CN104150567B - A kind of method of electrochemical pre-treatment imidacloprid pesticide wastewater - Google Patents
A kind of method of electrochemical pre-treatment imidacloprid pesticide wastewater Download PDFInfo
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- CN104150567B CN104150567B CN201410245634.3A CN201410245634A CN104150567B CN 104150567 B CN104150567 B CN 104150567B CN 201410245634 A CN201410245634 A CN 201410245634A CN 104150567 B CN104150567 B CN 104150567B
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Abstract
The invention discloses using a kind of method of electrochemical pre-treatment imidacloprid pesticide wastewater.The method prepares tin dioxide coating on titanium antimony cerium iridium electrode by coating thermal decomposition method.By high concentration imidacloprid wastewater by the electrolysis bath with titanio tin ash antimony cerium iridium electrode as anode；Waste water is processed persistently for a period of time under certain electric current density.Titanio tin ash antimony cerium iridium electrode has fabulous stability, and oxygen evolution potential is high, and catalysis oxidation ability is strong.As a result the present invention is shown using the high concentration produced in titanio tin ash antimony cerium iridium electrode pretreatment imidacloprid production process, difficult biochemical waste water：Under the conditions of certain pH, electric current density and process time, imidacloprid pesticide wastewater COD clearances reach more than 50%, BOD/COD and are increased to more than 0.3 from less than 0.1, and biodegradability is greatly improved.The pretreatment of the high-concentration waste water biochemical degradation for being especially suitable for produce in imidacloprid production using the electrochemical oxidation method of titanio tin ash antimony cerium iridium electrode.
Description
Technical field
The present invention relates to a kind of technical method and equipment, which is using the high analysis oxygen electricity of titanio tin ash antimony cerium iridium electrode
The features such as position and extremely strong electrocatalytic oxidation ability, the high salt high-concentration waste water that electrolysis is produced in processing imidacloprid pesticide production.
Belong to green technology and electrochemical field.
Background technology
Imidacloprid (imidacloprid) chemical name 1- (6- chloropyridine -3- pyridylmethyls)-N- nitros are sub-
Imidazolidine -2- base amine, molecular formula C9H10ClN5O2.Structural formula is
Which is mainly used in preventing and treating the sucking pest on the crops such as Oryza sativa L., Semen Tritici aestivi, Cotton Gossypii, such as aphid, leafhopper, Ji
Horse, trialeurodes vaporariorum and colorado potato bug and frit fly etc..Imidacloprid is nitro-methylene-type systemic insecticide, is nicotinic acetylcholine
The acting body of esterase receptor, interference pest movements nervous system make chemical signal transmit failure, no interactions resistance problem.For preventing
Control sucking pest and its resistant strain.Imidacloprid is chloro nicotine insecticide of new generation, with wide spectrum, efficient, low
Poison, low-residual, insect is not likely to produce resistance, the features such as to people, animal, plant and natural enemies security, and have tag, stomach toxicity and interior suction it is many
Weight drug effect, thus be widely used.
Imidacloprid wastewater BOD/COD values are less than 0.1, need just enter biochemical system process Jing after materialized pretreatment.It is Chinese special
It is the chemical dephosphorization that carries out successively, Fe-C micro- that sharp CN102040318A discloses a kind of method of materialized pretreatment imidacloprid wastewater
Electrolysis, then carries out Fenton oxidation and catalysis oxidation respectively；CN103007940A micro ware auxiliary catalysis oxidation processes imidacloprids
The preparation and application of Cu-series catalyst in agricultural chemicals waste water technique.Patent CN200610096785 is reclaimed using resin absorption,
CN101302072B is reclaimed using microfiltration, nanofiltration, reverse osmosiss etc., and CN101921261A is by extracting, being evaporated, crystallizing, filtering, washing
Wash the steps such as precipitation, distillation separation and recovery.These patents are divided into two classes, and a class is oxidative degradation, and its process is complicated, influence factor
It is many；One class is to recycle most of utility, realizes part resource, but still some waste water needs subsequent treatment.
The present invention directly processes imidacloprid wastewater using electrochemical oxidation method, and its advantage is：
1) strong oxidizer need not be used, treatment process is simple, it is only necessary to waste water is placed in into electrolysis bath Inner electrolysis and processes certain
Time；
2) secondary pollution is not produced.Traditional method can produce the secondary pollutions such as solid waste, add Calx after such as Fenton reactions
Molysite deposition etc. that breast is formed, or even technique itself also produces solid waste, the ferrum charcoal residue for such as failing；The catalyst of microwave oxidation gives up
Slag etc..And electrochemical oxidation rule is entirely without secondary pollution；
3) device is simple, technical arrangement plan facility.The main technologic parameters of electrolysis are that control electric current density and waste water exist
The time of staying in electrolysis bath, the adjustment of technological parameter extremely facilitate.
There is titanio tin ash antimony cerium iridium electrode very strong free radical to produce ability and preferable stability, for organic
The degradation capability of waste water is very strong, can greatly increase the clearance of waste water COD.
Although having report of many tin dioxide coating on titanium class application of electrode in terms of wastewater treatment in the past, due to different dirts
Dye substrate has different degradation characteristics, needs selective electrode matching.Sn provided by the present invention:Sb:Ce:
Ir mol ratios are 85-91:5-7:3-6:The titanio tin ash antimony cerium iridium electrode of 1-2 has very high oxygen evolution potential, very strong
The ability and preferable stability of hydroxyl radical free radical are produced, analysis oxygen side reaction is few during degraded, and degradation efficiency is high.The electrode is proved to
With having preferable degradation selectivity ability to the pollutant in imidacloprid pesticide wastewater.Jing is retrieved, there is not yet electrochemistry oxygen
Change method is used for the report for processing imidacloprid wastewater.The method both can be used to pretreatment imidacloprid wastewater raw water, it is also possible to locate
Manage the remaining waste liquid after early stage is reclaimed.
The content of the invention
It is an object of the invention to provide a kind of method of electrochemical pre-treatment imidacloprid pesticide wastewater, the titanium in the method
Base tin ash antimony cerium iridium electrode is prepared using coating-thermal decomposition method.Electrode Titanium base is first with the sulfur of concentration 30%, temperature 60 C
Acid etching 50 minutes, then use Sn:Sb:Ce:Ir=85-91:5-7:3-6:1-2 n-butyl alcohol saline solution coating, be dried after, 500
DEG C thermal oxide 10min, this process are repeated 15 times, and last 500 DEG C of heat treatment 1h are obtained final product.
To solve above-mentioned technical problem, the present invention provides following technical scheme：It is the pH value for adjusting waste water first, then will
High concentration imidacloprid wastewater is passed through the electrolysis bath with titanio tin ash antimony cerium iridium electrode as anode；Finally in certain electric current density
Under make waste water with certain flow velocity pass through electrolysis bath.
Present invention operating procedure specifically in the following order completes titanio tin ash antimony cerium iridium electrode and processes pyrrole worm
The method of quinoline agricultural chemicals waste water：
Step one, adjusts the pH value of imidacloprid wastewater；
Step 2, is made electrolysis bath and imidacloprid wastewater is electrolysed with certain electric current density；
Step 3, makes imidacloprid wastewater under certain electric current density with certain flow velocity and passes through electrolysis bath.
As a kind of preferred version of the method for the invention, the certain pH value wherein described in step one, regulation is referred to
Imidacloprid wastewater pH value is 3～5.
As a kind of preferred version of the method for the invention, the certain electric current density described in step 2, titanio is referred to
The electric current density of tin ash antimony cerium iridium electrode is controlled in 20mA/cm2～50mA/cm2。
Used as a kind of preferred version of the method for the invention, described in step 3, certain flow velocity refers to imidacloprid wastewater
Flow through the flow 0.01-0.3L/min of electrolysis bath.
Used as a kind of preferred version of the method for the invention, electrode of the present invention is using coating-thermal decomposition legal system
It is standby.Its process is：Electrode Titanium base is first with the sulphuric acid acid etching 50 minutes of concentration 30%, temperature 60 C, then uses Sn:Sb:Ce:Ir rubs
You are than being 85-91:5-7:3-6:It is the butanol solution coating of the butter of tin of 1-2, Butter of antimony., cerous nitrate and chloro-iridic acid, dry
After dry, 500 DEG C of oxidation 10min, this process repeat 10-15 time, and last 500 DEG C of thermal decompositions 1h is obtained.The present invention uses titanio two
The high salt high-concentration waste water that tin-antiomony oxide cerium iridium electrode is produced in processing imidacloprid production process, as a result shows：In certain pH
Under value, electric current density and time conditions, the COD clearances of imidacloprid pesticide wastewater reach more than 50%, COD/BOD from being less than
0.1 is increased to more than 0.3.The high salt that titanio tin ash antimony cerium iridium electrode is produced in being especially suitable for processing imidacloprid production is highly concentrated
Degree waste water.
The method of the electrochemical pre-treatment imidacloprid pesticide wastewater that the present invention is provided, can effectively improve imidacloprid wastewater can
Biochemical, while method is easy, device simple is with low cost, suitable to promote.
Description of the drawings
Accompanying drawing 1 is regulating reservoir schematic diagram of the present invention, and accompanying drawing 2 is electrolysis bath schematic diagram.
Specific embodiment
The method of the invention is described in detail with reference to specific embodiment.It should be noted that following examples
Only to illustrate technical scheme and unrestricted, although having carried out specifically to the present invention with reference to preferred embodiment
It is bright, it will be understood by those within the art that, technical scheme can be modified or equivalent, and
Without departing from technical scheme spirit and scope, which all should be covered in scope of the presently claimed invention.
Electrolytic cell assembly as shown in Figure 1, the electrode assemblie in electrolysis bath is core apparatus, by titanio tin ash antimony cerium iridium
Anode and stainless steel cathode composition.The preparation method of anode is first with the sulphuric acid acid etching of concentration 30%, temperature 60 C by Titanium base
50 minutes, then use Sn:Sb:Ce:Ir mol ratios are 85-91:5-7:3-6:The butter of tin of 1-2, Butter of antimony., cerous nitrate and chlorine
After the sour n-butyl alcohol saline solution coating of iridium, drying, 500 DEG C of thermal oxide 10min, this process are repeated 15 times, last 500 DEG C of heat treatments
1h is obtained final product.The size of monolithic titanio tin ash antimony cerium iridium anode is 200mm × 200mm, and monolithic negative electrode is the stainless of equidimension
Steel mesh.Electrolysis bath horizontal positioned, negative electrode and anode are parallel to each other, and are vertically arranged in electrolysis bath.Anode and cathode spacing are 1cm,
It is made up of 20 anodes and 21 negative electrodes altogether.
Electrolysis bath with titanio tin ash antimony cerium iridium electrode as anode is used to process imidacloprid pesticide wastewater.First by height
Concentration imidacloprid pesticide wastewater adds appropriate H in regulating reservoir2SO4Or NaOH is adjusted to suitable pH value.Jing electrolysis baths enter again
Mouth valve injection electrolysis bath (size：Length × width × height=300mm × 450mm × 300mm) in, regulating electrolytic tank electric current density is carried out
Electrooxidation degradation, waste water are discharged from water purifying valve by electrolysis bath with certain flow velocity.
Embodiment 1
Using Sn:Sb:Ce:Ir mol ratios are 85:7:6:2 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 3, and waste water is entered electrolysis bath with the flow velocity Jing inlet valves of 0.05L/min then, and adjusting constant-current dc power supply makes electric current
Density is 30mA/cm2, after before processing, water quality is as follows：
Embodiment 2
Using Sn:Sb:Ce:Ir mol ratios are 87:6:6:1 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 3, and waste water is entered electrolysis bath with the flow velocity Jing inlet valves of 0.2L/min then, and adjusting constant-current dc power supply makes electric current close
Spend for 40mA/cm2, after before processing, water quality is as follows：
Embodiment 3
Using Sn:Sb:Ce:Ir mol ratios are 88:6:5:1 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 4, and waste water is entered electrolysis bath with the flow velocity Jing inlet valves of 0.1L/min then, and adjusting constant-current dc power supply makes electric current close
Spend for 40mA/cm2, after before processing, water quality is as follows：
Embodiment 4
Using Sn:Sb:Ce:Ir mol ratios are 90:5:4:1 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 4, and imidacloprid wastewater is entered electrolysis bath with the flow velocity Jing inlet valves of 0.3L/min, and adjusting constant-current dc power supply makes electric current
Density is 50mA/cm2, after before processing, water quality is as follows：
Embodiment 5
Using Sn:Sb:Ce:Ir mol ratios are 88:6:5:1 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 5, and waste water is entered electrolysis bath with the flow velocity Jing inlet valves of 0.05L/min then, and adjusting constant-current dc power supply makes electric current
Density is 25mA/cm2, after before processing, water quality is as follows：
Embodiment 6
Using Sn:Sb:Ce:Ir mol ratios are 90:5:3:2 electrode is anode, adjusts imidacloprid wastewater and reclaims residual solution
PH value is 4, and waste water is entered electrolysis bath with the flow velocity Jing inlet valves of 0.1L/min then, and adjusting constant-current dc power supply makes electric current close
Spend for 50mA/cm2, after before processing, water quality is as follows：
Embodiment 7
Using Sn:Sb:Ce:Ir mol ratios are 88:6:5:1 to adjust imidacloprid wastewater raw water pH value be 4, then by waste water with
The flow velocity Jing inlet valves of 0.01L/min enter electrolysis bath, and it is 30mA/cm to adjust constant-current dc power supply and make electric current density2, before processing
Water quality is as follows afterwards：
Embodiment 8
Using Sn:Sb:Ce:Ir mol ratios are 88:6:5:1 to adjust imidacloprid wastewater raw water pH value be 4, then by waste water with
The flow velocity Jing inlet valves of 0.02L/min enter electrolysis bath, and it is 50mA/cm to adjust constant-current dc power supply and make electric current density2, before processing
Water quality is as follows afterwards：
Comparative example
Comparative example 1
Using chlorine industry titanio ruthenium-oxide Ti electrode as a comparison, except anode be changed to DSA titanio oxidation ruthenium titanium electricity
Extremely outer, negative electrode adopts rustless steel, and it is 4 to adjust imidacloprid wastewater raw water pH value, is then entered waste water with the flow velocity Jing of 0.1L/min
Mouth valve enters electrolysis bath, and it is 40mA/cm to adjust constant-current dc power supply and make electric current density2, after before processing, water quality is as follows：
Treatment effect is nothing like with tin dioxide coating on titanium antimony tantalum iridium as anode.
Comparative example 2
Using Fe2+-H2O2Fenton process is contrast, and after before processing, water quality is as follows：
Treatment effect is not as with tin dioxide coating on titanium antimony tantalum iridium as anode electrochemical processing method.
Comparative example 3
Using Sn:Sb:Ce mol ratios are 90:6:3 electrodes as a comparison, in addition to anode is changed to comparison electrode, adopt by negative electrode
With rustless steel, it is 4 to adjust imidacloprid wastewater raw water pH value, and waste water is entered electrolysis with the flow velocity Jing inlet valves of 0.1L/min then
Groove, it is 40mA/cm to adjust constant-current dc power supply and make electric current density2, after before processing, water quality is as follows：
Comparative example 4
Using Sn:Sb:Ir mol ratios are 90:6:1 electrode as a comparison, in addition to anode is changed to comparison electrode, adopt by negative electrode
With rustless steel, it is 4 to adjust imidacloprid wastewater raw water pH value, and waste water is entered electrolysis with the flow velocity Jing inlet valves of 0.1L/min then
Groove, it is 50mA/cm to adjust constant-current dc power supply and make electric current density2, after before processing, water quality is as follows：
Treatment effect can not show a candle to embodiment.
Comparative example 5
Using Sn:Sb:Ce:Ir mol ratios are 84:6:7:3 electrodes are as a comparison, in addition to anode is changed to comparison electrode, cloudy
Pole adopts rustless steel, and it is 4 to adjust imidacloprid wastewater raw water pH value, and then waste water is entered with the flow velocity Jing inlet valves of 0.1L/min
Electrolysis bath, it is 40mA/cm to adjust constant-current dc power supply and make electric current density2, after before processing, water quality is as follows：
Claims (5)
1. a kind of method of electrochemical pre-treatment imidacloprid pesticide wastewater, it is characterised in that anode electrolytic cell is used by methods described
Titanio tin ash antimony cerium iridium coating layer electrode, the electrode preparation method is：By Titanium base first with the sulfur of concentration 30%, temperature 60 C
Acid etching 50 minutes, then use Sn:Sb:Ce:Ir mol ratios are 85-91:5-7:3-6:The butter of tin of 1-2, Butter of antimony., nitric acid
Cerium and chloro-iridic acid n-butyl alcohol saline solution coating, be dried after, 500 DEG C of 10 min of thermal oxide, this coating, be dried, thermal oxidation process
It is repeated 15 times, 1 h of last 500 DEG C of heat treatments is obtained final product.
2. the method for electrochemical pre-treatment imidacloprid pesticide wastewater as claimed in claim 1, it is characterised in that：According to following behaviour
Electrochemical pre-treatment imidacloprid pesticide wastewater is carried out as step：
Step one, adjusts the pH value of imidacloprid wastewater；
Imidacloprid wastewater is passed through electrolysis bath, and is electrolysed with certain electric current density by step 2；
Step 3, under certain electric current density, imidacloprid wastewater passes through electrolysis bath with certain flow velocity.
3. the operating procedure of electrochemical pre-treatment imidacloprid pesticide wastewater as claimed in claim 2, it is characterised in that step one
Described pH value is 3～5.
4. the operating procedure of electrochemical pre-treatment imidacloprid pesticide wastewater as claimed in claim 2, it is characterised in that step 2
Described electric current density is 20～50 mA/cm2。
5. the operating procedure of electrochemical pre-treatment imidacloprid pesticide wastewater as claimed in claim 2, it is characterised in that step 3
Described flow velocity is 0.01-0.3 L/min.
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| CN105000759A (en) * | 2015-08-05 | 2015-10-28 | 丁德凤 | Imidacloprid waste water treating technology |
| CN105231764A (en) * | 2015-11-12 | 2016-01-13 | 中装环境科技（天津）有限公司 | Tea leaf purifier |
| CN114105880A (en) * | 2021-12-06 | 2022-03-01 | 江苏瑞祥化工有限公司 | Method for recycling imidacloprid wastewater |
| CN114950089A (en) * | 2022-06-11 | 2022-08-30 | 华中科技大学 | Electrochemical degradation method for chlorine-containing volatile/semi-volatile organic compound |
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| WO2006061192A1 (en) * | 2004-12-06 | 2006-06-15 | Basf Aktiengesellschaft | Method and device for the treatment of waste water containing pesticides |
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Effective date of registration: 20181130 Address after: 214404 No. 221 Yuedong Road, Yuecheng Industrial Park, Jiangyin City, Jiangsu Province Patentee after: Jiangsu ankaite Polytron Technologies Inc Address before: 224051 No. 1 hope road middle road, Ting Hu District, Yancheng City, Jiangsu Patentee before: Yangcheng Institute of Technology |
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