CN106976933A - A kind of electrode for handling agricultural chemicals waste water and its preparation and application - Google Patents
A kind of electrode for handling agricultural chemicals waste water and its preparation and application Download PDFInfo
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- CN106976933A CN106976933A CN201710201176.7A CN201710201176A CN106976933A CN 106976933 A CN106976933 A CN 106976933A CN 201710201176 A CN201710201176 A CN 201710201176A CN 106976933 A CN106976933 A CN 106976933A
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- waste water
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- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- 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
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- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of electrode for handling agricultural chemicals waste water and its preparation and application, the electrode is made up of Titanium base with the metal oxide layer for being covered in Titanium base surface；Described metal oxide layer is made up of platinum oxide, tin oxide and antimony oxide.Using the electrode as anode, using Ti electrode as negative electrode, electrochemical treatments are carried out to agricultural chemicals waste water, the COD value of agricultural chemicals waste water can be effectively reduced, while improving BOD/COD values.
Description
Technical field
The invention belongs to green technology and electrochemical field, and in particular to a kind of electrode of processing agricultural chemicals waste water and its preparation
And application.
Background technology
China is a large agricultural country, and pest species are various, in the production process of grain, cotton, vegetables etc. every year all
The threat from pest and disease damage can be run into.The appearance of agricultural chemicals drastically increases the level that the mankind prevent and treat agricultural pest, effectively
The development of modern agriculture is promoted.According to the statistics of the Ministry of Agriculture, China will use more than 140 ten thousand tons of agricultural chemicals every year.According to endless
Full statistics, the agricultural chemicals waste water that the whole nation is discharged every year is about more than ten00000000 tons, and wherein agricultural chemicals waste water handling rate is handled and reached less than 10%
Target only accounts for processed a few percent.
Agricultural chemicals waste water has following several features：(1) organic concentration is high；(2) complicated component, change of water quality is big；(3) salt
Content is high；(4) hardly degraded organic substance content is high.Agricultural chemicals waste water processing is not up to standard, and being discharged into natural environment can cause soil to move back
A series of problems, such as change, residues of pesticides, water source and environmental pollution, biological chain interruption, disruption of ecological balance.At present, enterprise generally first adopts
Materializing strategy agricultural chemicals waste water is used, to remove the part hardly degraded organic substance in agricultural chemicals waste water, and improves the biochemical of agricultural chemicals waste water
Property, then biochemical treatment is carried out to agricultural chemicals waste water using routine biochemistry system.
Because the concentration of agricultural chemicals waste water is higher, materializing strategy needs to consume substantial amounts of medicament, and operating cost is higher；Meanwhile,
The activated sludge concentration of routine biochemistry system is low, and biology drug resistance is poor, and biochemical system is easily hit, therefore, and agricultural chemicals waste water needs
Biochemical system could be introduced after dilution for many times and carries out biochemical treatment, the waste of dilution water is caused.
Waste water containing agricultural chemicals paraquat has complicated component, content of organics height, toxicity is big, colourity is deep, biodegradability
Poor the features such as.Traditional processing method is mainly the processing of chemical method, Physical, electrochemical process etc., wherein chemical method and Physical
Cost is high, it is also difficult to reach good treatment effect, and electrochemical process lacks effective processing electrode, limits it and extensively should
With.
The content of the invention
The invention provides a kind of electrode for handling agricultural chemicals waste water and its preparation and application, the electrode is used for agricultural chemicals waste water
During electrochemical treatments, treatment effeciency is high, especially the paraquat waste water to being difficult to processing.
A kind of electrode for handling agricultural chemicals waste water, is made up of Titanium base and the metal oxide layer for being covered in Titanium base surface；
Described metal oxide layer is made up of platinum oxide, tin oxide and antimony oxide.
Preferably, the mol ratio of described platinum oxide, tin oxide and antimony oxide is 1：0.03~0.05：0.03~
0.05。
Preferably, the thickness of described metal oxide layer is 0.05~0.1mm.
Present invention also offers a kind of preparation method of described electrode, comprise the following steps：
Titanium base is pre-processed 30 minutes~1 hour with dilute sulfuric acid, then uses and contains platinum tetrachloride, butter of tin and trichlorine
Change the n-butanol salting liquid coating of antimony, dry, then carrying out oxidation processes in 600~800 DEG C obtains described electrode.
Present invention also offers a kind of processing method of agricultural chemicals waste water, comprise the following steps：
Using Ti electrode as negative electrode, using electrode of the present invention as anode, electrochemical treatments are carried out to agricultural chemicals waste water,
Obtain processed waste water.
Preferably, described agricultural chemicals waste water is paraquat waste water, pH is adjusted before electrochemical treatments to alkalescence.
Preferably, regulation pH to 8~9.
Preferably, the current density of electrochemical treatments is 10mA/cm2~60mA/cm2。
Preferably, the temperature of electrochemical treatments is 20~50 DEG C.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
The present invention by covering one layer of metal oxide layer for being made up of platinum oxide, tin oxide and antimony oxide on Titanium base,
Then electrochemical treatments are carried out to agricultural chemicals waste water as anode, the COD value of agricultural chemicals waste water can be effectively reduced, improved simultaneously
BOD/COD values.
Embodiment
Embodiment 1
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.
Embodiment 1
By Titanium base first with concentration 20%, the sulfuric acid acid etching 50 minutes of temperature 60 C, then with the mol ratio of platinum, tin and antimony
For 100：3：4 platinum tetrachloride (0.1mol/L), butter of tin (0.003mol/L) and trichloride antimony (0.003mol/L) is just
The coating of butanol salting liquid, dry, 600 DEG C of thermal oxide 20min, this process repetition 30 times, last 600 DEG C of heat treatment 2h are obtained
Oxide skin(coating) is about 0.05mm.
Embodiment 2
By Titanium base first with concentration 20%, the sulfuric acid acid etching 50 minutes of temperature 60 C, then with the mol ratio of platinum and antimony it is
100：7 platinum tetrachloride (0.1mol/L) and the n-butanol salting liquid of trichloride antimony (0.007mol/L) are coated, dried, 600 DEG C
Thermal oxide 20min, this process is repeated 30 times, last 600 DEG C of heat treatment 2h, obtained oxide skin(coating) about 0.05mm.
Embodiment 3
By Titanium base first with concentration 20%, the sulfuric acid acid etching 50 minutes of temperature 60 C, then with the mol ratio of platinum and tin it is
100：7 platinum tetrachloride (0.1mol/L) and the n-butanol salting liquid of butter of tin (0.007mol/L) are coated, dried, 600 DEG C
Thermal oxide 20min, this process is repeated 30 times, last 600 DEG C of heat treatment 2h, obtained oxide skin(coating) about 0.05mm.
Embodiment 4
(1) pH value of white careless withered agricultural chemicals waste water is adjusted to 10 using aqueous sodium carbonate；
(2) using titanium as negative electrode, respectively using electrode made from embodiment 1~3 as anode, electrolyzer reaction device is assembled；
(3) waste water is made by electrolyzer reaction device, it is 20 DEG C to control temperature, and galvanization, current density is 15mA/cm2, water
The power residence time is 20 minutes, COD value and BOD values before and after detection hydrolysis, as a result be see the table below.
| Project | COD(mg/L) | BOD(mg/L) |
| Before processing | 7540 | 670 |
| After processing (embodiment 1) | 1950 | 551 |
| After processing (embodiment 2) | 4658 | 579 |
| After processing (embodiment 3) | 5326 | 583 |
Embodiment 5
(1) pH value of white careless withered agricultural chemicals waste water is adjusted to 9 using aqueous sodium carbonate；
(2) using titanium as negative electrode, respectively using electrode made from embodiment 1~3 as anode, electrolyzer reaction device is assembled；
(3) waste water is made by electrolyzer reaction device, it is 20 DEG C to control temperature, and galvanization, current density is 20mA/cm2, water
The power residence time is 1 hour, COD value and BOD values before and after detection hydrolysis, as a result be see the table below.
| Project | COD(mg/L) | BOD(mg/L) |
| Before processing | 7540 | 670 |
| After processing (embodiment 1) | 892 | 524 |
| After processing (embodiment 2) | 3945 | 557 |
| After processing (embodiment 3) | 5099 | 566 |
Embodiment 6
(1) pH value of white careless withered agricultural chemicals waste water is adjusted to 9 using aqueous sodium carbonate；
(2) using titanium as negative electrode, respectively using electrode made from embodiment 1~3 as anode, electrolyzer reaction device is assembled；
(3) waste water is made by electrolyzer reaction device, it is 40 DEG C to control temperature, and galvanization, current density is 15mA/cm2, water
The power residence time is 20 minutes, COD value and BOD values before and after detection hydrolysis, as a result be see the table below.
| Project | COD(mg/L) | BOD(mg/L) |
| Before processing | 7540 | 670 |
| After processing (embodiment 1) | 1231 | 541 |
| After processing (embodiment 2) | 4156 | 568 |
| After processing (embodiment 3) | 5129 | 572 |
Claims (9)
1. a kind of electrode for handling agricultural chemicals waste water, it is characterised in that aoxidized by Titanium base and the metal for being covered in Titanium base surface
Nitride layer is constituted；
Described metal oxide layer is made up of platinum oxide, tin oxide and antimony oxide.
2. the electrode of processing agricultural chemicals waste water according to claim 1, it is characterised in that described platinum oxide, tin oxide and
The mol ratio of antimony oxide is 1：0.03~0.05：0.03~0.05.
3. the electrode of processing agricultural chemicals waste water according to claim 1, it is characterised in that the thickness of described metal oxide layer
Spend for 0.05~0.1mm.
4. the preparation method of a kind of electrode as described in any one of claims 1 to 3, it is characterised in that comprise the following steps：
Titanium base is pre-processed 30 minutes~1 hour with dilute sulfuric acid, then uses and contains platinum tetrachloride, butter of tin and trichloride antimony
The coating of n-butanol salting liquid, dry, then carrying out oxidation processes in 600~800 DEG C obtains described electrode.
5. a kind of processing method of agricultural chemicals waste water, it is characterised in that comprise the following steps：
Using Ti electrode as negative electrode, using the electrode described in any one of claims 1 to 3 as anode, electricity is carried out to agricultural chemicals waste water
Chemical treatment, obtains processed waste water.
6. the processing method of agricultural chemicals waste water according to claim 5, it is characterised in that described agricultural chemicals waste water is paraquat
PH is adjusted before waste water, electrochemical treatments to alkalescence.
7. the processing method of agricultural chemicals waste water according to claim 6, it is characterised in that regulation pH to 8~9.
8. the processing method of agricultural chemicals waste water according to claim 5, it is characterised in that the current density of electrochemical treatments is
10mA/cm2~60mA/cm2。
9. the processing method of agricultural chemicals waste water according to claim 5, it is characterised in that the temperature of electrochemical treatments is 20~
50℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710201176.7A CN106976933A (en) | 2017-03-30 | 2017-03-30 | A kind of electrode for handling agricultural chemicals waste water and its preparation and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710201176.7A CN106976933A (en) | 2017-03-30 | 2017-03-30 | A kind of electrode for handling agricultural chemicals waste water and its preparation and application |
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| Publication Number | Publication Date |
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| CN106976933A true CN106976933A (en) | 2017-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710201176.7A Pending CN106976933A (en) | 2017-03-30 | 2017-03-30 | A kind of electrode for handling agricultural chemicals waste water and its preparation and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112756389A (en) * | 2020-12-24 | 2021-05-07 | 苏州山河水生态建设有限公司 | Soil pesticide residue treatment method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830542A (en) * | 2010-04-27 | 2010-09-15 | 华南师范大学 | Method for electrolyzing orange G by adopting cerium-doped tin antimony oxide coated titanium electrode |
| CN102320683A (en) * | 2011-06-03 | 2012-01-18 | 大连海事大学 | Titanium-based tin-antimony-platinum oxide electrode material and preparation method thereof |
| CN104030408A (en) * | 2014-06-12 | 2014-09-10 | 盐城工学院 | Method for electrochemically pretreating oxadiazon pesticide wastewater |
| CN105688677A (en) * | 2016-04-01 | 2016-06-22 | 中国科学院过程工程研究所 | Composite electrode for electrodialysis as well as preparation method and application thereof |
-
2017
- 2017-03-30 CN CN201710201176.7A patent/CN106976933A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830542A (en) * | 2010-04-27 | 2010-09-15 | 华南师范大学 | Method for electrolyzing orange G by adopting cerium-doped tin antimony oxide coated titanium electrode |
| CN102320683A (en) * | 2011-06-03 | 2012-01-18 | 大连海事大学 | Titanium-based tin-antimony-platinum oxide electrode material and preparation method thereof |
| CN104030408A (en) * | 2014-06-12 | 2014-09-10 | 盐城工学院 | Method for electrochemically pretreating oxadiazon pesticide wastewater |
| CN105688677A (en) * | 2016-04-01 | 2016-06-22 | 中国科学院过程工程研究所 | Composite electrode for electrodialysis as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李楹: "复合氧化物纳米电极的制备及催化氧化降解污染物", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112756389A (en) * | 2020-12-24 | 2021-05-07 | 苏州山河水生态建设有限公司 | Soil pesticide residue treatment method |
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