CN106395976A - Method and device for treating organophosphorus pesticide wastewater by virtue of photoelectrochemistry synergy based on titanium dioxide nanotube array - Google Patents
Method and device for treating organophosphorus pesticide wastewater by virtue of photoelectrochemistry synergy based on titanium dioxide nanotube array Download PDFInfo
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- CN106395976A CN106395976A CN201610967818.XA CN201610967818A CN106395976A CN 106395976 A CN106395976 A CN 106395976A CN 201610967818 A CN201610967818 A CN 201610967818A CN 106395976 A CN106395976 A CN 106395976A
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- organophosphorus pesticide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003987 organophosphate pesticide Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002351 wastewater Substances 0.000 title claims abstract description 57
- 239000002071 nanotube Substances 0.000 title claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 12
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000005518 electrochemistry Effects 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- -1 hydroxyl radical free radical Chemical class 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003905 agrochemical Substances 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000000575 pesticide Substances 0.000 abstract description 11
- 230000000593 degrading effect Effects 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 5
- 229960004373 acetylcholine Drugs 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 108090000371 Esterases Proteins 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 230000003851 biochemical process Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000001713 cholinergic effect Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 210000005036 nerve Anatomy 0.000 description 2
- 125000005461 organic phosphorous group Chemical group 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- 102000003914 Cholinesterases Human genes 0.000 description 1
- 108090000322 Cholinesterases Proteins 0.000 description 1
- 206010015958 Eye pain Diseases 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 102000003797 Neuropeptides Human genes 0.000 description 1
- 108090000189 Neuropeptides Proteins 0.000 description 1
- 101710138657 Neurotoxin Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229940048961 cholinesterase Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007831 electrophysiology Effects 0.000 description 1
- 238000002001 electrophysiology Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 231100000618 neurotoxin Toxicity 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003986 organophosphate insecticide Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009870 specific binding Effects 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method and a device for treating organophosphorus pesticide wastewater by virtue of photoelectrochemistry synergy based on a titanium dioxide nanotube array. According to the method, a titanium dioxide nanotube array anode plate with a photocatalysis function and titanium as a substrate is taken as an anode, graphite is taken as a cathode, organophosphorus pesticide wastewater is diluted, sodium sulfate is added into the wastewater, the wastewater is introduced into a reaction tank, and the anode generates photoelectrocatalysis under the actions of an electric field and a mercury lamp so as to directly degrade organophosphorus pesticides; and meanwhile, air is blown into the cathode, photoproductions generated by the anode reach the cathode by virtue of an outer circuit to react with oxygen to generate hydrogen peroxide free radicals, hydrogen peroxide or hydroxyl free radicals and the like, and the generated products have strong oxidability and are capable of oxidizing and degrading the organophosphorus pesticides, so that the degrading efficiency of the organophosphorus pesticides is improved. The method is wide in application range and is simultaneously used for treating final wastewater and intermediate wastewater.
Description
Technical field
The invention belongs to technical field of waste water processing, be related to a kind of based on the photoelectric-synergetic of Nano tube array of titanium dioxide at
The method and device of reason organophosphorus pesticide wastewater.
Background technology
Organophosphorus pesticide is due to insecticide that its broad-spectrum high efficacy is that China widely uses, consumption is maximum.Domestic at present have
2000 Yu Jia pesticide producing producers, up to more than 200 ten thousand tons of annual production, the agricultural chemicals waste water of the annual discharge in the whole nation is about 1.5 hundred million tons.By
It is all hypertoxicity material in most organophosphorus pesticides, endanger ecological and human health.The murder by poisoning of organophosphorus pesticide thing
Effect is because phosphate group can form phosphorylated with the hydroxyl reaction on cholinesterase activity center serine in organism
Acetylcholine esterase, thus the activity of inhibitory enzyme.And acetylcholine esterase function in vivo is to decompose internal neurotransmitter second
Phatidylcholine, ensures effective transmission of cholinergic nerve transmitter in central nervous system, participates in the metabolism of neuropeptide, adjusts the work of neuron electro physiology
The dynamic, growth of neurocyte, or even the function of neuranagenesis.If human body has eaten the food containing organic phosphates pesticide residue
Or drink water, organophosphorus insecticide then makes enzyme can not act the effect decomposing acetylcholine, cause group with the specific binding of acetylcholine esterase
Knit middle acetylcholine excessively to accumulate, so that cholinergic nerve is overexcited, the neurotoxin of generation also can cause on body metabolism
Untoward reaction such as ophthalmalgia, stomachache, respiratory disorder, paralysis etc., serious results even in death, must be had before therefore discharging
Effect is processed.The waste water discharged yet with organophosphorus pesticide production process is not only measured greatly, and COD value is high（Up to tens of thousands of mg/
L）, bio-degradable is poor, complicated components, treated organophosphorus pesticide wastewater only accounts for the 70% of total emission volumn at present, and controls
Reason compliance rate only has 1%, and therefore development organophosphorus pesticide wastewater handling process has become the vital task of current environment protection.
The technique processing organophosphorus pesticide wastewater at present mainly has biochemical process, chemical method, Physical and supercritical ultrasonics technology etc., often
Method is mainly biochemical process and chemical method.Although these methods have certain effect to organophosphorus pesticide wastewater, also deposit
In many shortcomings.
Biochemical process is or to be decomposed organophosphorus pesticide assimilation using the metabolism of microorganism, is to process agricultural chemicals waste water the most at present
One of important method.Its shortcoming is to take up an area big, one-time investment height, and growth is affected by environment big, and in biochemical treatment
Before need increase pretreating process, increased its expense.Additionally, containing high concentration difficult for biological degradation in organophosphorus pesticide wastewater
Noxious substance, can destroy cellularity or suppress growth of microorganism.
Chemical method includes the methods such as chemical oxidation, electrochemical oxidation and photochemical catalytic oxidation.Chemical oxidization method is by agriculture
Add oxidant in medicine waste water（Oxygen, hydrogen peroxide or ozone）With catalyst oxidation removal pesticide.The COD clearance of the method
Higher, but its subject matter to be reaction condition more harsh（High temperature, high pressure）, equipment is perishable, and catalyst can not be reused.
Electrocatalytic oxidation treatment technology is to utilize DC Electric Field, using gold such as activated carbon, inert metal and surface-coated lead oxide
The inert metal belonging to oxide-film is anode, and iron plate is negative electrode, is gone by a series of electrochemical process, chemical reaction or physical process
Organophosphorus pesticide in eliminating water, advantage is that reaction condition is gentle, and method is flexible, but electrode deficient in stability, easily it is passivated, COD goes
Except efficiency is low.Photochemical catalytic oxidation is by throwing in light-sensitive semiconductor material in organophosphorus pesticide wastewater, and light radiation makes partly to lead
Body material surface produces electron-hole pair, and light induced electron can react generation by force with the hydrone of material surface absorption, dissolved oxygen
The hydroxyl radical free radical of oxidisability, hydroxyl radical free radical and photohole can oxygenated organophosphorus pesticide, generate degradable centre
Product or generation mineralising reaction ultimately generate carbon dioxide and water.Photochemical catalytic oxidation is a kind of environmentally friendly technology, has
The wide advantage of process range.But it is easily compound that its subject matter is photo-generate electron-hole, light-sensitive semiconductor material reclaims difficult.
In sum, traditional organophosphorus pesticide wastewater handling process has that intractability is big, the low problem of efficiency is it is impossible to full
The requirement that sufficient organophosphorus pesticide wastewater is processed.Accordingly, it would be desirable to a kind of method processing organophosphorus pesticide wastewater, both can efficiently drop
Solution organophosphorus pesticide, can solve the recovery of catalyst and reusable problem simultaneously again, cost-effective.
Content of the invention
The purpose of the present invention is the weak point overcoming above-mentioned prior art to exist, and provides one kind to be based on nano titania
The Optical Electro-Chemistry of pipe array work in coordination with process organophosphorus pesticide wastewater method and device, by anode photoelectrocatalysiss direct oxidation,
Negative electrode produces the catalytic degradation efficiency that the effect such as hydroxyl radical free radical substantially increases the organophosphorus pesticide to difficult degradation.
The purpose of the present invention is achieved through the following technical solutions：
A kind of device working in coordination with process organophosphorus pesticide wastewater based on the Optical Electro-Chemistry of Nano tube array of titanium dioxide, including reaction
Groove, cover plate, anode, negative electrode, wherein：
The bottom of described reactive tank side is provided with water inlet, and another side roof part is provided with outlet；
Vertically parallel interval it is placed with multiple anodes in described reactive tank, be serially connected and adjacent between multiple anodes
Mercury lamp is installed between anode；
Described anode is the Nano tube array of titanium dioxide anode with titanium as substrate；
The both sides of described anode are respectively arranged with a negative electrode, be serially connected and be vertically arranged with anode between two negative electrodes；
Described negative electrode is graphite cathode；
It is provided with cover plate above described reactive tank, and the cover plate being located above negative electrode is provided with air vent and air inlet pipe.
A kind of method that process organophosphorus pesticide wastewater is worked in coordination with based on the Optical Electro-Chemistry of Nano tube array of titanium dioxide, including
Following steps：
Organophosphorus pesticide wastewater is diluted 50 times, adds sodium sulfate, be filled with reactive tank, open Hg lamp irradiation anode, in anode
And between apply DC voltage, form an Optical Electro-Chemistry catalytic reaction system, under electric field and mercury lamp act on, anode occurs light
Electrocatalysises direct degraded to organophosphorus pesticide；Meanwhile, negative electrode position blasts air, and the light induced electron that anode produces passes through outer
Circuit reaches negative electrode and oxygen and reacts generation Both peroxyl radical（HOO•）, hydrogen peroxide（H2O2）, hydroxyl radical free radical
（OH•）One or more of Deng, produced product has strong oxidizing property, and organophosphorus pesticide is carried out with oxidative degradation, thus
Improve the efficiency to degrading organic phosphor pesticides.
In the present invention, the addition of described sodium sulfate is that every liter of organophosphorus pesticide wastewater adds 1.5 ~ 4.5 grams of sodium sulfate.
In the present invention, the intensity of described mercury lamp is 50 mW/cm2.
In the present invention, the described Nano tube array of titanium dioxide positive plate with titanium as substrate adopts anodizing and calcining
Prepared by method, contain 0.25wt% NH in anodised electrolyte4F and 0.75 wt% H2O-EG solution, oxidation voltage be 20 ~
60 V, anodizing time is 0.5 ~ 10 hour, and titania nanotube length is 1.5 ~ 15 μm, and calcined gas are air or contain
There is the air of 1 ~ 4vol% hydrogen, temperature is 450 ~ 650 DEG C, calcination time is 1 ~ 3h.
In the present invention, described DC voltage is 0.5 ~ 1.2V.
In the present invention, described organophosphorus pesticide wastewater is 0.5 ~ 2 hour in the time of staying of reactive tank.
In the present invention, the know-why processing organophosphorus pesticide wastewater is：
Adopt the Nano tube array of titanium dioxide positive plate using titanium as substrate with photo-catalysis function as anode, graphite is the moon
Pole, produces hole-electron pair when the Nano tube array of titanium dioxide anode surface with titanium as substrate for the light irradiation, outer by applying
Biasing promote hole-electron to separate, stay anode photohole can with direct oxidation degrading organic phosphor pesticides, or
The hydroxide ion reaction on its surface for the oxidation-adsorption generates hydroxyl radical free radical, and hydroxyl radical free radical has very strong oxidability,
Thoroughly oxidative degradation organophosphorus pesticide and its intermediate product can be compared.Light induced electron transfers to graphite cathode by external circuit
React generation superoxide radical with the dissolved oxygen of cathode zone（O2 •-）, then by a series of reaction, including superoxide radical
Be combined the Both peroxyl radical that can generate strong oxidizing property with proton（HOO•）, hydrogen peroxide（H2O2）Or hydroxyl radical free radical
（OH•）Deng these materials all have the activity of very strong oxidative degradation organic pollution, can oxidative degradation organophosphors further
Pesticide and its intermediate product ultimately generate CO2And H2O.Light induced electron and hole participate in the catalytic degradation mistake of organophosphorus pesticide jointly
Journey, thus leading to organophosphorus pesticide and its intermediate product permineralization and being degraded to CO2And H2O.The all degradeds simultaneously of negative and positive two-stage have
Machine phosphorus insecticide, thus improve the degradation efficiency to organophosphorus pesticide wastewater.
The invention has the advantages that：
1）The method that the present invention processes organophosphorus pesticide wastewater is applied widely, is applicable not only to the final waste water of process for producing,
It is equally applicable to middle waste water；
2）The processing equipment treatment effeciency that the present invention provides is high, little power consumption, and operating cost is low；
3）Nano tube array of titanium dioxide anode with titanium as substrate of the present invention is reusable；
4）The processing equipment floor space that the present invention provides is little, and Operation and Maintenance is simple.
Brief description
Fig. 1 is the device that the photoelectric-synergetic based on Nano tube array of titanium dioxide for the present invention processes organophosphorus pesticide wastewater
Front view；
Fig. 2 is the vertical view of the device that the photoelectric-synergetic based on Nano tube array of titanium dioxide for the present invention processes organophosphorus pesticide wastewater
Figure；
Fig. 3 is that the device side of the photoelectric-synergetic process organophosphorus pesticide wastewater based on Nano tube array of titanium dioxide for the present invention regards
Figure；
In figure, 1- reactive tank；2- water inlet；3- anode；4- mercury lamp；5- negative electrode；6- cover plate；7- gas outlet；8- air inlet pipe；9- goes out
The mouth of a river.
Specific embodiment
Below in conjunction with the accompanying drawings technical scheme is further described, but is not limited thereto, every to this
Inventive technique scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should cover
In protection scope of the present invention.
Specific embodiment one：As shown in Fig. 1 ~ 3, photoelectrochemical based on Nano tube array of titanium dioxide in present embodiment
Learn the collaborative device processing organophosphorus pesticide wastewater to be made up of reactive tank 1, cover plate 6, anode 3, negative electrode 5, wherein：
The bottom of described reactive tank 1 side is provided with water inlet 2, and another side roof part is provided with outlet 9；
Vertically be placed with to parallel interval multiple anodes 3 in described reactive tank 1, be serially connected between multiple anodes 3 and
Mercury lamp 4 is installed between adjacent anode 3；
Described anode 3 is the Nano tube array of titanium dioxide anode with titanium as substrate；
The both sides of described anode 3 are respectively arranged with a negative electrode 5, be serially connected and vertical with anode 3 set between two negative electrodes 5
Put；
Described negative electrode 5 is graphite cathode；
It is provided with cover plate 6, the cover plate 6 of negative electrode 5 top is provided with air vent 7 and air inlet pipe 8, air inlet pipe 8 and gas above described reactive tank 1
The exhaust duct of pump is connected, and blasts air, and air vent 7 is used for excluding the gas producing in reactive tank.
Organophosphorus pesticide wastewater is filled with reactive tank 1 by the water inlet 2 of said apparatus, passes through hole, hydroxyl in reactive tank 1
Base free radical, superoxide radical（O2 •-）, Both peroxyl radical（HOO•）Action breaks, specific implementation step is as follows：
1）Organophosphorus pesticide wastewater is diluted 50 times, adds sodium sulfate, be filled with reactive tank, the addition controlling sodium sulfate is every
Rise organophosphorus pesticide wastewater and add 1.5 ~ 4.5 grams of sodium sulfate；
2）Air inlet pipe is connected with the exhaust outlet of air pump, opens air pump；
3）Open mercury lamp, the intensity of mercury lamp is 50 mW/cm2；
4）Open electrochemical workstation, apply between the Nano tube array of titanium dioxide anode with titanium as substrate and graphite cathode
The DC voltage of 0.5 ~ 1.2V, carries out photoelectric-synergetic and processes organophosphorus pesticide wastewater, controls retention time of sewage little 0.5 ~ 2
When.
Specific embodiment two：A certain pesticide producing producer is processed using the method and apparatus described in specific embodiment one
Organophosphorus pesticide comprehensive wastewater, in waste water total phosphorus content be 1837.5mg/L, organic phosphorous content be 1165mg/L.Concrete grammar
As follows：
First by 50 times of wastewater dilution, it is passed through in reactive tank, then carries out photoelectricity oxidative degradation.The volume of reactive tank is 50
ML, applied voltage 1.0V, ultraviolet ray intensity is 50 mW/cm2, add sodium sulfate 1.5g/L, the titanium dioxide with titanium as substrate is received
The area of mitron anode-array is 10 cm2, time of staying 2.5h in photovoltaic reaction system for the waste water, have in processed waste water
Machine phosphorus content is 0.35mg/L, and the degradation rate of organophosphorus pesticide reaches 98.5%.With Nano tube array of titanium dioxide photocatalytic degradation
Organism P wastewater efficiency 20% and Electrocatalysis Degradation efficiency 18% are compared, the catalyzing oxidizing degrading efficiency to organophosphorus pesticide for the present invention
It is significantly improved.The photoelectrocatalysiss stability of the Nano tube array of titanium dioxide anode with titanium as substrate as shown in table 1, can
To see, anode of the present invention has good stability, reusable.
Table 1
Specific embodiment three：A certain pesticide producing manufacturer production is processed using the method and apparatus described in specific embodiment one
During produce organophosphors in the middle of waste water, in waste water total phosphorus content be 2585mg/L, organic phosphorous content be 1135mg/L.Specifically
Method is as follows：
First by 50 times of wastewater dilution, it is passed through in reactive tank, then carries out photoelectricity oxidative degradation.The volume of reactive tank is 50
ML, applied voltage 1.0V, ultraviolet ray intensity is 50 mW/cm2, add sodium sulfate 1.5g/L, the titanium dioxide with titanium as substrate is received
The area of mitron anode-array is 10 cm2, time of staying 2.5h in photovoltaic reaction system for the waste water, have in processed waste water
Machine phosphorus content is 0.23mg/L, and the degradation rate of organophosphorus pesticide reaches 99%.
From specific embodiment two and three as can be seen that the present invention passes through anode photoelectrocatalysiss direct oxidation, negative electrode produces
The effect such as hydroxyl radical free radical substantially increases the catalytic degradation efficiency of the organophosphorus pesticide to difficult degradation.
Claims (8)
1. a kind of device working in coordination with process organophosphorus pesticide wastewater based on the Optical Electro-Chemistry of Nano tube array of titanium dioxide, its feature
It is that described device is made up of reactive tank, cover plate, anode, negative electrode, wherein：
The bottom of described reactive tank side is provided with water inlet, and another side roof part is provided with outlet；
Vertically parallel interval it is placed with multiple anodes in described reactive tank, be serially connected and adjacent between multiple anodes
Mercury lamp is installed between anode；
Described anode is the Nano tube array of titanium dioxide anode with titanium as substrate；
The both sides of described anode are respectively arranged with a negative electrode, be serially connected and be vertically arranged with anode between two negative electrodes；
Described negative electrode is graphite cathode；
It is provided with cover plate above described reactive tank, and the cover plate being located above negative electrode is provided with air vent and air inlet pipe.
2. a kind of Optical Electro-Chemistry based on Nano tube array of titanium dioxide for utilization claim 1 described device is worked in coordination with and is processed organophosphors
The method of agricultural chemicals waste water is it is characterised in that methods described step is as follows：
Organophosphorus pesticide wastewater is diluted 50 times, adds sodium sulfate, be filled with reactive tank, open Hg lamp irradiation anode, in anode
And between apply DC voltage, form an Optical Electro-Chemistry catalytic reaction system, under electric field and mercury lamp act on, anode occurs light
Electrocatalysises direct degraded to organophosphorus pesticide；Meanwhile, negative electrode position blasts air, and the light induced electron that anode produces passes through outer
Circuit is reached negative electrode and is reacted with oxygen, and produced product carries out oxidative degradation to organophosphorus pesticide.
3. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water adds 1.5 ~ 4.5 grams of sodium sulfate it is characterised in that the addition of described sodium sulfate is every liter of organophosphorus pesticide wastewater.
4. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water is it is characterised in that the intensity of described mercury lamp is 50 mW/cm2.
5. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water it is characterised in that the described Nano tube array of titanium dioxide positive plate with titanium as substrate using anodizing with forge
Prepared by firing method, contain 0.25wt% NH in anodised electrolyte4F and 0.75 wt% H2O-EG solution, oxidation voltage is
20 ~ 60 V, oxidization time is 0.5 ~ 10 hour, and titania nanotube length is 1.5 ~ 15 μm, and calcined gas are air or contain
There is the air of 1 ~ 4vol% hydrogen, temperature is 450 ~ 650 DEG C, calcination time is 1 ~ 3h.
6. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water is it is characterised in that described DC voltage is 0.5 ~ 1.2V.
7. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water is it is characterised in that described organophosphorus pesticide wastewater is 0.5 ~ 2 hour in the time of staying of reactive tank.
8. the Optical Electro-Chemistry based on Nano tube array of titanium dioxide according to claim 2 is worked in coordination with process organophosphorus pesticide and is given up
The method of water is it is characterised in that described product is one of Both peroxyl radical, hydrogen peroxide, hydroxyl radical free radical or several
Kind.
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| CN110526484A (en) * | 2019-10-11 | 2019-12-03 | 南京大学 | A kind of organophosphorus pesticide technique for treating industrial wastewater |
| CN111204847A (en) * | 2020-01-10 | 2020-05-29 | 广州大学 | Photoelectrochemistry wastewater recycling device and wastewater treatment method |
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