CN102701441A - Method for regulating and controlling nitrogen proportion of partial nitrosation effluent of low-ammonia-nitrogen continuous stirred-tank reactor (CSTR) at normal temperature - Google Patents
Method for regulating and controlling nitrogen proportion of partial nitrosation effluent of low-ammonia-nitrogen continuous stirred-tank reactor (CSTR) at normal temperature Download PDFInfo
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Abstract
The invention provides a method for regulating and controlling nitrogen proportion of partial nitrosation effluent of low-ammonia-nitrogen continuous stirred-tank reactor (CSTR) at normal temperature and belongs to the field of municipal wastewater treatment and recycling. The starting is performed in a four-stage mode, and 80%-100% of ammoxidation load in the low-ammonia-nitrogen operation period of sequencing batch reactor activated sludge process (SBR) serves as initial ammoxidation load of the CSTR to confirm hydraulic retention time (HRT) of the CSTR. DO/ALR serves as an iconic parameter for maintaining a nitrosation system, and a value of the iconic parameter is recommended to be not greater than 1.0 mgO2/gNd and is regarded as the regulating and controlling standard of the DO and the HRT. First, the HRT is constant, the DO is controlled singly, if the proportion is not reached or the ammoxidation load is not enough, the DO and the HRT can be regulated and controlled synchronously. The NO2--N/NH4+-N and ammonia-nitrogen oxidation rate (a)/nitrite nitrogen generating rate (b) and nitrite nitrogen generating rate (b)/nitrate nitrogen generating rate (c) of the effluent are compared. If an average value of the proportions of the effluent under the different working conditions is in a range of 1-1.32:1, when b/a is greater than 0.9 and more approximates to 1.0, b/c is greater, and the working condition is more suitable for long-term operation of the system. The NO2--N/NH4+-N of the effluent of the CSTR is guaranteed to be in a range of 1-1.32:1 so as to meet the water feeding requirement of an anaerobic oxidation technology.
Description
Technical field
The invention belongs to municipal sewage treatment and resource utilization field.Be specifically related to the part nitrosification process stabilizing operation of even flow hybrid fully (CSTR) reactor for treatment low ammonia nitrogen waste water under the normal temperature condition and the method for the suitable water outlet proportion of control; Make CSTR under the condition of higher nitrosification rate, obtain the water outlet that nitrite nitrogen/ammonia nitrogen is 1 ~ 1.32:1, to satisfy the water inlet demand of anaerobic ammonia oxidation process.
Background technology
The problem of controlling nitrate pollution in the dirty waste water is one of the important topic in present water pollution control field, and studies the hot issue that novel energy-saving and cost-reducing denitrogenation of waste water technology has become the water pollution control field.
Traditional is nitrated---denitrification process be one ripe and use wastewater biological denitrificaion technology the most widely, but the problem of its existence also highlights day by day: the time that nitration reaction needs is long and dissolved oxygen content that consume is many; Denitrification process needs additional carbon, a little less than the capacity of resisting impact load, need carry out acid-base neutralisation etc.Part nitrosification---Anammox (Anammox) technology is only compared with the traditional biological denitrification process 50% ~ 60% NH
4 +-N is oxidizing to nitrite nitrogen (NO
2 --N), prevent nitrate nitrogen (NO
3 --N) generation in the Anammox reactor drum, need not additional carbon under anaerobic condition, directly be the NO of 1 ~ 1.32:1 with ratio
2 --N and NH
4 +-N is converted into N
2Discharge into the atmosphere, realize the removal of nitrogen.Advantages such as it is few that it has oxygen-consumption, need not additional carbon, and sludge yield is low and receive the favor and the concern of more and more researchers.
Part nitrosification technology is to realize the key point of Anammox autotrophic denitrification, is required to be the water inlet that Anammox provides nitrite nitrogen/ammonia nitrogen 1-1.32:1.But because the own characteristic of ammonia oxidation bacteria (AOB), normal temperature, low NH
4 +The desirable growing environment of-N waste water and AOB has big gap, so the more difficult stable maintenance of nitrite nitrogen accumulation effect under this envrionment conditions.Intermittent activated sludge process is mainly adopted in the research of nitrosification technology in recent years, and less for the research of complete hybrid even flow (CSTR) technology.Owing to do not have characteristics such as the interior no specific indication parameter of concentration gradient and reactor drum in the CSTR reactor drum, need to be resolved hurrily so how to keep nitrosification effect and this problem of control constant water outlet proportion of system.
Summary of the invention
The object of the present invention is to provide the method for CSTR part nitrosification process stabilizing under a kind of normal temperature condition, efficient operation, guarantee that based on the principle of dissolved oxygen (DO) or DO and the dual control of hydraulic detention time (HRT) CSTR obtains the water outlet that nitrite nitrogen/ammonia nitrogen is 1 ~ 1.32:1 under the condition of higher nitrosification rate.
Operation method provided by the present invention is under normal temperature condition, is research object with the low ammonia nitrogen concentration waste water of human configuration, mainly the synchronization control through DO or HRT and DO realize CSTR part nitrosation reaction device efficiently, steady running.
Concrete steps are following:
Step 1: the CSTR reactor drum is built
Set gradually water tank, aeration tank and settling tank according to intaking to the order of water outlet.Sewage pumps into the aeration tank through intake pump from water tank, and the aeration tank water outlet is communicated to the settling tank pipe core through pipeline, through sludge reflux pump the mud in the settling tank is drawn back to the aeration tank.
Aeration rate is provided with DO, pH and temp probe through spinner-type flowmeter control in the complete hybrid reaction tank, and the parameter in the reaction tank is monitored.Water inlet and return flow meter are set, are convenient to the regulation and control of HRT.
Step 2: CSTR reactor start-up
CSTR starts employing stage mode and starts.Inoculation aeration tank, municipal sewage plant nitrifying sludge, the control sludge concentration is at 3000-4000mg/L, and temperature is at 17-25 ℃.
Fs, nitrated performance strain adopts the SBR mode to move; Control influent ammonium concentration 100-120mg/L, pH is 7.70-8.00, DO is 2.0-3.0mg/L; The cycle of carrying out experiment, promptly every 30min water sampling are once measured ammonia nitrogen, nitrite and nitrate concentration.Ammonia nitrogen residue be less than influent ammonia nitrogen 10% before, stop aeration, confirm the reaction times, the control ST is at 0.5-1h, draining, and confirm the SBR cycle with this.Calculate the ammonia nitrogen oxidation load in the one-period, when ammonia nitrogen oxidation load (ALR) reaches 0.20kgN/kgMLSS/d when above, think that the mud nitrification activity is higher, this stage finishes entering next stage.
Subordinate phase the unloading phase of the high ammonia nitrogen nitrosification of SBR, adopts the SBR mode to move, control influent ammonium concentration 180.0 ~ 250.0mg/L, and pH is 7.70 ~ 8.00, DO is 0.50 ~ 0.90mg/L, suppresses the growth of NOB with high free ammonia (FA).Confirm the SBR cycle through cycle experiment, the ammonia nitrogen residue be less than influent ammonia nitrogen 10% before stop aeration, the nitrite that prevents will to have accumulated because of extended aeration is beneficial to NOB propagation by further oxidation.The control ST is at 0.5-1h.Reach more than 90% when continuous 7 cycles of reactor drum nitrosification rate (nitrite nitrogen of the nitrite nitrogen/generation of generation, nitrate nitrogen sum), think that the nitrosation reaction device starts successfully, get into next stage.
Phase III, SBR hangs down the ammonia nitrogen nitrosification laundering period, adopts the SBR mode to move; The control influent ammonium concentration is 70.0 ~ 90.0mg/L; PH is 7.60 ~ 7.90, and DO concentration is 0.30 ~ 0.50mg/L, confirms the cycle through the cycle experiment; Ammonia nitrogen residue be less than influent ammonia nitrogen 10% before stop aeration, ST 0.4-0.5h.When continuous 10 days nitrosification rates of reactor drum 90% when above, think that low ammonia nitrogen nitrosification starts successfully, entering next stage.
Stage, SBR changes the CSTR operation phase.Utilize the ammonia nitrogen oxidation load of SBR and CSTR mud constant, confirm the CSTR controlled variable through the SBR controlled variable.Calculate low continuous 10 days of the ammonia nitrogen operating period nitrosification rate of SBR at 90% average ammonia nitrogen oxidation load when above, the 80%-100% that adopts this value is as CSTR ammonia nitrogen oxidation load ALR, and setting ammonia nitrogen oxidation ratio is 50%-60%; Confirm the flooding velocity and the HRT of reactor drum; And initial HRT controls influent ammonium concentration 70.0 ~ 90.0mg/L at 3.0 ~ 9.0h, and pH is 7.60 ~ 7.90; DO is at 0.20 ~ 0.50mg/L in the reactor drum, and return sludge ratio is 10 ~ 30% of a flooding velocity.
Step 3: single control DO control CSTR water outlet nitrogen ratio strategy
Significant parameter so that DO/ALR maintains as the nitrosification system recommends its value to be not more than 1.0mgO
2/ gNd regulates and control standard with this as DO and HRT.According to definite ALR of CSTR initial stage, and then definite DO higher limit, DO in codomain, adjusted, with regulation and control water outlet nitrite and ammonia nitrogen ratio.As water outlet NO
2 --N/NH
4 +-N value reduced DO concentration in the reactor drum, as water outlet NO greater than 1.32 o'clock
2 --N/NH
4 +-N value is less than 1 o'clock, in the augmenting response device DO concentration to this ratio in 1 ~ 1.32:1 scope till.Each DO change is no more than 0.1mg/L, each 3d at least at interval that changes.When water outlet nitrogen ratio reaches 1 ~ 1.32:1; The ammonia nitrogen oxidation is loaded and was reached 0.20kgN/kg MLSS/d in average 7 days when above; Think that CSTR part nitrosification nitrogen ratio regulates and control successfully, prescribe a time limit that ratio can not reach requirement if DO reaches; Perhaps ratio reaches requirement but ammonia nitrogen oxidation load needs further to improve, and then needs synchronization modulation HRT and DO.
Through measuring the water outlet nitrogen, though regulation and control DO has advantage of high precision, nitrogen is measured trouble, and does not have real-time operability.Show through research, can be poor through Inlet and outlet water pH value is done, draw △ pH, utilize △ pH and water outlet nitrite and ammonia nitrogen ratio linear, infer water outlet proportion, so can be more fast, more intuitively reactor drum controlled variable DO is adjusted.With x is △ pH, and y is water outlet NO
2 --N/NH
4 +-N ratio is set up the y=ax linear relationship, and a is 1.5 ~ 2.0.
Step 4: two control HRT and DO control CSTR water outlet nitrogen ratio strategy
Be not more than 1.0mg O with DO/ALR
2/ gN d is a standard, reduces HRT and can increase ALR, and the system DO upper limit improves; Each HRT reduction amplitude is 0.5 ~ 1.0h, and each adjustment is no less than 10d at interval, behind the change HRT; Calculate the DO higher limit with DO/ALR, in codomain, adjust DO, with regulation and control water outlet nitrite and ammonia nitrogen ratio.Each DO change is no more than 0.1mg/L, each 3d at least at interval that changes.When water outlet nitrogen ratio reaches 1 ~ 1.32:1, the ammonia nitrogen oxidation is loaded and was reached 0.20kgN/kg MLSS/d in average 7 days when above, thinks that CSTR part nitrosification nitrogen ratio regulates and control successfully.
Water outlet NO under the more different HRT
2 --N/NH
4 +-N and ammonia nitrogen rate of oxidation (a)/nitrite nitrogen generating rate (b), nitrite nitrogen generating rate (b)/nitrate nitrogen generating rate (c).If the water outlet proportion average of different operating modes is all between 1 ~ 1.32:1, then when b/a＞0.9 and more near 1.0, and the big more person of b/c, then suitable more operating mode as system's long-time running.
Compare with the treatment process of existing wastewater biological denitrificaion, the present invention has following beneficial effect:
1) compare with traditional nitration denitrification technology, saved aeration rate, its water outlet feeds Anammox technology and need not to add carbon source, greatly reduces the cost of wastewater treatment and has shortened the reaction times, has reduced reactor volume.
2) reactor start-up adopts intermittent operation, constant aerating time, high substrate concn to the mode of hanging down the substrate concn transition, can realize the quick startup of nitrosation reaction device in a short time.
3) through the combined regulating of DO or HRT and DO, obtained stable water outlet proportion, made the realization of part nitrosification technology in continuous flow reactor become possibility.
4) propose the indication parameter of suitable judgement CSTR part nitrosification art breading effect, and provided the relational expression between the two.
Below in conjunction with embodiment the present invention is done to further describe, but protection scope of the present invention is not limited thereto.
Description of drawings
Fig. 1 is complete hybrid even flow testing apparatus synoptic diagram, wherein 1. water tanks, 2.CSTR reactor drum, 3. second pond, 4. intake pump, 5. return sludge pump, 6. stirrer, 7. dissolved oxygen on-line determination appearance, 8. dissolved oxygen probe, 9.pH on-line determination appearance, 10.pH probe, 11. ultrasonic quiet adjustable air pumps, 12. aeration rings.
Fig. 2 is that the present invention adopts intermittent operation, constant aerating time, high substrate concn to start the design sketch of reactor drum to the mode of low substrate concn transition.
Fig. 3 is that the present invention is under constant HRT, through the design sketch of regulation and control DO acquisition stablizing water outlet proportion.
Fig. 4 is that the present invention adopts DO and HRT combined regulating, obtains to stablize the design sketch of water outlet proportion.
Fig. 5 is the match relation curve of CSTR reactor drum Inlet and outlet water pH difference and water outlet proportion.
Embodiment
Test is a basic water and to wherein adding partial raw water with the low ammonia nitrogen waste water of human configuration, and it is following to test concrete water quality: COD＜50mg/L, NH
4 +-N=60.8 ~ 85.0mg/L, NO
2 --N, NO
3 --N＜5.0mg/L, pH=7.70 ~ 8.20, TP＜1.0mg/L.Temperature is 17.0 ~ 23.0 ℃.
The concrete processing as follows:
As shown in Figure 2, according to step 2, mud initial nitrification better performances, ammonia nitrogen oxidation load is 0.2kgN/kgMLSS/d.Directly get into subordinate phase, control initial ammonia nitrogen concentration at 187.0 ~ 238.0mg/L, pH is 7.80, and DO is 0.40mg/L in the reactor drum.Guarantee water outlet ammonia nitrogen concentration residue 70.0mg/L, confirm that according to periodic test aeration time is 8h, 2 cycles of every day; Reach more than 90% through 34 cycles nitrosification rate; Then move 7 cycles, the nitrosification rate is all more than 90%, and the nitrosation reaction device starts successfully and gets into the phase III.The control influent ammonium concentration is 71.7 ~ 84.6mg/L, confirms that according to periodic test aeration time is 5h, moves for 2 cycles every day, operation 10d, and the nitrosification rate is all more than 90%, convertible operation scheme.
As shown in Figure 3, the ammonia nitrogen of low ammonia nitrogen operating period of SBR transforms load for 0.2kgN/kgMLSS/d, is foundation with this value, as water inlet NH
4 +When-N was 75.0mg/L, the amount of removing the part ammonia nitrogen was set at 38mg/L, V=30L, and initial HRT is 3.0h, DO concentration is 0.35mg/L.According to step 3, water outlet NO when DO was 0.35mg/L in the 1st, 2 day
2 --N/NH
4 +-N＜1.0 are so increased DO concentration to 0.45mg/L in the 3rd day, water outlet this moment NO
2 --N/NH
4 +-N is between 1 ~ 1.32:1.And when DO concentration was 0.39mg/L in the 9th day, water outlet proportion was 1.63＞1.32, so should reduce DO concentration.Operation 34d under HRT=3.0h, this stage water outlet NO
2 --N/NH
4 +The time of-N between 1 ~ 1.32:1 is longer than 7d, thinks water outlet NO
2 --N/NH
4 +-N regulates and control successfully, and definite water outlet NO
2 --N/NH
4 +-N between 1 ~ 1.32:1 the time corresponding DO/ALR be 0.75mgO
2/ g N d＜1.0mgO
2/ g N d has guaranteed stage nitrosification rate average to be 96%.
Embodiment 3
As shown in Figure 4, for improving the ammonia nitrogen oxidation load of reactor drum, still control constant DO/ALR value and be 0.75mgO
2/ g N d, according to step 4, HRT reduces to 2.5h from the 3.0h in last stage.Take steps three DO density adjusting method is 1.04 in the 53rd ~ 62d water outlet proportion average, thinks that water outlet proportion is regulated and control successfully and should the stage ammonia nitrogen transform load reach 0.27kgN/ (kgMLSSd).Continue to improve the ammonia nitrogen oxidation load of reactor drum, HRT reduces to 1.5h, three the DO density adjusting method of still taking steps.The 88th ~ 98d water outlet proportion average is 1.18, thinks that water outlet proportion regulates and control successfully, and this stage ammonia nitrogen transforms load and reaches 0.54kgN/ (kgMLSSd).
Average nitrite nitrogen rate of rise is respectively with the ratio b/c of the rate of rise of average nitrate nitrogen when HRT is 3.0h, 2.5h and 1.5h: 22.829,13.673 and 16.080, and average nitrite nitrogen rate of rise is respectively with the ratio b/a of average ammonia nitrogen rate of oxidation: 0.913,0.888 and 0.894.Average b/c during HRT=3.0h more approaches 1 at higher and b/a＞0.9, confirms that therefore HRT=3.0h is preferably as the secular operation condition of nitrosification system.
Because the interior sludge concentration fluctuation of reactor drum is bigger during HRT=1.5h, influenced the mensuration of DO, so only the Inlet and outlet water pH value of preceding 70d is measured.The △ pH of reactor drum and the relation of water outlet proportion roughly satisfy following formula: establishing x is △ pH, and y is water outlet NO
2 --N/NH
4 +-N ratio is carried out match to the two, draws the relational expression of y=1.62467x.When △ pH was in 0.62 ~ 0.81 scope, water outlet proportion was between 1 ~ 1.32:1, if △ pH＜0.62 of observation should increase DO concentration under constant HRT; If △ pH＞0.81 of observation then should reduce DO concentration under constant HRT.
Claims (1)
1. a normal temperature hangs down ammonia nitrogen CSTR part nitrosification water outlet nitrogen ratio regulate and control method, it is characterized in that:
1) the CSTR stage starts: inoculation aeration tank, municipal sewage plant nitrifying sludge, and sludge concentration is at 3000-4000mg/L; Fs, nitrated performance strain adopts the SBR mode to move; Control influent ammonium concentration 100-120mg/L, pH is 7.70-8.00, DO is 2.0-3.0mg/L; Ammonia nitrogen residue be less than influent ammonia nitrogen 10% before, stop aeration, confirm the reaction times; The control ST, draining reached more than the 0.20kgN/kgMLSS/d up to ammonia nitrogen oxidation load at 0.5-1h; Subordinate phase the unloading phase of the high ammonia nitrogen nitrosification of SBR, adopts the SBR mode to move, control influent ammonium concentration 180.0 ~ 250.0mg/L; PH is 7.70 ~ 8.00, and DO is 0.50 ~ 0.90mg/L, ammonia nitrogen residue be less than influent ammonia nitrogen 10% before; Stop aeration, control the ST at 0.5-1h, draining; Up to reactor drum nitrosification rate, the nitrite nitrogen that promptly generates and the nitrite nitrogen of generation, the ratio of nitrate nitrogen sum reached more than 90% in continuous 7 days; Phase III, SBR hangs down the ammonia nitrogen nitrosification laundering period, adopts the SBR mode to move; Control influent ammonium concentration 70.0 ~ 90.0mg/L, pH is 7.60 ~ 7.90, DO is 0.30 ~ 0.50mg/L; Ammonia nitrogen residue be less than influent ammonia nitrogen 10% before, stop aeration, ST 0.4-0.5h; Draining, up to continuous 10 days nitrosification rates of reactor drum more than 90%; Stage, SBR changes the CSTR operation phase, calculates low continuous 10 days of the ammonia nitrogen operating period nitrosification rate of SBR and loads in 90% average ammonia nitrogen oxidation when above; The 80%-100% that adopts this value is as CSTR ammonia nitrogen oxidation load ALR; Setting the ammonia nitrogen oxidation ratio is 50%-60%, confirms the flooding velocity and the HRT of reactor drum, and initial HRT is at 3.0 ~ 9.0h; Control influent ammonium concentration 70.0 ~ 90.0mg/L; PH is 7.60 ~ 7.90, and DO is at 0.20 ~ 0.50mg/L in the reactor drum, and return sludge ratio is 10 ~ 30% of a flooding velocity;
2) single control DO control CSTR water outlet nitrogen ratio strategy: be not more than 1.0mgO as its value of significant parameter that the nitrosification system maintains with DO/ALR
2/ gN d regulates and control standard with this as DO and HRT; According to definite ALR of CSTR initial stage, and then definite DO higher limit, DO in codomain, adjusted, with regulation and control water outlet nitrite and ammonia nitrogen ratio; Each DO change is no more than 0.1mg/L, each 3d at least at interval that changes; When water outlet nitrogen ratio reaches 1 ~ 1.32:1; The ammonia nitrogen oxidation is loaded and was reached 0.20kgN/kg MLSS/d in average 7 days when above; Think that CSTR part nitrosification nitrogen ratio regulates and control successfully, prescribe a time limit that ratio can not reach requirement if DO reaches; Perhaps ratio reaches requirement but ammonia nitrogen oxidation load needs further to improve, and then needs synchronization modulation HRT and DO;
3) two control HRT and DO control CSTR water outlet nitrogen ratio strategy: be not more than 1.0mgO with DO/ALR
2/ gN d is a standard, reduces HRT, can increase ALR, and the system DO upper limit improves; Each HRT reduction amplitude is 0.5 ~ 1.0h, and each adjustment is no less than 10d at interval, behind the change HRT; Calculate the DO higher limit with DO/ALR, in codomain, adjust DO, with regulation and control water outlet nitrite and ammonia nitrogen ratio; Each DO change is no more than 0.1mg/L, each 3d at least at interval that changes; When water outlet nitrogen ratio reaches 1 ~ 1.32:1, the ammonia nitrogen oxidation is loaded and was reached 0.20kgN/kg MLSS/d in average 7 days when above, thinks that CSTR part nitrosification nitrogen ratio regulates and control successfully;
4) different HRT compare with DO combination nitrosification stability: the water outlet NO under the more different HRT
2 --N/NH
4 +-N and ammonia nitrogen rate of oxidation (a)/nitrite nitrogen generating rate (b), nitrite nitrogen generating rate (b)/nitrate nitrogen generating rate (c); If the water outlet proportion average of different operating modes is all between 1 ~ 1.32:1, then when b/a＞0.9 and more near 1.0, and the big more person of b/c, then suitable more operating mode as system's long-time running.
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| CN103408140A (en) * | 2013-08-14 | 2013-11-27 | 哈尔滨工业大学 | Control method realizing CANON process high-efficiency stable operation |
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| CN107879469B (en) * | 2017-11-28 | 2020-05-15 | 苏州诺津环保科技有限公司 | Partial nitrosation starting and controlling method |
| CN110942343A (en) * | 2019-11-22 | 2020-03-31 | 马鞍山钢铁股份有限公司 | Proportioning obtaining method of coal blending |
| CN113772807A (en) * | 2021-10-20 | 2021-12-10 | 广西博世科环保科技股份有限公司 | Method for domesticating and operating ammonia oxidation biofilm reactor |
| CN113772807B (en) * | 2021-10-20 | 2023-03-14 | 广西博世科环保科技股份有限公司 | Method for domesticating and operating ammonia oxidation biofilm reactor |
| CN115010259A (en) * | 2022-08-04 | 2022-09-06 | 江苏海峡环保科技发展有限公司 | Intelligent environment-friendly monitoring data processing method and system |
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