CN108033600A - A kind of integrated preprocess method of highly concentrated high-toxic pesticide waste water and application - Google Patents
A kind of integrated preprocess method of highly concentrated high-toxic pesticide waste water and application Download PDFInfo
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- CN108033600A CN108033600A CN201711424777.0A CN201711424777A CN108033600A CN 108033600 A CN108033600 A CN 108033600A CN 201711424777 A CN201711424777 A CN 201711424777A CN 108033600 A CN108033600 A CN 108033600A
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- waste water
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- toxic pesticide
- concentrated high
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- 238000000034 method Methods 0.000 title claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010914 pesticide waste Substances 0.000 title claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 99
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 92
- 230000003197 catalytic effect Effects 0.000 claims abstract description 48
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- 230000009467 reduction Effects 0.000 claims abstract description 38
- 238000005189 flocculation Methods 0.000 claims abstract description 23
- 230000016615 flocculation Effects 0.000 claims abstract description 23
- 239000000575 pesticide Substances 0.000 claims abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims description 47
- 238000007254 oxidation reaction Methods 0.000 claims description 47
- 239000012530 fluid Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000006004 Quartz sand Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- -1 Bio-sil metal oxide Chemical class 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 1
- 238000010979 pH adjustment Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 230000006872 improvement Effects 0.000 description 13
- 231100000419 toxicity Toxicity 0.000 description 13
- 230000001988 toxicity Effects 0.000 description 13
- 150000004706 metal oxides Chemical class 0.000 description 10
- 238000004065 wastewater treatment Methods 0.000 description 10
- 231100000614 poison Toxicity 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000003905 agrochemical Substances 0.000 description 8
- 239000002574 poison Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000003672 processing method Methods 0.000 description 6
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000252212 Danio rerio Species 0.000 description 2
- 229910017112 Fe—C Inorganic materials 0.000 description 2
- 230000007059 acute toxicity Effects 0.000 description 2
- 231100000403 acute toxicity Toxicity 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- AHEWZZJEDQVLOP-UHFFFAOYSA-N monobromobimane Chemical compound BrCC1=C(C)C(=O)N2N1C(C)=C(C)C2=O AHEWZZJEDQVLOP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005906 Imidacloprid Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- 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)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Integrated preprocess method and application the invention discloses a kind of highly concentrated high-toxic pesticide waste water, belong to organic industrial sewage process field, and the integrated preprocess method is：Waste water is set to sequentially enter pH regulating reservoirs, Fenton fluidized-bed reactor, flocculation sedimentation tank, catalysis ozone reactor and reduction by catalytic iron pond are handled, whole processing procedure cost is low, effect is good, it is high that highly concentrated high-toxic pesticide concentration of organic wastewater can effectively be solved, the problems such as biodegradability difference and high bio-toxicity, and there is facilitation to subsequent biochemical processing, wastewater effluent after processing, which is stablized, meets subsequent biochemical processing requirement, it is aided with subsequent biochemical processing, water outlet can stably reach national grade one discharge standard, the method is applied to highly concentrated high-toxic pesticide Wastewater Pretreatment field.
Description
Technical field
The invention belongs to organic industrial sewage processing technology field, gives up more specifically to a kind of highly concentrated high-toxic pesticide
The pretreatment integrated processing method of water and its application.
Background technology
Pesticide has played vital effect in agricultural production, effectively promotes the development of modern agriculture.In recent years,
China's pesticide industry is quickly grown, and thing followed agricultural chemicals waste water yield is also increasingly all to be increased.Agricultural chemicals waste water contains largely to ring
Border and human body poisonous and harmful substance, therefore effective improvement of agricultural chemicals waste water is very crucial.
Highly concentrated high-toxic pesticide waste water has the characteristics that following several：1) its COD value is usually in 10000~40000mg/L, and general
Logical industrial park waste water COD≤500mg/L is compared, and the type waste water has the characteristics that organic concentration is high；2) complicated component, water
Qualitative changeization is big；3) salinity is higher；4) hardly degraded organic substance content is high；5) wastewater biological toxicity is high.Therefore the improvement of the waste water is deposited
In larger difficulty；With attention of the country to environmental issue, the Law on Environmental Protection of constantly improve, improves waste water in recent years
Discharge standard, therefore the improvement of agricultural chemicals waste water receives higher and higher concern.
Improvement for highly concentrated high-toxic pesticide waste water, the method for generally use are to carry out pretreatment first to waste water to remove agriculture
Part hardly degraded organic substance in medicine waste water, to improve the biodegradability of waste water, then carries out subsequent treatment using biochemical treatment and makes
Final outflow water meets standard.
Presently the most common preprocess method is materialized pretreatment method, including micro-electrolysis method, advanced oxidation processes, micro-
Group technology of electrolysis+advanced oxidation processes etc..Yet with the particularity of agricultural chemicals waste water water quality, the pretreatment side of existing technology
Usually there are the defects of the following aspects for method：1) pretreating effect is undesirable, when pretreatment take into consideration only improve waste water can
Biochemical, does not consider the reduction of wastewater biological toxicity, and the presence of high toxicity waste water suppresses the poison of microorganism in subsequent biochemical system
Property, microorganism is produced totally unfavorable influence from normal existence to the treatment effect of biochemical system, is further increased life
The difficulty of change system processing；2) it is unstable to pre-process treatment effect, often biochemical system is caused to impact, biochemical system processing unit
It is difficult to stable operation；3) concentration of agricultural chemicals waste water is higher, and when processing needs to consume substantial amounts of medicament, further increase operation into
This.
Through retrieval, the prior art has also disclosed more technical solution, and China Patent No. CN201010526394.6, is awarded
The power day for announcing discloses a kind of comprehensive processing method of high-concentration pesticide wastewater, this application for the application case on July 4th, 2012
Method in pretreatment to neutralize, oil removal flocculation or the combination of evaporation one or both of desalination above processing method, at this
Pretreated water quality situation is described in application case embodiment 1, the COD of waste water is still up to 22000mg/L after it is pre-processed, in advance
Treatment effect and unobvious.Number of patent application CN201610916590.1, the application case that publication date is on 01 11st, 2017 are public
A kind of high-concentration pesticide wastewater carbon cycle anaerobism combination MBBR processing methods are opened, waste water is carried out pH tune by the method for this application
Nutrition is added after section, anaerobic reaction, circulation, anaerobism outer circulation in anaerobism is then carried out, goes out water storage tank, at MBBR biochemical reactions
The processing of reason system.The preprocess method of above-mentioned two application case is relatively simple, raising and toxicity without reference to biodegradability
Reduction, therefore increase the difficulty and complexity of biochemical treatment, input cost is excessive.
Therefore how pretreatment stage efficiently, stablize, it is economical remove waste water in persistent organic pollutants,
Realize the raising of wastewater biodegradability and the abatement of bio-toxicity be pesticide wastewater treating key.
The prior art has also disclosed relevant application case, and such as China Patent No. CN201010561525.4, publication date is
The application case on May 4th, 2011 discloses the processing method of imidacloprid pesticide wastewater, and the preprocess method of this application is chemistry
The group technology of dephosphorization, Fe-C light electrolysis, Fenton oxidation and catalysis oxidation, it is organic which can effectively reduce waste water
Pollutant concentration, but the method for this application is limited by COD concentration, it is inadequate there are treatment effect when waste water COD is higher
The defects of preferable；COD is excessive after the precipitation water outlet of Fe-C light electrolysis, and such as >=15000mg/L, follow-up Fenton reaction effects are relatively not
It is highest, then needs to dilute by water distribution to reduce and enter Fenton after COD to≤15000mg/L and react, can just makes Fenton anti-
COD removal rates are answered to have greater efficiency；And the method for this application has only counted comprehensive COD indexs, does not count biodegradability
Data are improved, also do not refer to the reduction effect to wastewater biological toxicity.In addition, number of patent application CN201710201176.7, public
Open the application case that day is on July 25th, 2017 and disclose a kind of electrode for handling agricultural chemicals waste water and its preparation and application, this application
The preprocess method of case carries out pesticide using the electrode being made of Titanium base with the metal oxide layer for being covered in Titanium base surface
Wastewater treatment, the metal oxide layer are made of platinum oxide, tin oxide and antimony oxide, can be had using the method for this application
Effect reduces waste water COD and improves wastewater biodegradability, but does not refer to the effect that bio-toxicity is cut down, and electrode material requirement
It is high, cost of investment is added to a certain extent, and large-scale engineeringization is larger using difficulty.
The wastewater treatment method announced in the prior art is varied, but is directed to the highly concentrated high poison of agricultural chemicals waste water
Feature, it is how high in COD value of waste water, under conditions of organism kinds are extremely complex, toxicity is larger, it can still make waste water
Processing reaches preferable effect, it is necessary to solve the above problems in pretreatment stage, so as to provide bigger for subsequent biochemical processing
Facility.Therefore, based on prior art the defects of, there is an urgent need for develop a kind of new organic dirt of removal that can efficiently, stable, economic
Contaminate thing, the preprocess method for improving wastewater biodegradability, effectively cutting down wastewater biological toxicity.
The content of the invention
1. to solve the problems, such as
For effect is undesirable existing for existing highly concentrated high-toxic pesticide Wastewater Pretreatment, handle out water unstable, cannot
The stabilization of subsequent biochemical unit is effectively ensured, the problems such as operating cost is high, the present invention is intended to provide a kind of highly concentrated high-toxic pesticide gives up
The pretreatment integrated processing method of water and its application.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
The present invention provides a kind of integrated preprocess method of highly concentrated high-toxic pesticide waste water, the method makes waste water pass through successively
Cross the oxidation of Fenton fluid bed, flocculation sediment, O3 catalytic oxidation, reduction by catalytic iron step process.
As further improvement of the present invention, the method further includes the pH adjusting steps before Fenton fluid bed oxidation step
Suddenly.
As further improvement of the present invention, the COD value of the highly concentrated high-toxic pesticide waste water for 25000~
40000mg/L。
It is anti-using Fenton fluid bed in the Fenton fluid bed oxidation step as further improvement of the present invention
Device is answered to be handled, carrier is quartz sand in reactor, the filling rate 15~30% of the quartz sand.
As further improvement of the present invention, in the Fenton fluid bed oxidation step, hydraulic detention time is controlled
For 2~4h.
As further improvement of the present invention, in the Fenton fluid bed oxidation step, it is sub- to add hydrogen peroxide, sulfuric acid
Ferrous solution carries out Fenton oxidation processing, hydrogen peroxide and Fe in ferrous sulfate solution2+Molar ratio be 20~(30：1).
As further improvement of the present invention, in the O3 catalytic oxidation step, by catalysis ozone inside reactor
Bio-sil metal oxide supporting catalyst is loaded, the filling rate of the catalyst is 30%~50%.
As further improvement of the present invention, 1~2h of hydraulic detention time is controlled in the reduction by catalytic iron step；Urge
Change iron reduction bottom of pond portion by the way of air stirring, it is 5.0~10.0L/min to control aeration intensity in reduction by catalytic iron pond.
As further improvement of the present invention, the described method comprises the following steps：
Step 1), pH are adjusted：The pH value of waste water is adjusted to 4.0~5.0；
Step 2), the oxidation of Fenton fluid bed：Waste water after step 1) processing is introduced into Fenton fluidized-bed reactor, is added double
Oxygen water, ferrous sulfate solution carry out Fenton oxidation processing, water outlet after processing；
Step 3), flocculation sediment：Water outlet introducing flocculation sedimentation tank after step 2) is handled, adjusting wastewater pH to 7.5~
9.5, then add polyacrylamide and carry out flocculation precipitation reaction, water outlet is separated with precipitation after the flocculation precipitation reaction；
Step 4), O3 catalytic oxidation：Water outlet after step 3) processing is introduced into catalysis ozone reactor, carries out ozone oxidation
Processing, water outlet after processing；
Step 5), reduction by catalytic iron：Water outlet after step 4) processing is introduced into reduction by catalytic iron pond and carries out reduction treatment.
As further improvement of the present invention, the method is applied to highly concentrated high-toxic pesticide Wastewater Pretreatment field.
3. beneficial effect
Compared with the prior art, beneficial effects of the present invention are：
(1) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, is directed to highly concentrated high-toxic pesticide waste water tool
The features such as some COD values is high, hard-degraded substance is more, toxicity is big, make waste water pass through successively the oxidation of Fenton fluid bed, flocculation sediment,
O3 catalytic oxidation, reduction by catalytic iron method are pre-processed, and synergistic effect is produced between each step, is not only significantly improved
Wastewater biodegradability, also makes wastewater toxicity significantly cut down；So as to overcome in the prior art using micro-electrolysis method, advanced oxidation
Method, light electrolysis+advanced oxidation processes the problem of effect is undesirable when materilization freatment method is handled, utilize the method processing of the present invention
Stable water outlet meets subsequent biochemical processing requirement afterwards, provides a great convenience for subsequent biochemical processing, is combined with biochemical treatment
Processing water outlet can stably reach national grade one discharge standard；
(2) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, according to waste water characteristic, first from difficult degradation
Organic matter is more, the characteristic of species complexity is started with, strong using the non-selectivity of Fenton fluid bed oxidation processes, oxidative degradation ability
Feature acts on the hardly degraded organic substance in waste water first, a large amount of hardly degraded organic substances in waste water is significantly cut down, profit
A large amount of suspended particles of generation are removed with flocculation sediment effect, further reduce COD value；Made again using O3 catalytic oxidation
With specific aim processing is carried out, a large amount of macromolecular or heterocyclic material open loop chain ruptures are small molecule, and wastewater biodegradability improves, biology
Toxicity is effectively cut down；Wastewater biodegradability finally is further improved using reduction by catalytic iron effect, while is significantly cut down
Wastewater biological toxicity, final outflow water biodegradability significantly improves, waste water Poisoning substantially reduces, will suitable for biochemical system processing
Ask, which improves the impact resistance of subsequent biochemical processing；
(3) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, using Fenton fluid bed oxidation processes, wadding
Retrogradation shallow lake, O3 catalytic oxidation, the built-up sequence of reduction by catalytic iron, carry out multistep treatment, effectively after the oxidation of Fenton fluid bed
Avoid the H for carrying out being launched during Fenton fluid bed oxidation processes2O2The Antimicrobial produced to subsequent biochemical processing acts on, and is
Subsequent biochemical processing provides facility；
(4) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, not only solves highly concentrated high-toxic pesticide and gives up
The problem of the highly concentrated of water, high poison, poor biodegradability, stable water outlet meets the requirement of subsequent biochemical processing, and pre-processes water outlet
Low concentration ferrous ion containing nascent state, low concentration ferrous ion can be improved micro- in subsequent biochemical system by biological enzymatic
Bioactivity, while improve the flocculability of sludge；Therefore it can further improve subsequent biochemical using the preprocess method of the present invention
Treatment effeciency；
(5) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, is aoxidized using Fenton oxidation fluid bed and carried on a shoulder pole
The heterocatalysis effect for the ferriferous oxide that body surface face is formed, can effectively improve medicament utilization rate, at the same fluidized state increase it is useless
Surface area between water and catalyst, improves chemical oxidation efficiency, the removal effect highly significant of wastewater through organic matter, the present invention
Method can reduce added amount of chemical and sludge yield, operating cost is greatly lowered；
(6) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, is aoxidized using Bio-sil carried metal
Thing catalyst is as the catalyst in O3 catalytic oxidation method, and the reactive metal oxides are nickel, titanium, the metal oxygen of platinum
Compound, it can significantly improve the effective rate of utilization of ozone, will effectively can just divide greatly in room temperature with stronger catalytic capability
A variety of persistent organic pollutants open loop chain ruptures such as son, significantly improve wastewater biodegradability；Ozone dosage in the reaction process
Reduce, catalyst recycling, further reduces operating cost；
(7) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, is spent with iron plane in reduction by catalytic iron step
Electroless copper obtains efficient catalysis material composition packed bed, carries out wastewater reduction reaction, reaction condition is gentle, easy to operate；
Copper facing iron plane flower preparation method is simple, and input cost is relatively low；Waste material of the iron plane flower as mechanical processing factory, therefore the side of the present invention
Method can make waste material get utilization while wastewater treatment is carried out；
(8) the integrated preprocess method of highly concentrated high-toxic pesticide waste water of the invention, preprocess method is stable, it is reliable,
Expense is low, and is easily achieved, is easy to operate, is with a wide range of applications in terms of highly concentrated high-toxic pesticide Wastewater Pretreatment.
Embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The highly concentrated initial COD value of high poison waste water of certain pesticide producing enterprise is 25000mg/L, and pH value is 6.0~8.0；Utilize this
It is as follows that the method for invention carries out waste water treatment step：
1) pH is adjusted：Sulfuric acid is added into the highly concentrated high poison waste water and adjusts pH value of waste water to 4.0~5.0；
2) Fenton fluid bed aoxidizes：Make step 1) handle after waste water enter Fenton fluidized-bed reactor, in the reactor
Carrier is quartz sand, the quartz sand carrier particle diameter about 0.5mm, and the admission space of the quartz sand is 15%；H2O2According to dioxygen
Water (counts) ratio as 1 with COD using mg/L：4 ratio adds；Fe2+By hydrogen peroxide and Fe2+Molar ratio be 20：1 ratio is thrown
Add；It is 2h to control hydraulic detention time；
3) flocculation sediment：The waste water feeding lime after step 1) processing is set to adjust pH value of waste water to 7.5~9.5, Ran Houzai
Add polyacrylamide and carry out flocculation reaction, polyacrylamide dosage is 5mg/L, sedimentation time 1.5h；
4) O3 catalytic oxidation：Flocculation sediment water outlet enters catalysis ozone reactor, and catalyst filling rate is 30%；Ozone
Dosage is 20mg/L；It is 1.0h to control hydraulic detention time.The catalyst is the metal oxide-loaded catalysis of Bio-sil
Agent, the large aperture Bio-sil in the catalyst as carrier loaded active metal component, reactive metal oxides are nickel,
The metal oxide of titanium, platinum, the reactive metal oxides are stronger relative to the metal oxide oxidation catalyst oxidability of manganese, copper, iron.
5) reduction by catalytic iron：O3 catalytic oxidation water outlet enters reduction by catalytic iron pond, is filled out in the reduction by catalytic iron pond
Expect to spend for copper facing iron plane, copper facing rate is 0.15% (mass ratio), and the preparation method of the copper facing iron plane flower is：According to copper-plated matter
Amount is placed in prepared copper-bath than preparing copper-bath, by iron plane flower and carries out chemical substituting plating copper reaction, reaction
1.0h, surveys the remaining copper ion in solution by atomic absorption spectrophotometry, does not detect copper ion and then shown copper facing process
Complete.Bulk density of the copper facing iron plane flower in reduction by catalytic iron pond is 0.3t/m3, when the reaction of reduction by catalytic iron pond stops
Between be 1.5h, consumption of every 3 months supplements；Aeration intensity 5.0L/min is controlled in operational process；Reduction by catalytic iron processing
Water outlet reaches national grade one discharge standard through subsequent biochemical processing stable water outlet.
Table 1 is the wastewater treatment result of the present embodiment 1.
1 embodiment of table, 1 wastewater treatment result
As shown in Table 1, after the embodiment waste water is processed by the invention, COD value of waste water is down to 8500mg/L by 25000mg/L
Hereinafter, COD total removal rates are up to more than 66%；B/C is COD/BOD5, the biodegradability of waste water is represented, by the present embodiment
After method processing, waste water B/C is promoted to 0.3 wastewater biodegradability indicated above by 0 and effectively improves.
EC50,48h (V/V, %)The acute toxicity index of waste water is represented, is test organism measure waste water acute toxicity with zebra fish,
EC50,48h (%, V/V)When representing that zebra fish death toll is half in 48h, the percentage of wastewater volume, poison can be illustrated more than 50%
Property by abatement to can tolerance range.After the method processing of the present embodiment, EC50,48h (V/V, %)By 0 be promoted to 68.5% with
On, show that wastewater biological toxicity is effectively cut down.
Embodiment 2
The highly concentrated initial COD value of high poison waste water of certain pesticide producing enterprise is 35000mg/L, and pH value is 6.0~8.0；Utilize this
It is as follows that the method for invention carries out waste water treatment step：
1) pH is adjusted：Add sulfuric acid and adjust wastewater pH to 4.0~5.0；
2) Fenton fluid bed aoxidizes：After waste water adjusts pH, into Fenton fluidized-bed reactor, carrier quartz sand in reactor
Loaded by 20%, hydrogen peroxide is by hydrogen peroxide and COD (based on mg/L) ratios as 1：5 add, Fe2+By hydrogen peroxide and Fe2+Mole
Than for 25：1 adds；It is 3h to control hydraulic detention time；
3) flocculation sediment：After Fenton oxidation processing, feeding lime adjusts wastewater pH to 7.5~9.5, then adds poly- third again
Acrylamide carries out flocculation reaction, and polyacrylamide dosage is 10mg/L, sedimentation time 2.0h；
4) O3 catalytic oxidation：Flocculation sediment water outlet enters catalysis ozone reactor, and Bio-sil is metal oxide-loaded
Catalyst filling rate is 40%；Ozone dosage is 40mg/L；It is 1.5h to control hydraulic detention time；
5) reduction by catalytic iron：O3 catalytic oxidation water outlet enters reduction by catalytic iron pond, and filler is spent for copper facing iron plane in pond, plating
Copper rate 0.25% (mass ratio), bulk density of the copper facing iron plane flower in reduction by catalytic iron pond are 0.45t/m3, catalytic iron
Reduction pond reaction time is 1h, supplements a consumption within every 3 months；Aeration intensity 7.0L/min is controlled in operational process,
Reduction by catalytic iron handles water outlet and reaches national grade one discharge standard through subsequent biochemical processing stable water outlet.
Table 2 is the wastewater treatment result of the present embodiment 2.
2 embodiment of table, 2 wastewater treatment result
As shown in Table 2, waste water through should embodiment method processing after, COD value of waste water is down to by 35000mg/L
Below 10100mg/L, COD total removal rate are up to more than 71%；Waste water B/C is promoted to more than 0.3 by 0, shows that waste water is biochemical
Property effectively improves；EC50,48h (V/V, %)More than 65.3% is promoted to by 0, shows that wastewater biological toxicity is effectively cut down.
Embodiment 3
The highly concentrated initial COD value of high poison waste water of certain pesticide producing enterprise is 40000mg/L, and pH value is 6.0~8.0；Using this
Inventive method carries out comprising the following steps that for Wastewater Pretreatment：
1) pH is adjusted：Add sulfuric acid and adjust wastewater pH to 4.0~5.0；
2) Fenton fluid bed aoxidizes：After waste water adjusts pH, into Fenton fluidized-bed reactor, carrier quartz sand in reactor
Loaded by 30%；H2O2Dosage is by hydrogen peroxide and COD (based on mg/L) ratios as 1:6 add, Fe2+By hydrogen peroxide and Fe2+'s
Molar ratio is 30：1 adds；It is 4h to control hydraulic detention time；
3) flocculation sediment：After Fenton oxidation processing, feeding lime adjusts wastewater pH to 7.5~9.5, then adds poly- third again
Acrylamide carries out flocculation reaction, and polyacrylamide dosage is 10mg/L, sedimentation time 2.0h；
4) O3 catalytic oxidation：Flocculation sediment water outlet enters catalysis ozone reactor, and Bio-sil is metal oxide-loaded
Catalyst filling rate is 50%；Ozone dosage is 50mg/L；It is 2.0h to control hydraulic detention time；
5) reduction by catalytic iron：O3 catalytic oxidation water outlet enters reduction by catalytic iron pond, and filler is spent for copper facing iron plane in pond, plating
Copper rate 0.30% (mass ratio), bulk density of the copper facing iron plane flower in reduction by catalytic iron pond are 0.50t/m3, catalytic iron
Reduction pond reaction time is 2h, supplements a consumption within every 3 months；Aeration intensity 10.0L/min is controlled in operational process,
Reduction by catalytic iron handles water outlet and reaches national grade one discharge standard through subsequent biochemical processing stable water outlet, and table 3 is useless for the present embodiment 3
Water process result.
3 embodiment of table, 3 wastewater treatment result
As shown in Table 3, waste water through should embodiment method processing after, COD value of waste water is down to by 40000mg/L
Below 11800mg/L, COD total removal rate are up to more than 70%；Waste water B/C is promoted to more than 0.3 by 0, shows that waste water is biochemical
Property effectively improves；EC50,48h (V/V, %)More than 70.4% is promoted to by 0, shows that wastewater biological toxicity is effectively cut down.
Schematically the present invention and embodiments thereof are described above, the description is not restricted.So if
Those of ordinary skill in the art are enlightened by it, without departing from the spirit of the invention, are not inventively designed
Go out the frame mode similar to the technical solution and embodiment, be within the scope of protection of the invention.
Claims (10)
- A kind of 1. integrated preprocess method of highly concentrated high-toxic pesticide waste water, it is characterised in that：The method makes waste water pass through successively The oxidation of Fenton fluid bed, flocculation sediment, O3 catalytic oxidation, reduction by catalytic iron step process.
- 2. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 1, it is characterised in that：The method Further include the procedure of pH adjustment before Fenton fluid bed oxidation step.
- 3. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 1 or 2, it is characterised in that：It is described The COD value of highly concentrated high-toxic pesticide waste water be 25000~40000mg/L.
- 4. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 1 or 2, it is characterised in that：It is described Fenton fluid bed oxidation step in, handled using Fenton fluidized-bed reactor, carrier is quartz sand in reactor, described The filling rate 15~30% of quartz sand.
- 5. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 4, it is characterised in that：The sweet smell Pause in fluid bed oxidation step, it is 2~4h to control hydraulic detention time.
- 6. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 1 or 5, it is characterised in that：It is described Fenton fluid bed oxidation step in, add hydrogen peroxide, ferrous sulfate solution carries out Fenton oxidation processing, hydrogen peroxide and sulfuric acid are sub- Fe in ferrous solution2+Molar ratio be 20~(30：1).
- 7. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 6, it is characterised in that：The catalysis In ozone oxidation step, catalysis ozone inside reactor is loaded into Bio-sil metal oxide supporting catalyst, the catalysis The filling rate of agent is 30%~50%.
- 8. the integrated preprocess method of the highly concentrated high-toxic pesticide waste water according to claim 1 or 7, it is characterised in that：It is described 1~2h of hydraulic detention time is controlled in reduction by catalytic iron step；Reduction by catalytic iron bottom of pond portion is by the way of air stirring, control Aeration intensity is 5.0~10.0L/min in reduction by catalytic iron pond.
- 9. the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 3, it is characterised in that：Including following Step：Step 1), pH are adjusted：The pH value of waste water is adjusted to 4.0~5.0；Step 2), the oxidation of Fenton fluid bed：Waste water after step 1) processing is introduced into Fenton fluidized-bed reactor, adds dioxygen Water, ferrous sulfate solution carry out Fenton oxidation processing, water outlet after processing；Step 3), flocculation sediment：Water outlet after step 2) processing is introduced into flocculation sedimentation tank, adjusts wastewater pH to 7.5~9.5, then Add polyacrylamide and carry out flocculation precipitation reaction, separate water outlet with precipitation after the flocculation precipitation reaction；Step 4), O3 catalytic oxidation：Water outlet after step 3) processing is introduced into catalysis ozone reactor, is carried out at ozone oxidation Reason, water outlet after processing；Step 5), reduction by catalytic iron：Water outlet after step 4) processing is introduced into reduction by catalytic iron pond and carries out reduction treatment.
- 10. the application of the integrated preprocess method of highly concentrated high-toxic pesticide waste water according to claim 1, it is characterised in that： The method is applied to highly concentrated high-toxic pesticide Wastewater Pretreatment field.
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