CN103601297A - Starting and efficient operating method of normal-temperature high-ammonia-nitrogen completely autotrophic nitrogen-removal over nitrite (CANON) technique - Google Patents
Starting and efficient operating method of normal-temperature high-ammonia-nitrogen completely autotrophic nitrogen-removal over nitrite (CANON) technique Download PDFInfo
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Abstract
The invention relates to a starting and efficient operating method of a normal-temperature high-ammonia-nitrogen completely autotrophic nitrogen-removal over nitrite (CANON) technique, belonging to the field of aquatic environment restoration and regeneration. CANON filter column back flush sludge is inoculated to a reactor, and a biofilm formation stage, a variable substrate starting stage and an efficient operating stage are performed at normal temperature to achieve the level of treating 780-820 mg/L high-ammonia-nitrogen sewage within 150 days; and the average total nitrogen removal load is up to 3.03kg.m<-3>.d<-1>, which is many times higher than the Japanese Furukawa (0.83kg.m<-3>.d<-1>) and Spanish Vazquez-Padin (0.5kg.m<-3>.d<-1>).
Description
Technical field
The invention belongs to water surrounding recovers and regeneration field.Be specifically related to start and the efficient method of moving for various normal temperature, high-ammonia-nitrogen sewage biomembrance process whole process autotrophic denitrification (CANON) technique.
Background technology
Full Autotrophic Ammonium Removal Process refers to that first aerobic ammonia-oxidizing bacteria is with O under aerobic condition
2for electron acceptor(EA), with NH
4 +-N is that electron donor is by NH
4 +be oxidized to NO
2 --N, anaerobic ammonium oxidizing bacteria is with NO simultaneously
2 --N is electron acceptor(EA), by NH
4 +-N direct oxidation is N
2process.This technique is whole process autotrophic denitrification process, can process and only contain NH
4 +the sewage of-N, compares with traditional denitrification process, without additional carbon, can save a large amount of energy consumptions, and sludge yield is little, has broad application prospects.
Since TU Delft is found Anammox technology and technological development goes out after the Full Autotrophic Ammonium Removal Process such as CANON based on Anammox, Full Autotrophic Ammonium Removal Process is widely used in many places in Holland, Germany and Asia, its reactor types is varied, treatment effect difference is large, but all higher than traditional biological denitrificaion approach.
In recent years, for Full Autotrophic Ammonium Removal Process, conducted in-depth research and obtained certain achievement both at home and abroad.The people such as Furukawa of Japan are middle high temperature 30-35 ℃ at reaction conditions, and ammonia nitrogen concentration is 600-1000mg/L, and pH=7.5 has obtained respectively higher total nitrogen and removed load and nitrogen removal rate, has reached 0.83kgm
-3d
-1with 91%; The J.D.Villegas of Sweden etc. is 30 ℃ in temperature, and pH is 7.5, and DO adopts 10 times of dilution anaerobic digestion solution NH under 1~3mg/L condition
4 +-N=2.5g/L, adopts CSTR(with Biofilm carrier) reactor inoculation has nitrosification active sludge and at 40 days, has obvious total nitrogen loss, constantly reduces afterwards extension rate, and final total nitrogen is removed load can reach 0.33kgm
-3d
-1, nitrogen removal rate can reach 80%; Hispanic Vazquez-Padin etc. adopt sbr reactor device, and final removal effect is 80%, remove load average out to 0.5kgm
-3d
-1.Visible current Full Autotrophic Ammonium Removal Process is mainly used in the high ammonia nitrogen of high temperature field, and ubiquity the problem that load is lower of processing, and for the processing of normal temperature high-ammonia-nitrogen sewage, need further research.
Summary of the invention
The object of the invention is to provide a kind of biomembrance process whole process autotrophic deamination technique of processing high ammonia-nitrogen wastewater to start and the method for efficient operation.
In the present invention, first improve water inlet substrate concn, reactor is fully adapted to for high ammonia nitrogen matrix environment, improve again afterwards influent load, make reactor reach higher processing power, during the course, filter tank is for adapting to even more important for the adaptation that changes matrix environment compared with it because flooding velocity and rising gas speed increases the high flow rate bringing.
The present invention is applicable to 16-24 ℃ of normal temperature condition, and the Full Autotrophic Ammonium Removal Process of high ammonia nitrogen from process high temperature successfully starts the whole process autotrophic denitrification biological filter of processing normal temperature high-ammonia-nitrogen sewage; Nitrogen removal rate is nitrogen reduction and the ratio of water inlet nitrogen total mass, and it is the nitrogen quality that unit volume reactor is removed every day that total nitrogen is removed load; The concrete steps of method are as follows:
Step 1: reactor biofilm stage
Reactor adopts volcanic filling material, inoculation CANON filter post back flushing floc sludge out.Total nitrogen concentration 380-420mg/L of intaking, ammonia nitrogen and nitrite nitrogen mass concentration ratio are 1:1, CaCO
3basicity mass concentration 800-1000mg/L.Adopt intermittent operation mode, establish a peristaltic pump, pump speed 70-130rpm/min, draws water from reactor top, through bottom, reflux into reactor, and operation 4-6 cycle, each cycle 1 day.When nitrogen removal rate surpass 50% and steady running within 3 days, think above biofilm success.
Step 2: the unloading phase of becoming matrix
This stage running mode is continuously water inlet and continuous effluent, total nitrogen concentration 280-320mg/L of intaking, ammonia nitrogen and nitrite nitrogen mass concentration ratio are 2:1, control the initial section rising of reactor filtering velocity 0.45-0.55cm/min, nitrogen removal rate only has 10-20%, and total nitrogen is removed load 0.36-0.4kgm
-3d
-1.After nitrogen removal rate is elevated to more than 20% and stablizes more than 3 days, it is all ammonia nitrogen that water inlet total nitrogen becomes, and mass concentration is 180-220mg/L, and now starting aeration provides dissolved oxygen, controls initial dissolution oxygen DO concentration 0.2-0.4mg/L; Its total nitrogen concentration of intaking successively raises, each rising 30%-100%, adjust reactor rising filtering velocity simultaneously, make total nitrogen remove the 80%-100% that load maintains stage load while finishing, the adjusting of dissolved oxygen determines according to the ratio of total nitrogen consumption and nitrate nitrogen growing amount, when ratio be greater than 8 and water outlet nitrite nitrogen concentration be less than 10mg/L and stablize more than 7 days, improve dissolved oxygen, improve 50%-80% at every turn.For realizing the matrix process that becomes, after nitrogen removal rate surpasses 70% in continuous 7 days above, carry out next step and adjust, continue its total nitrogen concentration of intaking that raises, until 760-840mg/L.When nitrogen removal rate surpasses 80% in continuous 10 days, the success unloading phase of becoming matrix.
Step 3: efficient operation phase
Control the total nitrogen concentration 760-840mg/L of water inlet, water inlet CaCO
3basicity mass concentration 3200-3600mg/L, take and rise filtering velocity as controlling index.Initial rising filtering velocity is 0.14-0.16cm/min, successively improves rising filtering velocity, improves 0.03-0.06cm/min at every turn, when nitrogen removal rate surpasses 80% in continuous 7 days above, enters next round and promotes.The adjustment of dissolved oxygen determines according to the ratio of total nitrogen consumption and nitrate nitrogen growing amount, when ratio is greater than 8 and water outlet nitrite nitrogen concentration while being less than 10mg/L, improves dissolved oxygen, improves 50%-80% at every turn.When nitrogen removal rate all can not reach 80% in continuous 7 days above, think that adjusting front rising filtering velocity reaches capacity, limit rising filtering velocity may ultimately reach 0.3-0.36cm/min, dissolved oxygen 5.5-6.0mg/L, total nitrogen is removed load can reach 2.8-3.2kgm
-3d
-1, maintain reactor and move under the operating mode of limit filtering velocity.
Compare with existing Full Autotrophic Ammonium Removal Process, the present invention has following beneficial effect:
1) proposition of the invention intermittent operation mode biofilm, biological attachment success ratio is improved greatly;
2) ratio and the nitrite nitrogen concentration that the present invention proposes according to total nitrogen consumption and nitrate nitrogen growing amount jointly control the method for dissolved oxygen, and have provided selection principle;
3) the invention provides under the high matrix condition of normal temperature the strategy of whole process autotrophic deamination process operation and maintenance and method.
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Accompanying drawing explanation:
Fig. 1 is the whole process autotrophic denitrification testing apparatus schematic diagram that the present invention adopts
To be the reactor that adopts the inventive method change and removed load and account for total removal load per-cent with filter height variation diagram at the 129th, 130 two days experiment total nitrogens Fig. 2, efficient layer depth is 64% of total filtering layer degree of depth, should select section rising filtering velocity as controlling parameter
Fig. 3 is total nitrogen load and the concentration map that adopts the inventive method reactor, becomes the front 80-100% of last stage for it that loads that removes of matrix at every turn
Fig. 4 is nitrogen removal rate and the operating parameter figure that adopts the inventive method reactor, becomes the front nitrogen removal rate of matrix at every turn and all within continuous 7 days, surpasses 70% above, improves the front Δ TN/ Δ NO of dissolved oxygen at every turn
3 -n be greater than 8 and water outlet nitrite nitrogen concentration be less than 10mg/L over 7 days.
Embodiment
Embodiment 1
In process of the test, temperature is constant in 16-24 ℃ all the time, and testing apparatus is for take the biological filter that volcanics is filler, as shown in Figure 1.Testing apparatus is made by synthetic glass, internal diameter 28cm, high 1.2m, cubic capacity 74L, useful volume 64L.Reactor adopts cylindrical reactor, and footpath is dark in being 1:3-1:8, the volcanics filtrate of filling particle diameter 8-15mm, and nonuniformity coefficient is less than 1.2, inoculation CANON filter post back flushing floc sludge out.Filling volcanic filling material in post, loading height is 1.1m, filling particle diameter is 7-9mm.Reactor bottom is equipped with aeration ring, and on the wall of filter tank, every 10cm is provided with a thief hole, adopts peristaltic pump water inlet, and water (flow) direction is upward flow, is provided with water outlet topmost.
Reactor inoculation CANON filter post back flushing floc sludge out, through the cultivation of 147 days, in the situation of reactor through a series of change of load and operational conditions, successfully starting also can steady running.
First being the biofilm stage, is 1:1 at influent ammonia nitrogen and nitrite nitrogen mass concentration ratio, and total nitrogen TN is 390-420mg/L, water inlet CaCO
3basicity mass concentration is to adopt intermittent operation mode under the condition of 900mg/L, be specially with a peristaltic pump, from reactor top, draw water, from reactor bottom circulation, enter reactor again, pump speed 100rpm/min, moves 5 cycles, 1 day each cycle, between each cycle of operation, there is no idle mixing time, the mud of inoculation can be successfully attached on filtrate, through the operation nitrogen removal rate in 5 cycles, surpass 50% and can steady running 3 days.
After biofilm, enter the unloading phase of becoming matrix, reactor operation scheme becomes continuous water inlet, continuous effluent.The first step reduces water inlet total nitrogen to 290-300mg/L, the ratio 2:1 of ammonia nitrogen and nitrite nitrogen concentration, CaCO
3basicity mass concentration is 1000mg/L, and at this moment control section rising filtering velocity is 0.49cm/min, and initial nitrogen removal rate only has 18.1%, and total nitrogen is removed load 0.36kgm
-3d
-1, move 7 days after nitrogen removal rate be elevated to more than 20% and can steady running 3 days.Second step water inlet total nitrogen only has ammonia nitrogen, and water inlet total nitrogen is reduced to 190-220mg/L, CaCO
3basicity mass concentration is 1000mg/L, now starting aeration provides dissolved oxygen, initial dissolution oxygen concn 0.3mg/L, and rising filtering velocity is reduced to 0.36cm/min, initial total nitrogen of this stage remove load NRR when finishing on last stage 96%, through 34 days operation total nitrogens, on average remove load and reach 0.78kgm
-3d
-1the adjusting of dissolved oxygen determines according to the ratio of total nitrogen consumption and nitrate nitrogen growing amount, when ratio be greater than 8 and water outlet nitrite nitrogen concentration be less than 10mg/L and stablize more than 7 days, improve dissolved oxygen, the 25th day dissolved oxygen improves 50% and reaches 0.45mg/L, within the 36th day, improves 66% and reaches 0.75mg/L.The 3rd step raise the total nitrogen concentration of water inlet be on last stage 150%, reach 280-320mg/L, CaCO
3basicity mass concentration is 1300mg/L, reduces rising filtering velocity to 0.28cm/min, total nitrogen remove load on last stage 85%, through 19 day time, remove Load lifting to 1.02kgm
-3d
-1, clearance surpasses dissolved oxygen raising 60% in 70%, the 59 day and reaches 1.2mg/L.The 4th step improve total nitrogen concentration on last stage 200%, reach 590-610mg/L, CaCO
3basicity mass concentration is 2600mg/L, reduces rising filtering velocity to 0.21cm/min, total nitrogen remove load on last stage 94%, through 15 day time, total nitrogen was removed load and has been reached 1.32kgm
-3d
-1, clearance surpasses dissolved oxygen raising 58% in 70%, the 69 day and reaches 1.9mg/L.The 5th step improve total nitrogen concentration on last stage 133%, reach 780-820mg/L, CaCO
3basicity mass concentration is 3350mg/L, and rising filtering velocity is reduced to 0.15cm/min, total nitrogen remove load on last stage 80%, through 29 day time, total nitrogen was removed load and has been reached 1.41kgm
-3d
-1, nitrogen removal rate surpasses 80% and can steady running 10 days, and now dissolved oxygen reaches 1.9mg/L, the success unloading phase of becoming matrix.
The efficient operation phase, this stage total nitrogen concentration 780-820mg/L of intaking, CaCO
3basicity mass concentration is 3350mg/L, makes the total nitrogen of reactor remove load raising by improving section rising filtering velocity and dissolved oxygen.The first step rising filtering velocity is brought up to 0.203cm/min, and dissolved oxygen increases to 3.0mg/L, and initial total nitrogen is removed load for 1.66kgm
-3d
-1, through operation in 11 days, total nitrogen is removed load can reach 2.0kgm
-3d
-1, nitrogen removal rate can reach 80% and can steady running 7 days.Second step promotes rising filtering velocity 0.05cm/min on the basis of previous step, reaches 0.252cm/min, and dissolved oxygen increases to 4.8mg/L, and through operation in 9 days, total nitrogen is removed load can reach 2.5kgm
-3d
-1, nitrogen removal rate can reach 80% and can steady running 7 days.The 3rd step rising filtering velocity reaches 0.305cm/min, and dissolved oxygen increases to 5.6mg/L, and through operation in 11 days, total nitrogen is removed load can reach 3.03kgm
-3d
-1, nitrogen removal rate can reach 80% and can steady running 7 days.The 4th step rising filtering velocity reaches 0.357cm/min, but through operation in 15 days, nitrogen removal rate never reached 80%.So finally when rising filtering velocity reaches 0.305cm/min, during dissolved oxygen concentration 5.6mg/L, reach the whole process autotrophic denitrification effect of stability and high efficiency, now total nitrogen average removal rate reaches 87%, approach the nitrogen removal rate of theoretical whole process autotrophic denitrification 89%, total nitrogen is removed load up to 3.03kgm
-3d
-1, higher than the domestic and international achievement in research of major part.Maintain reactor and move under the operating mode of limit rising filtering velocity, can move continually and steadily.
Claims (1)
1. the high ammonia nitrogen Full Autotrophic Ammonium Removal Process of normal temperature starts and an efficient operation method, it is characterized in that:
1) the biofilm stage: reactor adopts volcanic filling material, inoculation CANON filter post back flushing floc sludge out; Water inlet total nitrogen TN mass concentration 380-420mg/L, ammonia nitrogen and nitrite nitrogen mass concentration ratio are 1:1, CaCO
3basicity mass concentration 800-1000mg/L; Adopt intermittent operation mode, establish a peristaltic pump, pump speed 70-130rpm/min, draws water from reactor top, through bottom, reflux into reactor, and operation 4-6 cycle, each cycle 1 day; When nitrogen removal rate surpass 50% and steady running within 3 days, think above biofilm success;
2) unloading phase of becoming matrix: this stage running mode is into intaking continuously and continuous effluent, total nitrogen concentration 280-320mg/L of intaking, ammonia nitrogen and nitrite nitrogen mass concentration ratio are 2:1, control the initial section rising of reactor filtering velocity 0.45-0.55cm/min, nitrogen removal rate only has 10-20%, and total nitrogen is removed load 0.36-0.4kgm
-3d
-1; After nitrogen removal rate is elevated to more than 20% and stablizes more than 3 days, it is all ammonia nitrogen that water inlet total nitrogen becomes, and mass concentration is 180-220mg/L, and now starting aeration provides dissolved oxygen, controls initial dissolution oxygen DO concentration 0.2-0.4mg/L; Its total nitrogen concentration of intaking successively raises, each rising 30%-100%, adjust reactor rising filtering velocity simultaneously, make total nitrogen remove the 80%-100% that load maintains stage load while finishing, the adjusting of dissolved oxygen determines according to the ratio of total nitrogen consumption and nitrate nitrogen growing amount, when ratio be greater than 8 and water outlet nitrite nitrogen concentration be less than 10mg/L and stablize more than 7 days, improve dissolved oxygen, improve 50%-80% at every turn; For realizing the matrix process that becomes, after nitrogen removal rate surpasses 70% in continuous 7 days above, carry out next step and adjust, continue its total nitrogen concentration of intaking that raises, until 760-840mg/L; When nitrogen removal rate surpasses 80% in continuous 10 days, the success unloading phase of becoming matrix;
3) the efficient operation phase: control the total nitrogen concentration 760-840mg/L of water inlet, water inlet CaCO
3basicity mass concentration 3200-3600mg/L, take and rise filtering velocity as controlling index; Initial rising filtering velocity is 0.14-0.16cm/min, successively improves rising filtering velocity, improves 0.03-0.06cm/min at every turn, when nitrogen removal rate surpasses 80% in continuous 7 days above, enters next round and promotes; The adjustment of dissolved oxygen determines according to the ratio of total nitrogen consumption and nitrate nitrogen growing amount, when ratio is greater than 8 and water outlet nitrite nitrogen concentration while being less than 10mg/L, improves dissolved oxygen, improves 50%-80% at every turn; When nitrogen removal rate all can not reach 80% in continuous 7 days above, think that adjusting front rising filtering velocity reaches capacity, and maintains reactor and moves under the operating mode of limit filtering velocity.
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Cited By (3)
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CN107253761A (en) * | 2017-07-31 | 2017-10-17 | 山东大学 | A kind of Anammox based on inactivated sludge quickly strengthens startup method |
CN107986443A (en) * | 2017-11-07 | 2018-05-04 | 同济大学 | A kind of whole process autotrophic denitrification method that big sewage is fluctuated suitable for COD/N |
WO2020113863A1 (en) * | 2018-12-05 | 2020-06-11 | 青岛思普润水处理股份有限公司 | Rapid start-up method for mbbr completely autotrophic nitrogen removal system |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107253761A (en) * | 2017-07-31 | 2017-10-17 | 山东大学 | A kind of Anammox based on inactivated sludge quickly strengthens startup method |
CN107253761B (en) * | 2017-07-31 | 2020-06-05 | 山东大学 | Anaerobic ammonia oxidation rapid enhanced starting method based on inactivated sludge |
CN107986443A (en) * | 2017-11-07 | 2018-05-04 | 同济大学 | A kind of whole process autotrophic denitrification method that big sewage is fluctuated suitable for COD/N |
WO2020113863A1 (en) * | 2018-12-05 | 2020-06-11 | 青岛思普润水处理股份有限公司 | Rapid start-up method for mbbr completely autotrophic nitrogen removal system |
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