CN104030407B - A kind of method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water - Google Patents
A kind of method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water Download PDFInfo
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- CN104030407B CN104030407B CN201410247141.3A CN201410247141A CN104030407B CN 104030407 B CN104030407 B CN 104030407B CN 201410247141 A CN201410247141 A CN 201410247141A CN 104030407 B CN104030407 B CN 104030407B
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- waste water
- metalaxyl
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Abstract
The invention discloses apply a kind of method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water.This method prepares tin dioxide coating on titanium antimony tantalum cerium electrode by coating thermal decomposition method.High concentration metalaxyl waste water is passed through into the electrolytic cell using titanium-based tin ash antimony tantalum cerium electrode as anode；Waste water is persistently handled under certain current density for a period of time.The present invention uses caused high concentration, high salt, difficult biochemical waste water in titanium-based tin ash antimony tantalum cerium electrode pretreatment metalaxyl production process, the results showed that：In certain pH, current density and under the conditions of processing time, metalaxyl agricultural chemicals waste water COD clearances reach more than 60%, BOD/COD and are increased to more than 0.3 from less than 0.1, and biodegradability greatly improves.The pretreatment of caused high-concentration waste water biochemical degradation in metalaxyl production is especially suitable for using the electrochemical oxidation of titanium-based tin ash antimony tantalum cerium electrode.
Description
Technical field
The present invention relates to a kind of technical method and equipment, and it is to utilize the high analysis oxygen electricity of titanium-based tin ash antimony tantalum cerium electrode
The features such as position and extremely strong electrocatalytic oxidation ability, electrolysis handles caused high salt high-concentration waste water in metalaxyl pesticide producing.
Belong to green technology and electrochemical field.
Background technology
Metalaxyl (imidacloprid), alias Apron, conservation spirit, metalaxyl, auspicious poison frost, the white peace of first, the more Mils of thunder,
Metalaxyl.Chemical name D, L-N- (2,6- 3,5-dimethylphenyls)-N- (2- methoxyl groups acetyl) methyl lactamine.CAS 57837-
19-1, molecular formula C15H21NO4, molecular weight 279.33.Structural formula is
It is mainly used in preventing and treating Pseudoperonospora cubensis, phytophthora germ and the microbial various crop downy mildew of maize ear rot, gourd, fruit and vegetable
The phytophthora root rot of class, the downy mildew of millet.Metalaxyl category phenylamide is efficient, low toxicity, low-residual, absorbability sterilization pesticide.It is closed
It is in the presence of sodium acid carbonate into method, 2,6- dimethylanilines and 2 bromopropionic acid methyl esters is reacted, DL-N- (2,6- bis- is made
Aminomethyl phenyl)-α-aminopropionic acid methyl esters.Acylation reaction is carried out with methoxyacetyl chloride again, produces metalaxyl.
Metalaxyl waste water BOD/COD values are less than 0.1, and biochemical system processing need to can be just entered after materialized pretreatment.At present still
Reported without the processing method to this production waste water.
The present invention handles metalaxyl waste water using electrochemical oxidation method, and its advantage is：
1) strong oxidizer need not be used, treatment process is simple, it is only necessary to which it is certain that waste water is placed in into the processing of electrolytic cell Inner electrolysis
Time；
2) secondary pollution is not produced.
3) device is simple, technical arrangement plan facility.
There is titanium-based tin ash antimony tantalum cerium 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 there is 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, and it is necessary to have the electrode of selectivity is matching.Sn provided by the present invention:Sb:Ta:
Ce mol ratios are 84-88:5-6:2-3:5-7 titanium-based tin ash antimony tantalum cerium electrode has very high oxygen evolution potential, very strong
The ability of hydroxyl radical free radical and preferable stability are produced, analyses that oxygen side reaction is few, and degradation efficiency is high during degraded.The electrode is proved to
With to the pollutant in metalaxyl agricultural chemicals waste water with preferable degradation selectivity ability.Through retrieval, there is not yet electrochemistry oxygen
Change method is used for the report for handling metalaxyl waste water.This method can both be used for pre-processing metalaxyl waste water raw water, can also locate
Manage the remaining waste liquid after reclaiming early stage.
The content of the invention
It is an object of the invention to provide a kind of method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water, the titanium in this method
Base tin ash antimony tantalum cerium electrode is prepared using coating-thermal decomposition method.Electrode Titanium base is first with concentration 30%, the sulphur of temperature 60 C
Acid etching 50 minutes, then use Sn:Sb:Ta:Ce mol ratios are 84-88:5-6:2-3:5-7 n-butanol salting liquid coating, dry
Afterwards, titanium-based tin ash antimony tantalum cerium electrode is made in 480 DEG C of oxidation 10min, 500 DEG C of heat treatments.
In order to solve the above technical problems, the present invention provides following technical scheme：It is the pH value for adjusting waste water first, then will
High concentration metalaxyl waste water is passed through the electrolytic cell using titanium-based tin ash antimony tantalum cerium as anode；Finally make under certain current density
Waste water is electrolysed the regular hour in a cell.
The present invention is specifically operating procedure completion titanium-based tin ash antimony tantalum cerium Electrode treatment first frost in the following order
The method of clever agricultural chemicals waste water：
Step 1, metalaxyl waste water is passed through to electrolytic cell；
Step 2, adjust the pH value of metalaxyl waste water；
Step 3, metalaxyl waste water certain time is persistently handled under certain current density.
As a kind of preferred scheme of the method for the invention, the electrolytic cell wherein described in step 1 is by titanium-based titanium dioxide
Tin antimony tantalum cerium electrode anode and stainless steel or graphite cathode and dc source composition.
As a kind of preferred scheme of the method for the invention, the certain pH value described in step 2, refer to adjust first frost
Clever pH value of waste water is 6~8.
As a kind of preferred scheme of the method for the invention, certain current density described in step 3, refer to titanium-based
The current density of tin ash antimony tantalum cerium electrode is controlled in 10mA/cm2~80mA/cm2.Certain time, refer to electrolytic processing time
Control is in 1~8h.
As a kind of preferred scheme of the method for the invention, described electrode is prepared using coating-thermal decomposition method.Its mistake
Cheng Wei：Electrode Titanium base is first with concentration 30%, the sulfuric acid acid etching 50 minutes of temperature 60 C, then uses Sn:Sb:Ta:Ce mol ratios are
84-88:5-6:2-3:5-7 butter of tin, antimony trichloride, tantalic chloride and cerous nitrate butanol solution coating, dry after,
480 DEG C of oxidation 10min, this process repeat 10-15 times, and last 500 DEG C of thermal decompositions 1h is made.The present invention uses titanium-based tin ash
Caused high salt high-concentration waste water in antimony tantalum cerium Electrode treatment metalaxyl production process, the results showed that：In certain pH value, electric current
Under density and time conditions, the COD clearances of metalaxyl agricultural chemicals waste water reach more than 60%, COD/BOD and are increased to from less than 0.1
More than 0.3.Titanium-based tin ash antimony tantalum cerium electrode is especially suitable for handling caused high salt high-concentration waste water in metalaxyl production.
The method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water provided by the invention, can effectively improve metalaxyl waste water can
Biochemical, while method is easy, device simple, cost is cheap, suitable to promote.
Brief description of the drawings
Accompanying drawing 1 is electrolytic cell schematic diagram of the present invention.
Specific embodiment
The method of the invention is described in detail with reference to specific embodiment.It should be noted that following examples
It is merely illustrative of the technical solution of the present invention and unrestricted, although having been 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 substitution, and
Technical scheme spirit and scope are not departed from, it all should cover in scope of the presently claimed invention.
Electrolytic cell assembly as shown in Figure 1, the electrode assemblie in electrolytic cell is core apparatus, by titanium-based tin ash antimony tantalum cerium
Anode and stainless steel or graphite cathode composition.The preparation method of anode is first with concentration 30%, the sulphur of temperature 60 C by Titanium base
Acid etching 50 minutes, then use Sn:Sb:Ta:Ce mol ratios are 84-88:5-6:2-3:5-7 butter of tin, antimony trichloride, pentachloro-
The butanol solution for changing tantalum and cerous nitrate coats, after drying, 480 DEG C of thermal oxide 10min, this process repetition 10-15 times, finally
500 DEG C of heat treatment 1h are produced.The size of monolithic titanium-based tin ash antimony tantalum cerium anode is 100mm × 100mm, and monolithic Ti cathode is
The titanium net of equidimension.Electrolytic cell is the 1000mL beakers for being configured with water bath with thermostatic control, and electrode is placed in beaker, die opening 10mm.
Electrolytic cell equipped with titanium-based tin ash antimony tantalum cerium electrode is applied in the method for processing metalaxyl agricultural chemicals waste water,
700mL high concentration metalaxyl agricultural chemicals waste waters are first added into appropriate H in a cell2SO4Or NaOH is adjusted to suitable pH value.
Regulating electrolytic tank current density carries out Electrooxidation degradation again, terminates after being electrolysed certain time.
Embodiment 1
Using Sn:Sb:Ta:Ce=88:5:2:5 electrode is anode, and regulation metalaxyl pH value of waste water is 6, close with electric current
Spend for 10mA/cm28h is electrolysed, water quality is as follows before and after the processing：
Embodiment 2
Using Sn:Sb:Ta:Ce=87:6:2:5 electrode is anode, and regulation metalaxyl pH value of waste water is 6, close with electric current
Spend for 30mA/cm23h is electrolysed, water quality is as follows before and after the processing：
Embodiment 3
Using Sn:Sb:Ta:Ce=87:6:2:5 electrode is anode, and regulation metalaxyl pH value of waste water is 6, close with electric current
Spend for 80mA/cm21h is electrolysed, water quality is as follows before and after the processing：
Embodiment 4
Using Sn:Sb:Ta:Ce=86:6:2:6 electrode is anode, and regulation metalaxyl pH value of waste water is 7, close with electric current
Spend for 10mA/cm28h is electrolysed, water quality is as follows before and after the processing：
Embodiment 5
Using Sn:Sb:Ta:Ce=86:6:2:6 electrode is anode, and regulation metalaxyl pH value of waste water is 7, close with electric current
Spend for 40mA/cm23h is electrolysed, water quality is as follows before and after the processing：
Embodiment 6
Using Sn:Sb:Ta:Ce=87:6:3:6 electrode is anode, and regulation metalaxyl pH value of waste water is 7, close with electric current
Spend for 80mA/cm21h is electrolysed, water quality is as follows before and after the processing：
Embodiment 7
Using Sn:Sb:Ta:Ce=86:6:2:6 electrode is anode, and regulation metalaxyl pH value of waste water is 8, close with electric current
Spend for 10mA/cm28h is electrolysed, water quality is as follows before and after the processing：
Embodiment 8
Using Sn:Sb:Ta:Ce=85:6:3:6 electrode is anode, and regulation metalaxyl pH value of waste water is 8, close with electric current
Spend for 30mA/cm24h is electrolysed, water quality is as follows before and after the processing：
Embodiment 9
Using Sn:Sb:Ta:Ce=84:6:3:7 electrode is anode, and regulation metalaxyl pH value of waste water is 8, close with electric current
Spend for 80mA/cm22h is electrolysed, water quality is as follows before and after the processing：
Comparative example
Comparative example 1
Using chlorine industry titanium-based ruthenium-oxide Ti electrode as a comparison, except anode be changed to DSA titanium-baseds oxidation ruthenium titanium electricity
Extremely outer, negative electrode uses stainless steel, and regulation metalaxyl pH value of waste water is 7, using current density as 40mA/cm23h is electrolysed, before and after the processing
Water quality is as follows：
It is nothing like the effect of embodiment anode.
Comparative example 2
Using Fe2+-H2O2Fenton process is contrast, and water quality is as follows before and after the processing：
Effect is not so good as embodiment.
Comparative example 3
Using Sn:Sb:Ce=89:6:As a comparison, in addition to anode is changed to comparison electrode, negative electrode is not using for 5 electrode
Become rusty steel, and regulation metalaxyl pH value of waste water is 7, using current density as 40mA/cm23h is electrolysed, water quality is as follows before and after the processing：
Effect is not so good as embodiment.
Comparative example 4
Using Sn:Sb:Ta=91:6:As a comparison, in addition to anode is changed to comparison electrode, negative electrode is not using for 3 electrode
Become rusty steel, and regulation metalaxyl pH value of waste water is 7, using current density as 40mA/cm23h is electrolysed, water quality is as follows before and after the processing：
Effect is not so good as embodiment.
Comparative example 5
Using Sn:Sb:Ta:Ce=90:6:2:4 electrode as a comparison, in addition to anode is changed to comparison electrode, adopt by negative electrode
With stainless steel, regulation metalaxyl pH value of waste water is 7, using current density as 40mA/cm23h is electrolysed, water quality is as follows before and after the processing：
Effect is not so good as embodiment.
Claims (3)
- A kind of 1. method of electrochemical pre-treatment metalaxyl agricultural chemicals waste water, it is characterised in that：Completed according to following operating procedure pre- Handle metalaxyl agricultural chemicals waste water：Step 1, metalaxyl waste water is passed through electrolytic cell；The electrolytic cellAnode be titanium-based tin ash antimony tantalum cerium electrode；The preparation method of the electrode is first with concentration 30%, temperature by Titanium base 60 DEG C of sulfuric acid acid etching 50 minutes, then use Sn:Sb:Ta:Ce mol ratios are 84-88:5-6:2-3:5-7 butter of tin, trichlorine The butanol solution for changing antimony, tantalic chloride and cerous nitrate coats, after drying, and 480 DEG C of min of thermal oxide 10, this process repeats 10- 15 times, 1 h of last 500 DEG C of heat treatment is produced；Step 2, adjust the pH value of metalaxyl waste water；Step 3, metalaxyl waste water certain time is electrolysed under certain current density.
- 2. the method for electrochemical pre-treatment metalaxyl agricultural chemicals waste water as claimed in claim 1, it is characterised in that：Institute in step 2 The pH value stated is 6~8.
- 3. the method for electrochemical pre-treatment metalaxyl agricultural chemicals waste water as claimed in claim 1, it is characterised in that：Institute in step 3 The current density stated is 10~80 mA/cm2, processing time is 1~8 h.
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| JPS62284095A (en) * | 1986-06-02 | 1987-12-09 | Permelec Electrode Ltd | Durable electrolytic electrode and its production |
| US6589405B2 (en) * | 2000-05-15 | 2003-07-08 | Oleh Weres | Multilayer oxide coated valve metal electrode for water purification |
| JP5199575B2 (en) * | 2003-10-29 | 2013-05-15 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | Noble metal oxide catalysts for water electrolysis |
| JP2008525164A (en) * | 2004-12-06 | 2008-07-17 | ビーエーエスエフ ソシエタス・ヨーロピア | Method and apparatus for treating pesticide-containing wastewater |
| CN1962471A (en) * | 2006-11-28 | 2007-05-16 | 北京科技大学 | Method for electrolyzing organic waste water using iridium tantalum stannum oxide coating titanium electrode |
| EP2436437A4 (en) * | 2009-05-25 | 2015-03-25 | Dalian Huaxinyuan Technology Dev Ltd Company | Anti-pollution electrocatalysis composite membrane and membrane reactor |
| CN101830542B (en) * | 2010-04-27 | 2011-09-14 | 华南师范大学 | Method for electrolyzing orange G by adopting cerium-doped tin antimony oxide coated titanium electrode |
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