CN105174448B - A kind of Anammox and denitrification coupling device and its control operation method - Google Patents
A kind of Anammox and denitrification coupling device and its control operation method Download PDFInfo
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Abstract
A kind of Anammox and denitrification coupling device and control operation method, belong to technical field of biological sewage treatment.It with ammonia nitrogen and nitrate nitrogen is reaction nitrogen source that its operation method is, while controlling the reaction conditions, wherein NH such as temperature, pH, organic carbon source, phosphorus source, DO4 ‑N concentration is 120~180mg/L, NO3 ‑N concentration is 165~198mg/L, and the concentration ratio of ammonia nitrogen and nitrate nitrogen is 1 in water inlet:(1.08~1.32), stage and Anammox are tamed by Anaerobic ammonium oxidation system culture to be tamed with the culture of denitrification coupling stages, realize that anaerobic ammonia oxidizing bacteria and denitrifying bacterium richness coexist union in reactor, realize Anammox and denitrifying effect simultaneously, the method of the present invention has operating condition simple, overcome nitrite nitrogen and be difficult to efficient accumulation, Anammox is coupled with denitrification and be effectively controlled, realize the stable operation of coupled reaction.
Description
Technical field
The invention belongs to technical field of biological sewage treatment, it is specifically related to a kind of Anammox and dress is coupled with denitrification
Put and control operation method.
Background technology
At present, biological denitrificaion method is one of most commonly used sewage water denitrification technology of domestic and international application, and Anammox is new
Type high-efficiency biological denitrification technology, is an important reaction in nitrogen cycle, compared with traditional nitrification and denitrification, Anammox
Have the advantages that oxygen demand is low, be not required to additional carbon, sludge yield lacks, and saves substantial amounts of operating cost.
Anammox principle is that anaerobic ammonia oxidizing bacteria is received by electronics of nitrite nitrogen under conditions of anaerobism or anoxic
Body, by NH4 +- N direct oxidations are N2Process, produces N during nitrogen2Two nitrogen-atoms respectively from NO2 -N and NH4 +-N。
NH4 ++NO2 -→N2+H2O (△ G=-297KJ/M)
NH4 +1.32NO2 -+0.066HCO3 -+0.13H+→1.02N2+0.26NO3 -+0.066CH2O0.5N0.15 +2.03H2O
Anammox is particularly suitable for processing low-carbon (LC) high ammonia-nitrogen wastewater, and Anammox is into research warm both at home and abroad in recent years
Point, but Anammox and two kinds of main anaerobism of denitrification are may be simultaneously present under organic environment, in reactor assembly
Denitrification reaction, if the synergy of Anammox and denitrification denitrogenation is realized in same reactor assembly, then to biology
Denitrogenation technological development is significant.
Denitrification refer to denitrifying bacteria under the conditions of anaerobic environment, reduce nitrate, discharge the process of dinitrogen, absolutely
Most of bacterial digestion is anaerobism heterotroph, and it carries out anaerobic respiration with organic matter as carbon source and energy.In denitrifying biology
During, produce the reaction (dissimilation) of energy and the formula of cell synthetic reaction (internalization)
1.6NO3 -+CH3COOH→0.8N2+2CO2+1.2H2O+1.60H-(△ G=-843KJ/M)
1.2NO3 -+CH3COOH+0.1NH4 +→0.1C5H7O2N+0.6N2+1.5CO2+1.1OH-+1.3H2O
Also little with the research of denitrification coupling technique on Anammox at present, Anammox is coupled with denitrification
Reaction system is set up and is based on two kinds of possibility:One be by the domestication culture of certain condition, Installed System Memory in two kinds of bacterium of function, i.e.,
Anaerobic ammonia oxidizing bacteria and denitrifying bacterium, they can coexist in special environment, vie each other, also mutually promote;Two be
There is a kind of special denitrification functions bacterium in this coupled system, it has Anammox and Denitrification Characteristics simultaneously, can
In the presence of organic carbon source, using ammonia nitrogen and nitrite nitrogen (control certain proportion condition) metabolism, by ammonia nitrogen and nitrite nitrogen
Nitrogen is converted into, denitrification effect is finally reached.
From the point of view of Anammox with denitrifying reaction equation, anti-nitration reaction consumption organic matter simultaneously produces CO2, it is
Anammox reaction eliminates the inhibitory action of organic carbon source and provides inorganic carbon source, what denitrifying bacterium was not enough in electron donor
Under the conditions of by NO3 -- N is reduced to NO2 -- N, for Anammox reaction provides substrate NO2 —N;And Anammox reaction produces one
Quantitative NO3 -- N can provide electron acceptor for denitrification, therefore, both coexist, and mutually promote.
From the point of view of the Gibbs free energy of reaction, anti-nitration reaction has lower free energy, when there is organic matter, instead
Nitrifier is easier to utilize NO than anaerobic ammonia oxidizing bacteria2 -- N, the two is to reaction substrate NO2 -There is limitation sexual competition in-N.
Anammox couples the influence for being vulnerable to condition element with denitrification, such as selects suitable reactor and control
Suitable hydraulic detention time;Control suitable environmental condition, such as DO concentration and pH value;Control suitable concentration of substrate, such as NH4 +、NO2 -With COD concentration and C/N etc., significant is set up to system.
Anammox and the usual influent ammonia nitrogen of denitrification coupled system and nitrite nitrogen, Anammox can only remove 90%
With the nitrogen that ammonia and nitrous acid form are present, still having 10% nitrogen to be converted into nitrate nitrogen can not be removed;And usual ammonia nitrogen in sewage
It is dense, nitrous nitrogen concentration is very low, and even without a large amount of accumulation are less susceptible to, denitrification effect is not fine.And in organic ring
Under the conditions of border, the denitrifying bacterium in coupling technique can be by biological agent using the NO for being capable of stable existence in the environment3- N, and
Change into the NO that anaerobic ammonia oxidizing bacteria can be utilized directly2 -- N, relieves the limitation sexual competition of the two, also overcomes NO2 -- N is difficult to
The problem of efficient accumulation, while the NO that anaerobic ammonium oxidation process is produced3 -- N is recycling, and these can improve the treatment effect of denitrogenation
Really.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of Anammox and denitrification coupling device and control
Operation method, realizes Anammox in when containing organic carbon source and denitrification synergistic denitrification, makes Anammox and denitrification coupling
Syzygy system control is good, runs stable water outlet.
A kind of Anammox and denitrification coupling device, including reactor, water feed apparatus, nitrogen pot, water-bath circulation dress
Put and exhaust apparatus, the Reactor inlet end connects water feed apparatus and nitrogen pot, port of export connection exhaust apparatus, in reactor
Periphery is provided with water bath sleeve, water bath sleeve connection water-bath EGR;Wastewater liquid is delivered when using, in the inlet water tank of water feed apparatus to mix
Compound.
Further, the water feed apparatus include inlet water tank, pH measuring instruments and measuring pump, and the delivery port of inlet water tank is by meter
Amount pump coupled reaction device entrance point, sets pH measuring instruments in inlet water tank.
Further, the water-bath EGR includes circulating pump, water bath and temperature controller, and water bath is connected by circulating pump
The water bath sleeve water inlet of reactor is connect, the water return outlet of water bath sleeve connects water bath, also set up in water bath by return line
There is temperature controller.
Further, the reactor is UASB reactors, and three phase separator is set in it, and reactor periphery sets water-bath
Set.
Further, the exhaust apparatus is gas collection bottle, and the gas outlet of reactor and three phase separator passes through respectively
Pipeline connection gas collection bottle.
Anammox of the present invention and the control operation method of denitrification coupling device, comprise the following steps:.
I step Anaerobic ammonium oxidation system culture domestications:
1) with municipal wastewater treatment plant second pond sludge as seed sludge, tamed by bioreactor culture, reaction uses continuous stream
Mode is run, and water inlet major control water inlet nitrogen source is ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N2 —N), wherein ammonia nitrogen is with NH4Cl is provided,
120~180mg/L of influent concentration;Nitrite nitrogen is with NaNO2There is provided, 150~200mg/L of influent concentration;
2) with NaHCO3As inorganic carbon source, NaHCO3Concentration is 0.1~0.15g/L;While NaHCO3Adjusted as buffer
Section pH value, pH value range is controlled 6.5~8.5;
3) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
4) other elements water inlet index:ρ(KH2PO4)=6mg/L, ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·
2H2O)=56mg/L;Micro- each 1mL of I, II is added in 1L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L,
ρ(FeSO4)=5000mg/L;Micro- II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ
(MnCl2·4H2O)=990mg/L, CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]
=220mg/L, ρ [(NaSeO4·10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
5) by the cherry elliposoidal of the ratio of domestication culture sludge 80%, the spherical particle sludge, anaerobism ammonia of 180d
Oxidative system is set up and stable operation;
Ii walks Anammox and denitrification coupling stages:
1) reaction is using continuous stream mode operation, water inlet major control index ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N3 —N), enter
With NO in water3 —N replaces NO2 —N, NO3 —N is by NaNO3There is provided, nitrogen source, wherein NH are provided to system4 -- N concentration be 120~
180mg/L, NO3 —N concentration is 165~198mg/L, and the concentration ratio of ammonia nitrogen and nitrate nitrogen is 1 in water inlet:(1.08~1.32);
2) pH value is adjusted with NaOH, pH value range is controlled 6.5~8.5;
3) provide organic through the combination of hydrolysed ferment liquid one or more of which with starch, sodium acetate, sewage plant excess sludge
Nitrogen source, organic carbon source COD concentration is 180~240mg/L, keeps C:N is 0.4~0.6, to promote coupling technique;
4) with KH2PO4Used as phosphorus source, 65~70mg/L of concentration keeps N:P=(3~5):1;
5) other elements water inlet index ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·2H2O)=56mg/L;It is micro
Each 1mL of element I, II is added in 2L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L, ρ (FeSO4)=5000mg/
L;Micro- II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ (MnCl2·4H2O)=990mg/
L, CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]=220mg/L, ρ [(NaSeO4·
10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
6) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
7) nitrogen is passed through to continuous in reactor, formation is difficult the compact grain sludge for disintegrating.
The beneficial effects of the invention are as follows:
Due to the stability of nitrate nitrogen overcome nitrite nitrogen be difficult to accumulation harsh conditions, be whole system constantly
Nitrogen source element material is provided, under the biological agent of denitrifying bacterium, using the teaching of the invention it is possible to provide the nitrite nitrogen of steady concentration meets anaerobism ammonia oxygen
The material requirement of change process, promotes constantly the tending towards stability of whole Anammox and denitrification coupling technique, efficiently.
Brief description of the drawings
Fig. 1 is coupling device schematic diagram of the invention.
Fig. 2 is control operation method schematic diagram of the invention.
In figure, 1, inlet water tank, 2, pH measuring instruments, 3, measuring pump, 4, nitrogen pot, 5, circulating pump, 6, water bath, 7, temperature control
Instrument, 8, three phase separator, 9, gas collection bottle, 10, reactor, 11, water bath sleeve, I, water-bath EGR, II, exhaust apparatus,
IIIth, water feed apparatus;
a、NH4 --N(NH4Cl);b、NO3 —N(NaNO3) or NO2 —N(NaNO2);C, carbon source;d、KH2PO4;e、MgSO4·
7H20;f、CaCl2·2H20。
Specific embodiment:
The present invention will be described in detail with reference to the accompanying drawings and examples:
Embodiment:As shown in Figure 1 and Figure 2, a kind of Anammox of the invention and denitrification coupling device, including reactor
10th, water feed apparatus III, nitrogen pot 4, water-bath EGR I and exhaust apparatus II, the entrance point of the reactor 10 connection water inlet dress
III and nitrogen pot 4 are put, port of export connection exhaust apparatus II is provided with water bath sleeve 11, the connection water of water bath sleeve 11 in the periphery of reactor 10
Bath EGR I;When using, wastewater liquid mixture is delivered in the inlet water tank 1 of water feed apparatus III.
The wastewater liquid mixture includes a, NH4 --N(NH4Cl);b、NO3 —N(NaNO3) or NO2 —N(NaNO2);C, carbon
Source;d、KH2PO4;e、MgSO4·7H20;f、CaCl2·2H20。
The water feed apparatus III include inlet water tank 1, pH measuring instruments 2 and measuring pump 3, and the delivery port of inlet water tank 1 is by metering
The entrance point of 3 coupled reaction device of pump 10, sets pH measuring instruments 2 in inlet water tank 1.
The water-bath EGR I includes circulating pump 5, water bath 6 and temperature controller 7, and water bath 6 is connected by circulating pump 5
The water inlet of water bath sleeve 11 of reactor 10, the water return outlet of water bath sleeve 11 connects water bath 6 by return line, in water bath 6
It is additionally provided with temperature controller 7.
The reactor 10 is UASB reactors, and three phase separator 8 is set in it, and the periphery of reactor 10 sets water bath sleeve 6.
The exhaust apparatus II is gas collection bottle 9, and the gas outlet of reactor 10 and three phase separator 8 passes through pipeline respectively
Connection gas collection bottle 9.
Anammox of the invention and the control operation method of denitrification coupling device, comprise the following steps:.
I step Anaerobic ammonium oxidation system culture domestications:
1) with municipal wastewater treatment plant second pond sludge as seed sludge, cultivated by reactor 10 and tamed, reaction is using continuous
Stream mode is run, and water inlet major control water inlet nitrogen source is ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N2 —N), wherein ammonia nitrogen is with NH4Cl is carried
For 120~180mg/L of influent concentration;Nitrite nitrogen is with NaNO2There is provided, 150~200mg/L of influent concentration;
2) with NaHCO3As inorganic carbon source, NaHCO3Concentration is 0.1~0.15g/L;While NaHCO3Adjusted as buffer
Section pH value, pH value range is controlled 6.5~8.5;
3) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
4) other elements water inlet index:ρ(KH2PO4)=6mg/L, ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·
2H2O)=56mg/L;Micro- each 1mL of I, II is added in 1L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L,
ρ(FeSO4)=5000mg/L;Micro- II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ
(MnCl2·4H2O)=990mg/L, CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]
=220mg/L, ρ [(NaSeO4·10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
5) by the cherry elliposoidal of the ratio of domestication culture sludge 80%, the spherical particle sludge, anaerobism ammonia of 180d
Oxidative system is set up and stable operation;
Ii walks Anammox and denitrification coupling stages:
1) reaction is using continuous stream mode operation, water inlet major control index ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N3 —N), enter
With NO in water3 —N replaces NO2 —N, NO3 —N is by NaNO3There is provided, nitrogen source, wherein NH are provided to system4 -- N concentration be 120~
180mg/L, NO3 —N concentration is 165~198mg/L, and the concentration ratio of ammonia nitrogen and nitrate nitrogen is 1 in water inlet:(1.08~1.32);
2) pH value is adjusted with NaOH, pH value range is controlled 6.5~8.5;
3) provide organic through the combination of hydrolysed ferment liquid one or more of which with starch, sodium acetate, sewage plant excess sludge
Nitrogen source, organic carbon source COD concentration is 180~240mg/L, keeps C:N is 0.4~0.6, to promote coupling technique;
4) with KH2PO4Used as phosphorus source, 65~70mg/L of concentration keeps N:P=(3~5):1;
5) other elements water inlet index ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·2H2O)=56mg/L;It is micro
Each 1mL of element I, II is added in 2L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L, ρ (FeSO4)=5000mg/
L;Micro- II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ (MnCl2·4H2O)=990mg/
L, CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]=220mg/L, ρ [(NaSeO4·
10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
6) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
7) nitrogen is passed through to continuous in reactor, promotes gas, liquid, solid three-phase collective effect, under stronger hydraulics,
The effect of mass transmitting of closely knit granule sludge, enhancement microbiological and pollutant can be formed, mud granule is difficult to disintegrate.
Claims (5)
1. the control operation method of a kind of Anammox and denitrification coupling device, it is characterised in that:Anammox with it is anti-
Nitrification coupling device includes reactor, water feed apparatus, nitrogen pot, water-bath EGR and exhaust apparatus, the Reactor inlet
End connection water feed apparatus and nitrogen pot, port of export connection exhaust apparatus are provided with water bath sleeve, water bath sleeve connection water in reactor periphery
Bath EGR;When using, wastewater liquid mixture is delivered in the inlet water tank of water feed apparatus, specifically include following steps:
I step Anaerobic ammonium oxidation system culture domestications:
1) with municipal wastewater treatment plant second pond sludge as seed sludge, tamed by bioreactor culture, reaction uses continuous stream mode
Operation, water inlet major control water inlet nitrogen source is ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N2 —N), wherein ammonia nitrogen is with NH4Cl is provided, water inlet
120~180mg/L of concentration;Nitrite nitrogen is with NaNO2There is provided, 150~200mg/L of influent concentration;
2) with NaHCO3As inorganic carbon source, NaHCO3Concentration is 0.1~0.15g/L;While NaHCO3PH is adjusted as buffer
Value, pH value range is controlled 6.5~8.5;
3) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
4) other elements water inlet index:ρ(KH2PO4)=6mg/L, ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·2H2O)
=56mg/L;Micro- each 1mL of I, II is added in 1L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L, ρ
(FeSO4)=5000mg/L;Micro- II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ
(MnCl2·4H2O)=990mg/L, CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]
=220mg/L, ρ [(NaSeO4·10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
5) by the cherry elliposoidal of the ratio of domestication culture sludge 80%, the spherical particle sludge, Anammox of 180d
System is set up and stable operation;
Ii walks Anammox and denitrification coupling stages:
1) reaction is using continuous stream mode operation, water inlet major control index ammonia nitrogen (NH4 —) and nitrate nitrogen (NO N3 —N), in water inlet
With NO3 —N replaces NO2 —N, NO3 —N is by NaNO3There is provided, nitrogen source, wherein NH are provided to system4 -- N concentration is 120~180mg/L,
NO3 —N concentration is 165~198mg/L, and the concentration ratio of ammonia nitrogen and nitrate nitrogen is 1 in water inlet:(1.08~1.32);
2) pH value is adjusted with NaOH, pH value range is controlled 6.5~8.5;
3) organic carbon source is provided through the combination of hydrolysed ferment liquid one or more of which with starch, sodium acetate, sewage plant excess sludge,
Organic carbon source COD concentration is 180~240mg/L, keeps C:N is 0.4~0.6, to promote coupling technique;
4) with KH2PO4Used as phosphorus source, 65~70mg/L of concentration keeps N:P=(3~5):1;
5) other elements water inlet index ρ (MgSO4·7H2O)=300mg/L, ρ (CaCl2·2H2O)=56mg/L;Micro- I,
Each 1mL of II are added in 2L water inlets, wherein:Micro- I:ρ (EDTA)=5000mg/L, ρ (FeSO4)=5000mg/L;It is micro
Element II:ρ (EDTA)=15000mg/L, ρ (ZnSO4·7H2O)=430mg/L, ρ (MnCl2·4H2O)=990mg/L,
CH3BO4)=14mg/L, ρ (CuSO4·5H2O)=250mg/L, ρ [(NaMoO4·2H2O]=220mg/L, ρ [(NaSeO4·
10H2O]=210mg/L, ρ (NiCl2·6H2O)=190mg/L;
6) control bath temperature is wrapped up in black plastic film and invests reactor surface with lucifuge at 20~35 DEG C;
7) nitrogen is passed through to continuous in reactor, formation is difficult the compact grain sludge for disintegrating.
2. the control operation method of Anammox as claimed in claim 1 and denitrification coupling device, it is characterised in that:It is described
Water feed apparatus include inlet water tank, pH measuring instruments and measuring pump, and the delivery port of inlet water tank passes through measuring pump coupled reaction device entrance point,
PH measuring instruments are set in inlet water tank.
3. the control operation method of Anammox as claimed in claim 1 and denitrification coupling device, it is characterised in that:It is described
Water-bath EGR includes circulating pump, water bath and temperature controller, and water bath is intake by the water bath sleeve of circulating pump coupled reaction device
Mouthful, the water return outlet of water bath sleeve connects water bath by return line, and temperature controller is additionally provided with water bath.
4. the control operation method of Anammox as claimed in claim 1 and denitrification coupling device, it is characterised in that:It is described
Reactor is UASB reactors, and three phase separator is set in it, and reactor periphery sets water bath sleeve.
5. the control operation method of Anammox as claimed in claim 1 and denitrification coupling device, it is characterised in that:It is described
Exhaust apparatus is gas collection bottle, and the gas outlet of reactor and three phase separator connects gas collection bottle by pipeline respectively.
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CN106430572B (en) * | 2016-11-28 | 2023-12-15 | 北京工业大学 | Method and device for combined denitrification by using denitrification and anaerobic ammonia oxidation embedded particles |
CN107129037B (en) * | 2017-05-22 | 2020-09-22 | 华南理工大学 | Method for quickly starting anaerobic ammonia oxidation coupling denitrification synergistic denitrification reactor |
CN109678242A (en) * | 2017-10-18 | 2019-04-26 | 中国石油化工股份有限公司 | The method for handling the waste water of nitrate nitrogen containing high concentration |
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CN111039498A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Method for treating wastewater containing high-concentration ammonia nitrogen |
CN109607779A (en) * | 2019-02-21 | 2019-04-12 | 合肥工业大学 | A kind of method of anerobic sowage ammoxidation coupling solid phase denitrification efficient denitrification |
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CN112680358A (en) * | 2021-01-13 | 2021-04-20 | 华沃德源环境技术(济南)有限公司 | Process for continuously producing denitrifying bacteria agent |
CN113072178B (en) * | 2021-04-01 | 2023-01-03 | 宜宾五粮液股份有限公司 | Method for improving denitrification performance of anaerobic ammonium oxidation bacteria by adopting brewing wastewater |
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