CN106927574A - A kind of methods and applications of the drowned flow artificial wet land containing natural minerals and its treatment glyphosate waste water - Google Patents
A kind of methods and applications of the drowned flow artificial wet land containing natural minerals and its treatment glyphosate waste water Download PDFInfo
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- CN106927574A CN106927574A CN201710251715.8A CN201710251715A CN106927574A CN 106927574 A CN106927574 A CN 106927574A CN 201710251715 A CN201710251715 A CN 201710251715A CN 106927574 A CN106927574 A CN 106927574A
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- Prior art keywords
- glyphosate
- waste water
- wet land
- treatment
- drowned flow
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 82
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 82
- 239000002351 wastewater Substances 0.000 title claims abstract description 35
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 17
- 239000011707 mineral Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052742 iron Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000012856 packing Methods 0.000 claims abstract description 31
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004927 clay Substances 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 27
- 239000011574 phosphorus Substances 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002689 soil Substances 0.000 claims description 18
- 239000006028 limestone Substances 0.000 claims description 14
- 235000019738 Limestone Nutrition 0.000 claims description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 11
- 235000014676 Phragmites communis Nutrition 0.000 claims description 8
- 239000003987 organophosphate pesticide Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 235000009508 confectionery Nutrition 0.000 claims description 5
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- HPNWUXSHPAXNKY-UHFFFAOYSA-N 2-(phosphonomethylamino)acetic acid;hydrate Chemical compound O.OC(=O)CNCP(O)(O)=O HPNWUXSHPAXNKY-UHFFFAOYSA-N 0.000 claims description 2
- 241001509286 Thiobacillus denitrificans Species 0.000 claims description 2
- 239000003905 agrochemical Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 239000000575 pesticide Substances 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000005842 biochemical reaction Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000008635 plant growth Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 244000005700 microbiome Species 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 241000276438 Gadus morhua Species 0.000 description 8
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 8
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- -1 water inlet Area Chemical compound 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 125000005499 phosphonyl group Chemical group 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 230000001651 autotrophic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 229910052952 pyrrhotite Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000292693 Poa annua Species 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Micro-Organisms Or Cultivation Processes Thereof (AREA)
Abstract
The invention discloses a kind of drowned flow artificial wet land containing natural minerals and its methods and applications for the treatment of glyphosate waste water, belong to water treatment field.The artificial swamp belongs to drowned flow artificial wet land, and packing area is using a certain proportion of natural magnetic iron ore filling, clay of the top filling for plant growth.The artificial swamp can remove the glyphosate pesticide in water body by the chemical action of the absorption of natural troilite and biochemical reaction product, and the Phos produced after glyphosate pesticide is decomposed in wetland can be simultaneously removed, with organic and Phos the effect of synchronous removal.At the same time also there is the deep purifying effect of certain COD, ammonia nitrogen and total nitrogen.The invention has convenient management, and low cost, the advantage of the recycling of natural crystal, application prospect is extensive.
Description
Technical field
The invention belongs to water treatment field, more specifically to a kind of drowned flow artificial wet land containing natural minerals and
The methods and applications of its treatment glyphosate waste water.
Background technology
Artificial swamp is typical ecological purification method, is a kind of wet land system by manually building and regulate and control, by it
The optimum organization of physics in the ecosystem, chemistry and biological agent carries out sewage disposal, and it has sustainability, and pollutant goes
Except effect is high, and can beautify the environment.
The principal mode of artificial swamp is surface current artificial wetland, and underflow type artificial wet land, surface current artificial wetland is easy
Mosquitos and flies and stench are produced, and the environment friendly of underflow type artificial wet land is more preferably, its biological adsorption, biodegradation can be very
Good organics removal, and the sedimentation and suction-operated inside wetland can remove Phos.And it is natural good in artificial swamp
The alternate environment of oxygen and anaerobism can effectively organics removal decompose after produce inorganic nitrogen and small organic molecule.
The minimizing technology of existing glyphosate includes biochemical treatment process, coagulant sedimentation, and advanced oxidation processes etc..But
Coagulant sedimentation can produce substantial amounts of sludge, improve processing cost；The oxidant cost of advanced oxidation processes is high, reaction condition control
System is strict；Although biochemical process can remove glyphosate, it is necessary to further in its water outlet or containing substantial amounts of inorganic nitrogen phosphorus
Subsequent treatment.
The A of Chinese patent application Publication No. CN 104058516, the applying date is the patent application text on May 30th, 2014
Part discloses a kind of processing method of the phosphorus-containing wastewater produced in glyphosate production process, employs Ca-Ti ore type nanometer LaFeO3
Rare earth complex chemical compound applies to photocatalysis treatment glyphosate waste water containing phosphine, after first step photocatalysis treatment as catalyst
Waste water add flocculant flocculation treatment, reach below 20mg/L by the total phosphorus content of the waste water after the treatment of 2 steps, but the invention
In catalyst synthesis high cost, and coagulating treatment produce a large amount of sludge more improve processing cost, practicality is not strong.
Chinese Patent Application No. is 201210502501.0, and the applying date is that the patent application document on November 30th, 2012 is public
The artificial swamp that a kind of utilization mineral process low carbon-nitrogen ratio sewage is opened, the invention includes water inlet pipe, inhalant region, exhalant region and goes out
Water pipe, water inlet pipe is connected with inhalant region；Outlet pipe is connected with exhalant region；Also include water distributing area, soil horizon and packing area, water inlet
Area, water distributing area, packing area and exhalant region are sequentially connected；Inhalant region is filled with lime stone；Packing area inside filled with pyrite and
Lime stone；The top of packing area is soil horizon.Above-mentioned patent is processed just for Phos, is not applied to organic nitrogen
The treatment of phosphorus.
Chinese Patent Application No. is 201310695460.6, and the applying date is that the patent application document on December 17th, 2013 is public
The step of a kind of method opened natural magnetic iron ore biofilter and nitrate nitrogen and phosphorus in water removal are removed using its synchronization, its method
For：(1) bio-filter stuffing is prepared and built；(2) startup of biofilter；(3) operation of biofilter；It utilizes sulphur certainly
Denitrifying bacterium is supported with magnetic iron ore as electron donor, is nitrogen by the reducing nitrate radical in water, go nitrate nitrogen in water removal；Magnetic Huang iron and
Its oxidation product is by the mode dephosphorization such as absorption, chemical precipitation, so as to realize the synchronous nitrate nitrogen gone in water removal and phosphorus.Above-mentioned patent
Processed just for Phos, do not applied to the treatment of organic nitrogen phosphorus.
China does not have the patent processed glyphosate pesticide wastewater using artificial swamp also now.
The content of the invention
1. the problem to be solved
Processing method high cost (physical-chemical process) for existing glyphosate pesticide wastewater, biodegradation cannot be removed
The inorganic nitrogen phosphorus that produces afterwards increased subsequent treatment cost, it is necessary to otherwise processed, and general removal of the artificial swamp for phosphorus
Effect is poor, it is impossible to the problems such as reaching the effect of advanced treating, and it is wet that the present invention provides a kind of drowned flow artificial containing natural minerals
The methods and applications on ground and its treatment glyphosate waste water.
2. technical scheme
In order to solve the above problems, the technical solution adopted in the present invention is as follows：
A kind of drowned flow artificial wet land of waste water of the utilization natural minerals treatment containing organophosphorus pesticide glyphosate, including water inlet
Area, packing area, soil area, exhalant region, described inhalant region, packing area and exhalant region are sequentially connected；Inside described packing area
Filled with magnetic iron ore and lime stone；The top of described packing area is soil horizon；Described soil horizon is filled with clay.
Preferably, the clay of described soil horizon inside filling, the thickness of soil horizon is 20cm.
Preferably, the described magnetic iron ore of packing area inside filling and the ratio of lime stone is 1：1, magnetic iron ore and stone
The particle diameter of lime stone is 20-30mm, and the height of packing area is 0.6-0.7m.
Preferably, planted in described soil horizon and be implanted with water plant, described water plant is reed, reed density is 3-
10 plants/m2。
Preferably, described packing area is provided with delivery port near the bottom of exhalant region.
Preferably, hydraulic detention time is 12-96 hours.
Preferably, being screened from anaerobic activated sludge carries out the denitrogenation sulphur of autotrophic denitrification using the sulphur source in magnetic iron ore
Bacillus is added to packing area as target strain.
The artificial swamp of above-mentioned utilization natural minerals waste water of the treatment containing organophosphorus pesticide glyphosate is in treatment containing organic
Application in phosphorus agricultural chemicals glyphosate waste water, its step is：Glyphosate waste water will be contained and pump into inhalant region, then flowing through packing area will be carried out
Treatment, flows out through the water outlet after treatment from exhalant region, and hydraulic detention time of the waste water in packing area is 12-96 hours.Glyphosate
, in below 50mg/L, in below 5mg/L, COD concentration is in below 100mg/L, and ammonia nitrogen is dense for total phosphorus concentration for waste water glyphosate concentration
, in below 15mg/L, TN concentration is in below 40mg/L for degree.
In existing document report, the effect on driving birds is not good of traditional biological degradation of glyphosate, its basic reason is glyphosate molecule
In phosphonate groups have certain toxic action for microbial degradation glyphosate, be unfavorable for the biodegradation of glyphosate.This
The ground of innovation and creation make use of magnetic iron ore to the adsorption capacity of phosphonyl group in glyphosate molecule, and phosphonate groups are hidden
In Surface of Pyrrhotite, and it is readily able to biodegradable primary amino radical and carboxyl exposure so that microorganism is easier to drop glyphosate
It is inorganic nitrogen phosphorus to solve, and thus fully solves negative effect of the phosphonate groups to microbial degradation；And applicant is in reality
The ability for finding troilite absorption glyphosate by adsorption dynamics adsorption kinetics research during testing is better than high temperature in low temperature aging fruit, so
Compensate for that temperature is relatively low when running in the winter time, the deficiency of the decline of glyphosate removal ability caused by microbial activity is not enough；And
To spring and summer, the glyphosate for being adsorbed in troilite surface can this ensures that there people by activity microbial degradation higher
The stabilization of work wetland removal glyphosate operation throughout the year.At the same time, magnetic iron ore artificial swamp has also combined magnetic iron ore to nothing
The coagulating treatment principle of machine phosphorus, synchronously eliminates the Phos that glyphosate and its degraded are produced, and realizes organophosphor and Phos
In the synchronization removal of same processing unit, solving during existing glyphosate removes technique needs biodegradation+coagulating sedimentation two
The problem of level technique, has saved processing cost, simplifies handling process.
Although having suction-operated of the literature research iron-stone to glyphosate at present, not correlative study shows micro-
Whether biology can be by carboxyl and amino degradation of glyphosate, and this is main innovation point of the invention.Final purpose of the invention is not
But independent degradation of glyphosate, in addition it is also necessary to which synchronous degradation glyphosate metabolite inorganic nitrogen phosphorus and a part of COD, this is this area
What technical staff cannot realize easily.Magnetic iron ore is also contemplated that whether plant is suitable for being grown in magnetic Huang for artificial swamp
Iron ore is in the middle of the environment of filler.
Difficult point of the invention：
1. the present invention needs to be fully understood by the biodegradable process of glyphosate, it is thus understood that the phosphonate groups of glyphosate are to micro-
Biodegradable toxic and side effect.
2. the present invention needs to be fully understood by adsorption mechanism of the magnetic iron ore for glyphosate, it is understood that magnetic iron ore is for grass
The sequestration of phosphate groups can effectively improve degradation effect of the microorganism to glyphosate in sweet phosphine molecule.
Above difficult point needs to understand adsorption capacity, troilite artificial swamp heterotrophism anti-nitre of the magnetic iron ore to phosphate radical simultaneously
Change ability, iron-stone dephosphorization ability and underflow type artificial wet land COD removal abilities, therefore the technical program is not readily conceivable that.
1st, according to experiment glyphosate adsorption experiment, it is found that glyphosate adsorption effect is preferably at low temperatures, this discovery
So that can all have preferable removal effect to glyphosate under Different climate temperature conditionss using magnetic iron ore artificial swamp, specifically
Discussion sees above, and has no document report magnetic iron ore absorption glyphosate before this and be subject to the influence situations such as temperature.Artificial swamp is transported
Temperature is the restraining factors of its microbial degradation ability during row, and the present invention well by absorption+it is biodegradable not
This problem is solved with the leading role of time period.
2nd, in adsorption process, often there is competitive Adsorption phenomenon, but in research process of the invention, applicant
It is found surprisingly that in adsorption experiment process, the Phos produced after degraded can promote magnetic iron ore to glyphosate in adsorption process
Absorption, applicant carried out substantial amounts of research to this, finally finds that this is because ion exchange produces iron ion, iron ion water
Solution produces complex compound to glyphosate also with caused by identical adsorption effect.
3rd, glyphosate has certain inhibitory action for microorganism, but the ground of the invention make use of magnetic Huang iron
Ore deposit is hidden in Surface of Pyrrhotite by phosphonate groups to the adsorption capacity of phosphonyl group in glyphosate molecule, and is readily able to life
The primary amino radical of thing degraded and carboxyl exposure so that it is inorganic nitrogen phosphorus that microorganism is easier glyphosate degradation, is thus fully solved
Negative effect of the phosphonate groups of having determined to microbial degradation.
4th, magnetic iron ore is oxidized easily so as to water outlet can mix by by lime stone with certain colourity with magnetic iron ore
Used as filler, regulation water body pH can accelerate the hydrolysis of coloured ferric ion between 6~9 so that water outlet ferric ion
Content is minimized, so as to reduce effluent color dilution.
3. beneficial effect
Compared to prior art, beneficial effects of the present invention are：
(1) packing area of the invention is filled with magnetic iron ore and lime stone, and magnetic iron ore is used as the useless of many minings
Barrow stone, easily produces acidic mine waste water, and the present invention recycles discarded natural crystal, serves resource reclaim and keeps away
Exempt from effect of pollution；
(2) magnetic iron ore Performance of Constructed Wetlands Substrates magnetic iron ore of the invention has certain adsorption effect for glyphosate,
After glyphosate is adsorbed, inorganic nitrogen phosphorus can be broken down into by the biological chemistry action of artificial swamp, and magnetic iron ore
Iron ion in artificial swamp can be as good dephosphorizing coagulant by inorganic phosphorus ligands, and magnetic iron ore is in itself for nothing
Machine phosphorus has certain adsorption effect, therefore with the effect of organophosphor and Phos in synchronous removal waste water, has simplified treatment
Technique and processing cost is saved；
(3) magnetic iron ore artificial swamp of the invention remove glyphosate while, it is also possible to the nitrate nitrogen in waste water,
The pollutants such as ammonia nitrogen, COD are removed because part denitrifying bacteria can using the sulphur in magnetic iron ore as sulphur source,
Autotrophic denitrification removal nitrate nitrogen is carried out, and the well foster region near root system can provide the place of ammonium oxidation, while removal
Ammonia nitrogen and nitrate nitrogen, and COD can be attached to aerobic microbiological near root system and the anaerobic biological decomposition of wetland bottom goes
Remove；
(4) plant of present invention plantation is reed, and it has good tolerance to organophosphorus pesticide, is suitable to having grass sweet
Grown in the environment of phosphine herbicide, and reed has certain absorption for inorganic nitrogen phosphorus, has higher for ammonia nitrogen
Tolerance, these speciality allow the effect of its removal glyphosate for lifting magnetic iron ore-lime stone artificial swamp；
(5) present invention can effectively stop the bulky grain suspension in waste water in the gravel filling of inhalant region laying, reduce
The problem that artificial swamp is blocked because of larger suspended particulate；
(6) present invention successfully solves the inhibitory action of the phosphonate groups to microorganism of glyphosate, improves microorganism
Process the efficiency of glyphosate；
(7) method for generally processing Phos using troilite in the prior art is made using the iron ion of troilite release
It is coagulant, the effect of local coagulating sedimentation is formed in artificial swamp or biofilter, so as to by inorganic phosphorus ligands；And this
Invention is, using the phosphonyl group in magnetic iron ore absorption glyphosate molecule, to recycle the microorganism in artificial swamp by glyphosate
Primary amino radical not to be adsorbed is degraded with carboxyl in molecule, ultimately generates Phos, and principle between the two is different；
(8) microorganism in the present invention in packing layer comes from original microorganism, nature in artificial swamp natural environment
In there is multiple-microorganism glyphosate degradation can be tamed and dociled by being constantly passed through the waste water containing glyphosate in artificial swamp
Change, the domestication time is three months.
Brief description of the drawings
Fig. 1 is the removal effect figure of glyphosate of the present invention；
Fig. 2 is the removal effect figure of total phosphorus in the present invention.
Specific embodiment
The present invention is further described below with reference to specific embodiment.
Embodiment 1
A kind of utilization natural minerals process the artificial swamp containing organophosphorus pesticide glyphosate waste water, including inhalant region, fill out
Material area, soil horizon and exhalant region, inhalant region, packing area and exhalant region are sequentially connected.Packing area inside filled with magnetic iron ore and
Lime stone；The top of packing area is soil horizon；Soil horizon is filled with clay, and packing area is provided with water outlet near the bottom of exhalant region
Mouthful.
Artificial swamp width 1m, wherein overall length 5.7m, 1.5m high, filler section length are 3.3m.It is overall to be formed using brick,
Bottom uses concrete bed, and wall and bottom all use waterproof material and coating, prevent wetland leak.Packing area filler is used
Natural magnetic iron ore and lime stone mixing, its ratio are about 1:1.Magnetic iron ore and limestone particle size are filler between 20-30mm
Area's packing course is highly 0.7m；Clay and gravel mixed zone thickness are 0.2cm；Height of water level is 0.7m in wetland；Planted in soil horizon 4
Water plant reed is implanted with, planting density is 10 plants/m2。
Waste water is pumped into wetland inhalant region, Pollutants in Wastewater concentration is 25~30mg/L of glyphosate or so, total phosphorus concentration
For 5mg/L or so, total nitrogen concentration are 20mg/L or so, ammonia nitrogen is in below 15mg/L, COD in below 80mg/L.Waste water is in wetland
In hydraulic detention time be 24h, continuous operation 10 months.The removal effect of its glyphosate and total phosphorus such as accompanying drawing 1, accompanying drawing 2, its
Remaining pollutant, TN, ammonia nitrogen, nitrate nitrogen, COD removal effects such as table 1.
Artificial swamp is annual to be respectively provided with preferable removal effect for glyphosate, and the clearance of glyphosate and total phosphorus can
More than 85% is reached, wherein winter average removal rate is also 82% or so.Water outlet total phosphorus can be less than 0.5mg/L, part-time
The aqueous concentration of interior total phosphorus is less than 0.3mg/L.Total phosphorus contains the other phosphorus in the total phosphorus and water body of glyphosate offer, water outlet
Glyphosate mean concentration is 2.5mg/L.At the same time, the nitrate nitrogen in artificial swamp, ammonia nitrogen and COD are obtained for a certain degree
Removal, specific removal effect is shown in Table 1.
The artificial swamp of table 1 is simultaneously to other pollutants removal rate effects
Embodiment 2
With embodiment 1, unlike：The height of packing area is 0.6m, and reed density is 3 plants/m2, the hydraulic retention of use
Time is 60 hours.Change the hydraulic detention time of artificial swamp, sampled after stable operation one week, rear continuous sampling one month
Carry out glyphosate and total phosphorus yield.
According to experimental result, artificial swamp is not decreased obviously for glyphosate clearance and total tp removal rate, winter grass
Sweet phosphine clearance can reach more than 85%, and summer glyphosate clearance reaches more than 95%, and water outlet glyphosate concentration stabilization is in 2-
5mg/L, water outlet total phosphorus concentration stabilization is in below 0.5mg/L.Magnetic iron ore artificial swamp is for other pollution factor removal effects
As shown in table 2.
The artificial swamp of table 2 is simultaneously to other pollutants removal rate effects
High-strength glyphosate does not produce influence to thiobacillus denitrificans degradation of glyphosate.
Embodiment 3
With embodiment 1, the difference is that the hydraulic detention time for using is 40 hours, handled is the river containing glyphosate
Water.River is pumped into storage tank by immersible pump, sewage is passed through by artificial swamp by peristaltic pump.The water inlet glyphosate of river
Concentration is 20mg/L or so, and total phosphorus is 3-5mg/L, and total nitrogen concentration is 20mg/L or so.The artificial swamp residence time is 40 hours,
Its removal effect, different pollutant removals such as table 3 is measured by sampling within stable latter continuous one week.
Removal effect of the artificial wetland treatment of table 3 by glyphosate polluted river water
Magnetic iron ore artificial swamp has a preferable removal effect for the glyphosate in river and inorganic nitrogen phosphorus, and with
The change of temperature, artificial swamp can maintain more than 80% for the clearance of glyphosate, total phosphorus.Simultaneously, manually
The clearance of wetland total nitrogen can also maintain 59.7%, and the change of glyphosate concentration is not to the anti-nitre of microorganism in artificial swamp
Change effect.
Claims (8)
1. a kind of drowned flow artificial wet land containing natural minerals, is made up of inhalant region, soil horizon, packing area and exhalant region, described
Inhalant region, packing area and exhalant region be sequentially connected；Described packing area inside is filled with magnetic iron ore and lime stone；Described
The top of packing area is soil horizon；Described soil horizon is filled with clay.
2. a kind of drowned flow artificial wet land containing natural minerals according to claim 1, it is characterised in that：Described fills out
The magnetic iron ore of material area inside filling and the ratio of lime stone are 1：1, the particle diameter of magnetic iron ore and lime stone is 20-30mm, is filled out
The height for expecting area is 0.6-0.7m.
3. a kind of drowned flow artificial wet land containing natural minerals according to claim 1, it is characterised in that：Described soil
Earth layer filling clay, the thickness of soil horizon is 20cm；Planted in soil horizon and be implanted with water plant, described water plant is reed,
Reed density is 3-10 plants/m2。
4. a kind of drowned flow artificial wet land containing natural minerals in claim 1-3 described in any one contains organophosphor in treatment
Application in agricultural chemicals glyphosate waste water.
5. a kind of drowned flow artificial wet land containing natural minerals described in claim 4 is in treatment glyphosate containing organophosphorus pesticide
Application in waste water, its step is：Glyphosate waste water will be contained and pump into inhalant region, and then flowed through packing area and processed, through treatment
Water outlet afterwards is flowed out from exhalant region, and hydraulic detention time of the waste water in packing area is 12-96 hours.
6. a kind of drowned flow artificial wet land containing natural minerals according to claim 5 is sweet in treatment grass containing organophosphorus pesticide
Application in phosphine waste water, it is characterised in that：, in below 50mg/L, total phosphorus concentration is in 5mg/L for glyphosate waste water glyphosate concentration
Hereinafter, in below 100mg/L, in below 15mg/L, TN concentration is in below 40mg/L for ammonia nitrogen concentration for COD concentration.
7. a kind of drowned flow artificial wet land containing natural minerals according to claim 5 or 6 contains organophosphorus pesticide in treatment
Application in glyphosate waste water, it is characterised in that：The pH value of glyphosate waste water is adjusted between 6~9 in treatment.
8. a kind of drowned flow artificial wet land containing natural minerals according to claim 5 is sweet in treatment grass containing organophosphorus pesticide
Application in phosphine waste water, it is characterised in that：To screen that carry out autotrophy using the sulphur source in magnetic iron ore anti-from anaerobic activated sludge
The thiobacillus denitrificans of nitrification are added to packing area as target strain.
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| CN108862574A (en) * | 2018-06-22 | 2018-11-23 | 河海大学 | Denitrifying artificial wet land system and its sewage denitrification method are cooperateed with based on reduction-state Fe autotrophy/sawdust heterotrophism |
| CN112279377A (en) * | 2020-09-30 | 2021-01-29 | 国河环境研究院(南京)有限公司 | Preparation method of wetland filler for purifying black and odorous water body and water purifying device using filler |
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| CN108862574A (en) * | 2018-06-22 | 2018-11-23 | 河海大学 | Denitrifying artificial wet land system and its sewage denitrification method are cooperateed with based on reduction-state Fe autotrophy/sawdust heterotrophism |
| CN112279377A (en) * | 2020-09-30 | 2021-01-29 | 国河环境研究院(南京)有限公司 | Preparation method of wetland filler for purifying black and odorous water body and water purifying device using filler |
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