CN103387309B - Be applied to method and device thereof that river ecosystem controls water pollution - Google Patents
Be applied to method and device thereof that river ecosystem controls water pollution Download PDFInfo
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Abstract
The invention discloses a kind of method being applied to river ecosystem control water pollution, the method for the combined method adopting biomembrance process and physisorphtion to combine controls water pollution, and described combined method is realized by same device.The described device for the method is combined by bio-contact oxidizing treatment device and physical adsorption treatment unit.The invention has the advantages that successful for biofilm haydite is loaded mesh bag makes bio-contact oxidizing treatment device, it can play the effect of good purifying water body in the season that weather is comparatively warm; In the autumn and winter that temperature is lower, use physical adsorption treatment unit wherein to carry out ammonia nitrogen in Adsorption water body and phosphorus effectively can control water pollution, use under being applicable to annual natural condition, and raw material is easy to get, do not produce secondary pollution, cost is more economical, is more convenient for promoting the use of.
Description
Technical field
The invention belongs to water pollution control and ecological restoration technical field, be specifically related to a kind ofly be applied in river ecosystem the method and device thereof of removing ammonia nitrogen in water body and phosphorus.
Background technology
Along with the development of industrial or agricultural, the sharp increase of population and urbanization universal, be discharged into natural water body containing ammonia nitrogen and phosphorous sanitary sewage and trade effluent in a large number, and result in the eutrophic state of water body.Research display, become the at present lake of eutrophication of China reaches more than 90%, and continuation is deepened by the Eutrophic Extent in most of waters.The main method of the removal ammonia nitrogen of report has biological process, chemical precipitation method, active carbon adsorption, coagulant sedimentation etc. both at home and abroad at present, front 2 kinds of methods have good effect for the process of high-concentration ammonia nitrogenous wastewater, but the cost intensive of its process Low Concentration Ammonia Containing Wastewater, and other harmful ion may be introduced; Rear 2 kinds of methods also fail to be used widely due to the reason of technique own and too high cost.Conventional phosphorus removing method mainly contains chemical precipitation method, electrolytic process, embrane method, biological dephosphorization and absorption and ion exchange method etc.Chemical precipitation method utilizes the phosphorus reaction in chemical reagent and sewage to generate to precipitate, thus reaches the object of dephosphorization, and its greatest drawback is just the introduction of new compound and easily causes secondary pollution, and the pharmaceutical quantities that the method uses is large, running cost is high; Electrolytic process device is simple, and operation is also uncomplicated, but its precipitation capacity is large and consumed electrode is large, and running cost is higher; Membrane technique dephosphorization and biological dephosphorization effect better, but need to design corresponding membrane technique and biotechnology for the sewage of different situation; Absorption method is the specific surface area utilizing sorbent material larger, phosphorus is utilized to remove phosphorus in water body in the attachment absorption of adsorbent surface, ion-exchange and surface precipitation process, absorption method technique is simple, effect stability, both as independent technique dephosphorization, also can technique can combine with other techniques as a supplement.Continue to explore efficient, low consumption, low cost, manageability, continuable phosphorus removing method be countries in the world environment-1-
An important directions of administering.Therefore, search out a kind of more effectively, the method for ammonia nitrogen and phosphorus in the cheaper removal water body of cost, be the focus of research both at home and abroad.
It is the one of the main reasons causing body eutrophication that ammonia nitrogen and phosphorus content exceed standard.In China's present stage, sewage disposal technology mainly have employed biological process, and in biological treatment system, the power of microorganism active will directly affect the effect of sewage disposal.Because microbe population aseptic under winter low temperature condition and activity are affected, therefore in winter low temperature situation water quality purification and keep be a difficult problem always.Physical adsorption also claims Van der Waals to adsorb, and it is caused by adsorbate and sorbent molecule intermolecular forces (also claiming Van der Waals force), can by the problem solving biological method purification Effects of Water Quality under cryogenic and restrict by microorganism active.Physisorphtion is the specific surface area utilizing sorbent material larger, the attachment absorption of adsorbent surface, ion-exchange and surface precipitation process is utilized to remove ammonia nitrogen in water body and phosphorus, physisorphtion technique is simple, effect stability, both as independent technique, also can technique can combine with other techniques as a supplement.In actual applications, for method often just independent employing biological process or the physisorphtion removing ammonia nitrogen in water body and phosphorus in river ecosystem, water pollution controls to be subject to such environmental effects, and general effect is all not ideal enough.
Summary of the invention
Under being subject to natural condition for the existing method being applied to river ecosystem control water pollution, low temperature limits, be difficult to the annual problem used, the object of the present invention is to provide one more economical, better effects and if control the method for stream pollution under being applicable to annual natural condition, and realize the special purpose device of the method.
The present invention solves the problems of the technologies described above taked technical scheme: a kind of method being applied to river ecosystem control water pollution, described method is the combined method that biomembrance process and physisorphtion combine, and described combined method realizes controlling water pollution by same device.
The technical scheme realizing aforesaid method is: one is applied to river ecosystem and controls water body dirt
The combined type sewage treatment equipment of the method for dye, is combined by bio-contact oxidizing treatment device and physical adsorption treatment unit.
As improvement, described bio-contact oxidizing treatment device by the haydite of particle diameter 3mm through high density-2-
Sewage artificial inoculation biofilm, then pack after the domestication of high, medium and low concentration sewage and be made; Described physical adsorption treatment unit is made with the clay mixing pack of 1 mass parts by the sand of 1 ~ 10 mass parts.
As further improvement, described physical adsorption treatment unit to be packed by the weight percent Homogeneous phase mixing of 1:1 by construction work sand and kaolin and forms, in described construction work sand, particle diameter is greater than the particle of 1mm more than 90%, and in described kaolin, particle diameter is less than the particle of 0.005mm more than 95%.
Compared with the existing technology, the present invention has following apparent outstanding progress and remarkable advantage: loaded in mesh bag by successful for biofilm haydite in actual applications and drop into river water can play good purifying water body effect in the season that weather is comparatively warm; And for using the autumn and winter that temperature is lower ecological pollution reducing bag to carry out ammonia nitrogen in Adsorption water body and phosphorus can control water pollution effectively.Utilize being combined of 2 kinds of methods can to overcome under natural condition temperature well for the impact of water technology, and a good co can be formed, while ensureing the functions such as original Drain contamination for river channel, flood discharge, achieve the purification of quality of river water.Present method also has following advantage in addition: 1. pollutent is degraded in original place, and repair time is shorter; 2. treatment in situ is easy and simple to handle, few to surrounding environment interference; 3. good purification, be convenient to management; 4. secondary pollution is not produced; 5. with low cost, be convenient to the popularization of method, the haydite of use, clay and sand are all lower-cost materials.Short, backward in technique for China's current environmental protection facility construction fund, the problems such as wastewater treatment rate is low, this technology has broad application prospects in the comprehensive improvement of China's middle and small river pollution.
Embodiment
Be further elaborated of the present invention below in conjunction with embodiment.
Embodiment 1: a kind of method being applied to river ecosystem control water pollution, the method adopting biomembrance process to combine with physisorphtion controls water pollution, comprises the steps:
The first step, forms combined sewage treatment system jointly by bio-contact oxidizing treatment device and a physical adsorption treatment unit; Second step, is placed in river water by described combined sewage treatment system.Wherein, bio-contact oxidizing treatment device by the haydite of particle diameter 3mm through the artificial-3-of high-concentration sewage
Inoculation membrane formation, then pack after the domestication of high, medium and low concentration sewage and be made, described physical adsorption treatment unit is made with the clay mixing pack of 1 mass parts by the sand of 10 mass parts.
Wherein, under non-cryogenic condition, leading role is played with bio-contact oxidizing treatment device.In the present embodiment, the core component of biomembrance process is biologic packing material, and the material of biologic packing material and external form are directly connected to biofilm biomass and handling property.This experiment selects haydite to do filler, biological ceramic particle voidage is high, specific surface area can reach 3.99m2/g, the general 3mm of particle diameter, haydite also serves as filtrate effect as biomembranous carrier simultaneously, be bonded together under the viscous substance effect that suspended particle in water body and colloidal particle produce in part microbial metabolism, form flco, retained removal by haydite, therefore have more superiority relative to general soft-filler or semi soft packing.And haydite is not chemical synthetic material, belongs to natural materials, for purifying river water quality, more meet the theory in restoration of the ecosystem river course.
Related experimental methods and data as follows:
Test the biological contact oxidation reactor that device used is designed, designed.Device is by inlet chest, microorganism reactor and settling tank composition.Wherein microorganism reactor is made up of synthetic glass, scale 0.2 m × 0.2 m × 0.3m, useful volume 12L, 15cm and 25cm place punching (mudhole and posticum) bottom the identity distance of side, respectively open a hole (posticum for subsequent use) apart from 26cm place, bottom the right and left, prosopyle is positioned at opposing floor portion, realizes bottom water inlet, top water outlet, makes sewage fully contact with the filler in reactor.Aeration head is placed in four corners of reactor bottom, makes inside reactor oxygenation even.Biofilm packing selects haydite, filler: water=1:3, and reactor connects peristaltic pump water inlet, aeration pump connection traffic meter, can change the value of dissolved oxygen by adjust flux meter.The biofilm stage needs sludge reflux and regular spoil disposal.Experiment is carried out in indoor laboratory, and sewage used is the simulated sewage of artificial preparation.The average water quality of the sewage during artificial inoculation biofilm: COD is 180 mg/L, NH
3-N is 10 mg/L, TP is 1.45 mg/L, the average water quality of high density water inlet: COD
Be 178 mg/L, NH3-N be 10.48 mg/L, TP be 1.24 mg/L; The average water quality of middle concentration water inlet: COD is 90.5 mg/L, NH3-N be 6.75 mg/L, TP is 0.81 mg/L; Low
The average water quality of concentration water inlet: COD is 48 mg/L, NH3-N be 3.39 mg/L, TP is 0.46
mg/L。For meeting microbial growth demand, except ensureing carbon source, beyond nitrogenous source and phosphorus, also-4-should be added
Add inorganic elements and trace element.The mud that the biofilm stage uses takes from the active sludge of sewage work.
In experimentation, the removal effect of COD is: first two weeks is the biofilm stage of biologic packing material, and seed sludge takes from the active sludge of sewage work, and its performance has higher sludge activity, and intake as the simulated sewage of laboratory preparation, average influent COD is 180mg/L.There is significantly fluctuation in the clearance of first week COD, changed new growing environment mainly due to microbe inoculation, need the adaptive phase of one period, the unsteady state shown in the adaptive phase, directly has influence on the removal effect of COD; The clearance of second week COD is stable and higher, and between 76.5% ~ 87.8% scope, average removal rate reaches 80.9%.15 ~ 23 days is process high concentration COD fill phase, and average influent COD is 178mg/L, a few days ago due to flip-flop environment, COD clearance drops to 68.7% by 78.8%, in period subsequently, the clearance of COD is in 70.3% ~ 79.3% scope, and average removal rate reaches 76.3%.24 ~ 35 days is concentration C OD fill phase in process, and average influent COD is 90.5mg/L, initial reaction stage, because environmental change is comparatively large, the clearance of COD drops to 23.7%, and microorganism enters the adaptive phase subsequently, clearance also rises gradually, and clearance when stablizing reaches 69.0%.36 ~ 44 days is process low strength COD fill phase, and average influent COD is 48mg/L, compared to inoculation step, the COD concentration of this period is lower, the adaptive phase of microorganism is longer, and water outlet COD average out to 18.6mg/L when finally reaching stable, average removal rate is 56.0%.
NH in experimentation
3the removal effect of-N is: biofilm stage NH
3the average influent concentration of-N is 10 mg/L, and within first week, seed sludge keeps active preferably, NH
3the clearance of-N on average reaches 77.6%, second week, may due to seed sludge being not suitable with laboratory preparation sewage, NH
3the average removal rate of-N drops to 60.9%.High density NH
3-N fill phase, the average influent concentration of NH3-N is 10.48 mg/L, and the initial stage is discharged due to the seed sludge in reactor, and a large amount of microorganism reduces, and NH3-N clearance is plummeted to 38.5%, and along with breeding and the adaptation of microorganism, NH3-N removes
Rate is in rising trend, and clearance when stablizing is 60.4%.Middle concentration NH3-N fill phase, the average influent concentration of NH3-N is the change procedure fill phase of 6.75 mg/L, NH3-N, and NH3-N's is flat
Equal influent concentration and high density water inlet similar process, when stablizing, the clearance of NH3-N is 52.1%.
Lower concentration NH
3-N is 3.39 mg/L, and the change performance of its microorganism is by the required adaptation gradually of discomfort-5-
Environment, last amount reproduction, reaches stable growth and decline, NH
3the clearance of-N also changes thereupon, when finally reaching stable, and water outlet NH
3-N mean concns is 1.25 mg/L, and its average removal rate is 54.7%.
The removal effect of TP in experimentation: on the whole, the clearance of TP is higher.In the inoculation membrane formation stage, water inlet TP mean concns is 1.45 mg/L.Within first week, be in the adaptive phase of active sludge to environment, the clearance of TP fluctuates to some extent, and the second week of biofilm tends towards stability, and average removal rate is 89.8%.High density TP fill phase, water inlet TP mean concns is that the clearance of 1.24 mg/L, TP presents first rapid drawdown, then fluctuates, and finally reach stable state, clearance when stablizing can reach 95.1%.Middle concentration TP fill phase, water inlet TP mean concns is 0.81 mg/L, and the TP clearance in this stage is similar with the variation tendency of high density fill phase, and average removal rate when finally reaching steady state is 89.7%.Lower concentration TP fill phase, water inlet TP mean concns is 0.46 mg/L, during 36 ~ 40 days, the clearance of TP in the fluctuation of higher scope, and with COD and NH of period
3the clearance of-N is all in lower scope, and during this is described, polyP bacteria breeding is very fast, and become dominant bacteria, heterotrophism bacterial classification and nitrobacteria are then in a disadvantageous position.Water outlet TP mean concns when later stage stablizes is 0.07 mg/L, and average removal rate is 83.6%.
What experiment filler was selected is haydite, its light specific gravity, runs most of filler after 5 days and just sinks to bottom.Biofilm mid-term, the filler hiked up on a small quantity is attached with yellow floss, during microscopy, finds that there is a large amount of bacterium, and start to exist with zoogleic form.The biofilm middle and later periods, there is the microbial film that tawny comes off, the region that dissolved oxygen is lower in most of filling surface stick-slip, occurs black anaerobe film in reactor, microscopy finds that there is protozoon and a small amount of metazoan.In the biofilm later stage, the biomembranous variation in thickness of filling surface is little, and microscopy finds that the biophase on filler is very abundant, mainly contains campanularian, tired branch worm, wheel animalcule, heliozooid, ciliate, nematode etc., and structure of community composition tends towards stability, and indicates that microbial film is ripe.Think, the life of under oligotrophic condition, carrier adhering to
Thing film thickness is less, usually at tens to hundreds of μm.
The experiment of biological contact oxidation process treatment of simulated river sewage shows, utilize high-concentration sewage artificial inoculation biofilm, scheme again through the microbial film process little Shahe low concentration pollution water quality of high, medium and low concentration sewage domestication is feasible, and can reach good decontamination effect improving :-6-falls in water outlet COD
To 18.6mg/L, average removal rate is 56.0%, reaches " Environmental Quality Standard of Surface Water " (GB3838-88) III class water quality standard; Water outlet NH
3-N mean concns is 1.25 mg/L, and its average removal rate is 54.7%, reaches " Environmental Quality Standard of Surface Water " (GB3838-88) IV class water quality standard; Water outlet TP mean concns is 0.07 mg/L, and average removal rate is 83.6%, reaches " Environmental Quality Standard of Surface Water " (GB3838-88) II class water quality standard.
Embodiment 2: a kind of method being applied to river ecosystem control water pollution, the method adopting biomembrance process to combine with physisorphtion controls water pollution, comprise the steps: the first step, bio-contact oxidizing treatment device and a physical adsorption treatment unit are consisted of combined sewage treatment system jointly; Second step, is placed in river water by described combined sewage treatment system.Wherein, bio-contact oxidizing treatment device by the haydite of particle diameter 3mm through high-concentration sewage artificial inoculation biofilm, pack after high, medium and low concentration sewage domestication again and be made, described physical adsorption treatment unit to be packed by the weight percent Homogeneous phase mixing of 1:1 by construction work sand and kaolin and forms, in described construction work sand, particle diameter is greater than the particle of 1mm more than 90%, and in described kaolin, particle diameter is less than the particle of 0.005mm more than 95%.The sand of 1 mass parts is made with the clay mixing pack of 1 mass parts.
Under cold condition, physical adsorption treatment unit plays a role.Select the clay and cheap widely distributed sand with adsorptive power to load in cloth bag according to different ratios Homogeneous phase mixing and make ecological pollution reducing bag as physical adsorption treatment unit, remove the element such as nitrogen, phosphorus in water body mainly through principles such as physical adsorptions, thus reach the object of purifying water body, reduction water body eutrophication degree.
Related experimental methods and data as follows:
The indoor static test of ecological pollution reducing bag is exactly by manually arranging different sands and clay ratios, study in the sewage of different concns ecological pollution reducing bag to water in nitrogen, phosphoric removal ability.In ecological pollution reducing bag, the mass ratio of sand and clay is set to 1:1(ratio 1 respectively), 5:1(ratio 2) and 10:1(ratio 3), sand and clay are fully mixed in rear loading bag, and make its gross weight all remain on 500g, each proportioning arranges 3 repetitions.Utilize NH
4cl and KH
2pO
4preparation simulated sewage, the configuration scope of this research simulation sewage ammonia nitrogen and phosphorus concentration is according to Shandong Province
Nansi Lake little Shahe water monitoring data determines to have realistic simulation meaning.-7-has been prepared at former water
Cheng Hou, utilizes HCl and NaOH to regulate former water pH value to make it remain on 7.Simulated sewage uses the wide-necked bottle of 9 2.5L to take up and arranges 2 blanks, uses 11 wide-necked bottles altogether, all loads corresponding 2L simulated sewage during test.The ecological pollution reducing bag good by 3 proportions is put into the wide-necked bottle filling simulated sewage respectively, makes it be immersed in completely in simulated sewage and be suspended from wide-necked bottle, add simulated sewage in control bottle but do not put into the ecological pollution reducing bag of any ratio.Normal temperature condition remains on 22 DEG C ~ 23 DEG C; Wide-necked bottle is then placed in electron temperature-control refrigerator and keeps water temperature at 4 DEG C by cold condition.Static test carry out 7d ~ 9d until ammonia nitrogen and phosphorus concentration substantially remain unchanged reach absorption saturated, carry out primary sample every 24h and measure the concentration of ammonia nitrogen and phosphorus in water sample.Water-quality guideline ammonia nitrogen and phosphorus concentration adopt reagent colorimetric method and the molybdenum-antimony anti-spectrophotometric method of national standard respectively.
Under cryogenic, proportionally the efficiencies of nitrogen removal of the ecological pollution reducing bag of 1 proportioning will be better than other 2 ratios significantly.The 9th day absorption be tending towards saturated in, the clearance of ecological pollution reducing bag to ammonia nitrogen of ratio 1 reaches 67%, and the clearance of dirty bag to ammonia nitrogen that subtract of ratio 2 and ratio 3 is respectively 40% and 32%.Because the clay main component of ecological pollution reducing bag is kaolin, it has good absorption and ion-exchange performance, and natural clay mineral has special surface chemical property, make it have cation exchange capacity (CEC) and adsorptive power that is organic and mineral compound, so the ratio 1 ecological pollution reducing bag that clay content is many when low temperature, switching performance is higher shows the good Adsorption ability of ammonia nitrogen in simulated sewage.At first 3 days that absorption starts, the ecological pollution reducing bag of 3 kinds of ratios all shows the ability of quick adsorption ammonia nitrogen, clearance reaches 39%, 21% and 20% respectively, and until adsorb saturated from the 4th day, the ecological pollution reducing bag of ratio 1 maintains comparatively faster removal speed, to remove the speed of ammonia nitrogen then relative mild for the dirty bag that subtracts of ratio 2 and ratio 3, and this shows under cryogenic, and clay particle content is more can obtain the effect of a lasting removal ammonia nitrogen in sewage.Ratio 2 and ratio 3 subtract dirty bag in whole adsorption process to the removal efficiency of ammonia nitrogen all relatively, the clearance of especially front 3 days is substantially identical, this to show under the condition of low temperature after in ecological pollution reducing bag, the content of clay particle is reduced to certain proportion, along with the minimizing of clay particle, ecological pollution reducing bag for ammonia nitrogen in sewage removal effect also
Significantly do not decline.When substantially reaching capacity, the ecological pollution reducing bag of 3 kinds of ratios removes-8-for phosphorus
Except rate is respectively 38%, 28% and 28%.Sand and clay ratios be the ecological pollution reducing bag of 1:1 for the adsorption effect of phosphor in sewage higher than other 2 ratios, and the removal effect of ratio 2 and ratio 3 is closely, and this is similar to the removal effect of ecological pollution reducing bag for ammonia nitrogen.The adsorption rate subtracting dirty bag in whole adsorption process is all relatively milder, different ratios subtract the effect that dirty bag all shows phosphorus in slow adsorbed water body, can show that ecological pollution reducing bag has the ability of phosphorus in lasting removal water body equally under cryogenic.
Test-results shows, ecological pollution reducing bag can play the effect of Adsorption to ammonia nitrogen in water body and phosphorus under cryogenic, and wherein sand and clay ratios are that the clearance of the ecological pollution reducing bag of 1:1 is the highest, reach 67% and 38% respectively; And sand and clay ratios to be the clearance of the ecological pollution reducing bag of 5:1 and 10:1 lower, the ecological pollution reducing bag of ratio 1 effectively and constantly can remove ammonia nitrogen in water body and phosphorus.Only the ecological pollution reducing bag of proportional 1 maintains ammonia nitrogen and the relatively high removal effect of phosphorus under cryogenic, therefore should increase the ratio of clay particle in ecological pollution reducing bag under cryogenic as much as possible in practice, good removal effect can be obtained like this.
Though it is pointed out that above-described embodiment to be contrasted detailed text description to the present invention, the simple description of these text descriptions just to mentality of designing of the present invention, instead of the restriction to thinking of the present invention.Any be no more than mentality of designing of the present invention combination, increase or amendment, all fall within the scope of protection of the present invention.
Claims (2)
1. one kind is applied to the method that river ecosystem controls water pollution, it is characterized in that the method that described method adopts biomembrance process to combine with physisorphtion controls water pollution, comprise the steps: the first step, by the combined sewage treatment system be jointly made up of bio-contact oxidizing treatment device and a physical adsorption treatment unit; Second step, is placed in river water by described combined sewage treatment system; Bio-contact oxidizing treatment device in wherein said combined sewage treatment system by the haydite of particle diameter 3mm through high-concentration sewage artificial inoculation biofilm, pack after high, medium and low concentration sewage domestication again and be made, the average water quality of described high, medium and low concentration sewage domestication process middle and high concentration water inlet: COD is 178mg/L, NH
3-N is 10.48mg/L, TP is 1.24mg/L; The average water quality of middle concentration water inlet: COD is 90.5mg/L, NH
3-N is 6.75mg/L, TP is 0.81mg/L; The average water quality of lower concentration water inlet: COD is 48mg/L, NH
3-N is 3.39mg/L, TP is 0.46mg/L; Described physical adsorption treatment unit is made with the clay mixing pack of 1 weight part by the sand of 1 ~ 10 weight part.
2. the method being applied to river ecosystem control water pollution according to claim 1, it is characterized in that described physical adsorption treatment unit all to be closed by the weight percent of 1:1 by construction work sand and kaolin to mix pack and form, in described construction work sand, particle diameter is greater than the particle of 1mm more than 90%, and in described kaolin, particle diameter is less than the particle of 0.005mm more than 95%.
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