CN103787499A - High-efficiency running method by using sequencing batch full-autotrophic denitration granular sludge - Google Patents

High-efficiency running method by using sequencing batch full-autotrophic denitration granular sludge Download PDF

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CN103787499A
CN103787499A CN201310536201.9A CN201310536201A CN103787499A CN 103787499 A CN103787499 A CN 103787499A CN 201310536201 A CN201310536201 A CN 201310536201A CN 103787499 A CN103787499 A CN 103787499A
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dissolved oxygen
stage
reactor
water
canon
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CN103787499B (en
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李冬
苏庆岭
吴青
梁瑜海
崔少明
张肖静
杨胤
张翠丹
范丹
张玉龙
周元正
门绚
何永平
曾辉平
张�杰
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Beijing University of Technology
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Abstract

The invention discloses a high-efficiency running method by using sequencing batch full-autotrophic denitration granular sludge and belongs to the field of treatment and regeneration of sewage and wastewater with the high ammonia nitrogen content. In a sequencing batch reactor, on the basis of the application of the started CANON granular sludge, the influence, caused by dissolved oxygen, on the running of the reactor is researched. The high-efficiency running method comprises the steps of, , and researching a method for enabling the reactor to run with the high efficiency under the conditions that the CANON granular sludge is taken as seed sludge, the dissolved oxygen which is necessary to reaction is supplied through aeration, and a certain dissolved oxygen gradient is controlled. The problem that the long-time influence, caused by the dissolved oxygen, on the running efficiency of the CANON granular sludge cannot be determined is solved; the small influence, caused by short-time or delay aeration, on the reaction is verified; a new concept is supplied to the engineering application of CANON in treatment of the wastewater with the high ammonia nitrogen content.

Description

A kind of efficient operation method of sequence batch (whole process autotrophic denitrification granule sludge
Technical field
The invention belongs to the dirty wastewater treatment of high ammonia nitrogen and regeneration field.Be specifically related to solve the efficient operation method of whole process autotrophic denitrification (CANON) technique granule sludge under high ammonia nitrogen condition.
Background technology
The life that develops into the mankind of science and technology provides many convenience, but also makes human society and Facing Natural Environment acid test.Take China as example, in China Environmental State Bulletin in 2012, explicitly point out: 2011, national surface water was totally slight pollution.Lake (reservoir) eutrophication problem is still outstanding.Wherein tributary of Yangtze, the Yellow River, Pearl River system ammonia and nitrogen pollution are still main pollution.The ammonia and nitrogen pollution overwhelming majority in these water systems is that anthropogenic discharge causes, especially the high ammonia-nitrogen wastewater of industrial discharge.At present, for the removal of ammonia nitrogen in water, especially the processing of high ammonia-nitrogen wastewater you, mainly adopt physico-chemical process and biological process.Physico-chemical process with respect to biological process have that cost is high, complicated operation and easily cause the shortcomings such as secondary pollution.So it is current main flow technique that biological process is processed high ammonia-nitrogen wastewater.
Process in high ammonia-nitrogen wastewater technique at many biological processes, CANON (completely autotrophic nitrogen removal over nitrite) technique becomes the focus of current research in its unique denitrogenation mode.CANON technique is combined by nitrosation reaction and Anammox reaction, the ammonia nitrogen in water is oxidized to nitrite nitrogen and anaerobic ammonia oxidizing bacteria (Anammox) by the nitrococcus (AOB) that carries out nitrosation reaction, and to utilize the nitrite nitrogen of oxidation be electron donor, and ammonia nitrogen is that electron acceptor(EA) react generation a small amount of nitrate nitrogen and N 2thereby, reach the object of removing ammonia nitrogen.
CANON technological reaction is as follows:
NH 3+0.85O 2→0.11NO 3 -+0.44N 2+0.14H ++1.43H 2O
CANON has plurality of advantages aspect ammonia nitrogen removal.First without additional organic carbon source, save a large amount of aerations and inorganic carbon source, can reduce infusion of financial resources; Product is a small amount of mud and N 2, can not cause secondary pollution.Nitrogen removal rate can reach more than 80% in theory, is the ideal chose of energy-efficient denitrification process.But CANON technique, the especially denitrification ability of the granule sludge of CANON technique are subject to the impact of dissolved oxygen (DO) more obvious, small dissolved oxygen changes the noticeable change that will cause denitrification effect.
Therefore, be subject to the problem of dissolved oxygen impact for CANON technique granule sludge, how address this problem this technique can be moved by efficient stable, significant for the application of CANON process engineeringization.
Summary of the invention
The object of the present invention is to provide a kind of method that makes the efficient operation of sequence batch (CANON granule sludge.For reaching above-mentioned technique effect, technical scheme of the present invention is achieved in that
The present invention is the method that adopts sequencing batch operation CANON granule sludge, and CANON granule sludge is to obtain in the cultivation in early stage, provides upflow velocity and hydraulic shear with aeration, and reactor is mixed.Concrete operations are as follows:
An efficient operation method for sequence batch (whole process autotrophic denitrification granule sludge, adopts cycle training method, and sbr reactor device, is characterized in that: comprise the steps:
1) inoculation kind of mud: the kind mud in reactor is CANON granule sludge, mud particle diameter 200-450nm, sludge concentration is 1.5-3g/L;
2) reactor operation method is: each cycle comprises into water, reaction, precipitation, draining, idle double teacher.The I stage: water inlet, adopt manual simulation's water distribution, controlling influent ammonia nitrogen mass concentration is 300-450mg/L, and phosphoric acid salt mass concentration is 5-10mg/L, and basicity mass concentration is with CaCO 3count 1400-2000mg/L; The II stage: reaction, adopt heating in water bath, control temperature is 27-33 ℃, water inlet pH is 7.7-8.3, in initial water, dissolved oxygen concentration is 0.1mg/L, when ammonia nitrogen removal frank is in the time that 40%-95% stablizes 3-4 days, improve dissolved oxygen concentration 0.05-0.15mg/L at next cycle, final dissolved oxygen concentration is 0.5mg/L; Hydraulic detention time HRT is 12h; The III stage: precipitation, sedimentation time is 4-6min; The IV stage: draining, change water than 50%; The V stage: idle, idle mixing time, 2-10h, looped next cycle after leaving unused.
3) efficiently operation: by nitrogen removal rate be greater than 75% and can continuous and steady operation 5 days above corresponding dissolved oxygen concentrations be set as the dissolved oxygen concentration of reactor operation; Be specially: the I stage: water inlet, adopt manual simulation's water distribution, controlling influent ammonia nitrogen mass concentration is 300-450mg/L, and phosphoric acid salt mass concentration is 5-10mg/L, and basicity mass concentration is with CaCO 3count 1400-2000mg/L; The II stage: reaction, adopt heating in water bath, controls temperature is 27-33 ℃, water inlet pH is 7.7-8.3, by nitrogen removal rate be greater than 75% and can continuous and steady operation more than 5 days corresponding dissolved oxygen concentration be set as the dissolved oxygen concentration that reactor moves; Hydraulic detention time HRT is 12h; The III stage: precipitation, sedimentation time is 4-6min; The IV stage: draining, change water than 50%; The V stage: idle, idle mixing time, 2-10h, looped next cycle after leaving unused.
Principle is described as follows:
1) the kind mud of inoculation in test: obtain by cultivating early stage the CANON granule sludge that median size is greater than 300nm, this granule sludge has similar round shape, sorrel, sludge concentration 1.5-3g/L.
2) in test, first determine little dissolved oxygen value, first maintain DO value at 0.05-0.1mg/L, when improving constantly DO value after steady running 3-4 days, ammonia nitrogen and nitrogen removal rate are improved, DO concentration is brought up to ammonia nitrogen removal frank and nitrogen removal rate 0.4 process from 0.1 and is all improved constantly, and reactor is stable.In the time that DO brings up to 0.5mg/L, there are a large amount of sub-nitrogen accumulation in reactor immediately, the trend not improving by several days operating performances, but after DO is reduced to 0.4mg/L, treatment effect can significantly be recovered.
3) impact of extended aeration: due to the difference of influent concentration and DO value, will inevitably cause there will be extended aeration phenomenon in the time that HRT is 14h.Make extended aeration 1-2h by manual control influent concentration, next cycle is in the time recovering original operational conditions, and ammonia nitrogen and total nitrogen treatment effect can recover very soon
The present invention has following beneficial effect:
1) on the basis of cultivating successful CANON granule sludge, test, greatly shortened the cycle of operation;
2) establish comparatively detailed dissolved oxygen master mode, found dissolved oxygen span of control comparatively applicable under this test conditions;
3) verified that extended aeration is less on the impact of CANON granule sludge, with the extended aeration time of dissolved oxygen meter control dissolved oxygen, simple to operation.
Accompanying drawing explanation:
Fig. 1 is the CANON testing apparatus schematic diagram that the present invention adopts.
1. intake pump; 2. pneumatic pump; 3. volcanic filling material; 4. thief hole; 5. material taking mouth
Fig. 2 be adopt the inventive method reactor over time, the relation between ammonia nitrogen removal frank, nitrogen removal rate and DO variation.
Fig. 3 is the reactor ammonia oxidation speed that adopts the inventive method, the variation relation that Anammox speed of reaction changes with DO.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
The present invention is conceived to solve the efficient operation method of high-ammonia-nitrogen sewage CANON technique granule sludge, its thinking is: in sbr reactor device, with the CANON granule sludge of having turned out be kind of a mud, adopt the mode of resting period operation, operation phase continuous aeration is also controlled the method for certain dissolved oxygen concentration gradient, the impact of research dissolved oxygen on whole process autotrophic denitrification process, the big or small major effect nitrite bacteria of dissolved oxygen and the activity of anaerobic ammonium oxidizing bacteria, the effect of aeration is not only confined to provide certain density dissolved oxygen, simultaneously by the control upflow velocity of aeration, thereby provide corresponding hydraulic shear, guarantee the normal operation of reactor.
Reactor kind mud of the present invention is the CANON granule sludge of having turned out.Owing to being CANON granule sludge, have in advance and adapted to for the condition of subsequent operations, be conducive to shorten the test period, also make more easily success of test.Because two kinds of bacterium of working in CANON technique are nitrite bacteria (AOB) and anaerobic ammonium oxidizing bacteria (Anammox), although Anammox is anerobe, but particle has certain dissolved oxygen depth, can allow certain dissolved oxygen concentration to exist and can not suppress Anammox activity.
Oxygen penetration depth is calculated by following formula:
δ pf=((2D.C si)/(q s max.C xf)) 1/2, wherein: D: diffusion coefficient (m 2/ s), Csi: microbial film and solution interface oxygen concn (mol/m 3), q s max: maximum oxygen intake speed (L/S), Cxf: the biomass (mol/m on microbial film 3).
The present invention adopts operation phase continuous aeration, controls the method for certain dissolved oxygen concentration gradient.When beginning, aeration is enough little, controls dissolved oxygen at 0.05-0.1mg/L, makes reactor have an adaptive process.After this improve gradually DO value, improve the clearance of reactor.Move from reactor, water inlet adopts manual simulation's water distribution, and controlling influent ammonia nitrogen mass concentration is 300-450mg/L, and phosphoric acid salt mass concentration is 5-10mg/L, and basicity mass concentration is with CaCO 3count 1400-2000mg/L, add the necessary trace element of microorganism growth simultaneously; Step of reaction control temperature is 27-33 ℃, and water inlet pH is 7.7-8.3, and in initial water, dissolved oxygen concentration is 0.1mg/L, in the time that ammonia nitrogen removal frank is stablized 3-4 days, improves dissolved oxygen concentration 0.05-0.15mg/L at next cycle, and final dissolved oxygen concentration is 0.5mg/L; Hydraulic detention time (HRT) is 12h; The III stage: precipitation, sedimentation time is 4-6min; The IV stage: draining, change water than 50%; The V stage: idle, idle mixing time, 2-10h, looped next cycle after leaving unused.
Each standard is different for defining of reactor efficiency, and the clearance of the average total nitrogen of optimal state of the present invention exceedes 75%, and maximum material removal rate approaches 80%, reaches the removal effect of expection.The present invention obtains the dissolved oxygen conditions of system high efficiency steady running by the mode of this feedback regulation.
Specific embodiment one:
The efficient operation method of sequence batch (whole process autotrophic denitrification granule sludge, water inlet is in tap water, to add a certain amount of (NH 4) 2sO 4, NaHCO 3and KH 2pO 4configuration forms, and adds appropriate trace element simultaneously, and concrete water quality is as follows:
Ammonia nitrogen mass concentration 380-420mg/L, phosphoric acid salt mass concentration is 5-10mg/L, basicity mass concentration is (with CaCO 3meter) be 1400-2000mg/L.The dosage of trace element mixed solution is 1mg/L, comprises (mg/L):
Nutritive medium I:EDTA5.00 FeSO 4.7H2O5.00 nutritive medium II:EDTA15.00H 3bO 40.014 MnCl 2.4H 2o0.099 CuSO 4.5H 2o0.25 ZnSO 4.7H 2o0.43NiCl 2.6H 2o0.19 Na 2seO 4.10H 2o0.21 Na 2moO 4.2H 2o0.22NaWO 4.2H 2o
Reactor types: reactor adopts synthetic glass to process, cylindrical, internal diameter 7mm, total height 1000mm, cumulative volume 3.8L, useful volume 3.4L.Microporous aeration device is equipped with in bottom, by gas rotameter control aeration rate size.
Operation scheme comprises into water, reaction, precipitation, draining, idle double teacher.Water inlet is to be intake from bottom by peristaltic pump; 30 ± 1 ℃ of step of reaction control water temperatures, aeration controls respectively 0.1,0.2,0.3,0.4, five concentration gradients of 0.5mg/L, pH8.0 ± 0.1, HRT is 11h; Sedimentation time 5min; Water discharge time 1.5min, changes water than 50%; Leave unused to the next cycle.Load removed by the maximum total nitrogen of reactor and the average nitrogen removal rate of maximum stable can reach respectively 0.45kg/ (m 3d) He 78%.
The test initial stage determines that dissolved oxygen concentration is 0.1mg/L, through 12 periodic duties, nitrogen removal rate is all the time in 30% left and right fluctuation, total nitrogen removal effect is poor, because ammonia nitrogen removal frank is equally very low, and without nitrite nitrogen accumulation (being less than 7mg/L), because DO is lower so can analyze, HRT causes compared with short-range missile, is not changing under the condition of HRT, can only be by improving the method for DO.Under this analytical procedure instructs, improve constantly DO until DO while being 0.4mg/L, nitrogen removal rate becomes positive correlation trend with DO value, is up to 78% left and right stable.The 47th, 48 two days extended aerations two hours, within the 49th day, return to that former operational condition can be recovered very soon and steady running, the extended aeration of short-term can not produce considerable influence to system.In the time that DO value is brought up to 0.5mg/L, nitrite nitrogen sharply increases, and is up to 190mg/L, and nitrogen removal rate is reduced to only has 42%, has exceeded the tolerance limit of reactor when DO can be described to 0.5mg/L.
In the present invention, the speed of reaction of AOB and Anammox bacterium the usefulness that is coupled in the time that DO is 0.4mg/L reaches maximum, stablizes average nitrogen removal rate maximum and reaches 85%, and maximum total nitrogen volumetric loading reaches 0.5kg/ (m 3d).
Specific embodiment two:
The water inlet of embodiment bis-and embodiment mono-are basic identical, and the key distinction is in the form of reactor.
Reactor types: reactor adopts synthetic glass to process, cylindrical, internal diameter 15mm, total height 500mm, cumulative volume 8.83L, useful volume 7L.Because cross-sectional reactor area is larger, there is the inhomogeneous situation of aeration in common aeration ring, so bottom is used emery disc aerating apparatus instead, by gas rotameter control aeration rate size.Plant mud and embodiment mono-from same reactor.
Operation scheme comprises into water, reaction, precipitation, draining, idle double teacher.Water inlet is to be intake from top by peristaltic pump; 30 ± 1 ℃ of step of reaction control water temperatures, aeration controls respectively 0.1,0.2,0.3,0.4, five concentration gradients of 0.5mg/L, pH8.0 ± 0.1, HRT is 11h; Sedimentation time 5min; Change water than 50%; Leave unused to the next cycle.Load removed by the maximum total nitrogen of reactor and the average nitrogen removal rate of maximum stable can reach respectively 0.4kg/ (m 3d) He 75%.
The test initial stage, because larger variation has occurred reactor types, first through a dissolved oxygen laundering period, determines that dissolved oxygen concentration is 0.05mg/L, and through 5 periodic duties, DO brings up to 0.1mg/L, and now nitrogen removal rate only has 25% left and right.It is 10 cycles of moving continuously under 0.1mg/L condition at DO, nitrogen removal rate can reach 35%, now ammonia oxidation speed and Anammox speed of reaction all than start time large, in system, do not have nitrite nitrogen content to be less than 7mg/L, so do not changing under the condition of HRT, improving reactor efficiency by the method that improves DO.Under this analytical procedure instructs, improve constantly DO until DO while being 0.4mg/L, nitrogen removal rate becomes positive correlation trend with DO value, is up to 75% left and right stable.In the time that DO value is brought up to 0.5mg/L, nitrite nitrogen sharply increases, and is up to 153mg/L, and nitrogen removal rate is reduced to only has 45%, has exceeded the tolerance limit of reactor when DO can be described to 0.5mg/L.
In system of the present invention, the speed of reaction of AOB and Anammox bacterium the usefulness that is coupled in the time that DO is 0.4mg/L reaches maximum, stablizes average nitrogen removal rate maximum and reaches 84%, and maximum total nitrogen volumetric loading reaches 0.44kg/ (m 3d).

Claims (1)

1. an efficient operation method for sequence batch (whole process autotrophic denitrification granule sludge, adopts cycle training method, and sbr reactor device, is characterized in that, comprises the steps:
1) inoculation kind of mud: the kind mud in reactor is CANON granule sludge, mud particle diameter 200-450nm, sludge concentration is 1.5-3g/L;
2) reactor operation method is: each cycle comprises into water, reaction, precipitation, draining, idle double teacher; The I stage: water inlet, adopt manual simulation's water distribution, controlling influent ammonia nitrogen mass concentration is 300-450mg/L, and phosphoric acid salt mass concentration is 5-10mg/L, and basicity mass concentration is with CaCO 3count 1400-2000mg/L; The II stage: reaction, adopt heating in water bath, control temperature is 27-33 ℃, water inlet pH is 7.7-8.3, in initial water, dissolved oxygen concentration is 0.1mg/L, when ammonia nitrogen removal frank is in the time that 40%-95% stablizes 3-4 days, improve dissolved oxygen concentration 0.05-0.15mg/L at next cycle, final dissolved oxygen concentration is 0.5mg/L; Hydraulic detention time HRT is 12h; The III stage: precipitation, sedimentation time is 4-6min; The IV stage: draining, change water than 50%; The V stage: idle, idle mixing time, 2-10h, looped next cycle after leaving unused;
3) efficiently operation: by nitrogen removal rate be greater than 75% and can continuous and steady operation 5 days above corresponding dissolved oxygen concentrations be set as the dissolved oxygen concentration of reactor operation; Be specially: the I stage: water inlet, adopt manual simulation's water distribution, controlling influent ammonia nitrogen mass concentration is 300-450mg/L, and phosphoric acid salt mass concentration is 5-10mg/L, and basicity mass concentration is with CaCO 3count 1400-2000mg/L; The II stage: reaction, adopt heating in water bath, controls temperature is 27-33 ℃, water inlet pH is 7.7-8.3, by nitrogen removal rate be greater than 75% and can continuous and steady operation more than 5 days corresponding dissolved oxygen concentration be set as the dissolved oxygen concentration that reactor moves; Hydraulic detention time HRT is 12h; The III stage: precipitation, sedimentation time is 4-6min; The IV stage: draining, change water than 50%; The V stage: idle, idle mixing time, 2-10h, looped next cycle after leaving unused.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384237A (en) * 2015-11-26 2016-03-09 北京城市排水集团有限责任公司 Autotrophic nitrogen removal integrated device for treating high ammonia-nitrogen wastewater and starting method
CN107188307A (en) * 2017-07-01 2017-09-22 清华大学 A kind of Integral waste water nitrogen rejection facility and a kind of method of denitrogenation of waste water
CN109292976A (en) * 2018-11-09 2019-02-01 重庆大学 A method of one-step autotrophic nitrogen removal granular sludge reactor performance is regulated and controled based on microbial activity
CN111410300A (en) * 2019-01-07 2020-07-14 清华大学 Method for removing nitrate in underground water by using hydrogen autotrophic denitrification granular sludge

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59193197A (en) * 1983-04-15 1984-11-01 Susumu Hashimoto Activated sludge method for denitrification and dephosphorization
KR100913726B1 (en) * 2008-12-19 2009-08-24 조정선 Method of controlling dissolved oxygen level in waste water treatment system
CN103172170A (en) * 2013-03-08 2013-06-26 北京工业大学 Sequencing batch completely autotrophic ammonia removal technology running method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59193197A (en) * 1983-04-15 1984-11-01 Susumu Hashimoto Activated sludge method for denitrification and dephosphorization
KR100913726B1 (en) * 2008-12-19 2009-08-24 조정선 Method of controlling dissolved oxygen level in waste water treatment system
CN103172170A (en) * 2013-03-08 2013-06-26 北京工业大学 Sequencing batch completely autotrophic ammonia removal technology running method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384237A (en) * 2015-11-26 2016-03-09 北京城市排水集团有限责任公司 Autotrophic nitrogen removal integrated device for treating high ammonia-nitrogen wastewater and starting method
CN105384237B (en) * 2015-11-26 2017-11-07 北京城市排水集团有限责任公司 A kind of autotrophic denitrification integrated apparatus for handling high ammonia-nitrogen wastewater and startup method
CN107188307A (en) * 2017-07-01 2017-09-22 清华大学 A kind of Integral waste water nitrogen rejection facility and a kind of method of denitrogenation of waste water
CN109292976A (en) * 2018-11-09 2019-02-01 重庆大学 A method of one-step autotrophic nitrogen removal granular sludge reactor performance is regulated and controled based on microbial activity
CN109292976B (en) * 2018-11-09 2021-08-24 重庆大学 Method for regulating performance of single-stage autotrophic nitrogen removal granular sludge reactor based on microbial activity
CN111410300A (en) * 2019-01-07 2020-07-14 清华大学 Method for removing nitrate in underground water by using hydrogen autotrophic denitrification granular sludge
CN111410300B (en) * 2019-01-07 2021-06-22 清华大学 Method for removing nitrate in underground water by using hydrogen autotrophic denitrification granular sludge

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