CN106554079A - A kind of biomembrane denitrogenation method of nitric wastewater - Google Patents
A kind of biomembrane denitrogenation method of nitric wastewater Download PDFInfo
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Abstract
The invention discloses a kind of biomembrane denitrogenation method of nitric wastewater, using the biomembrane denitrogenation reactor of following structure：Transverse slat a, riser b, riser c and transverse slat d are set in reactor, reactor is divided into upper and lower two parts by transverse slat a, and bottom is hydrolysis acidification area, and top is A/O areas；A/O areas are divided into three parts by riser b and c, it is followed successively by aerobic zone O, transition region and anaerobic zone A, riser b lower ends are tightly connected with transverse slat a, the mouth of a river was left with reactor head in upper end, and riser c upper ends are tightly connected with reactor head, and the mouth of a river was left with transverse slat a in lower end, transverse slat d left ends are connected with riser c sealed bottoms, and right-hand member is tightly connected with reactor wall；Transition region loads sponge iron deoxidizing agent granule.Intake from reactor bottom during sewage disposal, successively Jing after hydrolysis acidification area-aerobic zone-transition region-anaerobic zone, discharged by top.In reactor of the present invention, each region biomembrane carries out subregion culture, can more preferably form the biomembrane with particular characteristic, and biofilm is quick, denitrification effect is good.
Description
Technical field
The invention belongs to technical field of biological sewage treatment, and in particular to a kind of biomembrane denitrogenation method of nitric wastewater.
Background technology
In recent years, with developing rapidly for China's Urbanization Construction, the water environment pollution and Eutrophication Status of China is increasingly severe, many water body in lake can not play its normal function and severely impact industrial or agricultural and fish production, hamper the development of Chinese national economy increasingly severely.Nitrogen is the major pollutants for causing body eutrophication, and the control to total nitrogen content in the sewage of discharge is particularly important.
In biological denitrification process, A/O biological denitrification process has the advantages that pond holds that less, nitric efficiency is high, operational management is convenient.Traditional A/O reactors are often brought into into anaerobic zone by aerobic zone and are partly dissolved oxygen so that the not absolute anaerobism in anaerobic zone, produce certain impact to anaerobic zone；In addition, for the relatively low nitric wastewater of biochemical, only by the Ammonification of O sections by organic nitrogen compound oxidation Decomposition, cannot thoroughly remove organic nitrogen compound, these will all cause, and water outlet total nitrogen or COD are unqualified, and the harm to environment is still present.Therefore, researching and developing a kind of denitrogenation method of economical and efficient has become the focus of current sewage disposal research.
CN201210285312.2 discloses a kind of improvement A/O biological denitrification process, the Aerobic Pond of A/O techniques is divided into into tri- part of O1, O2, O3, O1 areas are using fixed biofilm, guarantee the sludge concentration in O1 areas between 5000～8000mg/L,, between 1.5～2.5kg/ (kgd), BOD clearances are up to more than 50% for sludge loading；O2 areas sludge loading≤0.25kg/ (kgd), improves the efficiency of nitration reaction, using the spherical biofilm that suspends；O3 areas adopt activated sludge process, sludge loading≤0.1kg/ (kgd).The invention adopts the biochemical process of multi-form, nitric efficiency to can reach more than 95% using different sections.But the water inlet in O1 areas is in middle and lower part, water outlet is easily caused sewage and directly flows away from bottom in bottom, and stagnant water state is formed at top, while aerobic part divide into three regions, floor space is larger.
CN
201210371701.7 disclose a kind of variable volume hydrolysis acidification and A/O integrated sewage treating apparatus.The hydrolysis acidification pool of the device is divided into eight lattice, is equipped with water inlet pipe per lattice, gate is provided between lattice dative, and whole hydrolysis acidification pool is provided with an outlet, is connected with outlet pipe.Anoxic pond is divided into four lattice, is provided with distribution well in center upper portion position, and distribution well is provided with inlet opening, backflow mixed liquor inlet and returned sludge mud inlet, and water distribution bottom is provided with four valves, and every lattice of anoxic pond are individually provided with outlet pipe.Aerobic Pond is divided into six lattice, and a lattice wherein are provided with water inlet, and the water inlet is connected with the outlet pipe of anoxic pond, is provided with gate between the lattice dative of Aerobic Pond, is individually provided with outlet pipe and mixed-liquor return pipe per lattice.The invention simple and flexible, for different quality runoff investigation volume, operational management is convenient.But Aerobic Pond outlet is joined directly together with anoxic pond import, easily make the dissolved oxygen amount in anoxic pond exceeded, the completeness of impact anti-nitration reaction.
The content of the invention
For the deficiencies in the prior art, the invention provides a kind of biomembrane denitrogenation method of nitric wastewater.The present invention arranges four reaction areas in biomembrane denitrogenation inside reactor, the biomembrane of each reaction zone carries out subregion single culture, the biological film system with particular characteristic can more preferably be formed, and can ensure that each reaction zone plays nitrogen removal performance under conditions of each suitable, have the advantages that biofilm is quick, denitrification effect is good.
The biomembrane denitrogenation method of the nitric wastewater of the present invention, using the biomembrane denitrogenation reactor of following structure：Transverse slat a, riser b, riser c and transverse slat d are set in reactor, the cross-sectional area of transverse slat a is identical with cross-sectional reactor area, reactor is divided transversely into into upper and lower two parts, bottom is hydrolysis acidification area, and top is A/O areas；Wherein A/O areas are divided longitudinally into three parts by riser b and riser c, it is followed successively by aerobic zone O, transition region and anaerobic zone A, riser b lower ends are tightly connected with transverse slat a, the mouth of a river was left between upper end and reactor head, and riser c upper ends are tightly connected with reactor head, the mouth of a river are left between lower end and transverse slat a, transverse slat d left ends are connected with riser c sealed bottoms, and right-hand member is tightly connected with reactor wall；Transition region loads sponge iron deoxidizing agent granule；Intake from reactor bottom during sewage disposal, after sequentially passing through hydrolysis acidification area-aerobic zone-transition region-anaerobic zone, discharged by reactor top.The inventive method can not only realize the baffling flowing of sewage, extend dwell time of sewage of the sewage in reactor, and the floor space of reactor is little, compact conformation, and biofilm and denitrification effect are good.
In the present invention, the ratio of height to diameter of the biological denitrification reactor is 3:1-10:1, transverse slat a are arranged away from reactor bottom 1/3-1/5 eminences, and its cross-sectional area is identical with cross-sectional reactor area, and bottom is hydrolysis acidification area；Riser b lower ends are deviated to the left 1/10-1/7 transverse slat length away from transverse slat a centrages, and upper end is aerobic zone on the left of reactor head 4-8cm, riser b；With the symmetrical parallel arrangement of the centrage of transverse slat a, its upper end is tightly connected riser c and riser b with reactor top, and apart from transverse slat a upper surface about 4-8cm, the region between riser b, c is transition region for bottom；Transverse slat d left ends are connected with riser c bottom end seals, and right-hand member is tightly connected with reactor wall, so as to surround anaerobic zone with reactor wall.In the present invention, the cross section of transverse slat a is divided into two kinds of forms by riser b, is latticed on the left of transverse slat a, and waste water enters aerobic zone by the grid on the left of transverse slat a by hydrolysis acidification area, is plate seal shape on the right side of transverse slat a；Riser b, the cross section of riser c are plate seal shape；The cross section of transverse slat d is latticed, and the waste water after crossing area enters anaerobic zone by transverse slat d.
In the present invention, the volume ratio of hydrolysis acidification area, aerobic zone, transition region and anaerobic zone is 0.8-1:0.8-1:0.3-0.5:0.8-1.Reactor lower part is provided with water inlet, and flush discharge mouth is provided between transverse slat a and transverse slat d, and reactor upper side is provided with outlet, and top is provided with air vent.Each reaction zone is equipped with aerating system, including compressor, air inlet pipe and gas distributor etc., so as to realize the supply of oxygen.
In the present invention, the biologic packing material of hydrolysis acidification area, aerobic zone and anaerobic zone can select biologic packing material commonly used in the art, the preferred 3 D elastic filler in hydrolysis acidification area；Aerobic zone and the biologic packing material of anaerobic zone, the larger biological active filling material of pref. cylindrical specific surface area；Above-mentioned packing volume accounts for the 3/5-4/5 of reaction zone volume.After biofilm packing is fixed, then activated sludge is loaded on the filler of each reactor, makes the sludge concentration in each reaction zone be 5-10g/L.
In the present invention, the upper surface of transition region filling sponge iron deoxidizing agent granule is concordant with the upper surface of riser b, sponge iron deoxidizing agent particle volume accounts for the 3/5-4/5 of transition region volume, both can be with filter sludge, prevent aerobic sludge from entering anaerobic zone, and can be with deoxygenation, it is to avoid adverse effect of the dissolved oxygen to anaerobic zone.
Biomembrane denitrogenation method of the present invention using the nitric wastewater of the biomembrane denitrogenation reactor, specifically includes three phases, and the first stage is the biofilm stage, and second stage is sewage disposal stage, and the phase III is the backwash stage；Specifically include following steps：
（1）The biofilm stage：Load corresponding biologic packing material in hydrolysis acidification area, aerobic zone and anaerobic zone, make packing volume account for the 3/5-4/5 of each reaction zone volume, and the amount according to sludge concentration 5-10g/L is spread to activated sludge point in the filler of three reaction zones；Transition region loads sponge iron deoxidizing agent granule, and volume accounts for the 3/5-4/5 of transition region volume.Then nitric wastewater being injected from reactor bottom, when whole reactor fills treatment sewage, stopping water inlet, close discharge outlet, start aerating system, the dissolved oxygen concentration for controlling hydrolysis acidification area, aerobic zone and anaerobic zone is 1-3mg/L；First whole aeration 24-48h, close hydrolysis acidification area and anaerobic zone afterwards in aerating system, aerobic zone still continues aeration, while opening water inlet and discharge outlet, continues culture by the way of continuum micromeehanics.During water inlet, due to the presence in hydrolysis acidification area, can be by the float in sewage and impurity effectively catching, the biomembranous blocking of A/O sections can be slowed down, simultaneously because the presence of transition region, the dissolved oxygen of aerobic zone will not be interfered to the anaerobic environment of anaerobic zone, be conducive to cultivating the biological film system with particular characteristic.After 72-144h, it can be seen that the sepia biomembrane of thickness about 2mm on the filler of three reaction zones, while it was observed that there is bubble formation near air vent, it is considered as extension and touches and complete.
It is 7.0-8.0 that present invention extension touches the pH value of stage control nitric wastewater, and treatment temperature is 25-35 DEG C, BOD in waste water5:N:P=100:5:1, influent ammonium concentration is 200-400mg/L, and COD is less than 500mg/L.If raw water is unsatisfactory for requiring, can be adjusted by diluting, adding the method such as potassium dihydrogen phosphate or glucose.From reactor bottom with the flow velocity injection nitric wastewater of (6/7H-H) m/h during biofilm, height of the wherein H for reactor, the flow velocity in whole biofilm stage are constant.
The present invention hangs the stage of touching and preferably adds microbial growth promoters in hydrolysis acidification area, shortens the biofilm time.The microbial growth promoters include slaine, polyamines and organic acid azanol, and wherein slaine is 40-100 weight portions, and polyamines are 5-30 weight portions, and organic acid azanol is 0.5-15 weight portions；The slaine is made up of calcium salt, mantoquita, magnesium salt and/or ferrous salt.Dosage is added according to promoter concentration 10-40mg/L in sewage disposal system, and preferred 20-30mg/L is added.
Slaine in microbial growth promoters of the present invention can be calcium salt, magnesium salt and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）, preferably（8-12）:（10-20）:（1-4）；Or calcium salt, ferrous salt and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）, preferably（8-12）:（2-6）:（1-4）；Or calcium salt, magnesium salt, ferrous salt and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）, preferably（8-12）:（10-20）:（2-6）:（1-4）.
Calcium salt in microbial growth promoters of the present invention is CaSO4Or CaCl2, preferred CaSO4；Magnesium salt is MgSO4Or MgCl2, preferred MgSO4；Ferrous salt is FeSO4Or FeCl2, preferred FeSO4；Mantoquita is CuSO4Or CuCl2, preferred CuSO4。
Polyamines in microbial growth promoters of the present invention are the mixture of spermine, spermidine or both.Described organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
（2）Sewage disposal stage：Sewage disposal stage is divided into starting period and steady operation period.
Pending nitric wastewater is injected from reactor bottom first, sewage initially enters hydrolysis acidification area, and larger molecular organicses are decomposed into small-molecule substance in hydrolysis acidification area by sewage, improve the biochemical of sewage, while retaining float and impurity in sewage；Sewage enters aerobic zone by the netted section of transverse slat a, and the organic nitrogen in this sewage is converted into ammonia nitrogen, nitrite nitrogen and nitrate nitrogen successively；When sewage reaches riser b tops, transition region is deflected into, the float in water and dissolved oxygen are removed；Then anaerobic zone is deflected into by transverse slat d, carries out the removal of nitrogen, discharged finally by discharge outlet.
Starting period of the invention intakes flow velocity by the way of gradually increasing, and injects pending nitric wastewater from reactor bottom with the flow velocity of (6/7H-H) m/h first, i.e. control dwell time of sewage is between 60-70min；When COD concentration in water outlet<150mg/L, ammonia nitrogen concentration<80mg/L, total nitrogen concentration<During 100mg/L, flow velocity is improved to (H-6/5H) m/h；When COD concentration in water outlet<70mg/L, ammonia nitrogen concentration<40mg/L, total nitrogen concentration<During 50mg/L, flow velocity is improved again to (6/5H-3/2H) m/h；When COD concentration in water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<During 20mg/L, flow velocity is improved again to (3/2H-2H) m/h；When COD concentration in water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and when relatively stablizing, into steady operation period, maintains that existing flow velocity is constant to be processed.
When fluctuating occurs in influent quality, flow velocity should be reduced as the case may be；If COD concentration is not above 70mg/L in water outlet, ammonia nitrogen concentration is not above 40mg/L, and total nitrogen concentration is not above 50mg/L, then reduce flow velocity to (6/5H-3/2H) m/h, after water outlet is qualified and stable, be gradually adjusted according still further to aforesaid way；If there is any one to exceed above-mentioned flow in three indexs, flow velocity is reduced to (H-6/5H) m/h, after water outlet is qualified and stable, be gradually adjusted according still further to aforesaid way.
It is 7.0-8.0 that sewage disposal stage of the present invention controls the pH value of nitric wastewater, and treatment temperature is 25-35 DEG C, and influent ammonium concentration is 400-800mg/L, and total nitrogen concentration is 500-900mg/L, and COD is 2-3mg/L less than 1000mg/L, the dissolved oxygen concentration for controlling aerobic zone.The dissolved oxygen concentration of anaerobic zone can be observed in below 0.5mg/L by the dissolved oxygen detector instrument of anaerobic zone, illustrate that sewage passes through transition region, dissolved oxygen in water is eliminated effectively, further enhance the anaerobic environment of anaerobic zone, be conducive to the anti-nitration reaction in reinforced anaerobic area, nitrogen in sewage is thoroughly removed, is finally discharged by the discharge outlet above anaerobic zone.When the dissolved oxygen concentration for detecting anaerobic zone is higher than persistently 0.5mg/L, sponge iron deoxidizing agent granule is replaced.
Sewage disposal stage of the present invention can add the microbial growth promoters in biofilm stage in hydrolysis acidification area, described microbial growth promoters are added according to the mode gradually successively decreased, add once per 8-24h, dosage is 10-25mg/L first, is gradually successively decreased according to 3-5mg/L afterwards.
（3）The backwash stage：Intake from the discharge outlet on reactor top during backwash, opening water inlet and backwash discharge outlet carries out draining, then the sewage of anaerobic zone and transition region is discharged from backwash discharge outlet, the sewage in aerobic zone and hydrolysis acidification area is discharged by water inlet.Reactor runs 5-7 days, carries out a backwash.During backwash according to (2H-3H) m/h flow velocity, that is, control dwell time of sewage between 20-30min, each backwash 1-2h.
Compared with prior art, the present invention has advantages below：
1st, hydrolysis acidification and A/O biochemistry pools are incorporated into one by the present invention, in inside reactor, 4 pieces of dividing plates are set, inside reactor is divided into into 4 different reaction zones, during biofilm, biomembrane in differential responses area carries out subregion single culture, can more preferably form the biological film system with particular characteristic；In sewage disposal process, the conversion for enhancing the oxidation Decomposition and nitrogen of dirty Organic substance in water is removed, stronger with impact resistance ability, the advantages of high treating effect.
2nd, the float in sewage and impurity effectively catching can be slowed down the biomembranous blocking of A/O sections by hydrolysis acidification area；And transition region is added between aerobic zone O and anaerobic zone A, not only can remove the dissolved oxygen of aerobic zone O areas residual, it is ensured that the anaerobic condition of anaerobic zone, strengthen denitrification denitrogenation reaction；Can also the non-film forming in effectively catching O areas activated sludge, the anaerobic environment in A areas can not only be ensured, moreover it is possible to ensure that the activated sludge in O areas is not lost in current.
3rd, the microbial growth promoters of specific composition are added in hydrolysis acidification area, accelerator enters each reaction zone with sewage, in making activated sludge, nitrobacteria is under the collective effect of slaine, polyamines and organic acid azanol, realize the fast breeding of cell, the population effect of denitrification microorganism can be given full play to, the ability of activated sludge degradation of contaminant is favorably improved, the denitrification rates and system run all right of whole system are further improved.
Description of the drawings
Fig. 1 is the structural representation of biomembrane denitrogenation reactor of the present invention；
Wherein 1- hydrolysis acidifications area, 2- hydrolysis acidifications area filler, 3- aerobic zones, 4- aerobic zones filler, 5- transition regions, 6- transition region fillers, 7- anaerobic zones, 8- anaerobic zones filler；
Cross-sectional views of the Fig. 2 for transverse slat a；
Cross-sectional views of the Fig. 3 for transverse slat d.
Specific embodiment
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The biomembrane denitrogenation structure of reactor that biomembrane denitrogenation method of the present invention is adopted is as shown in Figure 1, reactor outward appearance is in cylinder, in inside reactor, four blocks of column plates are set, respectively transverse slat a, riser b, riser c, transverse slat d, inside reactor is divided into into four regions, respectively hydrolysis acidification area 1, aerobic zone 3, transition region 5, anaerobic zone 7, wherein hydrolysis acidification area, aerobic zone, anaerobic zone are equipped with biologic packing material 2,4,8, and transition region is equipped with filter packing 6.Reactor is intake from bottom water inlet, sequentially passes through hydrolysis acidification area-aerobic zone-transition region-anaerobic zone, discharges from top discharge outlet, and top is provided with air vent, and during flushing, sewage is discharged by water inlet and flush discharge mouth.
The a diameter of 0.5m of reactor cross-section that the embodiment of the present invention is adopted, the high 2m of reactor, transverse slat a is apart from reactor base plate 0.5m, riser b is deviated to the left 0.05m away from transverse slat a centrages, and, apart from reactor head 0.05m, riser c and riser b is with the symmetrical parallel arrangement of the centrage of transverse slat a for riser b, its top is fixedly linked with reactor top board, distance from bottom transverse slat a upper surface 0.05m, in the bottom of riser b level connection joint transverse slat d to the right, transverse slat d is tightly connected with reactor wall to the right.Hydrolysis acidification area, aerobic zone, the volume ratio of 4 part of transition region and anaerobic zone are about 1: 1: 0.5: 1.The filler in hydrolysis acidification area is 3 D elastic filler, and packing volume accounts for the 3/4 of hydrolysis acidification area volume.The filler of aerobic zone and anaerobic zone is volcanic rock granular biological filler, and packing volume accounts for the 3/4 of each several part volume.Transition region loads sponge iron deoxidizing agent granule, and its volume accounts for the 3/4 of transition region volume.Amount according to sludge concentration 5-10g/L is spread to activated sludge point in the filler of 3 reaction zones.
Treatment sewage is certain sewage treatment plant's nitric wastewater, and ammonia nitrogen concentration is 400mg/L, and total nitrogen 600mg/L, COD concentration are 800mg/L.
Embodiment 1
1st, the biofilm stage
（1）Pending nitric wastewater is diluted into one times with sanitary sewage, ammonia nitrogen in sewage concentration is 250mg/L after dilution, and COD concentration is 400mg/L, the pH value for controlling sewage is 7.0-8.0, treatment temperature is 25-35 DEG C, adds glucose and potassium dihydrogen phosphate, adjusts BOD in waste water5:N:P=100:5:1。
（2）Load corresponding filler in hydrolysis acidification area, aerobic zone and anaerobic zone, make packing volume account for the 3/4 of each reaction zone volume, and the amount according to sludge concentration 5-10g/L is spread to activated sludge point in the filler of three reaction zones.Load sponge iron deoxidizing agent granule in transition region, volume accounts for the 3/4 of transition region volume.
（3）Water inlet pipe is opened, and it is Hm/h to adjust water inlet flow velocity, and wherein H is the height of reactor, nitric wastewater is injected into reactor, when whole reactor fills treatment sewage, stops water inlet, closes discharge outlet.Start aerating system, the dissolved oxygen concentration for controlling hydrolysis acidification area, aerobic zone and anaerobic zone is respectively 1.0mg/L, 2.0mg/L, 1.0mg/L；After aeration 30h, the aerating system in closing hydrolysis acidification area and anaerobic zone, aerobic zone still continue aeration, while opening water inlet and discharge outlet, continue culture by the way of continuum micromeehanics.After 104h, it can be seen that the sepia biomembrane of thickness about 2mm on the filler of three reaction zones, while it was observed that there is bubble formation near air vent, it is considered as extension and touches and complete.Jing is counted, and the biofilm stage takes 134h altogether.
2nd, sewage disposal stage
Sewage disposal stage is divided into starting period and steady operation period, by the way of continuum micromeehanics, closes the aerating system of hydrolysis acidification area and anaerobic zone, opens the aerating system of aerobic zone, and regulation dissolved oxygen concentration is 2.0mg/L.First run using low flow velocity, according to 6/7H（H is that reactor is high）Flow velocity, that is, control dwell time of sewage for 70min, larger molecular organicses are decomposed into small-molecule substance in hydrolysis acidification area by sewage, improve the biochemical of sewage, while retaining float and impurity in sewage.Then proceed to carry out nitration reaction in aerobic zone through transverse slat a upwards, when liquid level reaches riser b tops, baffling flows into transition region, the dissolved oxygen concentration of anaerobic zone can be observed in below 0.5mg/L by the dissolved oxygen detector instrument of anaerobic zone, illustrate that sewage, by transition region, effectively eliminates the dissolved oxygen in water, further enhance the anaerobic environment of anaerobic zone, be conducive to the anti-nitration reaction in reinforced anaerobic area, the nitrogen in sewage is thoroughly removed, finally discharged by the discharge outlet above anaerobic zone.
Startup stage using gradually increase water inlet flow velocity by the way of, every 40min detect a water outlet in COD, total nitrogen and ammonia nitrogen concentration；COD concentration in water outlet after 200min<150mg/L, ammonia nitrogen concentration<80mg/L, total nitrogen concentration<100mg/L and more stable, then improves flow velocity to Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen in 30min detects a water outlet；COD concentration in water outlet after 120min<70mg/L, ammonia nitrogen concentration<40mg/L, total nitrogen concentration<50mg/L and when relatively stablizing, improves flow velocity again to 6/5Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen in 20min detects a water outlet；COD concentration in water outlet after 60min<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, improves flow velocity again to 3/2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 20min in 10min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, reactor enters steady operation period.Calculating into steady operation period needs 200+120+60+20=400min altogether, and the flow velocity of maintenance 3/2Hm/h is constant to be processed.
When influent ammonium concentration increases, effluent COD concentration 50mg/L, ammonia nitrogen concentration 35mg/L, total nitrogen concentration 50mg/L, as COD concentration is not above 70mg/L, ammonia nitrogen concentration is not above 40mg/L, total nitrogen concentration is not above 50mg/L, flow velocity is reduced then to 6/5Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 40min in 20min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, now improves flow velocity to 3/2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 15min in 5min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, is considered as adjustment and finishes.
3rd, the backwash stage
Reactor runs 5-7 days, carries out a backwash.During backwash, intake from the discharge outlet on reactor top, opening water inlet and backwash discharge outlet carries out draining, then the sewage of anaerobic zone and transition region is discharged from backwash discharge outlet, the sewage in aerobic zone and hydrolysis acidification area is discharged by water inlet.During backwash according to 2Hm/h flow velocity, that is, control dwell time of sewage between 30min, each backwash 1h.When the dissolved oxygen concentration for detecting anaerobic zone is higher than persistently 0.5mg/L, sponge iron deoxidizing agent granule is changed.
Embodiment 2
Using biomembrane denitrogenation reactor shown in Fig. 1, nitric wastewater same as Example 1 is processed.
First run using low flow velocity when starting reactor, according to the flow velocity of Hm/h, that is, dwell time of sewage is controlled for 60min.The concentration of COD, total nitrogen and ammonia nitrogen in 30min detects a water outlet；COD concentration in water outlet after 180min<150mg/L, ammonia nitrogen concentration<80mg/L, total nitrogen concentration<100mg/L and more stable, then improves flow velocity to 6/5Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen in 20min detects a water outlet；COD concentration in water outlet after 140min<70mg/L, ammonia nitrogen concentration<40mg/L, total nitrogen concentration<50mg/L and when relatively stablizing, improves flow velocity again to 3/2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen in 10min detects a water outlet；COD concentration in water outlet after 50min<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, improves flow velocity again to 2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 25min in 5min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, is considered as reactor and enters steady operation period, and calculating into steady operation period needs 180+140+50+25=395min altogether, maintains the flow velocity of 2Hm/h constant to be processed.
When influent ammonium concentration increases, effluent COD concentration 50mg/L, ammonia nitrogen concentration 40mg/L, total nitrogen concentration 50mg/L, as COD concentration is not above 70mg/L, ammonia nitrogen concentration is not above 40mg/L, total nitrogen concentration is not above 50mg/L, flow velocity is reduced then to 3/2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 30min in 15min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, now improves flow velocity to 2Hm/h, the concentration of COD, total nitrogen and ammonia nitrogen, COD concentration in water outlet after 20min in 5min detects a water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, is considered as adjustment and finishes.
Embodiment 3
Using reactor shown in Fig. 1, nitric wastewater same as Example 1 is processed.Difference is to add microbial growth promoters in the hydrolysis acidification area of biofilm stage, sewage disposal stage.Involved microbial growth promoters can be prepared according to the method described in CN201410585430.4 and CN201410585449.9 etc., ratio and formula according to 1 accelerator of table prepares the nitrobacteria growth promoter of two kinds of models, and the promoter concentration is 0.5g/L.
The formula and ratio of 1 accelerator of table
Microbial growth promoters A is added in the biofilm stage, dosage is added according to promoter concentration 25mg/L in sewage disposal system.After culture, the biofilm stage only needs to 84h.
Microbial growth promoters B is added in the biofilm stage, dosage is added according to promoter concentration 30mg/L in sewage disposal system.After culture, the biofilm stage only needs to 80h.
Microbial growth promoters A is added in sewage disposal stage, is added according to the mode gradually successively decreased, added once per 12h, dosage is 20mg/L first, is gradually successively decreased according to 5mg/L afterwards.After treatment, startup stage only need to 260min.
Microbial growth promoters B is added in sewage disposal stage, is added according to the mode gradually successively decreased, added once per 10h, dosage is 20mg/L first, is gradually successively decreased according to 5mg/L afterwards.After treatment, startup stage only need to 240min.
Comparative example 1
Treatment process condition is same as Example 1, and difference is that transition region does not adopt sponge iron deoxidizing agent granule in reactor, only with common filter packing.The flow velocity of 6/7H, 200min after in water outlet COD concentration 200mg/L, ammonia nitrogen concentration 120mg/L, total nitrogen concentration 150mg/L, 280min after COD concentration are used when starting reactor first<150mg/L, ammonia nitrogen concentration<80mg/L, total nitrogen concentration<100mg/L and more stable, then the COD concentration in water outlet after 180min<70mg/L, ammonia nitrogen concentration<40mg/L, total nitrogen concentration<50mg/L and more stable, the COD concentration in water outlet after 80min<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and more stable, enters steady operation period through 30min reactors, expends altogether 280+180+80+30=570min.
Comparative example 2
Treatment process condition is same as Example 1, and difference is not carry out sewage disposal using gradually stepping up into by the way of water flow velocity, maintains the flow velocity of 6/7Hm/h constant to be processed.Reactor enters steady operation period, expends altogether 460min.
Comparative example 3
Treatment process condition is same as Example 1, and difference is not carry out sewage disposal using gradually stepping up into by the way of water flow velocity, maintains the flow velocity of 3/2Hm/h constant to be processed.Reactor enters steady operation period, expends altogether 480min.
Claims (16)
1. a kind of biomembrane denitrogenation method of nitric wastewater, it is characterised in that using the biomembrane denitrogenation reactor of following structure：Transverse slat a, riser b, riser c and transverse slat d are set in reactor, the cross-sectional area of transverse slat a is identical with cross-sectional reactor area, reactor is divided transversely into into upper and lower two parts, bottom is hydrolysis acidification area, and top is A/O areas；Wherein A/O areas are divided longitudinally into three parts by riser b and riser c, it is followed successively by aerobic zone O, transition region and anaerobic zone A, riser b lower ends are tightly connected with transverse slat a, the mouth of a river was left between upper end and reactor head, and riser c upper ends are tightly connected with reactor head, the mouth of a river are left between lower end and transverse slat a, transverse slat d left ends are connected with riser c sealed bottoms, and right-hand member is fixed with reactor wall and connected；Transition region loads sponge iron deoxidizing agent granule；Intake from reactor bottom during sewage disposal, successively Jing after hydrolysis acidification area-aerobic zone-transition region-anaerobic zone, finally discharged by reactor top.
2. method according to claim 1, it is characterised in that：The ratio of height to diameter of the biomembrane denitrogenation reactor is 3:1-10:1, transverse slat a are arranged away from reactor bottom 1/3-1/5 eminences, and bottom is hydrolysis acidification area；Riser b lower ends are deviated to the left 1/10-1/7 transverse slat length away from transverse slat a centrages, and upper end is aerobic zone on the left of reactor head 4-8cm, riser b；With the symmetrical parallel arrangement of the centrage of transverse slat a, its upper end is tightly connected riser c and riser b with reactor top, and apart from transverse slat a upper surface 4-8cm, the region between riser b, c is transition region for bottom.
3. method according to claim 1 and 2, it is characterised in that：In the biomembrane denitrogenation reactor, the cross section of transverse slat a is divided into two kinds of forms by riser b, is latticed on the left of transverse slat a, and waste water enters aerobic zone by the grid on the left of transverse slat a by hydrolysis acidification area, is plate seal shape on the right side of transverse slat a；Riser b, the cross section of riser c are plate seal shape；The cross section of transverse slat d is latticed, and the waste water after crossing area enters anaerobic zone by transverse slat d.
4. method according to claim 1 and 2, it is characterised in that：The volume ratio of hydrolysis acidification area, aerobic zone, transition region and anaerobic zone is 0.8-1:0.8-1:0.3-0.5:0.8-1.
5. method according to claim 1 and 2, it is characterised in that：The biologic packing material in hydrolysis acidification area selects the biologic packing material of 3 D elastic filler, aerobic zone and anaerobic zone from the larger biological active filling material of cylindrical specific surface area, and packing volume accounts for the 3/5-4/5 of reaction zone volume；After biologic packing material is fixed, then activated sludge is loaded on the filler of each reactor, makes the sludge concentration in each reaction zone be 5-10g/L.
6. method according to claim 1 and 2, it is characterised in that：The upper surface of transition region filling sponge iron deoxidizing agent granule is concordant with the upper surface of riser b, and sponge iron deoxidizing agent particle volume accounts for the 3/5-4/5 of transition region volume.
7. method according to claim 1, it is characterised in that：Three phases are included using the denitrogenation method of the biomembrane denitrogenation reactor, the first stage is the biofilm stage, and second stage is sewage disposal stage, and the phase III is the backwash stage, specifically includes following steps：
（1）The biofilm stage：Load corresponding filler in hydrolysis acidification area, aerobic zone and anaerobic zone, make packing volume account for the 3/5-4/5 of each reaction zone volume, and the amount according to sludge concentration 5-10g/L is spread to activated sludge point in the filler of three reaction zones；Transition region loads sponge iron deoxidizing agent granule, and particle diameter is 3-5mm, and volume accounts for the 3/5-4/5 of transition region volume；Then nitric wastewater being injected from reactor bottom, when whole reactor fills sewage, stopping water inlet, close discharge outlet, start aerating system, the dissolved oxygen concentration for controlling hydrolysis acidification area, aerobic zone and anaerobic zone is 1-3mg/L；First whole aeration 24-48h, close hydrolysis acidification area and anaerobic zone afterwards in aerating system, aerobic zone still continues aeration, while opening water inlet and discharge outlet, continues culture by the way of continuum micromeehanics；After 72-144h, it can be seen that the sepia biomembrane of thickness about 2mm on the filler of three reaction zones, while it was observed that there is bubble formation near air vent, it is considered as extension and touches and complete；
（2）Sewage disposal stage：Sewage disposal stage is divided into starting period and steady operation period；Pending nitric wastewater is injected from reactor bottom first, sewage initially enters hydrolysis acidification area, and larger molecular organicses are decomposed into small-molecule substance in hydrolysis acidification area by sewage, while retaining float and impurity in sewage；Sewage enters aerobic zone by the netted section of transverse slat a, and the organic nitrogen in this sewage is converted into ammonia nitrogen, nitrite nitrogen and nitrate nitrogen successively；When sewage reaches riser b tops, transition region is deflected into, the float in water and dissolved oxygen are removed；Then anaerobic zone is deflected into by transverse slat d, carries out the removal of nitrogen, discharged finally by discharge outlet；
（3）The backwash stage：Intake from the discharge outlet on reactor top during backwash, opening water inlet and backwash discharge outlet carries out draining, then the sewage of anaerobic zone and transition region is discharged from backwash discharge outlet, the sewage in aerobic zone and hydrolysis acidification area is discharged by water inlet.
8. method according to claim 7, it is characterised in that：Step（1）The middle pH value for controlling nitric wastewater is 7.0-8.0, and treatment temperature is 25-35 DEG C, BOD in waste water5:N:P=100:5:1, influent ammonium concentration is 200-400mg/L, and COD is less than 500mg/L.
9. method according to claim 7, it is characterised in that：Step（1）Microbial growth promoters are added in hydrolysis acidification area, the microbial growth promoters include slaine, polyamines and organic acid azanol, wherein slaine is 40-100 weight portions, and polyamines are 5-30 weight portions, and organic acid azanol is 0.5-15 weight portions；The slaine is made up of calcium salt, mantoquita, magnesium salt and/or ferrous salt.
10. method according to claim 9, it is characterised in that：Slaine in the microbial growth promoters is calcium salt, magnesium salt and mantoquita, wherein Ca2+、Mg2+And Cu2+Mol ratio be（5-15）:（5-25）:（0.5-5）；Or calcium salt, ferrous salt and mantoquita, wherein Ca2+、Fe2+And Cu2+Mol ratio be（5-15）:（1-8）:（0.5-5）；Or calcium salt, magnesium salt, ferrous salt and mantoquita, wherein Ca2+、Mg2+、Fe2+And Cu2+Mol ratio be（5-15）:（5-25）:（1-8）:（0.5-5）；The calcium salt is CaSO4Or CaCl2, magnesium salt is MgSO4Or MgCl2, ferrous salt is FeSO4Or FeCl2, mantoquita is CuSO4Or CuCl2；The polyamines are the mixture of spermine, spermidine or both；The organic acid azanol is the mixture of formic acid azanol, hydroxylamine acetate or both.
11. methods according to claim 9 or 10, it is characterised in that：The dosage of the microbial growth promoters is added according to promoter concentration 10-40mg/L in sewage disposal system.
12. methods according to claim 7, it is characterised in that：Step（2）The middle starting period intakes flow velocity by the way of gradually increasing, and injects pending nitric wastewater from reactor bottom with the flow velocity of (6/7H-H) m/h first, i.e. control dwell time of sewage is between 60-70min；When COD concentration in water outlet<150mg/L, ammonia nitrogen concentration<80mg/L, total nitrogen concentration<During 100mg/L, flow velocity is improved to (H-6/5H) m/h；When COD concentration in water outlet<70mg/L, ammonia nitrogen concentration<40mg/L, total nitrogen concentration<During 50mg/L, flow velocity is improved again to (6/5H-3/2H) m/h；When COD concentration in water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<During 20mg/L, flow velocity is improved again to (3/2H-2H) m/h；When COD concentration in water outlet<50mg/L, ammonia nitrogen concentration<15mg/L, total nitrogen concentration<20mg/L and when relatively stablizing, into steady operation period, maintains that existing flow velocity is constant to be processed.
13. methods according to claim 12, it is characterised in that：When fluctuating occurs in influent quality, flow velocity should be reduced as the case may be；If COD concentration is not above 70mg/L in water outlet, ammonia nitrogen concentration is not above 40mg/L, and total nitrogen concentration is not above 50mg/L, then reduce flow velocity to (6/5H-3/2H) m/h, after water outlet is qualified and stable, be gradually adjusted according still further to aforesaid way；If there is any one to exceed above-mentioned flow in three indexs, flow velocity is reduced to (H-6/5H) m/h, after water outlet is qualified and stable, be gradually adjusted according still further to aforesaid way.
14. methods according to claim 7, it is characterised in that：Step（2）The middle pH value for controlling nitric wastewater is 7.0-8.0, and treatment temperature is 25-35 DEG C, and influent ammonium concentration is 400-800mg/L, and total nitrogen concentration is 500-900mg/L, and COD is 2-3mg/L less than 1000mg/L, the dissolved oxygen concentration for controlling aerobic zone.
15. methods according to claim 7, it is characterised in that：Step（2）In add the microbial growth promoters that the biofilm stage uses in hydrolysis acidification area, added according to the mode gradually successively decreased, added once per 8-24h, dosage is 10-25mg/L first, is gradually successively decreased according to 3-5mg/L afterwards.
16. methods according to claim 7, it is characterised in that：Step（3）Reactor run 5-7 days, carry out a backwash, during backwash according to (2H-3H) m/h flow velocity, that is, control dwell time of sewage between 20-30min, each backwash 1-2h.
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