CN105174448A - Anaerobic ammonia oxidation and denitrification coupling device and controlled operation method thereof - Google Patents

Anaerobic ammonia oxidation and denitrification coupling device and controlled operation method thereof Download PDF

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CN105174448A
CN105174448A CN201510670767.XA CN201510670767A CN105174448A CN 105174448 A CN105174448 A CN 105174448A CN 201510670767 A CN201510670767 A CN 201510670767A CN 105174448 A CN105174448 A CN 105174448A
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nitrogen
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anammox
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于鹏飞
周明俊
叶友林
傅金祥
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Sichuan Zhonghua Yu Environmental Protection Engineering Co., Ltd.
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Shenyang Jianzhu University
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Abstract

The invention relates to an anaerobic ammonia oxidation and denitrification coupling device and a controlled operation method thereof, belonging to the technical field of biological sewage treatment. According to the method disclosed by the invention, ammonia nitrogen and nitrate nitrogen are used as reaction nitrogen sources, and meanwhile, the reaction conditions, such as temperature, pH, an organic carbon source, a phosphorus source and DO are controlled, wherein the concentration of NH4--N is 120 to 180mg/L, and the concentration of NO3-N is 165 to 198mg/L, and the concentration ratio of the ammonia nitrogen to the nitrate nitrogen in feedwater 1: (1.08 to 1.32); coexistence and enrichment of anaerobic ammonium oxidation bacteria and denitrifying bacteria in a reactor are realized through culture and acclimation in a culture and acclimation stage and an anaerobic ammonia oxidation and denitrification coupling stage of an anaerobic ammonia oxidation system, and the effect of carrying out anaerobic ammonia oxidation and denitrification simultaneously is realized. The anaerobic ammonia oxidation and denitrification coupling device is simple in operation conditions; the defect that the nitrite nitrogen is difficult to accumulate at high efficiency is overcome, so that the anaerobic ammonia oxidation and denitrification coupling is effectively controlled, and the stability in the operation of a coupling reaction is achieved.

Description

A kind of Anammox and denitrification coupling device and controlling run method thereof
Technical field
The invention belongs to technical field of biological sewage treatment, specifically relate to a kind of Anammox and denitrification coupling device and controlling run method.
Background technology
At present, biological denitrificaion method is domestic and international application one of sewage water denitrification technology the most widely, Anammox is new and effective bio-denitrification technology, it is an important reaction in nitrogen cycle, compared with traditional nitrification and denitrification, Anammox has that oxygen requirement is low, the advantage such as do not need additional carbon, sludge yield few, saves a large amount of working costs.
Anammox principle is that anaerobic ammonia oxidizing bacteria is electron acceptor(EA) with nitrite nitrogen, by NH under the condition of anaerobism or anoxic 4 +-N direct oxidation is N 2process, produces N in nitrogen process 2two nitrogen-atoms respectively from NO 2 -n and NH 4 +-N.
NH 4 ++NO 2 -→N 2+H 2O(△G＝-297KJ/M)
NH 4 +1.32NO 2 -+0.066HCO 3 -+0.13H +→1.02N 2+0.26NO 3 -+0.066CH 2O 0.5N 0.15 +2.03H 2O
Anammox is particularly suitable for process low-carbon (LC) high ammonia-nitrogen wastewater, Anammox has become domestic and international study hotspot in recent years, but under organic environment, Anammox may be there is and the main anaerobic denitrification of denitrification two kinds reacts in reactor assembly simultaneously, if realize the synergy of Anammox and denitrification denitrogenation in same reactor assembly, then significant to bio-denitrification technology exploitation.
Denitrification refers to that denitrifying bacterium is under anaerobic environment condition, and reduction nitrate, discharge the process of dinitrogen, most bacterial digestion is anaerobism heterotrophic bacterium, and it take organism as carbon source and energy, carries out anaerobic respiration.In denitrifying bioprocess, the formula of energy-producing reaction (dissimilation) and cell building-up reactions (internalization)
1.6NO 3 -+CH 3COOH→0.8N 2+2CO 2+1.2H 2O+1.60H -(△G＝-843KJ/M)
1.2NO 3 -+CH 3COOH+0.1NH 4 +→0.1C 5H 7O 2N+0.6N 2+1.5CO 2+1.1OH -+1.3H 2O
Also little about the research of Anammox and denitrification coupling technique at present, Anammox and denitrification coupling reaction system are set up based on two kinds of possibilities: one is cultivated by the domestication of certain condition, Installed System Memory is the bacterium of two kinds of functions, i.e. anaerobic ammonia oxidizing bacteria and denitrifying bacteria, they can coexist in special environment, vie each other, also mutually promote; Two is in this coupled system, there is a kind of special denitrification functions bacterium, it has Anammox and Denitrification Characteristics simultaneously, can deposit in case at organic carbon source, utilize ammonia nitrogen and nitrite nitrogen (controlling certain proportion condition) metabolism, ammonia nitrogen and nitrite nitrogen are converted into nitrogen, finally reach denitrification effect.
From Anammox and denitrifying reaction equation, anti-nitration reaction consumes organism and produces CO 2, for Anammox reaction eliminate organic carbon source restraining effect and inorganic carbon source is provided, denitrifying bacteria under the condition of electron donor deficiency by NO 3 --N is reduced to NO 2 --N, for Anammox reaction provides substrate NO 2 -n; And Anammox reaction produces a certain amount of NO 3 --N can provide electron acceptor(EA) for denitrification, and therefore, both coexist, and mutually promote.
From the Gibbs free energy of reaction, anti-nitration reaction has lower free energy, and when there is organism, denitrifying bacteria is easier than anaerobic ammonia oxidizing bacteria utilizes NO 2 --N, the two is to reaction substrate NO 2 -there is restricted competition in-N.
Anammox is coupled with denitrification and is vulnerable to the impact of condition element, as selected suitable reactor and controlling suitable hydraulic detention time; Control suitable envrionment conditions, as DO concentration and pH value; Control suitable concentration of substrate, as NH 4 +, NO 2 -with COD concentration and C/N etc., system is set up significant.
Anammox and the usual influent ammonia nitrogen of denitrification coupled system and nitrite nitrogen, Anammox can only remove 90% nitrogen existed with ammonia and nitrous acid form, still has the nitrogen transformation of 10% to be that nitric nitrogen can not be removed; And usual ammonia nitrogen dense in sewage, nitrite nitrogen concentration is very low, even more not easily accumulates in a large number, and denitrification effect is not fine.And under organic environment condition, the denitrifying bacteria in coupling technique utilizes by biological action in the environment can the NO of stable existence 3-N, and the NO changing into that anaerobic ammonia oxidizing bacteria can directly utilize 2 --N, relieves the restricted competition of the two, also overcomes NO 2 --N is difficult to a difficult problem for efficient accumulation, the NO of anaerobic ammonium oxidation process generation simultaneously 3 --N is recycling, and these can improve the treatment effect of denitrogenation.
Summary of the invention
For the technical problem of above-mentioned existence, the invention provides a kind of Anammox and denitrification coupling device and controlling run method, realize Anammox containing organic carbon source time and denitrification synergistic denitrification, make Anammox and denitrification coupled system control well, operation stable water outlet.
A kind of Anammox and denitrification coupling device, comprise reactor, water feed apparatus, nitrogen pot, water-bath circulation device and gas barrier, described Reactor inlet end connects water feed apparatus and nitrogen pot, exit end connects gas barrier, be provided with water bath sleeve in reactor periphery, water bath sleeve connects water-bath circulation device; During use, in the inlet chest of water feed apparatus, throw in wastewater liquid mixture.
Further, described water feed apparatus comprises inlet chest, pH survey meter and volume pump, and the water outlet of inlet chest, by volume pump ligation device entrance end, arranges pH survey meter in inlet chest.
Further, described water-bath circulation device comprises recycle pump, water bath and temperature controller, and water bath is by the water bath sleeve water-in of recycle pump ligation device, and the water return outlet of water bath sleeve connects water bath by return line, in water bath, be also provided with temperature controller.
Further, described reactor is UASB reactor, arranges triphase separator in it, and reactor periphery arranges water bath sleeve.
Further, described gas barrier is collection and confinement of gases bottle, and reactor is connected collection and confinement of gases bottle with the air outlet of triphase separator respectively by pipeline.
The controlling run method of Anammox of the present invention and denitrification coupling device, comprises the steps:.
I walks Anaerobic ammonium oxidation system and cultivates domestication:
1) with municipal wastewater treatment plant second pond mud for seed sludge, tamed by bioreactor culture, reaction adopts Continuous Flow mode to run, and water inlet major control water inlet nitrogenous source is ammonia nitrogen (NH 4 -and nitric nitrogen (NO N) 2 -n), wherein ammonia nitrogen with NH 4cl provides, influent concentration 120 ~ 180mg/L; Nitrite nitrogen is with NaNO 2there is provided, influent concentration 150 ~ 200mg/L;
2) with NaHCO 3as inorganic carbon source, NaHCO 3concentration is 0.1 ~ 0.15g/L; NaHCO simultaneously 3as buffer reagent adjust ph, pH value range controls 6.5 ~ 8.5;
3) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
4) other element water inlet index: ρ (KH 2pO 4)=6mg/L, ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 1L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
5) through the cherry elliposoidal of domestication culture sludge 80% ratio, the spherical particle mud of 180d, Anaerobic ammonium oxidation system is set up and steady running;
II walks Anammox and denitrification coupling stages:
1) reaction adopts Continuous Flow mode to run, water inlet major control index ammonia nitrogen (NH 4 -and nitric nitrogen (NO N) 3 -n), in water inlet with NO 3 -n replaces NO 2 -n, NO 3 -n is by NaNO 3there is provided, provide nitrogenous source to system, wherein NH 4 --N concentration is 120 ~ 180mg/L, NO 3 -n concentration is 165 ~ 198mg/L, and in water inlet, the concentration ratio of ammonia nitrogen and nitric nitrogen is 1:(1.08 ~ 1.32);
2) with NaOH adjust ph, pH value range controls 6.5 ~ 8.5;
3) with starch, sodium acetate, sewage plant excess sludge through hydrolysed ferment liquid wherein one or more combinations organic nitrogen source is provided, organic carbon source COD concentration is 180 ~ 240mg/L, keep C:N be 0.4 ~ 0.6, to promote coupling technique;
4) with KH 2pO 4as phosphorus source, concentration 65 ~ 70mg/L, keeps N:P=(3 ~ 5): 1;
5) other element water inlet index ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 2L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
6) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
7) in reactor, pass into nitrogen continuously, form the compact grain mud not easily disintegrated.
The invention has the beneficial effects as follows:
Stability due to nitric nitrogen overcomes the severe condition being difficult to accumulate of nitrite nitrogen, for whole system constantly provides nitrogenous source element material, under the biological action of denitrifying bacteria, the nitrite nitrogen of steady concentration can be provided to meet the material requirement of anaerobic ammonium oxidation process, promote constantly the tending towards stability of whole Anammox and denitrification coupling technique, efficiently.
Accompanying drawing explanation
Fig. 1 is coupling device schematic diagram of the present invention.
Fig. 2 is controlling run Method And Principle figure of the present invention.
In figure, 1, inlet chest, 2, pH survey meter, 3, volume pump, 4, nitrogen pot, 5, recycle pump, 6, water bath, 7, temperature controller, 8, triphase separator, 9, collection and confinement of gases bottle, 10, reactor, 11, water bath sleeve, I, water-bath circulation device, II, gas barrier, III, water feed apparatus;
A, NH 4 --N (NH 4cl); B, NO 3 -n (NaNO 3) or NO 2 -n (NaNO 2); C, carbon source; D, KH 2pO 4; E, MgSO 47H 20; F, CaCl 22H 20.
Embodiment:
Describe the present invention below in conjunction with drawings and Examples:
Embodiment: as shown in Figure 1 and Figure 2, a kind of Anammox of the present invention and denitrification coupling device, comprise reactor 10, water feed apparatus III, nitrogen pot 4, water-bath circulation device I and gas barrier II, described reactor 10 entrance end connects water feed apparatus III and nitrogen pot 4, exit end connects gas barrier II, be provided with water bath sleeve 11 in reactor 10 periphery, water bath sleeve 11 connects water-bath circulation device I; During use, in the inlet chest 1 of water feed apparatus III, throw in wastewater liquid mixture.
Described wastewater liquid mixture comprises a, NH 4 --N (NH 4cl); B, NO 3 -n (NaNO 3) or NO 2 -n (NaNO 2); C, carbon source; D, KH 2pO 4; E, MgSO 47H 20; F, CaCl 22H 20.
Described water feed apparatus III comprises inlet chest 1, pH survey meter 2 and volume pump 3, and the water outlet of inlet chest 1, by volume pump 3 ligation device 10 entrance end, arranges pH survey meter 2 in inlet chest 1.
Described water-bath circulation device I comprises recycle pump 5, water bath 6 and temperature controller 7, water bath 6 is by water bath sleeve 11 water-in of recycle pump 5 ligation device 10, the water return outlet of water bath sleeve 11 connects water bath 6 by return line, in water bath 6, be also provided with temperature controller 7.
Described reactor 10 is UASB reactor, arranges triphase separator 8 in it, and reactor 10 periphery arranges water bath sleeve 6.
Described gas barrier II is collection and confinement of gases bottle 9, and reactor 10 is connected collection and confinement of gases bottle 9 with the air outlet of triphase separator 8 respectively by pipeline.
The controlling run method of Anammox of the present invention and denitrification coupling device, comprises the steps:.
I walks Anaerobic ammonium oxidation system and cultivates domestication:
1) with municipal wastewater treatment plant second pond mud for seed sludge, cultivate domestication by reactor 10, reaction adopts Continuous Flow mode to run, and water inlet major control water inlet nitrogenous source is ammonia nitrogen (NH 4 -and nitric nitrogen (NO N) 2 -n), wherein ammonia nitrogen with NH 4cl provides, influent concentration 120 ~ 180mg/L; Nitrite nitrogen is with NaNO 2there is provided, influent concentration 150 ~ 200mg/L;
2) with NaHCO 3as inorganic carbon source, NaHCO 3concentration is 0.1 ~ 0.15g/L; NaHCO simultaneously 3as buffer reagent adjust ph, pH value range controls 6.5 ~ 8.5;
3) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
4) other element water inlet index: ρ (KH 2pO 4)=6mg/L, ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 1L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
5) through the cherry elliposoidal of domestication culture sludge 80% ratio, the spherical particle mud of 180d, Anaerobic ammonium oxidation system is set up and steady running;
II walks Anammox and denitrification coupling stages:
1) reaction adopts Continuous Flow mode to run, water inlet major control index ammonia nitrogen (NH 4 -and nitric nitrogen (NO N) 3 -n), in water inlet with NO 3 -n replaces NO 2 -n, NO 3 -n is by NaNO 3there is provided, provide nitrogenous source to system, wherein NH 4 --N concentration is 120 ~ 180mg/L, NO 3 -n concentration is 165 ~ 198mg/L, and in water inlet, the concentration ratio of ammonia nitrogen and nitric nitrogen is 1:(1.08 ~ 1.32);
2) with NaOH adjust ph, pH value range controls 6.5 ~ 8.5;
3) with starch, sodium acetate, sewage plant excess sludge through hydrolysed ferment liquid wherein one or more combinations organic nitrogen source is provided, organic carbon source COD concentration is 180 ~ 240mg/L, keep C:N be 0.4 ~ 0.6, to promote coupling technique;
4) with KH 2pO 4as phosphorus source, concentration 65 ~ 70mg/L, keeps N:P=(3 ~ 5): 1;
5) other element water inlet index ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 2L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
6) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
7) in reactor, pass into nitrogen continuously, promote the acting in conjunction of gas, liquid, solid three-phase, under stronger hydraulics, can form closely knit granule sludge, the effect of mass transmitting of enhancement microbiological and pollutent, mud granule not easily disintegrates.

Claims (6)

1. an Anammox and denitrification coupling device, it is characterized in that: comprise reactor, water feed apparatus, nitrogen pot, water-bath circulation device and gas barrier, described Reactor inlet end connects water feed apparatus and nitrogen pot, exit end connects gas barrier, be provided with water bath sleeve in reactor periphery, water bath sleeve connects water-bath circulation device; During use, in the inlet chest of water feed apparatus, throw in wastewater liquid mixture.
2. Anammox and denitrification coupling device as claimed in claim 1, it is characterized in that: described water feed apparatus comprises inlet chest, pH survey meter and volume pump, the water outlet of inlet chest, by volume pump ligation device entrance end, arranges pH survey meter in inlet chest.
3. Anammox and denitrification coupling device as claimed in claim 1, it is characterized in that: described water-bath circulation device comprises recycle pump, water bath and temperature controller, water bath is by the water bath sleeve water-in of recycle pump ligation device, the water return outlet of water bath sleeve connects water bath by return line, in water bath, be also provided with temperature controller.
4. Anammox and denitrification coupling device as claimed in claim 1, it is characterized in that: described reactor is UASB reactor, arranges triphase separator in it, reactor periphery arranges water bath sleeve.
5. Anammox and denitrification coupling device as claimed in claim 1, it is characterized in that: described gas barrier is collection and confinement of gases bottle, reactor is connected collection and confinement of gases bottle with the air outlet of triphase separator respectively by pipeline.
6. the controlling run method of Anammox as claimed in claim 1 and denitrification coupling device, is characterized in that: comprise the steps:.
I walks Anaerobic ammonium oxidation system and cultivates domestication:
1) with municipal wastewater treatment plant second pond mud for seed sludge, tamed by bioreactor culture, reaction adopts Continuous Flow mode to run, and water inlet major control water inlet nitrogenous source is ammonia nitrogen (NH 4-N) and nitric nitrogen (NO 2-N), wherein ammonia nitrogen is with NH 4cl provides, influent concentration 120 ~ 180mg/L; Nitrite nitrogen is with NaNO 2there is provided, influent concentration 150 ~ 200mg/L;
2) with NaHCO 3as inorganic carbon source, NaHCO 3concentration is 0.1 ~ 0.15g/L; NaHCO simultaneously 3as buffer reagent adjust ph, pH value range controls 6.5 ~ 8.5;
3) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
4) other element water inlet index: ρ (KH 2pO 4)=6mg/L, ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 1L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
5) through the cherry elliposoidal of domestication culture sludge 80% ratio, the spherical particle mud of 180d, Anaerobic ammonium oxidation system is set up and steady running;
II walks Anammox and denitrification coupling stages:
1) reaction adopts Continuous Flow mode to run, water inlet major control index ammonia nitrogen (NH 4-N) and nitric nitrogen (NO 3-N), with NO in water inlet 3-N replaces NO 2-N, NO 3-N is by NaNO 3there is provided, provide nitrogenous source to system, wherein NH 4 --N concentration is 120 ~ 180mg/L, NO 3-N concentration is 165 ~ 198mg/L, and in water inlet, the concentration ratio of ammonia nitrogen and nitric nitrogen is 1:(1.08 ~ 1.32);
2) with NaOH adjust ph, pH value range controls 6.5 ~ 8.5;
3) with starch, sodium acetate, sewage plant excess sludge through hydrolysed ferment liquid wherein one or more combinations organic nitrogen source is provided, organic carbon source COD concentration is 180 ~ 240mg/L, keep C:N be 0.4 ~ 0.6, to promote coupling technique;
4) with KH 2pO 4as phosphorus source, concentration 65 ~ 70mg/L, keeps N:P=(3 ~ 5): 1;
5) other element water inlet index ρ (MgSO 47H 2o)=300mg/L, ρ (CaCl 22H 2o)=56mg/L; The each 1mL of trace element I, II adds in 2L water inlet, wherein: micro-I: ρ (EDTA)=5000mg/L, ρ (FeSO 4)=5000mg/L; Trace element II: ρ (EDTA)=15000mg/L, ρ (ZnSO 47H 2o)=430mg/L, ρ (MnCl 24H 2o)=990mg/L, CH 3bO 4)=14mg/L, ρ (CuSO 45H 2o)=250mg/L, ρ [(NaMoO 42H 2o]=220mg/L, ρ [(NaSeO 410H 2o]=210mg/L, ρ (NiCl 26H 2o)=190mg/L;
6) control bath temperature at 20 ~ 35 DEG C, wrap up in black plastic film and invest reactor surface with lucifuge;
7) in reactor, pass into nitrogen continuously, form the compact grain mud not easily disintegrated.
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