CN103739071B - Micro-polluted surface water denitrifying method - Google Patents
Micro-polluted surface water denitrifying method Download PDFInfo
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Abstract
The present invention is relevant a kind of micro-polluted surface water denitrifying method, this micro-polluted surface water enters from the bottom in bio-filter stuffing district and is discharged by top, it comprises the following steps: in the bottom of the packing area of this biofilter, the aerobic microbiological of filling surface utilizes the dissolved oxygen in water and carbon source to carry out metabolism, consume the dissolved oxygen in this micro-polluted surface water, be internally formed anaerobic environment in the packing area of this biofilter; Inside the filler of the packing area of this biofilter, denitrifying bacterium is by the NO in this micro-polluted surface water3 --N changes into NO2 --N and/or N2; And the middle and upper part of the packing area in this biofilter, anaerobic ammonia oxidizing bacteria is by NH4 +-N and NO2 --N changes into N2. The micro-polluted surface water denitrifying method of the present invention, carbon source amount is low, and operating cost is low.
Description
Technical field
The present invention relates to a kind of micro-polluted surface water and process technique, particularly relate to low-carbon high-nitrogen micro-polluted surface water denitrification treatment process.
Background technology
Along with developing rapidly of China's industrial or agricultural and improving constantly of living standards of the people, substantial amounts of sanitary sewage, industrial wastewater and agricultural fertilizer pollution of area source carry nitrogen-containing pollutant and enter receiving water body, exceed the self-purification capacity of water body, cause that the surface water eutrophication such as China's rivers, lake are serious, wawter bloom phenomenon happens occasionally, and causes certain environmental problem and social problem. Showing according to the study, algal grown Nutrient limit is mainly nitrogen, phosphorus concentration and concentration proportion thereof, and therefore surface water denitrogenation becomes control China surface water body eutrophication, reach control Cutleriales important means. The main physical chemistry method of mode of current surface water denitrogenation, ecological method and biological method. Physical chemistry method is mainly medium absorption namely by Vermiculitum, zeolite and the converted products adsorption to nitrogen thereof, by the N immobilization in surface water in media as well, although medium adsorption method one-stage completion later maintenance is relatively simple, but medium adsorption capacity is limited, needing after medium is saturated to change medium, quantities is bigger. Ecological method mainly has biological floating bed, the methods such as artificial swamp, its cardinal principle is that the synergism utilizing plant absorption and microbial metabolism carrys out denitrogenation, although ecological method has certain denitrification and good landscape effect, but its floor space is big, remove the inefficient of nitrogen, and is easily subject to the impact of weather and the destruction of extreme weather. Biological method is the artificial conditions of existence creating nitration denitrification microorganism mainly, the reaction of its metabolism is utilized to realize the removal of nitrogen, bioanalysis is the most efficient at present, the most ripe method, but it is the inability to form stable active pollution index, traditional activated sludge process is not suitable for the surface water that pollutant levels are low, is adapted to, with biofilter for the biological treatment of representative, the surface water treatment that concentration is extremely low.Additionally, aerobic microbiological and anaerobe, nitrobacteria are different with denitrifying bacteria growth conditions, in Biochemical method technique, often think that aerobic microbiological needs to carry out in the reactor different at two with anaerobe, nitrification and denitrification, system complex, energy consumption is relatively big, and manages inconvenience.
The analysis of China's micro-polluted surface water nitrogen pollutant is learnt: the primary chemical form of China's surface water nitrogen pollutant is nitric nitrogen (NO3 --N), it is secondly ammonium nitrogen (NH4 +-N), it is nitrite nitrogen (NO again2 --N), nitric nitrogen (NO3 --N) and nitrite nitrogen (NO2 --N) it is referred to as nitrate nitrogen (NOx --N). The biodegradability of organic matter of micro-polluted surface water is poor, substantially can not be used as carbon source by microorganism, show that China's micro-polluted surface water water quality presents the feature of high nitrogen low-carbon (LC), therefore conventional denitrification denitrogenation method to add substantial amounts of additional carbon, traditional denitrification denitrogenation experiment and engineering operation experience have shown that, only as water inlet Biochemical oxygen demand (CODcr) with the ratio of total nitrogen (TN) more than 8 time, good denitrification effect could be realized. Therefore tradition earth's surface denitrogenation of water realizes mainly by denitrifying method, owing to surface water content of organics is low, it is impossible to meet the demand to carbon source in denitrification process, it is necessary to add substantial amounts of additional carbon, both add operating cost, add again the risk of secondary pollution. Although conventional denitrification technique can also reduce corresponding operating cost by the dosage of minimizing additional carbon, but now the concentration of water outlet nitrite can be higher, and nitrite has bio-toxicity, adds biohazardous.
Summary of the invention
Because the defect existing for above-mentioned prior art, it is an object of the invention to, it is provided that a kind of micro-polluted surface water denitrifying method so that it is only need to add a small amount of additional carbon, reduce operating cost.
To achieve these goals, according to a kind of micro-polluted surface water denitrifying method that the present invention proposes, this micro-polluted surface water enters from the bottom in bio-filter stuffing district and is discharged by top, it comprises the following steps: in the bottom of the packing area of this biofilter, the aerobic microbiological of filling surface utilizes the dissolved oxygen in water and carbon source to carry out metabolism, consume the dissolved oxygen in this micro-polluted surface water, be internally formed anaerobic environment in the packing area of this biofilter; Inside the filler of the packing area of this biofilter, denitrifying bacterium is by the NO in this micro-polluted surface water3 --N changes into NO2 --N and/or N2; And the middle and upper part of the packing area in this biofilter, anaerobic ammonia oxidizing bacteria is by NH4 +-N and NO2 --N changes into nitrogen (N2)。
The present invention also can be applied to the following technical measures to achieve further.
Aforesaid micro-polluted surface water denitrifying method, before wherein said micro-polluted surface water enters biofilter, first passes through coagulating kinetics, removes the float in water.
Aforesaid micro-polluted surface water denitrifying method, wherein, also included before micro-polluted surface water enters biofilter, regulates the NH of micro-polluted surface water4 +-N and NOx -The concentration ratio of-N and/or CODcrWith the concentration of (TN+DO) ratio.
Aforesaid micro-polluted surface water denitrifying method, the wherein said COD regulating micro-polluted surface watercrWith the concentration of (TN+DO) ratio, including: measure the COD in micro-polluted surface watercr, TN, dissolved oxygen (DO) concentration, in described micro-polluted surface water add carbon source.
Aforesaid micro-polluted surface water denitrifying method, wherein said carbon source be in acetic acid, methanol, propanoic acid, sodium acetate, starch, o-phthalic acid dibutyl ester and cellulose one or more.
Aforesaid micro-polluted surface water denitrifying method, the wherein said NH regulating micro-polluted surface water4 +-N and NOx -The concentration ratio of-N, including: measure the NH in micro-polluted surface water4 +-N concentration and NOx --N concentration, adds ammonium salt and/or nitrite in described micro-polluted surface water.
Aforesaid micro-polluted surface water denitrifying method, wherein said (NH4 +-N) and NOx -The concentration ratio of-N is 1.5 ± 3%; Described CODcrIt is 1.2 with the concentration of (TN+DO) ratio; Wherein NH4 +-N concentration, NOx --N concentration, CODcr, TN, DO testing result unit be mg/L.
Aforesaid micro-polluted surface water denitrifying method, wherein the volumetric loading of this biofilter is not more than 1kgN/m3·d。
The present invention compared with prior art has clear advantage and beneficial effect. By technique scheme, the micro-polluted surface water denitrifying method of the present invention, at least have the advantage that
1, micro-polluted surface water denitrifying method of the present invention, utilizes the synergism of anaerobic ammonia oxidizing bacteria and denitrifying bacterium to remove the total nitrogen of high nitrogen low-carbon (LC) micro-polluted surface water, and method is simple.
2, micro-polluted surface water denitrifying method of the present invention, only need to add a small amount of additional carbon and nitrogenous source, it is not necessary to Air Exposure compared with common denitrification process, and operating cost is relatively low, and without worrying to add the excessive problem causing secondary pollution of carbon source.
3, micro-polluted surface water denitrifying method of the present invention, flexible form is changeable, as made the terrestrial life filter tank of river levee slope protection form, for the in-situ treatment of river, reduces lifting and the conveying of river.
4, micro-polluted surface water denitrifying method of the present invention, it is adaptable to the surface water denitrogenation processing such as rivers, lake and reservoir, view.
Accompanying drawing explanation
Fig. 1 is an illustration for the schematic diagram of the denitrification processing device of micro-polluted surface water denitrifying method of the present invention.
Detailed description of the invention
For further setting forth that the present invention reaches technological means and effect that predetermined goal of the invention is taked, below in conjunction with accompanying drawing and preferred embodiment, its detailed description of the invention of micro-polluted surface water denitrifying method proposed according to the present invention, step, structure, feature and effect thereof are described in detail.
Refer to shown in Fig. 1, be an illustration for the schematic diagram of the denitrification processing device of micro-polluted surface water denitrifying method of the present invention. Micro-polluted surface water denitrogenation processing equipment includes, coagulative precipitation tank 1, throwing device I, II and III, pipe-line mixer IV and biofilter 2. Coagulative precipitation tank 1 utilizes pipeline 3, connects with biofilter 2 through pipe-line mixer IV.
Above-mentioned coagulative precipitation tank 1 is for removing the float of micro-polluted surface water. Coagulative precipitation tank 1 is provided with mensuration water quality Biochemical oxygen demand (CODCr), total nitrogen (TN), ammonia nitrogen (NH4 +-N), nitrate nitrogen (NOX-N), the on-line checking instrument 5 of dissolved oxygen (DO).
Above-mentioned throwing device I, II and III, includes variable frequency pump and medicine pond respectively. Throwing device I, II connects with the pipeline 3 before pipe-line mixer IV with III. In the present embodiment, the medicine pond of throwing device I is used for holding carbon source; The medicine pond of throwing device II and III is respectively used to hold ammonium salt, nitrite.
Above-mentioned pipe-line mixer IV, in order to medicine mix homogeneously micro-polluted surface water and throwing device I, II and III added.
Above-mentioned biofilter 2 includes water distribution area A, packing area B, gathering ground C; Water distribution area A side or bottom are provided with water inlet, with pipeline communication;Packing area B, is arranged at the side of described water distribution area A, is filled with filler in it, and described filler is load aerobic microbiological, anaerobic denitrifying bacterium and anaerobic ammonia oxidizing bacteria simultaneously; Gathering ground C, is arranged at described side contrary with water distribution area A for packing area B, and gathering ground C is provided with outlet. When micro-polluted surface water enters the water distribution area A side of packing area B, due to the existence of dirty oxygen in water, aerobic microbiological is dominant microflora, consumes the dissolved oxygen in micro-polluted surface water and carbon source carries out metabolism, generate CO2Deng inorganic substances; When micro-polluted surface water enters C side, gathering ground or the filler inside of packing area B, owing to the dissolved oxygen in micro-polluted surface water is depleted, above-mentioned zone forms oxygen-free environment district, and anaerobic denitrifying bacterium utilizes the carbon source in micro-polluted surface water to carry out anti-nitration reaction, by the NO in water inlet3 --N changes into NO2 --N and/or N2; Anaerobic ammonia oxidizing bacteria utilizes the NH in micro-polluted surface water4 +-N、NO2 -The chemical energy of-N and inorganic matter carries out Anammox reaction, by the NH in water inlet4 +-N and NO2 --N changes into N2。
Shown in Fig. 1, the micro-polluted surface water denitrifying method of present pre-ferred embodiments, comprise the following steps: first, micro-polluted surface water processes through coagulative precipitation tank 1, removes the float in water, enters (squeezing into through pump 8) biofilter 2; Then, micro-polluted surface water, after the water distribution area A water distribution of biofilter 2, uniformly rises slowly in the packing area B of biofilter 2, and the nitrogen in water is processed by the microorganism being attached on the filler of packing area B in the process risen; Finally, the water after process collects discharge in water catchment area, top, biofilter.
Nitrogen in water is processed by the above-mentioned microorganism being attached on filler, specifically include: the filling surface of B bottom, packing area, biofilter 2 exists aerobic microbiological, aerobic microbiological utilizes the dissolved oxygen in water and carbon source to carry out metabolism, forms the internal anaerobic environment of biofilter 2 packing area B; Being in anaerobic environment inside the filler of biofilter 2 packing area B, the denitrifying bacterium existed inside filler utilizes carbon source to carry out anti-nitration reaction, by the NO in water inlet3 --N changes into NO2 --N, small part changes into N2; The middle and upper part of biofilter 2 packing area B is in anaerobic environment, is dominant microflora at this part anaerobic ammonia oxidizing bacteria, and anaerobic ammonia oxidizing bacteria utilizes the NH in water4 +-N、NO2 -The chemical energy of-N and inorganic matter carries out Anammox reaction, by NH4 +-N and NO2 --N changes into N2. The CO that the aerobic microbiological metabolism of B bottom, packing area, biofilter 2 produces2Can be used by anaerobic ammonia oxidizing bacteria Deng inorganic matter, promoted denitrification reaction.
Above-mentioned micro-polluted surface water denitrifying method, before micro-polluted surface water enters (squeezing into through pump 8) biofilter 2, also includes regulating CODcrStep with the concentration of (TN+DO) ratio. Specifically include, coagulative precipitation tank 1 is installed CODCr, TN, DO on-line checking instrument, detection water inlet in CODCr, TN, DO concentration; According to CODCr, TN, DO measured value calculate add additional carbon concentration so that influent CODcrIt is 1.2 with the concentration of (TN+DO) ratio; After determining additional carbon dosage, return signal, to additional carbon throwing device I, carries out carbon source and adds. In this example, carbon source is acetic acid, in other embodiments carbon source can also be in methanol, propanoic acid, sodium acetate, starch, o-phthalic acid dibutyl ester and cellulose one or more. Wherein CODcr, TN, DO testing result unit be mg/L.
Above-mentioned micro-polluted surface water denitrifying method, before micro-polluted surface water enters (squeezing into through pump 8) biofilter 2, also includes regulating water inlet NH4 +-N and NOx -The step of the concentration ratio of-N. Specifically include, according to the NH that on-line checking instrument measures4 +-N、NOXThe concentration of-N, calculates the dosage of ammonium salt or nitrite so that water inlet NH4 +-N and NOx -The concentration ratio of-N controls 1.5 ± 3%. After determining ammonium salt or nitrite dosage, return signal adds to throwing device II and III. Described throwing device I, II and III is preferably variable frequency pump. Wherein NH4 +-N concentration, NOx --N concentration unit is mg/L.
Refer to shown in table 1, be different NH4 +-N and NOx --N concentration is than the TN of water outlet, and water outlet TN is along with NH4 +-N and NOx -The change of-N concentration ratio.
The different NH of table 14 +-N and NOx --N concentration is than the TN of water outlet
As can be drawn from Table 1, water outlet TN is along with NH4 +-N and NOx -The rising progressively first to reduce of-N concentration ratio raises afterwards, NH4 +-N and NOx -When-N concentration ratio is 1.4～1.6, effluent quality meets water environment quality standard GB3838-2002 III class standard, it is preferable that NH4 +-N and NOx --N concentration ratio is 1.5 ± 3%.
Can also drawing from table 1, water outlet TN is along with CODcrIncrease with the ratio of (TN+DO) and reduce, namely the more many denitrification effects of additional carbon are more good, but namely additional carbon too much increases operating cost, increase again the risk of secondary pollution, therefore comprehensive above reason, it is preferable that CODcrWith the Ratio control of (TN+DO) 1.2.
After above-mentioned carbon source, ammonium salt and/or nitrite add, after pipe-line mixer is sufficiently mixed, enter biofilter with water inlet.
Above-mentioned micro-polluted surface water denitrifying method, operating biofilter volumetric loading, it is preferred to be not more than 1kgN/m3·d。
Above-mentioned filler is load aerobic microbiological, anaerobic denitrifying bacterium and anaerobic ammonia oxidizing bacteria simultaneously, is realized by the natural membrane with domestication of cultivating of biofilter 2 initial start stage. The startup stage of biofilter, anaerobic activated sludge is inoculated into inside the packing area B of biofilter 2, adds micro-polluted surface water, influent COD to biofilter 2crWith the concentration of (TN+DO) than setting 1.2 and NH4 +-N and NOx -The concentration ratio of-N is set as 1.5 ± 3%, biofilter 2 is carried out biofilm and domestication, the Electronic Speculum photographic analysis that biofilm and the judgment criteria tamed are biofilter 2 stable effluent quality (main criterion) and biofilter Internal biological judges (auxiliary judgment), through domestication, after biofilter biofilm completes, it is achieved that the purpose of described filler load aerobic microbiological, anaerobic denitrifying bacterium and anaerobic ammonia oxidizing bacteria simultaneously.
Above-mentioned micro-polluted surface water denitrifying method, in view of China micro-polluted surface water NOx --N is dense higher, NH4 +The feature that-N concentration is relatively low, it is necessary to denitrifying bacterium is by NO3 -Change into NO2 -, it is necessary first in water inlet, add additional carbon carry out denitrifying first step reaction, by NO3 -Change into NO2 -, carbon source adds can not be excessive, if carbon source adds excessive, denitrifying bacterium can utilize carbon source by NO2 -Continue to change into N2, now carbon source dosage is big, and operating cost is higher; Denitrifying bacterium can be competed with anaerobic ammonia oxidizing bacteria simultaneously, and anaerobic ammonia oxidizing bacteria existence is unfavorable. In addition denitrifying bacterium and anaerobic ammonia oxidizing bacteria are more sensitive to oxygen, so needing the aerobic bacteria bottom the packing area B of biofilter 2 to be fallen by the dissolved oxygen depletion in water inlet, it is therefore desirable to add appropriate organic carbon source for aerobic microbiological metabolism.Through analysis of experiments, CODcrCan reaching good denitrification effect with (TN+DO) Ratio control when 1.2, the too high operating cost of carbon dosage is high, and the too low denitrification effect of dosage is bad. Aerobic microbiological assimilation to consume NH4 +-N realizes breeding and the growth of self, and anaerobic ammonia oxidizing bacteria needs to utilize NH4 +-N is by NO2 --N changes into N2, and NH in surface water4 +-N concentration is relatively low, it is therefore desirable to additional ammonium salt, and test shows NH4 +-N and NOx -The concentration ratio of-N controls to reach good denitrification effect 1.5 ± 3%. Therefore by controlling the parameter of above water inlet, it is possible to achieve the synergism of different microorganisms strain, equipment is simplified, it is achieved the surface water denitrogenation under low operating cost. Run the reduction adding drug expenditure to refer to shown in table 2.
Table 2 the inventive method and conventional denitrification technique add amount of medicament and the contrast of dosing expense
By table 2, identical surface water is processed, the handling of the inventive method reduces 780 yuan/ten thousand tons than the dosing expense of conventional denitrification technique, and the improvement that the effect of minimizing running cost is polluted for the large-area water of China has more great practical significance.
Although the present invention is disclosed above with preferred embodiment, being so not limited to scope of the invention process, the simple equivalence made according to claims and the description of the present invention changes and modifies, and still falls within the scope of technical solution of the present invention.
Claims (7)
1. a micro-polluted surface water denitrifying method, this micro-polluted surface water enters from the bottom in bio-filter stuffing district and is discharged by top, comprises the following steps:
Before micro-polluted surface water enters biofilter, including by adding ammonium salt and/or the NH of nitrite adjustment micro-polluted surface water4 +-N and NOx -The concentration ratio of-N and regulate the COD of micro-polluted surface water by adding carbon sourcecrWith the concentration of (TN+DO) ratio; In the bottom of the packing area of this biofilter, the aerobic microbiological of filling surface utilizes the dissolved oxygen in water and carbon source to carry out metabolism, consumes the dissolved oxygen in this micro-polluted surface water, is internally formed anaerobic environment in the packing area of this biofilter;
Inside the filler of the packing area of this biofilter, denitrifying bacterium is by the NO in this micro-polluted surface water3 --N changes into NO2 --N and/or N2; And
In the middle and upper part of the packing area of this biofilter, anaerobic ammonia oxidizing bacteria is by NH4 +-N and NO2 --N changes into N2,
It is characterized in that described NH4 +-N and NOx -The concentration ratio of-N is 1.5 ± 3%; Described CODcrIt is 1.2 with the concentration of (TN+DO) ratio, wherein NH4 +-N concentration, NOx --N concentration, CODcr, TN, DO unit be mg/L.
2. micro-polluted surface water denitrifying method as claimed in claim 1, it is characterised in that before wherein said micro-polluted surface water enters biofilter, first pass through coagulating kinetics, remove the float in water.
3. micro-polluted surface water denitrifying method as claimed in claim 1 or 2, it is characterised in that the wherein said COD regulating micro-polluted surface watercrWith the concentration of (TN+DO) ratio, including:
Measure the COD in micro-polluted surface watercr, TN, DO concentration, in described micro-polluted surface water add carbon source.
4. micro-polluted surface water denitrifying method as claimed in claim 3, it is characterised in that wherein said carbon source be in acetic acid, methanol, propanoic acid, sodium acetate, starch, o-phthalic acid dibutyl ester and cellulose one or more.
5. micro-polluted surface water denitrifying method as claimed in claim 1 or 2, it is characterised in that the wherein said NH regulating micro-polluted surface water4 +-N and NOx --N concentration ratio, including:
Measure the NH in micro-polluted surface water4 +-N concentration and NOx --N concentration, adds ammonium salt and/or nitrite in described micro-polluted surface water.
6. micro-polluted surface water denitrifying method as claimed in claim 1 or 2, it is characterised in that wherein the volumetric loading of this biofilter is not more than 1kgN/m3·d。
7. the denitrifying method of micro-polluted surface water as claimed in claim 1 or 2, it is characterized in that the coagulative precipitation tank of coagulating kinetics is provided with on-line checking instrument, be used for detecting Biochemical oxygen demand, total nitrogen, ammonia nitrogen, nitrate nitrogen, dissolved oxygen and controlling throwing device adding medicament.
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| CN111533255B (en) * | 2020-05-09 | 2022-08-02 | 绿源(北京)环保设备股份有限公司 | Method for treating nitrogen-containing wastewater by using controllable bed biological filter |
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| CN101774703A (en) * | 2010-03-17 | 2010-07-14 | 上海交通大学 | Method for depriving nitrogen nutritive salt in surface water |
| CN102963981A (en) * | 2012-10-11 | 2013-03-13 | 北京工业大学 | Method for deep denitrification of integrated biological aerated filter |
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| CN101774703A (en) * | 2010-03-17 | 2010-07-14 | 上海交通大学 | Method for depriving nitrogen nutritive salt in surface water |
| CN102963981A (en) * | 2012-10-11 | 2013-03-13 | 北京工业大学 | Method for deep denitrification of integrated biological aerated filter |
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Denomination of invention: Slightly-polluted surface water denitrification method Effective date of registration: 20200430 Granted publication date: 20160615 Pledgee: Beijing urban construction and development branch of China Construction Bank Co., Ltd Pledgor: Poten Industrial Technology (Beijing) Co., Ltd|POTEN ENVIRONMENT GROUP Co.,Ltd.|BOTIAN ENVIRONMENTAL PLANNING AND DESIGN INSTITUTE (BEIJING) Co.,Ltd. Registration number: Y2020990000419 |