H4), with NO present in system2 ‑React generation azide anion (N3 ‑) or to add azide (N directly into reactor3X form) makes the certain density N of the holding in reactor3 ‑, N3 ‑With very strong reactivity, the activity of nitrate reductase (Nar) that can be in the of short duration inhibition anaerobic ammonia oxidizing bacteria of selectivity, so as to avoid the generation of nitrate nitrogen in anaerobic ammonium oxidation process.This method effectively prevents nitrate nitrogen (N during anaerobic oxidation3 ‑) accumulation problem, improve anaerobic ammonia oxidation process water outlet total nitrogen compliance rate, easy to operate, at low cost, non-secondary pollution.
Description
Technical field
It is generated the present invention relates to nitrate nitrogen in bio-denitrifying sewage field more particularly to a kind of reduction anaerobic ammonium oxidation process
Method.
Background technology
Anammox (anammox) is a kind of cost-effective nitrogen removal technique, is played in earth nitrogen cycle important
Effect, which completed by the anaerobic bacteria of the inorganic autotrophic type of chemistry, it is with nitrite (NO2 -) urged as electron acceptor
Change oxidation ammonia nitrogen (NH4 +), generate nitrogen (N2).The anaerobism and autotrophy performance of these microorganisms save aeration power, eliminate to having
The demand of machine carbon, and sludge generation is reduced, therefore, it is commonly used for high energy efficiency wastewater treatment.
Hydrazine (N2H4) it is intermediate product in anaerobic ammonium oxidation process, anaerobic ammonia oxidizing bacteria can be synthesized and is metabolized certain dense
The N of degree2H4, it is the electron storage pond in anaerobic ammonium oxidation process, in the metabolic process that Anammox system is maintained to stablize
Play an important roll.(pH in acid condition<1.0),NO2 -And N2H4Chemical reaction generation azide anion (N can occur3 -), and
In Anammox system, under the action of anaerobic ammonia oxidizing bacteria, in neutrallty condition, additional N2H4Also can and NO2 -Reaction life
Into azide anion (N3 -), N3 -Ability with very strong suction proton, the transmembrane process of its energy accelerating proton, meanwhile, it also has
Stronger toxicity, is often used as biostatic agent.
Nitrate reductase (Nar) is the multifunctional enzyme in ANAMMOX bacterium, and main function is catalytic oxidation NO2 -Generation
Nitrate nitrogen (NO3 -), it had both had oxidation NO2 -Functional subunits, and with by NO3 -The functional subunits of reduction, therefore when the external world
When having the electronics of surplus in environment, it can absorb electronics in environment by NO in system3 -It is reduced into NO2 -, and when the external world is one
When kind owes (scarce) electronic environment state, it can be by NO2 -It is oxidized to NO3 -, while discharge electronics.Contain molybdenum cofactor in the enzyme, because
This, it is to azide (N3X it is) more sensitive.
NO3 -Accumulation is a defect of anaerobic ammonia oxidation process.Anaerobic ammonia oxidizing bacteria is in removal NH4 +And NO2 -While
About 1/10 NO can be generated3 -, and the NO generated3 -Usually it can all be accumulated in system, it is total so as to low anaerobic ammonia oxidation process
Nitrogen removal efficiency.
At present, there are no one kind in the prior art to be effectively prevented from nitrate nitrogen (NO in anaerobic ammonium oxidation process3 -) generation and
The method of accumulation.
The content of the invention
The method that nitrate nitrogen generates in anaerobic ammonium oxidation process is reduced the embodiment provides a kind of, is avoided with realizing
Nitrate nitrogen (NO in anaerobic ammonium oxidation process3 -) generation.
To achieve these goals, this invention takes following technical solutions.
A kind of method that nitrate nitrogen generates in reduction anaerobic ammonium oxidation process, including：
The anaerobic ammonia oxidizing bacteria that nitrogen removal performance is stablized is taken to be seeded to reactor, is added in into the reactor containing certain dense
The oxidation ammonia nitrogen NH of degree4 +With nitrite NO2 -Substrate reaction liquid；
Appropriate substance is added in into the reactor makes azide anion N in the reactor3 -Concentration maintain 20.0~
200.0uM。
Further, NH in the reactor4 +Concentration is 1.0~7.0mM, NO2 -Concentration is 1.0~9.0mM, and is reacted
NO in device2 -Concentration and NH4 +Concentration ratio be 1.20~1.50.
Further, it is described appropriate substance is added in into the reactor to make N in the reactor3 -Concentration maintain
20.0~200.0uM, including：
The intermediate product hydrazine N of Anammox is added in into the reactor2H4, make hydrazine N2H4With the reactor
Present in nitrite NO2 -React generation N3 -, the N2H4Add as a solution, dosage for 0.5~
5.0mM。
Further, it is described appropriate substance is added in into the reactor to make nitrate nitrogen N in the reactor3 -Concentration dimension
It holds in 20.0~200.0uM, including：
Azide N is added into the reactor3X makes nitrate nitrogen N in the reactor3 -Concentration be maintained at 20.0~
200.0uM, the azide N3X is added as a solution, and dosage is 20.0~200.0uM.
Further, the azide N3X is hydrazoic acid N3H or sodium azide N3Na。
Further, the condition of culture of anaerobic ammonia oxidizing bacteria is in the reactor：32~35 DEG C of temperature, pH for 7.5~
8.0, dissolved oxygen (DO)<0.1mg/l.
The method of the embodiment of the present invention is by anti-it can be seen from the technical solution provided by embodiments of the invention described above
It answers and suitable Anammox intermediate product hydrazine (N is added in device2H4), make its life that reacts with nitrous present in system
Into azide anion (N3 -) or to add azide (N directly into reactor3X form) makes the holding one in reactor
Determine the N of concentration3 -, can realize the activity for selectively inhibiting the nitrate reductase (Nar) in anaerobic ammonia oxidizing bacteria, effectively
The accumulation problem of nitrate nitrogen during anaerobic oxidation is avoided, improves the compliance rate of anaerobic ammonia oxidation process water outlet total nitrogen.
The additional aspect of the present invention and advantage will be set forth in part in the description, these will become from the following description
It obtains substantially or is recognized by the practice of the present invention.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, for this
For the those of ordinary skill of field, without creative efforts, others are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1 is a kind of processing stream for reducing the method that nitrate nitrogen generates in anaerobic ammonium oxidation process provided in an embodiment of the present invention
Cheng Tu；
Fig. 2 is a kind of conversion performance schematic diagram of normal ANAMMOX processes mesostroma provided in an embodiment of the present invention；
Fig. 3 is that 1mM N are added in a kind of system to ANAMMOX provided in an embodiment of the present invention2H4Turn of system mesostroma afterwards
Change performance schematic diagram；
Fig. 4 and Fig. 5 is a kind of additional N provided in an embodiment of the present invention2H4And NO2 -Reaction generation N3 -Inhibit nitrate reduction
The schematic diagram of enzyme (Nar) activity.
Specific embodiment
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning
Same or similar element is represented to same or similar label eventually or there is same or like element.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and is only used for explaining the present invention, and is not construed as limiting the claims.
Those skilled in the art of the present technique are appreciated that unless expressly stated, singulative " one " used herein, " one
It is a ", " described " and "the" may also comprise plural form.It is to be further understood that is used in the specification of the present invention arranges
Diction " comprising " refers to there are the feature, integer, step, operation, element and/or component, but it is not excluded that presence or addition
Other one or more features, integer, step, operation, element, component and/or their group.It should be understood that when we claim member
Part is " connected " or during " coupled " to another element, it can be directly connected or coupled to other elements or there may also be
Intermediary element.In addition, " connection " used herein or " coupling " can include wireless connection or coupling.Wording used herein
"and/or" includes any cell of one or more associated list items and all combines.
Those skilled in the art of the present technique are appreciated that unless otherwise defined all terms used herein are (including technology art
Language and scientific terminology) there is the meaning identical with the general understanding of the those of ordinary skill in fields of the present invention.Should also
Understand, those terms such as defined in the general dictionary, which should be understood that, to be had and the meaning in the context of the prior art
The consistent meaning of justice, and unless defined as here, will not be with idealizing or the meaning of overly formal be explained.
For ease of the understanding to the embodiment of the present invention, done further by taking several specific embodiments as an example below in conjunction with attached drawing
Explanation, and each embodiment does not form the restriction to the embodiment of the present invention.
Embodiment one
A kind of process flow for reducing the method that nitrate nitrogen generates in anaerobic ammonium oxidation process provided in an embodiment of the present invention is such as
Shown in Fig. 1, including following processing step：
Step 1：The anaerobic ammonia oxidizing bacteria that nitrogen removal performance is stablized is taken to be seeded to reactor.
Step 2：It is added in into reactor and contains certain density NH4 +And NO2 -Substrate reaction liquid, wherein NH4 +Concentration exists
1.0~7.0mM, NO2 -Concentration is in 1.0~9.0mM, and concentration ratio NO both in reactor2 -/NH4 +For 1.20~1.50；
Step 3：Appropriate substance is added in into reactor makes N in reactor3 -Concentration maintain 20.0~200.0uM.
Selectively, the Anammox intermediate product N added in into reactor2H4, make itself and Asia present in reactor
Nitrate NO2 -React generation N3 -, N2H4It adds as a solution, dosage is 0.5~5.0mM；
Selectively, azide N is added directly into reactor3X makes N in reactor3 -Concentration be maintained at 20.0
~200.0uM；The azide N3X is added as a solution, refers to that generation azide anion N can be ionized in water3 -Object
Matter, including N3H and its esters etc..
Preferentially, above-mentioned azide (N3X hydrazoic acid (N) is used3) or sodium azide (N H3Na), both substances are equal
It adds as a solution, dosage is 20.0~200.0uM；
The condition of culture of anaerobic ammonia oxidizing bacteria is in the reactor：
1：32~35 DEG C of temperature, pH are 7.5~8.0, dissolved oxygen (DO)<0.1mg/l；
2：Reactor is maintained continually and steadily to run, NH in setting time sampling detection architecture4 +,NO2 -,NO3 -And N3 -It is dense
Degree.
Embodiment two
Additional N2H4Avoid the accumulation of nitrate nitrogen in Anammox system
Control group：ANAMMOX strains (MLSS 3313mg/L) are first inoculated with, 200ml is then contained into NH4 +-N、NO2 -- N and
NO3 -- N concentration is respectively that the simulated wastewater of 2.4mM, 3.7mM and 1.5mM are added in serum bottle, uses N2Blow 5min, after sealing
Start to do batch experiment in constant-temperature table.It is 7.7~7.8 to control pH in serum bottle, and temperature is 32 ± 1 DEG C, rotating speed 135r/
Min, experiment run 225min altogether, and inspection NH is sampled every 45min4 +-N、NO2 -- N and NO3 -The concentration situation of change of-N.
Experimental group：N is added into bottle2H4, making its concentration, other conditions are such as control group for 1mM.
Fig. 2 is a kind of conversion performance schematic diagram of normal ANAMMOX processes mesostroma provided in an embodiment of the present invention, is schemed
3 be to add 1mMN in a kind of system to ANAMMOX provided in an embodiment of the present invention2H4The conversion performance signal of system mesostroma afterwards
Figure, as seen from Figure 2, in the preceding 180min of operation, NH4 +And NO2 -Concentration all declined, wherein NH4 +Concentration from
2.3mM is down to 0.045mM, and NO2 -Concentration is down to 0.715mM from 3.7mM.Meanwhile the NO in system3 -It is increased to from 1.5mM
2.170mM.As seen from Figure 3, although the N for the 1mM that the starting stage adds in into ANAMMOX systems2H4, but run 90min
Afterwards, the N in system2H4Concentration already below detection line, in this 90min, NH4 +And NO2 -Concentration also decreased,
Wherein NH4 +0.93mM, NO are rapidly decreased to from 2.3mM2 -1.43mM is rapidly decreased to from 3.7mM, after running 180min, in system
NH4 +And NO2 -All it has been completely degraded, and the concentration of nitrate has almost no change, meanwhile, it is not detected in whole process
To azanol.Obviously, additional N2H4Certain influence is generated to the nitrogen removal performance of ANAMMOX systems, adds in N2H4Afterwards, anaerobism ammonia
NO in oxidation system3 -Do not accumulate.
Embodiment three
Additional N2H4And NO2 -Reaction generation N3 -Inhibit the activity of nitrate reductase (Nar)
200ml is contained into NO2 -、NO3 -And N2H4The simulated wastewater that concentration is followed successively by 4.7,2.3 and 4.7mM is added to and has connect
Batch experiment is done in the serum bottle of kind ANAMMOX sludge.Sludge concentration 3013mg/L, it is 7.7~7.8 to control pH, temperature 32
± 1 DEG C, rotating speed 135r/min runs 6h altogether, and inspection N is sampled every 45min2H4- N, NO2 --N、NO3 -- N and N3 -Variation feelings
Condition.
Fig. 4 and Fig. 5 is a kind of additional N provided in an embodiment of the present invention2H4And NO2 -Reaction generation N3 -Inhibit nitrate reduction
The schematic diagram of enzyme (Nar) activity.As seen from Figure 4, in the preceding 45min of operation, N in system2H4And NO2 -Concentration it is rapid
Decline, and NO3 -Concentration have almost no change.The state is continued for, until NO in 225min, system2 -Concentration be less than
0.18mM.At this point, N2H4Degradation rate less than 0.25mM/h, after this, the NO in system3 -Concentration just start with
The rate linear of 0.18mM/h reduces, and with reference to Fig. 5 as can be seen that in the experimentation, observes and is accumulated in ANAMMOX systems
N3 -, concentration increases continuously, and reaches peak value 104uM in 135min.Then, quickly fallen to after 225min 30uM with
Under, as seen from Figure 4, NO in system at this time2 -Almost it is degraded, and NO3 -It also begins to degrade.Obviously, the ANAMMOX
Additional N in system2H4And NO2 -Reaction generation N3 -The of short duration activity for inhibiting nitrate reductase (Nar), with N in system3 -It is dense
Degree continuously decreases, and the activity of nitrate reductase (Nar) gradually shows, NO in system3 -Start to degrade.Therefore, when there is NO2 -It deposits
When, additional N2H4Can in reduction system nitrate nitrogen generation, and work as NO2 -When concentration is relatively low, additional N2H4It can be in promotion system
NO3 -Degradation, therefore, N is added into Anammox system2H4It can be to avoid NO in system3 -Accumulation.
In conclusion the method for the embodiment of the present invention utilizes N3 -Can selectively it is of short duration inhibit anaerobic ammonia oxidizing bacteria in nitre
The active principle of hydrochlorate reductase (Nar), by adding in suitable Anammox intermediate product hydrazine into reactor
(N2H4), it is made to react with nitrous present in system and generates azide anion (N3 -) or directly to add into reactor
Add azide (N3X form) makes the certain density N of the holding in reactor3 -, can realize selectively inhibition anaerobism ammonia
The activity of nitrate reductase (Nar) in oxidation bacteria, so as to avoid the generation of nitrate nitrogen in anaerobic ammonium oxidation process.This method has
Effect avoids nitrate nitrogen (NO during anaerobic oxidation3 -) accumulation problem, improve anaerobic ammonia oxidation process water outlet total nitrogen compliance rate,
It is easy to operate, at low cost, non-secondary pollution.
One of ordinary skill in the art will appreciate that：Attached drawing is the schematic diagram of one embodiment, module in attached drawing or
Flow is not necessarily implemented necessary to the present invention.
Each embodiment in this specification is described by the way of progressive, identical similar portion between each embodiment
Point just to refer each other, and the highlights of each of the examples are difference from other examples.Especially for device or
For system embodiment, since it is substantially similar to embodiment of the method, so describing fairly simple, related part is referring to method
The part explanation of embodiment.Apparatus and system embodiment described above is only schematical, wherein the conduct
The unit that separating component illustrates may or may not be it is physically separate, the component shown as unit can be or
Person may not be physical location, you can be located at a place or can also be distributed in multiple network element.It can root
Factually border needs to select some or all of module therein realize the purpose of this embodiment scheme.Ordinary skill
Personnel are without creative efforts, you can to understand and implement.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
Subject to.
Claims (6)
1. a kind of reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, which is characterized in that including：
The anaerobic ammonia oxidizing bacteria that nitrogen removal performance is stablized is taken to be seeded to reactor, is added in into the reactor containing certain density
Aoxidize ammonia nitrogen NH4 +With nitrite NO2 -Substrate reaction liquid；
Appropriate substance is added in into the reactor makes azide anion N in the reactor3 -Concentration maintain 20.0~
200.0uM。
2. according to claim 1 reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, which is characterized in that described anti-
Answer NH in device4 +Concentration is 1.0~7.0mM, NO2 -Concentration is 1.0~9.0mM, and NO in reactor2 -Concentration and NH4 +Concentration
Than for 1.20~1.50.
3. according to claim 1 reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, which is characterized in that described
Appropriate substance is added in into the reactor makes N in the reactor3 -Concentration maintain 20.0~200.0uM, including：
The intermediate product hydrazine N of Anammox is added in into the reactor2H4, make hydrazine N2H4With existing in the reactor
Nitrite NO2 -React generation N3 -, the N2H4It adds as a solution, dosage is 0.5~5.0mM.
4. according to claim 1 reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, which is characterized in that described
Appropriate substance is added in into the reactor makes nitrate nitrogen N in the reactor3 -Concentration maintain 20.0~200.0uM, including：
Azide N is added into the reactor3X makes nitrate nitrogen N in the reactor3 -Concentration be maintained at 20.0~
200.0uM, the azide N3X is added as a solution, and dosage is 20.0~200.0uM.
5. according to claim 4 reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, which is characterized in that described folded
Nitride N3X is hydrazoic acid N3H or sodium azide N3Na。
6. according to any one of claims 1 to 5 reduce the method that nitrate nitrogen generates in anaerobic ammonium oxidation process, feature exists
In the condition of culture of anaerobic ammonia oxidizing bacteria is in the reactor：32~35 DEG C of temperature, pH are 7.5~8.0, dissolved oxygen (DO)<
0.1mg/l。
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