CN104891655B - Device and method for treating high ammonia nitrogen wastewater - Google Patents

Device and method for treating high ammonia nitrogen wastewater Download PDF

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CN104891655B
CN104891655B CN201510296019.XA CN201510296019A CN104891655B CN 104891655 B CN104891655 B CN 104891655B CN 201510296019 A CN201510296019 A CN 201510296019A CN 104891655 B CN104891655 B CN 104891655B
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nitrogen
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carbon source
water
wastewater
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CN104891655A (en
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陈梅雪
姜超
郁达伟
张岚
刘吉宝
隋倩文
魏源送
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Research Center for Eco Environmental Sciences of CAS
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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

Process the device and method of high ammonia-nitrogen wastewater
Technical field
The present invention relates to processing the device and method of high ammonia-nitrogen wastewater, utilize SBR technique and membrance separation particularly to a kind of The device and method of technical finesse high ammonia-nitrogen wastewater, belongs to sewage treatment area.
Background technology
With the mankind, environmental requirement is gradually stepped up, sewage drainage standard is constantly tightened up.Biological nitrification and denitrification is mesh Front commonly used sewage denitrification method.Traditional bioanalysises generally adopt complete nitrification and denitrification technique denitrogenation, that is, aerobic Unit is become ammonium oxidation after nitrite nitrogen by ammonia oxidation bacteria (Ammonia Oxidizing Bacteria, AOB), then by nitrifier (Nitrite Oxidizing Bacteria, NOB) is oxidized to nitrate nitrogen;And oxygen (anaerobism) unit is then by the nitrate nitrogen generating also It is then reduced into nitrogen after former one-tenth nitrite nitrogen.This processing procedure in actual motion, particularly to high ammonia nitrogen, low ratio of carbon to ammonium waste water In, in aerobic section, ammonium oxidation becomes the supplement that nitrate nitrogen is reduced into external carbon source needed for nitrogen with nitrate nitrogen in simultaneous oxygen section all can produce High operating cost.The denitrogenation new technology of therefore research and development optimization energy resource consumption is extremely urgent.1989, YamamotoK etc. After delivering the research of first piece immersion MBR, immersion MBR, compared with external MBR, reduces energy because eliminating circulating pump The advantages of consumption, occupation of land are compact, be progressively taken seriously in research and engineer applied (YamamotoK, HiasaH, TalatM, etal.1989.Direct solid liquid separation using holllowfibe membranes in Activated sludge aeration tanks) .1998, Hellinga C etc. is shorter than using ammonia oxidation bacteria generation time Nitrifier, selects suitable sludge retention time (SRT) to eliminate nitrifier and retain ammonia oxidation bacteria, thus in single reactor The nitrosation achieving first-anti-nitrosation process, is directly reduced into nitrogen after that is, ammonia nitrogen is oxidized to nitrite nitrogen (Hellinga C, 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).This technique at most can be saved relative to complete nitrification-denitrification 25% aeration rate, 40% external carbon source, and reduce by 40% biological increment.This causes each follow-up research work purport in the world In the range of application widening shortcut nitrification denitrification or reduce its requirement to service condition, and seek traditional handicraft and MBR Optimize integration.Peng Yongzhen etc. has invented the low C/N sanitary sewage of anoxia/aerobic SBR+ Anammox+aerobic SBR PROCESS FOR TREATMENT The apparatus and method of advanced nitrogen;Fan Yaobo etc. has invented integrated A 2/O-MBR reactor.Additionally, automatic control system also by Step is applied to sewage treatment process to facilitate management, saves manpower.
Although SBR can reach good denitrification effect in the studies above, need higher mud for high ammonia-nitrogen wastewater Concentration (more than 10000mg/L), which results in the water outlet sedimentation time longer HRT that increased technique, simultaneously as high mud is dense Lower water outlet SS is higher for degree, directly results in effluent quality unstable.Therefore, develop using sequencing batch active sludge and membrance separation The device and method of technical finesse high ammonia-nitrogen wastewater is extremely urgent.
Content of the invention
It is an object of the invention to provide processing the device and method of high ammonia-nitrogen wastewater, this device is efficiently retained the film of effect Technology is optimized with SBR technique and combines, and shortens the hydraulic detention time of technique while realizing good effluent quality (HRT), there is batch-type water inlet, the operation characteristic of continuous effluent;Meanwhile, the present invention is respectively adopted pH probe, DO (dissolved oxygen) Probe and ORP (oxidation-reduction electrode current potential) probe continuously monitor to reactor and set up robot control system(RCS), can control carbon in time Source, nitrification-denitrification process is changed into short-cut nitrification-denitrification process.
A kind of device of process high ammonia-nitrogen wastewater that the present invention provides, it includes water inlet system, aerating system, carbon source add System, response system, film separation system and outlet system;
Described response system includes a reactor, and described reactor is a container, and the top of described reactor is provided with stirring Device;
Described water inlet system includes a raw water box, and described raw water box is connected with described reactor by intake pump;
Described aerating system includes air compressor machine, gas flowmeter and aerator, and described aerator is placed in described reactor;
Described carbon source dosing system includes a carbon source storage tank, and described carbon source storage tank adds pump and described reactor by carbon source Connect;
Described film separation system is a membrane module, and described membrane module is placed in described reactor;
Described outlet system includes a product water tank, and the outlet of described membrane module is by going out water pump with described product water tank even Connect.
Apparatus of the present invention in running, first, by activated sludge inoculation with described reactor in;Described high ammonia nitrogen gives up Water is stored in described raw water box, and in the presence of described intake pump, described high ammonia-nitrogen wastewater is transported in described reactor; When described aerating system is closed, in the presence of the carbon source that carbon source dosing system adds, described high ammonia-nitrogen wastewater In nitrite nitrogen be reduced to nitrate nitrogen, nitrate nitrogen is reduced to nitrogen (and oxygen stage or anaerobic stages);When described aeration When system is in opening, described aerating system can provide oxygen, the ammonia in described waste water for the waste water in described reactor State nitrogen is oxidized to nitrite nitrogen in the presence of ammonia oxidizing bacteria in mud, and nitrite nitrogen is in the effect of nitrite-oxidizing bacteria Under be oxidized to nitrate nitrogen (aerobic stage);Treated waste water, after film separation system, is purified, further by described Go out water pump to be discharged in described product water tank.
In said apparatus, described device also includes a real-time control system, described enforcement control system include probe, integrated Circuit box and touch sensitive digitizer panel;Described probe includes pH probe, ORP probe and dissolved oxygen DO probe, all with described integrated circuit Case connects, and described integrated circuit case is connected described real-time control system with described touch sensitive digitizer panel;By described integrated circuit case Real-time monitoring with described touch sensitive digitizer panel record and calculating described pH probe, described ORP probe and described dissolved oxygen DO probe Data, thus passing in and out, according to the programme-control setting, the start and stop that water pump, carbon source add pump, aerating system and agitator, controls in real time Make each reaction member alternately.
In said apparatus, described aerator is placed in the bottom of described reactor, with abundant aeration.
In said apparatus, described membrane module is placed in the side-walls of described reactor, to avoid hindering on described reactor The operation of the agitator of side, it is to avoid the damage of described reactor and described agitator;
Described membrane module is plate and frame module, and described plate and frame module includes 1~2 film unit, each described film Unit is made up of two panels film;The material of described film is Kynoar, aperture≤0.1 μm, each described film unit (membrane component) Effective area be 0.5m2;The inside of described membrane module is additionally provided with aerator, successively with another air compressor machine and another gas flow Meter connects, and is described film aeration, reduces the pollution of described film, extends the service life of described film.
Invention further provides a kind of method processing high ammonia-nitrogen wastewater, comprise the steps:
Inoculation of activated-sludge, to described reactor, opens described agitator, repetitive cycling following step (1)-step (4):
(1) fill phase:Open described aerating system and described intake pump, using batch-type water inlet, according to Design Treatment Amount, pending described high ammonia-nitrogen wastewater is transfused in described reactor, closes described intake pump;
(2) the simultaneous oxygen stage:Close described aerating system, in the presence of carbon source, the nitrate nitrogen in waste water is reduced to Asia Nitrate nitrogen, nitrite nitrogen is reduced to nitrogen;
(3) aerobic stage:Open described aerating system, the ammoniacal nitrogen in waste water and Organic substance are oxidized, described ammoniacal nitrogen It is oxidized to nitrite nitrogen, nitrite nitrogen is oxidized to nitrate nitrogen;
(4) bleeding stage:After described aerobic stage starts 60~120min, described in unlatching, go out water pump, Design Treatment amount Described waste water discharge after the filtration of film in described membrane module, successively close described in go out water pump and described aerating system.
In said method, methods described also includes the whole step opening real-time control system, monitors described high ammonia nitrogen and gives up The size of oxidation-reduction electrode current potential, pH value and dissolved oxygen in water;
Aerator in described membrane module is whole to be opened, and aeration flow can be 5~15L/min, specifically can arrange two panels and expose Air film, aeration flow is 8L/min, to reduce fouling membrane, extends the service life of film.
In said method, the concentration of the activated sludge of described inoculation can for 5000mg/L~5500mg/L, 5000mg/L or 5500mg/L, specifically may be from the returned sludge of municipal sewage plant;Process due to high ammonia-nitrogen wastewater of the present invention needs Carry out under high sludge concentration, gradient improve sewage influent concentration, can by activated sludge concentration increase to 10000mg/L~ 12000mg/L, specifically can increase to 11000mg/L;
Described gradient improves and is divided into three phases, and first stage can be 5~10, concretely 5~7 days, 5 days or 7 Day, the 1/4 of water inlet dilution most raw sewage concentration;Second stage can be 5~10, concretely 5~7 days, 5 days or 7 days, Water inlet is diluted to the 1/2 of raw sewage concentration;Three phases can be 30~55, concretely 45 days, completes to startup stage;
When the clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of ammoniacal nitrogen in described high ammonia-nitrogen wastewater is more than 80%, When nitrate nitrogen in the waste water discharged accounts for the content of described Determination of Total Nitrogen in Waste Water more than 70%, reactor reaches the denitrogenation of stable whole process, Startup stage completes, and gradient improves can make the microorganism in described mud adapt to described raw sewage water quality and reactor environment as early as possible Condition.
In said method, in step (1), in described high ammonia-nitrogen wastewater, the concentration of ammoniacal nitrogen can be 400~900mg/L, COD Content can be 2000~6000mg/L;
Described high ammonia-nitrogen wastewater is derived from livestock breeding wastewater, percolate or sludge-digestion liquid;
Described Design Treatment amount can be 0.5~1.5L/cycle, concretely 1~1.5L/cycle, 1L/cycle or 1.5L/cycle;
The flow of described input can be 0.5~1L/min, concretely 0.5L/min;
Pending described high ammonia-nitrogen wastewater is transfused in described reactor holding 3~5min, concretely 5min, and anti- After answering the active sludge intermixture mix homogeneously of device middle and high concentration, enter the follow-up simultaneous oxygen stage.
In said method, in step (2), Organic substance in described high ammonia-nitrogen wastewater can be preferentially described and oxygen as carbon source The reduction of nitrate nitrogen described in the stage and described nitrite nitrogen provides electronics, when the carbon source in described waste water is not enough, more in time Open described carbon source and add pump and add carbon source for described reactor, the dosage of carbon source can be made by this kind of mode more accurate Really, carbon source, reduces cost are saved.
When the oxidation-reduction electrode current potential of waste water be worth over time i.e. dORP/dt be 0~-5 when, judge carbon source not Foot, opens described carbon source and adds pump, be that described reactor adds carbon source, each opening time can be 0.5~1min, concretely 0.5min or 1min, after keeping 10~20min, after specifically can keeping 10~15min, 10min or 15min, enters and sentences next time Fixed;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 denitrification by time delay Fully carry out.
In said method, in step (3), the time of described aerobic stage can be 9~180min, concretely 120~ 150min, 120~135min, 135min or 150min, aeration flow can be 0.5~10L/min, concretely 4~5L/min, 4L/min or 5L/min;
In said method, in step (4), the time of described bleeding stage can be 30~90min, concretely 40~ 60min, 40min or 60min, described go out water pump be batch (-type) suction, can often open 8~10 minutes and stop 2~4 minutes, specifically can be every Open 8 minutes and stop 2 minutes.
In said method, the temperature of described reactor can be 20~30 DEG C, concretely 20~25 DEG C, 20 DEG C or 25 DEG C.
In said method, in order to complete nitrification-denitrification is changed into short-cut nitrification-denitrification, need to promote ammoxidation Antibacterial (AOB) grows, and suppresses nitrite-oxidizing bacterium (NOB) growth, using following 1) -3) at least one of method by whole nitre Change-denitrification is converted into short-cut nitrification-denitrification:
1) optimize aeration time method:After denitrogenation is stable, in the described aerobic stage of every wheel circulation, when the pH value in waste water with Time do not change i.e. dpH/dt=0 when, close described aerating system;
2) the controlled method of cumulative scale of free ammonia:After denitrogenation is stable, in described aerobic stage, reduce the aeration stream of described aerating system Amount, when the concentration of ammonia free in waste water raises to above equal to 20mg/L, recovers aeration flow;
Aeration flow 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;
Said method 1) in, in the aerobic unit of every wheel circulation, according to " ammonia valley point " on pH continuous monitoring curve (ammoniavalley) duration of real-time control aerobic unit, first adopts suitable aeration flow to continue aeration, when pH is continuous Monitoring curve stops aeration after " ammonia valley point " immediately.Gradually reduce the oxidation of nitrite nitrogen by optimizing aeration time, from And making denitrification process gradually be changed into short-cut nitrification and denitrification by complete nitrification-denitrification, nitrosoation rate can persistently increase simultaneously It is finally reached 80%.
Said method 2) in, by reducing aeration flow, control low dissolved oxygen (DO) to make free ammonia in reaction system Concentration (FA) raises to above equal to 20mg/L, and the growth rate of ammonia oxidizing bacteria is more than nitrite-oxidizing bacterium simultaneously.Then will Aeration flow recovers to the lasting aeration of suitable aeration flow, until nitrosoation rate reaches more than 80%, again to recover normal afterwards Inlet and outlet water processing cycle, realizes the nitrosation-anti-nitrosation of ammonia nitrogen waste water process.
Above-mentioned 1) and 2) described in denitrogenation stably each mean when the ammoniacal nitrogen in described waste water clearance be more than 80%, and When nitrate nitrogen in the waste water discharged accounts for the content of described Determination of Total Nitrogen in Waste Water more than 70%;
3) SRT control methods:The step that methods described also includes spoil disposal, described spoil disposal, after described aerobic stage, controls The mean residence time of the mud in described reactor is 12~15 days.
Said method 3) in, because the sludge age of ammonia oxidizing bacteria is typically at 10~12 days, and the dirt of nitrite-oxidizing bacterium Then typically at 18~20 days, control system mud mean residence time can make quantity gradually decrease for 12~15 days to sludge age, thus Ratio in nitrifying bacteria community really for the ammonia oxidizing bacteria is improved constantly, nitrosoation rate is able to sustainable growth.
Can achieve that nitrosation-anti-nitrosation approach processes high ammonia-nitrogen wastewater (nitrosoation rate using apparatus of the present invention and method Reach 80%) it is ensured that reactor efficiently goes to denitrogenate (about 95%TN, about 99%NH3- N and about 98%COD), aquifer yield is 2~6 (L/h), decrease hydraulic detention time, reduce aeration energy consumption, and save external carbon source.
The apparatus and method that the present invention processes high ammonia-nitrogen wastewater have the advantage that:
1) high sludge concentration SBR technique is combined by the present invention with membrane separation technique, has batch-type water inlet, continuously goes out The operation characteristic of water it is achieved that anoxia/aerobic SBR sequence batch reaction and membrane separation technique continuous run optimize integration;
2) effluent quality by the way of film water outlet it is ensured that under compared with high sludge concentration for the present invention, simplifies conventional SBR Operation, shorten HRT;
3) present invention, by the use of the unit interval changing value of ORP as the basis for estimation of anti-nitrosation process, controls carbon source to throw Plus pump carries out pulsed and adds, 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 ammoxidation reaction process, judge NO2Maximum integration time, optimize aeration time with Save aeration rate and reduce cost of sewage disposal.
In a word, high sludge concentration SBR technique is combined by the present invention with membrane separation technique, adopts pH, DO (dissolving simultaneously Oxygen) and ORP (oxidation-reduction potential) electrode pair reactor continuously monitor and set up robot control system(RCS), for brand-new SBR+MBR half Continuous operation process.
Brief description
Fig. 1 processes the structural representation of the device of high ammonia-nitrogen wastewater for the present invention.
Fig. 2 is that in embodiment 3, " ammonia valley point " optimizes aeration time and realize nitrosation-anti-sub- on 25 DEG C about pH real-time curves The schematic diagram of nitrification.
Fig. 3 is the operation logic figure processing high ammonia-nitrogen wastewater in embodiment 3.
The each labelling of in figure is as follows:
1.1 raw water boxs, 1.2 intake pumps, 2.1 first air compressor machines, 2.2 first gas effusion meters, 2.3 aeration plates, 3.0 lack Oxygen/aerobic sbr reactor device, 3.1 agitators, 3.2 sampling valves, 3.3 mud valves, 3.4 plus carbon pipe, 3.5 water inlet pipes, 4.1 Flat Membrane, 4.2 lucite film shells, 4.3 outlets, 4.4 porous tubular aerators, 4.5 second air compressor machines, 4.6 second gas flows Meter, 4.7 peristaltic pumps, 4.8 pressure gauges, 4.9 product water tanks, 5.1 carbon source containers, 5.2 carbon sources add pump, 6.1 pH probes, 6.2 ORP probe, 6.3 dissolved oxygen DO probes, 6.4 integrated circuit casees, 6.5 touch sensitive digitizer panel.
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.
Material used, reagent etc. in following embodiments, if no special instructions, all commercially obtain.
When in following embodiments to buck, anaerobic sludge digestion liquid, landfill leachate treatment, the denitrifying carbon source of employing is Industrial methanol.And the process of waste water of livestock poultry is to save operating cost to adopt feces of livestock and poultry underflow (Manure Slurry) conduct Denitrifying carbon source.Feces of livestock and poultry underflow preparation method is:Pig manure is ground (10 mesh) after sieving and be diluted with water to underflow shape, its COD content is 50000-100000mg/L.
In following embodiments, the aeration flow needing in reactor is calculated by following empirical equation:
Q=q × MLSS × In (formula 1)
Wherein, Q suitable aeration flow, unit is L/min;
MLSS (mixed liquor concentration of suspension) is used for representing activated sludge concentration, and unit is mg/L;
In water inlet NH3- N concentration, unit is mg/L;
Q experience computational constant, comes from experiment.For suitable aeration flow, its value is 200~400.
Pass through the aeration flow that in equation below calculate flat board membrane module, film needs in following embodiments:
Aeration rate=n × q (formula 2) that membrane component needs
Wherein, n membrane component quantity (piece);
Q monolithic membrane institute air demand (L/min), comes from experiment.For suitable aeration flow, its value is 5~15.
In following embodiments, the COD (COD) of waste water, the content (TP) of phosphorus, total organic carbon (TOC), biochemistry are aerobic Amount (BOD5), ammoniacal nitrogen (NH3- N) content, nitrite nitrogen (NO2- N) content and nitrate nitrogen (NO3- N) content can pass through In table 1 below, method and instrument detection obtain:
Table 1 testing index and research method
With reference to Figure of description, by specific embodiment, the present invention will be further described, but the present invention not office It is limited to following embodiments.
Embodiment 1, the device of process high ammonia-nitrogen wastewater
As shown in figure 1, the invention provides a kind of process high ammonia nitrogen using sequencing batch active sludge and membrane separation technique The device of waste water, it includes water inlet system, aerating system I, response system, film separation system, outlet system, carbon source dosing system With enforcement control system;
Response system includes a reactor (3.0), and it is an open-top receptacle, and the top of open-top receptacle is provided with an agitator (3.1) sampling valve (3.2), mud valve (3.3), are respectively equipped with the wall of side, add carbon pipe (3.4) and water inlet pipe (3.5);
Water inlet system includes a raw water box (1.1), by intake pump (1.2) and anoxia/aerobic sbr reactor device (3.0) Water inlet pipe (3.5) connects;
Aerating system I includes the first air compressor machine (2.1), first gas effusion meter (2.2) and to be placed in anoxia/aerobic SBR anti- Answer the aeration plate (2.3) of device (3.0) bottom;
Film separation system is the plate and frame module of the side-walls being placed in anoxia/aerobic sbr reactor device (3.0), and it is by 1 ~2 Flat Membrane film units (4.1) and outside lucite shell (4.2) are constituted, and it is connected with extraneous sewage up and down, each By Flat Membrane, (material is Flat Membrane film unit (4.1):Kynoar PVDF, effective membrane area:0.25m2, membrane aperture≤0.1 μm) be fixed on and obtain on film frame, each film frame is provided with one and separates the mouth of a river, the top of whole plate and frame module be provided with one with each The individual outlet (4.3) separating mouth of a river connection, the bottom of lucite shell (4.2) is provided with a porous tubular aerator (4.4), It is connected with the second air compressor machine (4.5), second gas effusion meter (4.6), constitute aerating system II, be the film in plate and frame module Washed away, it is to avoid pollution;Outlet system includes a product water tank (4.9), by going out of peristaltic pump (4.7) and plate and frame module The mouth of a river (4.3) connection carries out aspirating draining (mixed liquor oozed Flat Membrane face), monitors transmembrane pressure using pressure gauge (4.8), Sewage through membrane separation is pumped down in product water tank;
Carbon source dosing system includes a carbon source container (5.1), adds pump (5.2) by carbon source anti-with anoxia/aerobic SBR The carbon pipe (3.4) that adds answering device (3.0) connects;
Real-time control system includes pH probe (6.1), ORP probe (6.2) and dissolved oxygen DO probe (6.3), three probes In waste water in the insertion reaction device when using, and is connected with integrated circuit case (6.4) respectively, integrated circuit case (6.4) with several Word Trackpad (6.5) connects, and the programme-control turnover water pump according to setting is intake pump and peristaltic pump, carbon source add pump, aeration System and the start and stop of agitator, thus each reaction member of real-time control is alternately.
Embodiment 2, using sequencing batch active sludge and membrane separation technique, breeding wastewater is processed
Using the device in embodiment 1, certain intensive culture waste water is processed, control reactor temperature be 25 ± 0.5 DEG C, processing procedure comprises the steps:
Municipal sewage plant's returned sludge for 5500mg/L for the concentration is seeded in reactor, turn on agitator, exposure Gas system I (aeration flow be 5L/min), (aeration flow is 8L/min to aerating system II, and the aeration rate that whole film washes away, by two Piece film set), intake pump and implement control system, using gradient water inlet (sewage) by the way of, so that sludge concentration is progressively risen to 11000mg/L, it is as follows that gradient enters water management:First stage is 7, the 1/4 of water inlet dilution most raw sewage concentration, second Stage is 7, and water inlet is diluted to the 1/2 of raw sewage concentration, and three phases start, and water inlet uses raw sewage, treats ammonia in sewage The clearance (influent ammonium concentration/water outlet ammonia nitrogen concentration) of state nitrogen is more than 80%, and the nitrate nitrogen in the waste water of discharge accounts for described useless When in water, the content of total nitrogen is more than 70%, reactor reaches stable whole process denitrogenation (three phases totally 45 days), and startup stage is complete Become, close intake pump and aerating system I, repetitive cycling following step (1)-step (4) is discharged to all waste water, close stirring Device, aerating system II and enforcement control system:
(1) fill phase:Open intake pump and aerating system I, using batch-type water inlet, according to Design Treatment amount (1.5L/ Cycle), pending breeding wastewater is rapidly input (input flow rate is 0.5L/min) after reactor, closes intake pump, keeps 5min.
(2) the simultaneous oxygen stage:Close aerating system I, in the presence of carbon source, the nitrate nitrogen in waste water is reduced to nitrous state Nitrogen, nitrite nitrogen is reduced to nitrogen.When dORP/dt is more than -5, judge that the carbon source deficiency in waste water can not be carried out completely anti- Nitrosation, opens in time carbon source and adds pump and carry out pulsed and add adding carbon source for reactor, and each opening time is 0.5min, After keeping 10min, continue with the value of dORP/dt as basis for estimation afterwards, so circulate, until appropriate additional carbon has ensured Be all-trans nitrosation i.e. when dORP/dt value is less than -5, judge carbon source enough, extend 20min it is ensured that anti-nitrosation is smoothed out.
(3) aerobic stage:Open aerating system I, the NH in breeding wastewater3- N and COD is oxidized to NO2- N, NO2- N quilt It is oxidized to NO3-N.
(4) bleeding stage:After above-mentioned aerobic stage starts 80min, open wriggling pumping draining, wriggling pump operation side Formula is often to open 8min to stop 2min, and the sewage that (1.5L/cycle) of Design Treatment amount is processed through step (2) is through plate and frame module Discharge after the diafiltration of flat sheet membranes, complete draining before aerobic process terminates, close peristaltic pump and aerating system I.
The time about 170min of each circulation in the present embodiment, the average time of aerobic stage is 120min, often takes turns total row The water time is 40min, and suction aquifer yield is about 3L/h.
In the present embodiment, complete nitrification-denitrification process is controlled to by short-cut nitrification-denitrification by the following two kinds method During:
(1) the controlled method of cumulative scale of free ammonia:
First 20 days water outlet NH after stable operation for the reactor3- N and NO2- N-dimensional is held in low concentration level, and NO3- N accounts for always More than 80%, NH of nitrogen (TN)3The clearance of-N is more than 90%.20th day to the 32nd day, by aeration flow from 5.0L/min It is contracted to 0.5L/min, NH in system3- N gradually rises, and NO3- N then reduces rapidly.When ammonia density free in system is increased to About 36.3mg/L (NH3-N≈205mg/L;PH=8.8), immediately aeration rate is recovered to 3.0L/min continuous aeration.NH3- N exists Drop to less than 5mg/L in subsequent 6 days.In the process, system NO2- N occurs significantly to accumulate, up to about 160mg/L, and NO3- N is only increased to 30mg/L.This shows that reactor is obvious to the oxidation susceptibility of nitrite nitrogen after controlling FA (free ammonia) to raise It is suppressed.Hereafter, corresponding carbon source, water outlet NO are supplemented by real-time control2- N and NO3- N declines, but NO2- N (average out to 38mg/L) concentration is still significantly higher than NO3- N (average out to 9mg/L).The nitrosoation rate of the continuous longtime running of reactor is up to 85%.
(2) SRT control methods:
In the present embodiment, control system mud mean residence time is 15 days, due to (T=under the present embodiment control condition 25 DEG C, pH >=7.0) sludge age of ammonia oxidizing bacteria is typically at 10-12 days, and the sludge age of nitrite-oxidizing bacterium then typically exists 18-20 days, nitrite-oxidizing bacteria quantity can be made to gradually decrease, so that ammonia oxidizing bacteria is in nitrifying bacteria community really Ratio improves constantly, and nitrosoation rate is able to sustainable growth.
In breeding wastewater after above-mentioned steps before processing be Inlet and outlet water in pollutant levels and clearance be shown in Table 1.
Pollutant levels in Inlet and outlet water in table 1 embodiment 1 and clearance
ND:Do not detect
Embodiment 3, using sequencing batch active sludge and membrane separation technique, percolate is processed
Using the device in embodiment 1, percolate is processed, controls the temperature of reactor to be 25 ± 0.5 DEG C, Processing procedure comprises the steps:
Municipal sewage plant's returned sludge for 5500mg/L for the concentration is seeded in reactor, turn on agitator, exposure Gas system I (aeration flow is 4L/min), aerating system II (aeration flow is 8L/min), intake pump and enforcement control system, By the way of gradient water inlet (sewage), sludge concentration is made progressively to rise to 11000mg/L, it is as follows that gradient enters water management:First The individual stage is 5, the 1/4 of water inlet dilution most raw sewage concentration, second stage is 5, and water inlet is diluted to raw sewage concentration 1/2, three phases start, water inlet use raw sewage, and completed after 15 days start.Treat the clearance of ammoniacal nitrogen in sewage (influent ammonium concentration/water outlet ammonia nitrogen concentration) is more than 80%, and the nitrate nitrogen in the waste water of discharge accounts for containing of described Determination of Total Nitrogen in Waste Water When amount is more than 70%, reactor reaches the denitrogenation of stable whole process, and startup stage completes, and closes intake pump and aerating system I, repeats to follow Ring following step (1)-step (4) is discharged to all waste water, closes agitator, aerating system II and implements control system, runs Logic chart is as shown in Figure 3:
(1) fill phase:Open intake pump and aerating system I, using batch-type water inlet, according to Design Treatment amount (1L/ Cycle), pending breeding wastewater is rapidly input (input flow rate is 0.5L/min) after reactor, closes intake pump, keeps 5min.
(2) the simultaneous oxygen stage:Close aerating system I, in the presence of carbon source in sewage, the nitrate nitrogen in breeding wastewater is gone back Originally it was nitrite nitrogen, nitrite nitrogen is reduced to nitrogen, when dORP/dt is more than -5, judged that the carbon source deficiency in waste water could not Carry out completely anti-nitrosation, open in time carbon source and add pump and carry out pulsed and add adding carbon source for reactor, when opening every time Between be 1min, after keeping 15min, continue with the value of dORP/dt as basis for estimation afterwards, so circulate, until appropriate is additional Carbon source ensures that completely anti-nitrosation, i.e. when dORP/dt value is less than -5, judges carbon source enough, and prolongation 30min is it is ensured that anti-nitrosation It is smoothed out, as shown in Fig. 2 after the simultaneous oxygen stage starts, if dORP/dt is more than -5, judging that carbon source amount is not enough, putting into additional carbon And after keeping 15min, judge dORP/dt again, until ORP rapid decrease, it is enough, such as that dORP/dt is less than judgement carbon source when -5 Shown in ellipse in Fig. 2, stop adding carbon source, the NO that in sewage, last round of circulation aerobic unit produces2- N and NO3- N all quilts It is reduced into N2.
(3) aerobic stage:Open aerating system I, the NH in breeding wastewater3- N and COD is oxidized to NO2- N, NO2- N quilt It is oxidized to NO3- N, as dpH/dt=0, as shown in rectangular boxes in Fig. 2, stops aeration immediately.
(4) bleeding stage:After above-mentioned aerobic stage starts 80min, open wriggling pumping draining, wriggling pump operation side Formula is often to open 8min to stop 2min, and the sewage that (1L/cycle) of Design Treatment amount is processed through step (2) is through in plate and frame module Discharge after the diafiltration of Flat Membrane, complete draining before aerobic process terminates, close peristaltic pump and aerating system I.
About 230min average time of each circulation in the present embodiment, often the average time of wheel aerobic stage is 150min, The average time often taking turns total draining is 40min, and suction aquifer yield is about 2L/h.
In the present embodiment, complete nitrification-denitrification process is controlled to by short-cut nitrification-denitrification using the following two kinds method During:
1) optimize aeration time method:
First 20 days water outlet NH after stable operation for the reactor3- N and NO2- N-dimensional is held in low concentration level, and NO3- N accounts for always More than the 85% of nitrogen (TN), the clearance of ammoniacal nitrogen is more than 90%.
As shown in Fig. 2 115~220min is aerobic stage, the NH in waste water3- N and COD is oxidized, and pH is gradually lowered, When reduce as far as possible i.e. ammonia valley point (dpH/dt=0) when, immediately stop aeration, as shown in rectangular boxes in Fig. 2.In aeration During (115~220min), the concentration of useless oxygen in water is 0.2~3.5mg/L, maintains reduced levels, ammonium oxidation Speed (about 15.1mgN/h L) is much larger than nitrite nitrogen oxidation rate (about 2.8mgN/h L).Reactor water outlet NO2- N level (about 50mg/L) is apparently higher than NO3- N (about 10mg/L) and NH3- N (< 3mg/L), nitrosoation rate is about 83%.
(2) SRT control methods:
In the present embodiment, control system mud mean residence time is 15 days, due to (T=under the present embodiment control condition 25 DEG C, pH >=7.0) sludge age of ammonia oxidizing bacteria is typically at 10-12 days, and the sludge age of nitrite-oxidizing bacterium then typically exists 18-20 days, nitrite-oxidizing bacteria quantity can be made to gradually decrease, so that ammonia oxidizing bacteria is in nitrifying bacteria community really Ratio improves constantly, and nitrosoation rate is able to sustainable growth.
In percolate after above-mentioned steps before processing be Inlet and outlet water in pollutant levels and clearance be shown in Table 2.
Pollutant levels in Inlet and outlet water in table 2 embodiment 3 and clearance
ND:Do not detect
Embodiment 4, using sequencing batch active sludge and membrane separation technique, sludge-digestion liquid is processed
Using the device in embodiment 1, percolate is processed, controls the temperature of reactor to be 20 ± 0.5 DEG C, Processing procedure comprises the steps:
Municipal sewage plant's returned sludge for 5000mg/L for the concentration is seeded in reactor, turn on agitator, exposure Gas system I (aeration flow is 5L/min), aerating system II (aeration flow is 8L/min), intake pump and enforcement control system, By the way of gradient water inlet (sewage), sludge concentration is made progressively to rise to 11000mg/L, it is as follows that gradient enters water management:First The individual stage is 7, the 1/4 of water inlet dilution most raw sewage concentration, second stage is 7, and water inlet is diluted to raw sewage concentration 1/2, three phases start, water inlet use raw sewage, and completed after 45 days start.Treat the clearance of ammoniacal nitrogen in sewage (influent ammonium concentration/water outlet ammonia nitrogen concentration) is more than 80%, and the nitrate nitrogen in the waste water of discharge accounts for containing of described Determination of Total Nitrogen in Waste Water When amount is more than 70%, reactor reaches the denitrogenation of stable whole process, and startup stage completes, and closes intake pump and aerating system I, repeats Circulation following step (1)-step (4) is discharged to all waste water, closes agitator, aerating system II and implements control system:
(1) fill phase:Open intake pump and aerating system I, using batch-type water inlet, according to Design Treatment amount (1.5L/ Cycle), pending breeding wastewater is rapidly input (input flow rate is 0.5L/min) after reactor, closes intake pump, keeps 5min.
(2) the simultaneous oxygen stage:Close aerating system, in the presence of carbon source in sewage, the nitrate nitrogen in breeding wastewater is gone back Originally it was nitrite nitrogen, nitrite nitrogen is reduced to nitrogen, when dORP/dt is more than -5, judged that the carbon source deficiency in waste water could not Carry out completely anti-nitrosation, open in time carbon source and add pump and carry out pulsed and add adding carbon source for reactor, when opening every time Between be 1min, after keeping 15min, continue with the value of dORP/dt as basis for estimation afterwards, so circulate, until appropriate is additional Carbon source ensures that completely anti-nitrosation, i.e. when dORP/dt value is less than -5, judges carbon source enough, and prolongation 25min is it is ensured that anti-nitrosation It is smoothed out.
(3) aerobic stage:Open aerating system, the NH in breeding wastewater3- N and COD is oxidized to NO2- N, NO2- N is by oxygen Turn to NO3-N.
(4) bleeding stage:After above-mentioned aerobic stage starts 60min, open wriggling pumping draining, wriggling pump operation side Formula is often to open 8min to stop 2min, and the sewage that (1.5L/cycle) of Design Treatment amount is processed through step (2) is through in plate film assembly Discharge after the filtration of Flat Membrane, complete draining before aerobic process terminates.
In the present embodiment, the average time of each circulation is about 200min, and the aerobic average time often taking turns circulation is about 135min, often taking turns total water discharge time is 60min, and suction aquifer yield is about 2L/h.
Using the controlled method of cumulative scale of free ammonia as follows and SRT control methods by complete nitrification-denitrification process control in the present embodiment It is made as short-cut nitrification-denitrification process, process is as follows:
Initially with the controlled method of cumulative scale of free ammonia, that is, control FA concentration to gradually rise and turned to nitrosation with realizing complete nitrification Become:First 20 days reactor water outlet NO3- N accounts for TN and maintains more than 90%, and, more than 95%, the 21st day extremely for the clearance of ammoniacal nitrogen Reactor aeration flow was contracted to about 0.5L/min by 5L/min in 33rd day, in system, free ammonia density is therewith by about 0.3mg/ L is increased to 20mg/L (pH=8.9), subsequently recalls to aeration flow to 3.5L/min continuous aeration, until NO2/(NO2+NO3) Reach more than 80%.Along with the oxidation of ammonia nitrogen, NO2- N is increased to 160mg/L, far above NO3- N (only up to 40mg/L). After FA occurs controlled accumulation, the aerobic unit of reactor adopts control mode 1) optimize aeration time i.e. when pH is down to ammonia paddy During point (dpH/dt=0), stop aeration, the continuous nitrosoation rate average out to 82% running immediately.
In sludge-digestion liquid after above-mentioned steps before processing be Inlet and outlet water in pollutant levels and clearance be shown in Table 3.
Pollutant levels in Inlet and outlet water in table 3 embodiment 4 and clearance
ND:Do not detect.

Claims (8)

1. a kind of process high ammonia-nitrogen wastewater device it is characterised in that:It includes water inlet system, aerating system, carbon source add and be System, response system, film separation system and outlet system;
Described response system includes a reactor, and described reactor is a container, and the top of described reactor is provided with agitator;
Described water inlet system includes a raw water box, and described raw water box is connected with described reactor by intake pump;
Described aerating system includes air compressor machine, gas flowmeter and aerator, and described aerator is placed in described reactor;
Described carbon source dosing system includes a carbon source storage tank, and described carbon source storage tank adds pump with described reactor even by carbon source Connect;
Described film separation system is a membrane module;
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 includes 1~2 film unit, each described film unit It is made up of two panels film, the material of described film is Kynoar, aperture≤0.1 μm, and effective area is 0.5m2;Described membrane module Inside be additionally provided with aerator, be connected with another air compressor machine and another gas flowmeter successively, be described film aeration;
Described outlet system includes a product water tank, and the outlet of described membrane module is connected with described product water tank by going out water pump;
Described device also includes a real-time control system, and described enforcement control system includes probe, integrated circuit case and numeral and touches Control plate;
Described probe includes pH probe, ORP probe and dissolved oxygen DO probe, is all connected with described integrated circuit case, described integrated Circuit box is connected with described touch sensitive digitizer panel.
2. the method utilizing the device described in claim 1 to process high ammonia-nitrogen wastewater, comprises the steps:
Inoculation of activated-sludge, to described reactor, opens described agitator, repetitive cycling following step (1)-step (4):
(1) fill phase:Open described aerating system and described intake pump, using batch-type water inlet, according to Design Treatment amount, treat The described high ammonia-nitrogen wastewater processing is transfused in described reactor, closes described intake pump;
(2) the simultaneous oxygen stage:Close described aerating system, in the presence of carbon source, the nitrate nitrogen in waste water is reduced to nitrous state Nitrogen, nitrite nitrogen is reduced to nitrogen;
(3) aerobic stage:Open described aerating system, the ammoniacal nitrogen in waste water and Organic substance are oxidized, described ammoniacal nitrogen is by oxygen Turn to nitrite nitrogen, nitrite nitrogen is oxidized to nitrate nitrogen;
(4) bleeding stage:After described aerobic stage starts 60~120min, described in unlatching, go out water pump, the institute of Design Treatment amount State waste water to discharge after the filtration of film in described membrane module, go out water pump and described aerating system described in closing successively.
3. method according to claim 2 it is characterised in that:Described real-time control system is whole to open, and monitors described height The size of oxidation-reduction electrode current potential, pH value and dissolved oxygen in ammonia nitrogen waste water;
Aerator in described membrane module is whole to be opened, and aeration flow is 5~15L/min piece.
4. according to the method in claim 2 or 3 it is characterised in that:The concentration of the activated sludge of described inoculation is 5000mg/ L~5500mg/L, gradient improves the influent concentration of sewage, and activated sludge concentration is increased to 10000mg/L~12000mg/L;
Described gradient raising is divided into three phases, and first stage is 5~10, and the 1/4 of water inlet dilution most raw sewage concentration; Second stage is 5~10, and water inlet is diluted to the 1/2 of raw sewage concentration;Three phases are 30~55.
5. according to the method in claim 2 or 3 it is characterised in that:In step (1), ammoniacal nitrogen in described high ammonia-nitrogen wastewater Concentration 500~900mg/L, COD content be 5000~10000mg/L;
Described high ammonia-nitrogen wastewater is derived from livestock breeding wastewater, percolate or sludge-digestion liquid;
Described Design 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 to after keeping 3~5min in described reactor and enters the described and oxygen stage.
6. according to the method in claim 2 or 3 it is characterised in that:In step (2), when the oxidation-reduction electrode electricity of waste water Position over time value be dORP/dt be 0~-5 when, judge carbon source deficiency, unlatching described carbon source add pump, be described reaction Device adds carbon source, and each opening time is 0.5~1min, after keeping 10~20min, enters and judges next time;As described dORP/ When dt is less than -5, after time delay 10~30min, open described aerating system, enter in step (3).
7. according to the method in claim 2 or 3 it is characterised in that:In step (3), time of described aerobic stage is 9~ 180min, aeration flow is 0.5~10L/min;
In step (4), time of described bleeding stage is 30~90min, described go out water pump be batch (-type) suction, often open 8~10 Minute stops 2~4 minutes.
8. according to the method in claim 2 or 3 it is characterised in that:Using following 1) -3) at least one of method by whole process Nitrification-denitrification is converted into short-cut nitrification-denitrification:
1) optimize aeration time method:After denitrogenation is stable, in the described aerobic stage of every wheel circulation, when the pH value in waste water in time Do not change i.e. dpH/dt=0 when, close described aerating system;
2) the controlled method of cumulative scale of free ammonia:After denitrogenation is stable, in described aerobic stage, reduce the aeration flow of described aerating system, When the concentration of ammonia free in waste water raises to above equal to 20mg/L, recover aeration flow;
Aeration flow in the whole circulation of described aerating system is reduced to 0.2~1L/min;
Above-mentioned 1) and 2) described in denitrogenation stably each mean when the ammoniacal nitrogen in described waste water clearance be more than 80%, and arrange When nitrate nitrogen in the waste water going out accounts for the content of described Determination of Total Nitrogen in Waste Water more than 70%;
3) SRT control methods:The step that methods described also includes spoil disposal, described spoil disposal, after described aerobic stage, controls described The mean residence time of the mud in reactor is 12~15 days.
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