CN104891655A - Device and method for treating high ammonia nitrogen wastewater - Google Patents
Device and method for treating high ammonia nitrogen wastewater Download PDFInfo
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- CN104891655A CN104891655A CN201510296019.XA CN201510296019A CN104891655A CN 104891655 A CN104891655 A CN 104891655A CN 201510296019 A CN201510296019 A CN 201510296019A CN 104891655 A CN104891655 A CN 104891655A
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Abstract
The invention discloses a device and a method for treating high ammonia nitrogen wastewater. The method comprises the following steps: inoculating active sludge to a reactor, starting a stirrer, and circulating the following steps: 1) starting an aeration system and a water feed pump, feeding water in a sequencing batch, delivering the high ammonia nitrogen wastewater to the reactor according to the designed treatment quantity, and closing the water feed pump; 2) closing the aeration system, under the action of a carbon source, reducing nitrate nitrogen in the wastewater into nitrite nitrogen, and reducing the nitrite nitrogen into nitrogen; 3) starting the aeration system, to oxidize ammonia nitrogen and organic matters in the wastewater, wherein the ammonia nitrogen is oxidized into nitrite nitrogen, and the nitrite nitrogen is oxidized into nitrate nitrogen; and 4) after 60-120min at the beginning of an aerobic stage, starting a water discharge pump, filtering the wastewater of the designed treatment quantity by a membrane in a membrane assembly, then discharging the filtered wastewater, and sequentially closing the water discharge pump and the aeration system. By combining the high sludge concentration SBR (sequencing batch reactor) process with the membrane separation technology, the device and the method have the operating characteristics of sequencing batch water feed and continuous water discharge; and the adding quantity of the carbon source is more accurate.
Description
Technical field
The present invention relates to the device and method of process high ammonia-nitrogen wastewater, particularly a kind of device and method utilizing SBR technique and membrane separation technique process high ammonia-nitrogen wastewater, belongs to sewage treatment area.
Background technology
Along with the mankind improve gradually to environmental requirement, sewage drainage standard will constantly be tightened up.Biological nitrification and denitrification is the sewage denitrification method generally adopted at present.Traditional biological process adopts complete nitrification-denitrification process denitrogenation usually, namely aerobic unit is by ammonia oxidation bacteria (Ammonia Oxidizing Bacteria, AOB) after ammonium oxidation being become nitrite nitrogen, nitric nitrogen is oxidized to again by nitrifier (Nitrite Oxidizing Bacteria, NOB); Hold concurrently after the nitrate-nitrogen reduction of generation is then become nitrite nitrogen by oxygen (anaerobism) unit and restore into nitrogen.This is in actual motion, in the treating processes particularly to high ammonia nitrogen, low ratio of carbon to ammonium waste water, in aerobic section ammonium oxidation become nitre nitrogen in nitre nitrogen and double oxygen section be reduced into external carbon source needed for nitrogen supplement all can produce too high running cost.Therefore the denitrogenation novel process of research and development optimization energy consumption is extremely urgent.1989, after YamamotoK etc. deliver the research of first section immersion MBR, immersion MBR is compared with external placed type MBR, energy consumption is reduced because eliminating recycle pump, take up an area the advantages such as compact, progressively come into one's own (YamamotoK in research and engineer applied, HiasaH, TalatM, etal.1989.Direct solid liquid separation using holllowfibe membranes in activated sludge aeration tanks) .1998, Hellinga C etc. utilizes ammonia oxidation bacteria to be shorter than nitrifier generation time, suitable sludge retention time (SRT) is selected to eliminate nitrifier and retain ammonia oxidation bacteria, thus the nitrosification first achieved in single reactor-anti-nitrosation process, namely ammonia nitrogen is directly reduced into nitrogen (Hellinga C after being oxidized to nitrite nitrogen, Schellen AAJC, Mulder JW, van LoosdrechtMCM, Heijen, JJ, 1998.The SHARON Process:an innovative method for nitrogen removal from ammonium-rich wastewater.Water Sci.Technol.37, 135-142).Relative complete nitrification-the denitrification of this technique can save at most the aeration rate of 25%, the external carbon source of 40%, and the biological increment reducing 40%.This causes each follow-up research work in the world to be intended to widen nitrosification-anti-nitrosifying range of application or reduces its requirement to operational conditions, and seeks optimizing integration of traditional technology and MBR.Peng Yongzhen etc. have invented the apparatus and method of anoxic/aerobic SBR+ Anammox+aerobic SBR art breading low C/N domestic sewage advanced denitrogenation; Fan Yaobo etc. have invented integrated A 2/O-MBR reactor.In addition, automatic control system is also progressively applied to sewage treatment process to facilitate management, saves manpower.
Although SBR can reach good denitrification effect in above-mentioned research, but need higher sludge concentration (more than 10000mg/L) for high ammonia-nitrogen wastewater, which results in the longer HRT adding technique of water outlet sedimentation time, simultaneously, because under high sludge concentration, water outlet SS is higher, directly cause effluent quality unstable.Therefore, develop and utilize the device and method of sequencing batch active sludge and membrane separation technique process high ammonia-nitrogen wastewater extremely urgent.
Summary of the invention
The object of this invention is to provide the device and method of process high ammonia-nitrogen wastewater, the membrane technique and SBR technique that efficiently retain effect are optimized combination by this device, the hydraulic detention time (HRT) of technique is shortened while realizing good effluent quality, there is sequence batch (water inlet, the operation characteristic of continuous effluent; Simultaneously, the present invention adopts pH probe, DO (dissolved oxygen) probe and ORP (redox electrode current potential) probe to carry out monitoring continuously to reactor respectively and sets up robot control system(RCS), can control carbon source in time, be short-cut nitrification-denitrification process by nitrification-denitrification process transition.
A kind of device processing high ammonia-nitrogen wastewater provided by the invention, it comprises water inlet system, aerating system, carbon source dosing system, reactive system, film separating system and outlet system;
Described reactive system comprises a reactor, and described reactor is a container, and the top of described reactor is provided with agitator;
Described water inlet system comprises a raw water box, and described raw water box is connected with described reactor by intake pump;
Described aerating system comprises air compressor machine, gas meter and aerator, and described aerator is placed in described reactor;
Described carbon source dosing system comprises a carbon source storage tank, and described carbon source storage tank adds pump by carbon source and is connected with described reactor;
Described film separating system is a membrane module, and described membrane module is placed in described reactor;
Described outlet system comprises a product water tank, and the water outlet of described membrane module passes through water pump and is connected with described product water tank.
Active sludge, in operational process, first, is inoculated with described reactor by apparatus of the present invention; Described high ammonia-nitrogen wastewater is stored in described raw water box, and under the effect of described intake pump, described high ammonia-nitrogen wastewater is transported in described reactor; When described aerating system is in closing condition, under the effect of the carbon source added at carbon source dosing system, the nitrite nitrogen in described high ammonia-nitrogen wastewater is reduced to nitric nitrogen, and nitric nitrogen is reduced to nitrogen (hold concurrently oxygen stage or anaerobic stages); When described aerating system is in opened condition, the waste water that described aerating system can be in described reactor provides oxygen, be oxidized to nitrite nitrogen under the effect of the ammonia oxidizing bacteria in mud of the ammonia-state nitrogen in described waste water, nitrite nitrogen is oxidized to nitric nitrogen (aerobic stage) under the effect of nitrite-oxidizing bacteria; Treated waste water, after film separating system, is purified further, by described go out water pump be discharged in described product water tank.
In said apparatus, described device also comprises a real-time control system, and described enforcement Controlling System comprises probe, unicircuit case and touch sensitive digitizer panel; Described probe comprises pH probe, ORP probe and dissolved oxygen DO and pops one's head in, and be all connected with described unicircuit case, described unicircuit case is connected described real-time control system with described touch sensitive digitizer panel; By the Real-time Monitoring Data that described unicircuit case and described touch sensitive digitizer panel record are popped one's head in the described pH probe of calculating, described ORP probe and described dissolved oxygen DO, thus according to the start and stop that the time variable control set passes in and out water pump, carbon source adds pump, aerating system and agitator, control hocketing of each reaction member in real time.
In said apparatus, described aerator can be placed in the bottom of described reactor, with abundant aeration.
In said apparatus, described membrane module can be placed in the side-walls of described reactor, to avoid the operation of the agitator hindered above described reactor, avoids the damage of described reactor and described agitator;
Described membrane module is plate and frame module, and described plate and frame module comprises 1 ~ 2 film unit, and each described film unit is made up of two panels film; The material of described film is polyvinylidene difluoride (PVDF), aperture≤0.1 μm, and the useful area of each described film unit (membrane element) is 0.5m
2; The inside of described membrane module is also provided with aerator, is connected successively, is described film aeration, reduces the pollution of described film, extend the work-ing life of described film with another air compressor machine and another gas meter.
Invention further provides a kind of method processing high ammonia-nitrogen wastewater, comprise the steps:
In inoculation of activated-sludge to described reactor, open described agitator, the following step of recirculation (1)-step (4):
(1) fill phase: open described aerating system and described intake pump, adopt sequence batch (water inlet, according to designing treatment amount, pending described high ammonia-nitrogen wastewater is transfused in described reactor, closes described intake pump;
(2) hold concurrently the oxygen stage: close described aerating system, under the effect of carbon source, the nitric nitrogen in waste water is reduced to nitrite nitrogen, and nitrite nitrogen is reduced to nitrogen;
(3) aerobic stage: open described aerating system, the ammonia-state nitrogen in waste water and organism oxidized, described ammonia-state nitrogen is oxidized to nitrite nitrogen, and nitrite nitrogen is oxidized to nitric nitrogen;
(4) bleeding stage: after described aerobic stage starts 60 ~ 120min, go out water pump described in unlatching, the described waste water of designing treatment amount is discharged after the filtration of film in described membrane module, goes out water pump and described aerating system described in closing successively.
In aforesaid method, described method also comprises omnidistance step of opening real-time control system, monitors the size of redox electrode current potential, pH value and the dissolved oxygen in described high ammonia-nitrogen wastewater;
Aerator whole process in described membrane module is opened, and aerate flux can be 5 ~ 15L/min, specifically can arrange two panels aeration film, and aerate flux is 8L/min, to reduce fouling membrane, extends the work-ing life of film.
In aforesaid method, the concentration of the active sludge of described inoculation can be 5000mg/L ~ 5500mg/L, 5000mg/L or 5500mg/L, specifically can from the returned sluge of municipal sewage plant; Process due to high ammonia-nitrogen wastewater of the present invention needs to carry out under high sludge concentration, and gradient improves the influent concentration of sewage, can increase to 10000mg/L ~ 12000mg/L by activated sludge concentration, specifically can increase to 11000mg/L;
Described gradient improves and is divided into three phases, and first stage can be 5 ~ 10, specifically can be 5 ~ 7,5 days or 7 days, and 1/4 of most raw waste water concentration is diluted in water inlet; Second stage can be 5 ~ 10, specifically can be 5 ~ 7,5 days or 7 days, and water inlet is diluted to 1/2 of raw waste water concentration; Three phases can be 30 ~ 55, specifically can be 45, to unloading phase complete;
When the clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of ammonia-state nitrogen in described high ammonia-nitrogen wastewater is greater than 80%, when the content that nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%, reactor reaches stable omnidistance denitrogenation, unloading phase, completes, and gradient improves can make the microorganism in described mud adapt to described raw waste water water quality and reactor envrionment conditions as early as possible.
In aforesaid method, in step (1), in described high ammonia-nitrogen wastewater, the concentration of ammonia-state nitrogen can be 400 ~ 900mg/L, and COD content can be 2000 ~ 6000mg/L;
Described high ammonia-nitrogen wastewater is from livestock breeding wastewater, percolate or sludge-digestion liquid;
Described designing treatment amount can be 0.5 ~ 1.5L/cycle, specifically can be 1 ~ 1.5L/cycle, 1L/cycle or 1.5L/cycle;
The flow of described input can be 0.5 ~ 1L/min, specifically can be 0.5L/min;
Pending described high ammonia-nitrogen wastewater is transfused to maintenance 3 ~ 5min in described reactor, specifically can be 5min, after mixing, enters the follow-up double oxygen stage with the active sludge intermixture of reactor middle and high concentration.
In aforesaid method, in step (2), organism in described high ammonia-nitrogen wastewater can preferentially as carbon source for the reduction of nitric nitrogen described in the described double oxygen stage and described nitrite nitrogen provides electronics, when the carbon source in described waste water is not enough, the described carbon source of unlatching adds pump in time is again that described reactor adds carbon source, the dosage of carbon source can be made more accurate by this kind of mode, save carbon source, reduce costs.
When the redox electrode current potential of waste water is worth that namely dORP/dt is 0 ~-5 over time, judge that carbon source is not enough, open described carbon source and add pump, for described reactor adds carbon source, each opening time can be 0.5 ~ 1min, specifically can be 0.5min or 1min, after keeping 10 ~ 20min, after specifically can keeping 10 ~ 15min, 10min or 15min, enter and judge next time; When described dORP/dt is less than-5, can after time delay 10 ~ 30min, specifically can time delay 20 ~ 30min, 20 ~ 25min, 25 ~ 30min, 20min, 25min or 30min, open described aerating system, enter in step (3), can ensure denitrifyingly fully to carry out by time delay.
In aforesaid method, in step (3), the time of described aerobic stage can be 9 ~ 180min, specifically can be 120 ~ 150min, 120 ~ 135min, 135min or 150min, aerate flux can be 0.5 ~ 10L/min, specifically can be 4 ~ 5L/min, 4L/min or 5L/min;
In aforesaid method, in step (4), the time of described bleeding stage can be 30 ~ 90min, specifically can be 40 ~ 60min, 40min or 60min, described go out water pump be intermittent type suction, often can open and stop 2 ~ 4 minutes in 8 ~ 10 minutes, specifically often can open and stop 2 minutes in 8 minutes.
In aforesaid method, the temperature of described reactor can be 20 ~ 30 DEG C, specifically can be 20 ~ 25 DEG C, 20 DEG C or 25 DEG C.
In aforesaid method, in order to change complete nitrification-denitrification into short-cut nitrification-denitrification, need to promote ammonia oxidizing bacteria (AOB) growth, suppress nitrite-oxidizing bacterium (NOB) to grow, utilize following 1)-3) at least one method complete nitrification-denitrification is converted into short-cut nitrification-denitrification:
1) optimize aeration time method: after denitrogenation is stable, often taking turns the described aerobic stage of circulation, when the pH value in waste water do not change in time namely dpH/dt=0 time, close described aerating system;
2) the controlled accumulative of free ammonia: after denitrogenation is stable, at described aerobic stage, reduce the aerate flux of described aerating system, when the concentration of ammonia free in waste water be increased to be more than or equal to 20mg/L time, recover aerate flux;
Aerate flux in the whole circulation of described aerating system can be reduced to 0.2 ~ 1L/min, specifically can be reduced to 0.5 L/min;
Aforesaid method 1) in, often taking turns the aerobic unit of circulation, the duration of aerobic unit is controlled in real time according to " ammonia valley point " (ammoniavalley) on the continuous monitoring curve of pH, namely suitable aerate flux is first adopted to continue aeration, when the continuous monitoring curve of pH occurs stopping aeration immediately after " ammonia valley point ".By optimizing aeration time to gradually reduce the oxidation of nitrite nitrogen, thus make denitrification process change short-cut nitrification and denitrification into by complete nitrification-denitrification gradually, nitrosoation rate can continue increase and finally reach 80%.
Aforesaid method 2) in, by reducing aerate flux, control dissolved oxygen (DO) on the low side free ammonia density (FA) in reaction system to be increased to be more than or equal to 20mg/L, the growth velocity of ammonia oxidizing bacteria is greater than nitrite-oxidizing bacterium simultaneously.Then aerate flux is returned to suitable aerate flux and continue aeration until nitrosoation rate reaches more than 80%, again recover normal Inlet and outlet water cycle for the treatment of afterwards, realize the nitrosification-anti-nitrosification of ammonia nitrogen waste water process.
Above-mentioned 1) and 2) described in denitrogenation stablize and all refer to that the clearance when the ammonia-state nitrogen in described waste water is greater than 80%, and when the content that the nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%;
3) SRT control methods: described method also comprises the step of spoil disposal, described spoil disposal is after described aerobic stage, and the mean residence time controlling the mud in described reactor is 12 ~ 15 days.
Aforesaid method 3) in, because the sludge age of ammonia oxidizing bacteria is generally at 10 ~ 12 days, the sludge age of nitrite-oxidizing bacterium is then general at 18 ~ 20 days, Controlling System mud mean residence time can make quantity reduce gradually for 12 ~ 15 days, thus the ratio of ammonia oxidizing bacteria in nitrifying bacteria community is really improved constantly, nitrosoation rate is able to sustainable growth.
Utilize apparatus of the present invention and method can realize nitrosification-anti-nitrosification approach process high ammonia-nitrogen wastewater (nitrosoation rate reaches 80%), ensure that reactor efficiently removes nitrogen (about 95%TN, about 99%NH
3-N and about 98%COD), water production rate is 2 ~ 6 (L/h), decreases hydraulic detention time, reduces aeration energy consumption, and save external carbon source.
The apparatus and method tool of process high ammonia-nitrogen wastewater of the present invention has the following advantages:
1) high sludge concentration SBR technique combines with membrane separation technique by the present invention, has sequence batch (water inlet, the operation characteristic of continuous effluent, and what achieve that anoxic/aerobic SBR sequence batch reaction and membrane separation technique run continuously optimizes integration;
2) the present invention adopts the mode of film water outlet, ensure that compared with the effluent quality under high sludge concentration, simplifies the operation of conventional SBR, shortens HRT;
3) the present invention utilizes the unit time changing value of ORP as the basis for estimation of anti-nitrosification process, controls carbon source and adds pump and carry out pulsed and add, improve the accuracy that carbon source adds, save external carbon source dosage and reduce cost of sewage disposal;
4) adopt pH probe on-line monitoring oxidative ammonolysis process, judge NO
2maximum integration time, optimize aeration time and reduce cost of sewage disposal to save aeration rate.
In a word, high sludge concentration SBR technique combines with membrane separation technique by the present invention, adopting pH, DO (dissolved oxygen) and ORP (redox potential) electrode pair reactor to carry out monitoring continuously simultaneously and set up robot control system(RCS), is the semicontinuous operation process of brand-new SBR+MBR.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device of process high ammonia-nitrogen wastewater of the present invention.
Fig. 2 is that in embodiment 3, on about 25 DEG C pH real-time curves, " ammonia valley point " is optimized aeration time and realized nitrosification-anti-nitrosifying schematic diagram.
Fig. 3 is the operation logic figure processing high ammonia-nitrogen wastewater in embodiment 3.
In figure, each mark is as follows:
1.1 raw water box, 1.2 intake pump, 2.1 first air compressor machines, 2.2 first gas meters, 2.3 aeration plate, 3.0 anoxics/aerobic sbr reactor device, 3.1 agitator, 3.2 sampling valve, 3.3 mud valve, 3.4 add carbon pipe, 3.5 water inlet pipe, 4.1 flat sheet membrane, 4.2 synthetic glass film shells, 4.3 water outlet, 4.4 porous tubular aerator, 4.5 second air compressor machines, 4.6 second gas meters, 4.7 peristaltic pump, 4.8 tensimeter, 4.9 produce water tank, 5.1 carbon source retention tanks, 5.2 carbon sources add pump, 6.1 pH probes, 6.2 ORP probes, 6.3 dissolved oxygen DO pop one's head in, 6.4 unicircuit casees, 6.5 touch sensitive digitizer panel.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Time in following embodiment to buck, anaerobic sludge digestion liquid, landfill leachate treatment, the denitrifying carbon source of employing is industrial methyl alcohol.And the process of waste water of livestock poultry adopts feces of livestock and poultry underflow (Manure Slurry) as denitrifying carbon source for saving running cost.Feces of livestock and poultry underflow preparation method is: after pig manure grinding being sieved, (10 order) is diluted with water to underflow shape, and its COD content is 50000-100000mg/L.
Calculated the aerate flux needed in reactor by following experimental formula in following embodiment:
Q=q × MLSS × In (formula 1)
Wherein, the aerate flux of Q-suitable, unit is L/min;
MLSS (mixed solution concentration of suspension)-be used for representing activated sludge concentration, unit is mg/L;
In-water inlet NH
3-N concentration, unit is mg/L;
Q-empirical Calculation constant, comes from experiment.For suitable aerate flux, its value is 200 ~ 400.
By the aerate flux of film needs in following formulae discovery plate film assembly in following embodiment:
Aeration rate=n × q (formula 2) that membrane element needs
Wherein, n-membrane element quantity (sheet);
Q-monolithic membrane institute air demand (L/min), comes from experiment.For suitable aerate flux, its value is 5 ~ 15.
Chemical oxygen demand (COD) (COD), the content (TP) of phosphorus, total organic carbon (TOC), the biochemical oxygen demand (BOD) (BOD of waste water in following embodiment
5), ammonia-state nitrogen (NH
3-N) content, nitrite nitrogen (NO
2-N) content and nitric nitrogen (NO
3-N) content detect by method in following table 1 and instrument and obtain:
Table 1 testing index and research method
Below in conjunction with Figure of description, by specific embodiment, the present invention will be further described, but the present invention is not limited to following embodiment.
The device of embodiment 1, process high ammonia-nitrogen wastewater
As shown in Figure 1, the invention provides a kind of device utilizing sequencing batch active sludge and membrane separation technique process high ammonia-nitrogen wastewater, it comprises water inlet system, aerating system I, reactive system, film separating system, outlet system, carbon source dosing system and implements Controlling System;
Reactive system comprises a reactor (3.0), it is an open container, and the top of open container is provided with and an agitator (3.1), sidewall is respectively equipped with sampling valve (3.2), mud valve (3.3), adds carbon pipe (3.4) and water inlet pipe (3.5);
Water inlet system comprises a raw water box (1.1), is connected by the water inlet pipe (3.5) of intake pump (1.2) with anoxic/aerobic sbr reactor device (3.0);
Aerating system I comprises the first air compressor machine (2.1), the first gas meter (2.2) and is placed in the aeration plate (2.3) of anoxic/aerobic sbr reactor device (3.0) bottom;
Film separating system is a plate and frame module being placed in the side-walls of anoxic/aerobic sbr reactor device (3.0), it is made up of 1 ~ 2 flat sheet membrane film unit (4.1) and outside synthetic glass shell (4.2), it is communicated with extraneous sewage up and down, by flat sheet membrane, (material is each flat sheet membrane film unit (4.1): polyvinylidene difluoride (PVDF) PVDF, effective film area: 0.25m
2membrane pore size≤0.1 μm) be fixed on film frame and obtain, each film frame is provided with one point of water outlet, the top of whole plate and frame module is provided with a water outlet be communicated with each point of water outlet (4.3), the bottom of synthetic glass shell (4.2) is provided with a porous tubular aerator (4.4), be connected with the second air compressor machine (4.5), the second gas meter (4.6), form aerating system II, for the film in plate and frame module washes away, avoid polluting; Outlet system comprises a product water tank (4.9), to be connected with the water outlet (4.3) of plate and frame module by peristaltic pump (4.7) and to carry out suction draining (mixed solution infiltrate flat sheet membrane face), use tensimeter (4.8) monitoring transmembrane pressure, the sewage through membrane sepn is pumped down in product water tank;
Carbon source dosing system comprises a carbon source retention tank (5.1), adds pump (5.2) be connected with the carbon pipe (3.4) that adds of anoxic/aerobic sbr reactor device (3.0) by carbon source;
Real-time control system comprises in the waste water in pH probe (6.1), ORP probe (6.2) and dissolved oxygen DO probe (6.3), three insertion reaction devices in use of popping one's head in, and be connected with unicircuit case (6.4) respectively, unicircuit case (6.4) is connected with touch sensitive digitizer panel (6.5), pass in and out according to the time variable control of setting the start and stop that water pump and intake pump and peristaltic pump, carbon source add pump, aerating system and agitator, thus control hocketing of each reaction member in real time.
Embodiment 2, sequencing batch active sludge and membrane separation technique is utilized to process breeding wastewater
Adopt the device in embodiment 1 to process certain intensive culture waste water, the temperature controlling reactor is 25 ± 0.5 DEG C, and treating processes comprises the steps:
Be that municipal sewage plant's returned sluge of 5500mg/L is seeded in reactor by concentration, turn on agitator, aerating system I (aerate flux is 5L/min), (aerate flux is 8L/min to aerating system II, the aeration rate that whole film washes away, by the setting of two panels film), intake pump and enforcement Controlling System, adopt the mode of gradient water inlet (sewage), sludge concentration is made progressively to rise to 11000mg/L, gradient water inlet controls as follows: first stage is 7, 1/4 of most raw waste water concentration is diluted in water inlet, second stage is 7, water inlet is diluted to 1/2 of raw waste water concentration, three phases starts, water inlet uses raw waste water, treat that the clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of ammonia-state nitrogen in sewage is greater than 80%, when the content that nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%, reactor reaches stable omnidistance denitrogenation (three phases totally 45 days), unloading phase, completes, close intake pump and aerating system I, the following step of recirculation (1)-step (4) is discharged to all waste water, close agitator, aerating system II and enforcement Controlling System:
(1) fill phase: open intake pump and aerating system I, employing sequence batch (is intake, and according to designing treatment amount (1.5L/cycle), pending breeding wastewater is by (input flow rate is 0.5L/min) after quick input reactor, close intake pump, keep 5min.
(2) hold concurrently the oxygen stage: close aerating system I, under the effect of carbon source, the nitric nitrogen in waste water is reduced to nitrite nitrogen, and nitrite nitrogen is reduced to nitrogen.When dORP/dt is greater than-5, judge that the carbon source deficiency in waste water can not carry out complete anti-nitrosification, timely unlatching carbon source adds pump and carries out pulsed and add as reactor adds carbon source, and each opening time is 0.5min, keeps after 10min, continue afterwards with the value of dORP/dt as basis for estimation, circulation like this, until appropriate additional carbon ensures that complete anti-nitrosification is namely when dORP/dt value is less than-5, judges that carbon source is enough, extend 20min, ensure that anti-nitrosification is carried out smoothly.
(3) aerobic stage: open aerating system I, the NH in breeding wastewater
3-N and COD is oxidized to NO
2-N, NO
2-N is oxidized to NO
3-N.
(4) bleeding stage: after above-mentioned aerobic stage starts 80min, open peristaltic pump suction draining, peristaltic pump operation scheme often opens 8min to stop 2min, the sewage that (1.5L/cycle) of designing treatment amount processes through step (2) is discharged after the diafiltration of plate and frame module flat sheet membranes, before aerobic processes terminates, complete draining, close peristaltic pump and aerating system I.
In the present embodiment, the time of each circulation is about 170min, and the mean time of aerobic stage is 120min, and often taking turns total water discharge time is 40min, and suction water production rate is about 3L/h.
By the following two kinds method, complete nitrification-denitrification process is controlled as in short-cut nitrification-denitrification process in the present embodiment:
(1) the controlled accumulative of free ammonia:
The first 20 day water outlet NHs of reactor after steady running
3-N and NO
2-N maintains lower concentration level, and NO
3-N accounts for more than 80%, NH of total nitrogen (TN)
3the clearance of-N is more than 90%.Within 20th day, to the 32nd day, aerate flux is contracted to 0.5L/min from 5.0L/min, NH in system
3-N raises gradually, and NO
3-N then reduces rapidly.When ammonia density free in system is increased to about 36.3mg/L (NH
3-N ≈ 205mg/L; PH=8.8), immediately aeration rate is returned to 3.0L/min continuous aeration.NH
3-N dropped to less than 5mg/L in 6 days subsequently.In the process, system NO
2there is significantly accumulation in-N, is up to about 160mg/L, and NO
3-N is only increased to 30mg/L.This shows that the oxidation susceptibility of reactor to nitrite nitrogen is obviously suppressed after control FA (free ammonia) raises.After this, by controlling supplementary corresponding carbon source in real time, water outlet NO
2-N and NO
3-N declines, but NO
2-N (average out to 38mg/L) concentration is still apparently higher than NO
3-N (average out to 9mg/L).The nitrosoation rate of the continuous long-time running of reactor is up to 85%.
(2) SRT control methods:
In the present embodiment, Controlling System mud mean residence time is 15 days, due to (T=25 DEG C under the present embodiment control condition, pH >=7.0) sludge age of ammonia oxidizing bacteria is generally at 10-12 days, the sludge age of nitrite-oxidizing bacterium is then general at 18-20 days, nitrite-oxidizing bacteria quantity can be made to reduce gradually, thus the ratio of ammonia oxidizing bacteria in nitrifying bacteria community is really improved constantly, nitrosoation rate is able to sustainable growth.
Pollutant levels in breeding wastewater before and after above-mentioned steps process namely in Inlet and outlet water and clearance are in table 1.
Pollutant levels in table 1 embodiment 1 in Inlet and outlet water and clearance
ND: do not detect
Embodiment 3, sequencing batch active sludge and membrane separation technique is utilized to process percolate
Adopt the device in embodiment 1 to process percolate, the temperature controlling reactor is 25 ± 0.5 DEG C, and treating processes comprises the steps:
Be that municipal sewage plant's returned sluge of 5500mg/L is seeded in reactor by concentration, turn on agitator, aerating system I (aerate flux is 4L/min), aerating system II (aerate flux is 8L/min), intake pump and enforcement Controlling System, adopt the mode of gradient water inlet (sewage), sludge concentration is made progressively to rise to 11000mg/L, gradient water inlet controls as follows: first stage is 5, 1/4 of most raw waste water concentration is diluted in water inlet, second stage is 5, water inlet is diluted to 1/2 of raw waste water concentration, three phases starts, water inlet uses raw waste water, and startup was completed after 15 days.Treat that the clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of ammonia-state nitrogen in sewage is greater than 80%, when the content that nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%, reactor reaches stable omnidistance denitrogenation, unloading phase, completes, close intake pump and aerating system I, the following step of recirculation (1)-step (4) is discharged to all waste water, closes agitator, aerating system II and implements Controlling System, operation logic figure as shown in Figure 3:
(1) fill phase: open intake pump and aerating system I, employing sequence batch (is intake, and according to designing treatment amount (1L/cycle), pending breeding wastewater is by (input flow rate is 0.5L/min) after quick input reactor, close intake pump, keep 5min.
(2) hold concurrently the oxygen stage: close aerating system I, in sewage carbon source effect under, nitric nitrogen in breeding wastewater is reduced to nitrite nitrogen, nitrite nitrogen is reduced to nitrogen, when dORP/dt is greater than-5, judge that the carbon source deficiency in waste water can not carry out complete anti-nitrosification, timely unlatching carbon source add pump carry out pulsed add into reactor add carbon source, each opening time is 1min, after keeping 15min, continue afterwards with the value of dORP/dt as basis for estimation, circulation like this, until appropriate additional carbon ensures that complete anti-nitrosification is namely when dORP/dt value is less than-5, judge that carbon source is enough, extend 30min, ensure that anti-nitrosification is carried out smoothly, as shown in Figure 2, after the double oxygen stage starts, if dORP/dt is greater than-5, judge carbon source quantity not sufficient, drop into additional carbon after keeping 15min, again judge dORP/dt, until ORP declines fast, dORP/dt judges that carbon source is enough when being less than-5, as in Fig. 2 shown in ellipse, stop adding carbon source, the NO that in sewage, last round of circulation aerobic unit produces
2-N and NO
3-N is all reduced into N
2.
(3) aerobic stage: open aerating system I, the NH in breeding wastewater
3-N and COD is oxidized to NO
2-N, NO
2-N is oxidized to NO
3-N, as dpH/dt=0, as in Fig. 2 shown in rectangular boxes, stops aeration immediately.
(4) bleeding stage: after above-mentioned aerobic stage starts 80min, open peristaltic pump suction draining, peristaltic pump operation scheme often opens 8min to stop 2min, the sewage that (1L/cycle) of designing treatment amount processes through step (2) is discharged after the diafiltration of plate and frame module flat sheet membranes, before aerobic processes terminates, complete draining, close peristaltic pump and aerating system I.
In the present embodiment, the mean time of each circulation is about 230min, and the mean time of often taking turns aerobic stage is 150min, and the mean time of often taking turns total draining is 40min, and suction water production rate is about 2L/h.
The following two kinds method is adopted to be controlled by complete nitrification-denitrification process as in short-cut nitrification-denitrification process in the present embodiment:
1) aeration time method is optimized:
The first 20 day water outlet NHs of reactor after steady running
3-N and NO
2-N maintains lower concentration level, and NO
3-N accounts for more than 85% of total nitrogen (TN), and the clearance of ammonia-state nitrogen is more than 90%.
As shown in Figure 2,115 ~ 220min is aerobic stage, the NH in waste water
3-N and COD is oxidized, and pH reduces gradually, when reduce as far as possible namely ammonia valley point (dpH/dt=0) time, stop aeration immediately, as in Fig. 2 shown in rectangular boxes.In aeration process (115 ~ 220min), the concentration of useless oxygen in water is 0.2 ~ 3.5mg/L, maintain lower level, ammonium oxidation speed (about 15.1mgN/hL) is much larger than nitrite nitrogen rate of oxidation (about 2.8mgN/hL).Reactor water outlet NO
2-N level (about 50mg/L) is apparently higher than NO
3-N (about 10mg/L) and NH
3-N (< 3mg/L), nitrosoation rate is about 83%.
(2) SRT control methods:
In the present embodiment, Controlling System mud mean residence time is 15 days, due to (T=25 DEG C under the present embodiment control condition, pH >=7.0) sludge age of ammonia oxidizing bacteria is generally at 10-12 days, the sludge age of nitrite-oxidizing bacterium is then general at 18-20 days, nitrite-oxidizing bacteria quantity can be made to reduce gradually, thus the ratio of ammonia oxidizing bacteria in nitrifying bacteria community is really improved constantly, nitrosoation rate is able to sustainable growth.
Pollutant levels in percolate before and after above-mentioned steps process namely in Inlet and outlet water and clearance are in table 2.
Pollutant levels in table 2 embodiment 3 in Inlet and outlet water and clearance
ND: do not detect
Embodiment 4, sequencing batch active sludge and membrane separation technique is utilized to process sludge-digestion liquid
Adopt the device in embodiment 1 to process percolate, the temperature controlling reactor is 20 ± 0.5 DEG C, and treating processes comprises the steps:
Be that municipal sewage plant's returned sluge of 5000mg/L is seeded in reactor by concentration, turn on agitator, aerating system I (aerate flux is 5L/min), aerating system II (aerate flux is 8L/min), intake pump and enforcement Controlling System, adopt the mode of gradient water inlet (sewage), sludge concentration is made progressively to rise to 11000mg/L, gradient water inlet controls as follows: first stage is 7, 1/4 of most raw waste water concentration is diluted in water inlet, second stage is 7, water inlet is diluted to 1/2 of raw waste water concentration, three phases starts, water inlet uses raw waste water, and startup was completed after 45 days.Treat that the clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of ammonia-state nitrogen in sewage is greater than 80%, when the content that nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%, reactor reaches stable omnidistance denitrogenation, unloading phase, completes, close intake pump and aerating system I, the following step of recirculation (1)-step (4) is discharged to all waste water, closes agitator, aerating system II and implements Controlling System:
(1) fill phase: open intake pump and aerating system I, employing sequence batch (is intake, and according to designing treatment amount (1.5L/cycle), pending breeding wastewater is by (input flow rate is 0.5L/min) after quick input reactor, close intake pump, keep 5min.
(2) hold concurrently the oxygen stage: close aerating system, in sewage carbon source effect under, nitric nitrogen in breeding wastewater is reduced to nitrite nitrogen, nitrite nitrogen is reduced to nitrogen, when dORP/dt is greater than-5, judge that the carbon source deficiency in waste water can not carry out complete anti-nitrosification, timely unlatching carbon source add pump carry out pulsed add into reactor add carbon source, each opening time is 1min, after keeping 15min, continue afterwards with the value of dORP/dt as basis for estimation, circulation like this, until appropriate additional carbon ensures that complete anti-nitrosification is namely when dORP/dt value is less than-5, judge that carbon source is enough, extend 25min, ensure that anti-nitrosification is carried out smoothly.
(3) aerobic stage: open aerating system, the NH in breeding wastewater
3-N and COD is oxidized to NO
2-N, NO
2-N is oxidized to NO
3-N.
(4) bleeding stage: after above-mentioned aerobic stage starts 60min, open peristaltic pump suction draining, peristaltic pump operation scheme often opens 8min to stop 2min, the sewage that (1.5L/cycle) of designing treatment amount processes through step (2) is discharged after the filtration of plate film assembly flat sheet membranes, before aerobic processes terminates, complete draining.
In the present embodiment, the mean time of each circulation is about 200min, and the aerobic mean time of often taking turns circulation is about 135min, and often taking turns total water discharge time is 60min, and suction water production rate is about 2L/h.
Adopt the controlled accumulative of following free ammonia and SRT control methods to control complete nitrification-denitrification process for short-cut nitrification-denitrification process in the present embodiment, process is as follows:
First adopt the controlled accumulative of free ammonia, namely control FA concentration raises to realize complete nitrification gradually and changes to nitrosification: first 20 days reactor water outlet NO
3-N accounts for TN and maintains more than 90%, the clearance of ammonia-state nitrogen is more than 95%, within 21st day, to the 33rd day, reactor aerate flux is contracted to about 0.5L/min by 5L/min, in system, free ammonia density is increased to 20mg/L (pH=8.9) by about 0.3mg/L thereupon, subsequently aerate flux is recalled to 3.5L/min continuous aeration, until NO
2/ (NO
2+ NO
3) reach more than 80%.Along with the oxidation of ammonia nitrogen, NO
2-N is increased to 160mg/L, far above NO
3-N (only up to 40mg/L).After controlled accumulation occurs FA, the aerobic unit of reactor adopts control mode 1) optimize aeration time namely when pH is down to ammonia valley point (dpH/dt=0), stop aeration immediately, the nitrosoation rate average out to 82% run continuously.
Pollutant levels in sludge-digestion liquid before and after above-mentioned steps process namely in Inlet and outlet water and clearance are in table 3.
Pollutant levels in table 3 embodiment 4 in Inlet and outlet water and clearance
ND: do not detect.
Claims (10)
1. process a device for high ammonia-nitrogen wastewater, it is characterized in that: it comprises water inlet system, aerating system, carbon source dosing system, reactive system, film separating system and outlet system;
Described reactive system comprises a reactor, and described reactor is a container, and the top of described reactor is provided with agitator;
Described water inlet system comprises a raw water box, and described raw water box is connected with described reactor by intake pump;
Described aerating system comprises air compressor machine, gas meter and aerator, and described aerator is placed in described reactor;
Described carbon source dosing system comprises a carbon source storage tank, and described carbon source storage tank adds pump by carbon source and is connected with described reactor;
Described film separating system is a membrane module, and described membrane module is placed in described reactor;
Described outlet system comprises a product water tank, and the water outlet of described membrane module passes through water pump and is connected with described product water tank.
2. device according to claim 1, is characterized in that: described device also comprises a real-time control system, and described enforcement Controlling System comprises probe, unicircuit case and touch sensitive digitizer panel;
Described probe comprises pH probe, ORP probe and dissolved oxygen DO and pops one's head in, and be all connected with described unicircuit case, described unicircuit case is connected with described touch sensitive digitizer panel.
3. device according to claim 1 and 2, is characterized in that: described membrane module is placed in the side-walls of described reactor;
Described membrane module is plate and frame module, and described plate and frame module comprises 1 ~ 2 film unit, and each described film unit is made up of two panels film, and the material of described film is polyvinylidene difluoride (PVDF), aperture≤0.1 μm, and useful area is 0.5m
2; The inside of described membrane module is also provided with aerator, and being connected with another air compressor machine and another gas meter successively, is described film aeration.
4. utilize the method for the device process high ammonia-nitrogen wastewater according to any one of claim 1-3, comprise the steps:
In inoculation of activated-sludge to described reactor, open described agitator, the following step of recirculation (1)-step (4):
(1) fill phase: open described aerating system and described intake pump, adopt sequence batch (water inlet, according to designing treatment amount, pending described high ammonia-nitrogen wastewater is transfused in described reactor, closes described intake pump;
(2) hold concurrently the oxygen stage: close described aerating system, under the effect of carbon source, the nitric nitrogen in waste water is reduced to nitrite nitrogen, and nitrite nitrogen is reduced to nitrogen;
(3) aerobic stage: open described aerating system, the ammonia-state nitrogen in waste water and organism oxidized, described ammonia-state nitrogen is oxidized to nitrite nitrogen, and nitrite nitrogen is oxidized to nitric nitrogen;
(4) bleeding stage: after described aerobic stage starts 60 ~ 120min, go out water pump described in unlatching, the described waste water of designing treatment amount is discharged after the filtration of film in described membrane module, goes out water pump and described aerating system described in closing successively.
5. method according to claim 4, is characterized in that: described real-time control system whole process is opened, and monitors the size of redox electrode current potential, pH value and the dissolved oxygen in described high ammonia-nitrogen wastewater;
Aerator whole process in described membrane module is opened, and aerate flux is 5 ~ 15L/min sheet.
6. the method according to claim 4 or 5, is characterized in that: the concentration of the active sludge of described inoculation is 5000mg/L ~ 5500mg/L, and gradient improves the influent concentration of sewage, is increased by activated sludge concentration to 10000mg/L ~ 12000mg/L;
Described gradient raising is divided into three phases, and first stage is 5 ~ 10, and 1/4 of most raw waste water concentration is diluted in water inlet; Second stage is 5 ~ 10, and water inlet is diluted to 1/2 of raw waste water concentration; Three phases is 30 ~ 55.
7. the method according to any one of claim 4-6, is characterized in that: in step (1), the concentration 500 ~ 900mg/L of ammonia-state nitrogen in described high ammonia-nitrogen wastewater, and COD content is 5000 ~ 10000mg/L;
Described high ammonia-nitrogen wastewater is from livestock breeding wastewater, percolate or sludge-digestion liquid;
Described designing treatment amount is 0.5 ~ 1.5L/cycle;
The flow of described input is 0.5 ~ 1L/min;
Pending described high ammonia-nitrogen wastewater is transfused in described reactor and keeps entering the described double oxygen stage after 3 ~ 5min.
8. the method according to any one of claim 5-7, it is characterized in that: in step (2), when the redox electrode current potential of waste water is worth that namely dORP/dt is 0 ~-5 over time, judge that carbon source is not enough, open described carbon source and add pump, for described reactor adds carbon source, each opening time is 0.5 ~ 1min, after keeping 10 ~ 20min, enter and judge next time; When described dORP/dt is less than-5, after time delay 10 ~ 30min, open described aerating system, enter in step (3).
9. the method according to any one of claim 4-8, is characterized in that: in step (3), and the time of described aerobic stage is 9 ~ 180min, and aerate flux is 0.5 ~ 10L/min;
In step (4), the time of described bleeding stage is 30 ~ 90min, described in go out water pump be intermittent type suction, often open and stop 2 ~ 4 minutes in 8 ~ 10 minutes.
10. the method according to any one of claim 5-9, is characterized in that: utilize following 1)-3) at least one method complete nitrification-denitrification is converted into short-cut nitrification-denitrification:
1) optimize aeration time method: after denitrogenation is stable, often taking turns the described aerobic stage of circulation, when the pH value in waste water do not change in time namely dpH/dt=0 time, close described aerating system;
2) the controlled accumulative of free ammonia: after denitrogenation is stable, at described aerobic stage, reduce the aerate flux of described aerating system, when the concentration of ammonia free in waste water be increased to be more than or equal to 20mg/L time, recover aerate flux;
Aerate flux in the whole circulation of described aerating system is reduced to 0.2 ~ 1L/min;
Above-mentioned 1) and 2) described in denitrogenation stablize and all refer to that the clearance when the ammonia-state nitrogen in described waste water is greater than 80%, and when the content that the nitric nitrogen in the waste water of discharging accounts for described Determination of Total Nitrogen in Waste Water is greater than 70%;
3) SRT control methods: described method also comprises the step of spoil disposal, described spoil disposal is after described aerobic stage, and the mean residence time controlling the mud in described reactor is 12 ~ 15 days.
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