CN108558138A - A kind for the treatment of process of high ammonia nitrogen pesticide wastewater - Google Patents

A kind for the treatment of process of high ammonia nitrogen pesticide wastewater Download PDF

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Publication number
CN108558138A
CN108558138A CN201810399397.4A CN201810399397A CN108558138A CN 108558138 A CN108558138 A CN 108558138A CN 201810399397 A CN201810399397 A CN 201810399397A CN 108558138 A CN108558138 A CN 108558138A
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Prior art keywords
treatment
ammonia nitrogen
lime stone
treatment fluid
natural zeolite
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CN201810399397.4A
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Chinese (zh)
Inventor
郑炜
万梅
杨兴兴
皱利华
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ZHEJIANG SHUANGYI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co Ltd
Yangtze Delta Region Institute of Tsinghua University Zhejiang
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ZHEJIANG SHUANGYI ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co Ltd
Yangtze Delta Region Institute of Tsinghua University Zhejiang
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Priority to CN201810399397.4A priority Critical patent/CN108558138A/en
Publication of CN108558138A publication Critical patent/CN108558138A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F2003/001Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/15N03-N
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/30Aerobic and anaerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention discloses a kind for the treatment of process of high ammonia nitrogen pesticide wastewater, which includes the following steps:(1) coagulant and flocculant are added into high ammonia nitrogen pesticide wastewater, carries out coagulation pretreatment, obtains treatment fluid I;(2) treatment fluid I is passed through successively in anoxic pond, anaerobic pond and aerobic tank, through level-one biochemical treatment, obtains treatment fluid II;(3) treatment fluid II is passed through successively in biozeolite bed membrane bioreactor, after secondary biochemical treatment, the water outlet discharged;For the packing layer of the biozeolite bed using the mixture of natural zeolite and lime stone as carrier filler, the mass ratio of the natural zeolite and lime stone is 1:1~3:1, the grain size of natural zeolite is 3~5mm, and the grain size of lime stone is 1~2mm.Present invention process realizes effectively removing for the polluters such as ammonia nitrogen in industrial waste water with high ammoniac nitrogen, phosphorus, ensures stable water outlet, realize combination the qualified discharge of Process for Effluent.

Description

A kind for the treatment of process of high ammonia nitrogen pesticide wastewater
Technical field
The present invention relates to technical field of waste water processing more particularly to a kind for the treatment of process of high ammonia nitrogen pesticide wastewater.
Background technology
With Socialization and process of industrialization, ammonia nitrogen accounting increasingly increases in pesticide wastewater, the discharge of ammonia nitrogen Measure the capacity that remote hyperenvironment can carry.High ammonia nitrogen pesticide wastewater pollutional load is big, keeps ammonia nitrogen in water body exceeded, and water body is certainly I declines repair ability.Meanwhile a large amount of mineralized nitrogens are that nitrate nitrogen, nitrite nitrogen cause a large amount of numerous of microorganism and algae in water It grows, forms the environmental problems such as body eutrophication.Therefore, high ammonia nitrogen pesticide wastewater treatment technology level is improved to have carved not Rong Huan.
The administering method of high ammonia nitrogen pesticide wastewater mainly has physico-chemical process, chemical method, bioanalysis and its mutual Combination technique etc..Though the physico-chemical process such as traditional stripping, stripping have many advantages, such as that treatment effect is stable, technological process is simple, its It is easy to bring fouling, secondary pollution problems.There is operating cost height, by-product by the chemical rule of representative of break point chlorination The defects of various.Currently, the research for such waste water is concentrated mainly on bioanalysis and combinations thereof technique.
Ding Shaolan etc. is using walnut shell and combination of zeolites as aerating biological filter pool filler, and research BAF techniques are to high ammonia nitrogen The treatment effect of waste water influences.The result shows that walnut shell performance is stable, has stephanoporate framework supporting role, boiling can be preferably supported Stone ensures the stable structure of composite filling.Zeolite has preferable adsorptivity, ion exchangeable etc., to the ammonia nitrogen etc. in waste water Substance has certain removal effect.Meanwhile it being enriched with a large amount of microorganism on the combination carrier after being combined with walnut shell, it can not Disconnected bio-regeneration zeolite, reinforces the performance and efficiency of biological denitrification system.But the processing waste water of the technique is simulated wastewater, can not The engineer application of industrial waste water with high ammoniac nitrogen is unfolded.
Zhang Zhanli etc., which is devised, just exposes the simultaneous gas pond in pond-- aerobic tank (O/A/O) technique development chemical fertilizer industrial waste water with high ammoniac nitrogen Treatment research.Experiments have shown that being discharged COD mean values by coupling technique system is down to 35.5mg/L, ammonia nitrogen mean value is down to 1mg/L, Water outlet reaches《Composite wastewater discharge standard》
(GB8978-1996) primary standard.But the technique is only unfolded the removal of the substances such as ammonia nitrogen in high ammonia-nitrogen wastewater Research lacks the materialized pretreatment research of waste water early period, and when making waste water HI high impact load, the stability of O/A/O techniques needs It inquires into.In addition, the removal of the substances such as the Process on Ammonia Nitrogen only relies on biological effect, it is raw when system is influenced by impact load Object system convalescence is slow, influences effluent quality, can not ensure to be discharged qualified discharge steady in a long-term.
Therefore, in conjunction with physics denitrogenation, biological denitrificaion etc., ensure efficient, the stable operation of processing system, realize reaching for waste water Mark discharge is the main contents and developing direction of industrial waste water with high ammoniac nitrogen Processing Technology Research.
Invention content
The present invention provides a kind for the treatment of process of high ammonia nitrogen pesticide wastewater, which realizes high ammonia nitrogen Industry Waste The polluters such as ammonia nitrogen, phosphorus effectively remove in water, ensure stable water outlet, realize combination the qualified discharge of Process for Effluent.
Specific technical solution is as follows:
A kind for the treatment of process of high ammonia nitrogen pesticide wastewater, includes the following steps:
(1) coagulant and flocculant are added into high ammonia nitrogen pesticide wastewater, carries out coagulation pretreatment, obtains treatment fluid I;
(2) treatment fluid I is passed through successively in anoxic pond, anaerobic pond and aerobic tank, through level-one biochemical treatment, obtains treatment fluid II;
(3) treatment fluid II is passed through successively in biozeolite bed-membrane bioreactor, after secondary biochemical treatment, is obtained The water outlet of discharge;
The packing layer of the biozeolite bed is described natural using the mixture of natural zeolite and lime stone as carrier filler The mass ratio of zeolite and lime stone is 1:1~3:1, the grain size of natural zeolite is 3~5mm, and the grain size of lime stone is 1~2mm.
Absorption, exchange interaction and the nitrification for being attached to bacterium on zeolite of zeolite can cooperate with removal pesticide producing useless Ammonia nitrogen in water and phosphorus.When adsorption capacity one timing of the zeolite to ammonia nitrogen, the biology at zeolite interface is by nitrification to zeolite Desorption.But since the rate of biological nitration is slower, cause the zeolite regeneration time longer;And lime stone under microbial action by delaying The Ca released2+, the exchange release of ammonia nitrogen ion in zeolite can be strengthened, the nitrifying microorganisms in biozeolite surface biological film is made to be more easy to In obtaining ammonia nitrogen, promote zeolite regeneration.
Preferably, in step (1), the coagulant is aluminium polychloride, the dosage of aluminium polychloride is 10~ 80ppm.Coagulant polymeric aluminium chloride is Al (III) salt hydrolysis-polymerizate, to the colloidal solid or colloid pollution in waste water Object electrically neutralize, takes off the effects that steady and adsorption bridging generation coarse granule " alumen ustum ".
Preferably, in step (1), the flocculant is polyacrylamide, the dosage of polyacrylamide is 6~ 14ppm.The flocculant polyacrylamide of input makes " alumen ustum " to form the larger wadding of particle by the effects that absorption, winding, bridge formation Solidifying body, the polluters such as ammonia nitrogen, the organic matter in high pesticide wastewater is removed by gravitational settling, to reduce subsequent bio The impact load of system increases the capacity of resisting impact load of combined process system, ensures the stable operation of system.
Further preferably, the dosage of aluminium polychloride is 45ppm, and the dosage of polyacrylamide is 12ppm.
Further preferably, the hydraulic detention time of the coagulation pretreatment is 0.3h.
Preferably, in step (2), the total hrt of the level-one biochemical treatment is 7.5~14h;Wherein, it lacks The hydraulic detention time in oxygen pond, anaerobic pond and aerobic tank is followed successively by 0.5~4h, 1~2h and 6~8h.
Preferably, in step (3), the hydraulic detention time of the secondary biochemical treatment is 18~for 24 hours;The biology boiling The return sludge ratio of stone bed-membrane bioreactor is 100~300%.Biozeolite bed-the membrane bioreactor is that integral type is dirty Water treatment facilities.
Further preferably, the membrane module material of the membrane bioreactor is polyvinylidene fluoride film, and membrane aperture is 0.02 μm. Above-mentioned membrane material have tensile strength is big, filtration flux is big, chemical stability is excellent, antifouling property is excellent, acid and alkali-resistance, to clear Wash agent it is of less demanding the features such as, and membrane material blanking aperture is 0.02 μm, and distribution is to keep membrane module filtering accuracy high, filtering Performance is good, and cutoff performance is notable.
Preferably, the biozeolite bed divides buffering area and packing layer, the height ratio of buffering area and packing layer is 1:6. It is separated by porous barrier between buffering area and packing layer.
Compared with prior art, the invention has the advantages that:
The present invention uses coagulation-A2The technique of O- biozeolites bed-membrane biological reaction, and by the mixing of zeolite and lime stone Object carries out the processing of pesticide wastewater as the filling carrier of biozeolite bed, not only increases the polluters such as ammonia nitrogen, phosphorus Treatment effeciency and capacity of resisting impact load, realize the combination of physics denitrogenation and biological denitrificaion in system;And effectively Biological nitration effect is promoted, realizes the fast desorption of zeolite, ensure that treatment process is stable to polluter, efficiently remove Efficiency.
Specific implementation mode
With reference to specific embodiment, the invention will be further described, and what is be exemplified below is only the specific implementation of the present invention Example, but protection scope of the present invention is not limited only to this.
Embodiment 1
The COD of pending high ammonia nitrogen pesticide wastewater is 932mg/L, NH in the present embodiment3- N is 129mg/L.
The processing method of above-mentioned high ammonia nitrogen pesticide wastewater, is as follows:
(1) pending high ammonia nitrogen pesticide wastewater is passed through in coagulative precipitation tank, dosing coagulant aluminium polychloride With flocculant polyacrylamide, coagulation pretreatment is carried out, treatment fluid I is obtained;Control the throwing of aluminium polychloride and polyacrylamide Dosage is respectively 45ppm and 12ppm, hydraulic detention time 0.3h.
The COD for the treatment of fluid I is down to 560mg/L, NH3- N is down to 82mg/L.
(2) treatment fluid I is passed through A2/ O process sections (anoxic-anaerobic-aerobic treatment technique), are passed through anoxic pond, detest successively In oxygen pond and aerobic tank, biochemical treatment is carried out, treatment fluid II is obtained;In processing procedure, control anoxic section, anaerobism section and aerobic section Hydraulic detention time be followed successively by 2h, 1.5h and 8h.
The COD for the treatment of fluid II is 350mg/L, NH3- N is 24mg/L.
(3) treatment fluid II is passed through in biozeolite bed-membrane bioreactor (ZB-MBR devices), controls ZB-MBR techniques Hydraulic detention time be that for 24 hours, return sludge ratio is adjusted to 200%, in biozeolite bed the height of buffering area and packing layer it Than 1:6, the mass ratio of natural zeolite and lime stone is 5 in mixed fillers:1, the grain size of natural zeolite and lime stone is respectively The membrane material of 3mm and 2mm, membrane bioreactor are polyvinylidene fluoride film, and membrane aperture is 0.02 μm, into the physical action for crossing technique And biochemical action, obtain discharge water outlet.
The COD of water outlet is 40mg/L, NH3- N is 0.8mg/L, and effluent quality reaches《Urban wastewater treatment firm pollutant is arranged Put standard》(GB18918-2002) the level-one A standards in, water stabilization.
Comparative example 1
The flow for the treatment of process is substantially the same manner as Example 1, differs only in the filling carrier of the biozeolite bed of use Only biozeolite, and without lime stone.
Test indicate that the COD for discharging water outlet is 63mg/L, NH3- N is 2.4mg/L.
Embodiment 2
In the present embodiment, the nitrobacteria of enrichment is added in the natural zeolite after 100g cleanings, culture solution is added, exposes Gas is inoculated with, and forms biozeolite.
It is respectively 5 to take biozeolite and lime stone mass ratio:1、10:1 and 15:1 three groups of mixed fillers and biozeolite (being denoted as absorption sample 1, absorption sample 2, absorption sample 3 and control sample respectively) total 4 class samples, control biozeolite amount in 4 class samples Respectively 20g, and input 100mL NH respectively3The NH of a concentration of 250mg/L of-N4In Cl solution, inhaled in constant-temperature shaking incubator Attached 30min, 25 DEG C of temperature, rotating speed 100r/min.
After absorption, quickly removes 4 class samples and be respectively put into 50mL deionized waters and gently shake to remove biozeolite table The ammonia nitrogen in face;4 class samples are respectively put into 100mL regenerated liquids (deionized water), continuous aeration 12d, 4 classes is taken to regenerate respectively Liquid measures NO in regenerated liquid3 --N、NO2 -- N and NH3The content of-N.
Test indicate that after zeolite desorbs 12d, the oxidation state nitrogen (NO of absorption sample 13 -- N and NO2 -- N) total amount highest, For 6.615mg;The oxidation state nitrogen total amount of absorption sample 2, absorption sample 3 and control sample is respectively 3.445mg, 1.59mg and 1.304mg; The oxidation state nitrogen total amount of 3 class absorption samples is above control sample.The ammonia nitrogen of absorption sample 1, absorption sample 2, absorption sample 3 and control sample desorption Content is respectively 2.448mg, 2.146mg, 2.236mg and 1.968mg, the ammonia-nitrogen content highest of absorption sample 1, and the ammonia of absorption sample Nitrogen content is above control sample.
The result shows that the lime stone by adding proper ratio, can slowly release Ca under microbial action2+, from And the ion exchange of ammonia nitrogen discharges in enhanced biological zeolite, and the nitrifying microorganisms in biozeolite surface biological film is made to be easier to obtain Ammonia nitrogen is obtained, the nitrification effect of system is made to get a promotion.Meanwhile 4 class sample generate oxidation state nitrogen in NO3 -Based on-N, respectively NO in sample2 -- N concentration is below 0.3mg/L, shows that the reoxygenation effect of biozeolite system is fine, no NO2 -The accumulation of-N.

Claims (8)

1. a kind for the treatment of process of high ammonia nitrogen pesticide wastewater, which is characterized in that include the following steps:
(1) coagulant and flocculant are added into high ammonia nitrogen pesticide wastewater, carries out coagulation pretreatment, obtains treatment fluid I;
(2) treatment fluid I is passed through successively in anoxic pond, anaerobic pond and aerobic tank, through level-one biochemical treatment, obtains treatment fluid II;
(3) treatment fluid II is passed through successively in biozeolite bed-membrane bioreactor, after secondary biochemical treatment, is discharged Water outlet;
The packing layer of the biozeolite bed is using the mixture of natural zeolite and lime stone as carrier filler, the natural zeolite Mass ratio with lime stone is 1:1~3:1, the grain size of natural zeolite is 3~5mm, and the grain size of lime stone is 1~2mm.
2. treatment process as described in claim 1, which is characterized in that in step (1), the coagulant is aluminium polychloride, The dosage of aluminium polychloride is 10~80ppm.
3. treatment process as described in claim 1, which is characterized in that in step (1), the flocculant is polyacrylamide, The dosage of polyacrylamide is 6~14ppm.
4. treatment process as described in claim 1, which is characterized in that the hydraulic detention time of the coagulation pretreatment is 0.15 ~0.75h.
5. treatment process as described in claim 1, which is characterized in that in step (2), total waterpower of the level-one biochemical treatment Residence time is 7.5~14h;Wherein, the hydraulic detention time of anoxic pond, anaerobic pond and aerobic tank be followed successively by 0.5~4h, 1~ 2h and 6~8h.
6. treatment process as described in claim 1, which is characterized in that in step (3), the waterpower of the secondary biochemical treatment is stopped Stay the time be 18~for 24 hours;The return sludge ratio of the biozeolite bed-membrane bioreactor is 100~300%.
7. treatment process as described in claim 1, which is characterized in that the membrane module material of the membrane bioreactor is poly- inclined Fluoride film, membrane aperture are 0.02 μm.
8. treatment process as described in claim 1, which is characterized in that the biozeolite bed divides buffering area and packing layer, delays The height ratio for rushing area and packing layer is 1:6.
CN201810399397.4A 2018-04-28 2018-04-28 A kind for the treatment of process of high ammonia nitrogen pesticide wastewater Pending CN108558138A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110498562A (en) * 2019-08-08 2019-11-26 苏州苏净环保工程有限公司 Treatment method of high-concentration stripping liquid wastewater

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CN103449669A (en) * 2013-09-05 2013-12-18 浙江清华长三角研究院 Treatment method for wastewater in production of synthetic rubber
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Publication number Priority date Publication date Assignee Title
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CN110498562B (en) * 2019-08-08 2022-05-13 苏州苏净环保工程有限公司 Treatment method of high-concentration stripping liquid wastewater

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Application publication date: 20180921