CN102701329B - Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes - Google Patents
Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes Download PDFInfo
- Publication number
- CN102701329B CN102701329B CN201210172442.5A CN201210172442A CN102701329B CN 102701329 B CN102701329 B CN 102701329B CN 201210172442 A CN201210172442 A CN 201210172442A CN 102701329 B CN102701329 B CN 102701329B
- Authority
- CN
- China
- Prior art keywords
- electrode
- preparation
- sno
- porous
- nanometer crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a preparation method of porous nanometer crystal Ti/SnO2-Sn/Ce-PbO2 electrodes and a method for using the porous nanometer crystal Ti/SnO2-Sn/Ce-PbO2 electrodes for degrading and mineralizing perfluoro caprylic acid in water, and belongs to the technical field of electrochemistry. Waste water containing perfluoro caprylic acid is subjected to electrolytic oxidation treatment by using the porous nanometer crystal Ti/SnO2-Sn/Ce-PbO2 electrodes as anodes and Ti or 304 stainless steel as cathodes. The method is characterized in that the perfluoro caprylic acid can be efficiently mineralized under the mild condition. An electrochemical oxidation method is adopted, the technical flow process is simple, the operation is convenient, the reaction condition is mild, the treatment effect is good, in addition, stability and reliability are realized, and the industrial application is easy to realize. The adopted porous nanometer crystal Ti/SnO2-Sn/Ce-PbO2 electrodes have the advantages that the oxidation capacity is high, the service life is long, the processing is easy, the cost is low, and the like.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of porous and receive the method for Perfluorocaprylic Acid in the preparation method of brilliant electrode and the efficient mineralized water of electrochemical oxidation.
Background technology
Perfluorocaprylic Acid (PFOA, C7F15COOH) is as tensio-active agent, stain control agent, additive, fire foam, macromolecule emulsifier and agrochemical, and its production and use have exceeded 50 years.Perfluorocaprylic Acid is one of main home to return in environment as perfluorochemical (PFCs), its stable chemical property, characteristic not volatile and that can not be degraded by the ecosystem are extensively present in natural water, settling, animal and human body it, and ecotope and HUMAN HEALTH in serious threat.At present, global Perfluorocaprylic Acid pollutes and the impact of HUMAN HEALTH has been caused to showing great attention to of national governments and scientific circles, in June, 2000 EPA (USEPA) starts the harm of noticing that Perfluorocaprylic Acid is possible, proposing low-level Perfluorocaprylic Acid and salt thereof exposes and may be harmful to HUMAN HEALTH, Perfluorocaprylic Acid can residue in human body for a long time, therefore according to " U.S.'s TSCA ", Perfluorocaprylic Acid was listed in forbidding chemical directoryof in 2003, on December 30th, 2009, USEPA has issued first " chemical action plan ", health and environmental problem that long-chain perfluorochemical to including Perfluorocaprylic Acid is caused are processed.In addition, European Union combine in European Parliament and council of ministers on December 27th, 2006 and issued " about restriction Perfluorooctane sulfonates sell and the finger that uses with ", suspect that Perfluorocaprylic Acid and salt thereof also exist the risk level that is similar to Perfluorooctane sulfonates, and promise to undertake and the discharge of Perfluorocaprylic Acid and the content in product thereof were reduced to 95% in 2010, by 2015, it is eliminated completely.
At present, the existing relevant domestic patent for Perfluorocaprylic Acid degradation technique in water body is recorded only 1, number of patent application is 200510011126.X (Granted publication CN 100347137C), name is called " a kind of method of defluorinating and degrading complete fluorine substituted compounds ", disclose a kind of under 185nm and 172nm ultraviolet condition the degradation method of photodissociation and photocatalytic degradation Perfluorocaprylic Acid or perfluoro octane sulfonate.
So far, there is no and adopt electrochemistry Perfluorocaprylic Acid in water to be carried out to the report of efficient mineralising purification techniques.
Summary of the invention
The object of the invention is to prevent and treat the environmental pollution of Perfluorocaprylic Acid, for the deficiencies in the prior art, provide a kind of can be under mild conditions to water in Perfluorocaprylic Acid carry out the new type purification technology of efficient mineralising.
The object of the present invention is achieved like this, and a kind of porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2the preparation method of electrode, comprises the following steps:
1. Ti substrate pretreated: be first that Ti matrix sand paper is polished, remove oxide on surface, then immerse 1～2h in 5%～10% the sodium hydroxide solution of 100 DEG C, to remove surperficial greasy dirt, taking-up is cleaned with distilled water, etching 2～3h in 100 DEG C of oxalic acid solutions of 10%～15% afterwards, to obtain grey even curface;
2. the polymerization forerunner colloidal sol of tin antimony preparation: at 50～70 DEG C of temperature, a certain amount of citric acid is dissolved in to (citric acid and ethylene glycol mol ratio are 1: 4～6) in ethylene glycol, and after dissolving completely, steady temperature 30～60min is with fully esterified, then be heated to 90 DEG C, add SnCl
45H
2o and SbCl
3(citric acid and SnCl
45H
2o mol ratio is 1: 0.05～0.1; SnCl
45H
2o and SbCl
3mol ratio is 1: 0.1～0.2), fully stir until complete dissolving, be warming up to afterwards 100 DEG C and constant temperature 1～3h, after naturally cooling, obtain the polymeric precursor colloidal sol of tin-antimony;
3. Ti/SnO
2-Sb electrode preparation: adopt and draw formulation that the polymeric precursor colloidal sol of the tin-antimony of preparation is overlayed on Ti matrix, in the baking oven of 120～160 DEG C, keep afterwards 10～20min to make colloidal sol transfer gel to, then proceed in 450～550 DEG C of retort furnaces roasting 10～30min in air atmosphere, after taking out naturally cooling cleaning, drying, repeat again front process, 20～40 times repeatedly, when last roasting, 1～3h annealing naturally, make Ti/SnO
2-Sb electrode;
4. porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode preparation: first prepare electrodeposit liquid, composition 0.5mol/L lead nitrate, 0.001mol/L cerous nitrate and 0.2～1.0g/L Sodium Fluoride, and with nitre acid for adjusting pH value to 1.2～1.8, with Ti/SnO
2-Sb electrode, as base electrode, taking Ti as negative electrode, is 100～200A/m at electric current
2under carry out galvanic deposit 10～30min and prepare porous and receive brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode.
Perfluorocaprylic Acid technical scheme in electrochemical oxidation mineralized water: preparation is containing the solution of 5～1000mg/L Perfluorocaprylic Acid taking 1.0～2.0g/L sodium perchlorate as supporting electrolyte.Porous with preparation is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode is anode, and taking Ti or 304 stainless steels as negative electrode, at room temperature carrying out the processing of electrochemical oxidation mineralising containing Perfluorocaprylic Acid waste water, actuating current is 5～40mA/cm
2, polar plate spacing is 5～20mm.
As seen from the above technical solution provided by the invention, the method for the efficient mineralising of Perfluorocaprylic Acid in water provided by the invention, owing to adopting electrochemical oxidation process, there is technical process simple, easy to operate, reaction conditions gentleness, treatment effect is good and reliable and stable, is easy to realize industrial applications.The porous adopting is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode has that oxidation capacity is strong, work-ing life is strong, be easy to processing and the advantage such as cheap.
Brief description of the drawings
Fig. 1 is that porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode surface pattern.
The setting drawing of Perfluorocaprylic Acid in the efficient mineralized water of electrochemical oxidation that Fig. 2 provides for the embodiment of the present invention, wherein: 1-direct supply, 2-electrolyzer, 3-terminal stud, 4-pneumatic outlet, 5-negative electrode, 6-anode.
Fig. 3 is that electrochemical oxidation is to Perfluorocaprylic Acid degraded and mineralising effect and treatment time graph of a relation.
Embodiment
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in further detail.
The method of Perfluorocaprylic Acid in the efficient mineralized water of a kind of electrochemical oxidation of the present invention, its preferably embodiment comprise step:
Porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode preparation:
1. first with 200 order sand paper to the capable polishing of Ti matrix, then immerse 1h in 8% the sodium hydroxide solution of 100 DEG C, for taking out, distilled water cleans, etching 2.5h in 100 DEG C of oxalic acid solutions of 10% afterwards;
2. at 60 DEG C of temperature, a certain amount of citric acid is dissolved in ethylene glycol, steady temperature 30min after dissolving completely, is then heated to 90 DEG C, adds SnCl
45H
2o and SbCl
3, fully stir until complete dissolving, be warming up to afterwards 100 DEG C and constant temperature 1～3h, after naturally cooling, obtain the polymeric precursor colloidal sol of tin-antimony, wherein ethylene glycol: citric acid: SnCl
45H
2o: SbCl
3(mol ratio) is 120: 30: 9: 1;
3. adopt and draw formulation that the polymeric precursor colloidal sol of the tin-antimony of preparation is overlayed on Ti matrix, in the baking oven of 140 DEG C, keep afterwards 15min to make colloidal sol transfer gel to, then proceed in 500 DEG C of retort furnaces roasting 15min in air atmosphere, after taking out naturally cooling cleaning, drying, repeat again front process, 20 times repeatedly, when last roasting, 2h annealing naturally, make Ti/SnO
2-Sb electrode;
4. prepare the electrodeposit liquid of 0.5mol/L lead nitrate, 0.001mol/L cerous nitrate and 0.5g/L Sodium Fluoride composition, and with nitre acid for adjusting pH value to 1.4, with Ti/SnO
2-Sb electrode, as base electrode, taking Ti as negative electrode, is 200A/m at electric current
2under carry out galvanic deposit 20min and prepare porous and receive brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode.
The porous of preparation is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode surface pattern as shown in Figure 1.Electrode surface becomes vesicular as can be seen from Figure 1, is conducive to pollutent and adsorbs at electrode surface; PbO
2granular size is hundreds of nanometers, is nanomorphic and surface compact, greatly increases reactive behavior point position.
Perfluorocaprylic Acid technical scheme in electrochemical oxidation mineralized water: preparation is containing the solution of 1.4g/L sodium perchlorate and 100mg/L Perfluorocaprylic Acid.Get 100mL and inject Fig. 2 electrolyzer, receive brilliant Ti/SnO with the porous of preparing
2-Sn/Ce-PbO
2electrode is anode, and taking Ti or 304 stainless steels as negative electrode, two electrode areas are 60cm
2.Adjusting polar plate spacing is 10mm, power-on to regulate electric current to keep outward current density be 10mA/cm
2, under room temperature, carrying out electrolysis treatment 90min, interval 15～30min adopts analysis.
Fig. 3 is that the present invention is to Perfluorocaprylic Acid degraded and mineralising effect and treatment time relation, after 90min processes, PFOA clearance is greater than 99.9% as shown in Figure 3, defluorinate rate approaches 90%, be equivalent to existing 13.5 fluorine of 15 fluorine contained in PFOA molecule and be shed in solution, TOC has declined 92.6% simultaneously.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.In the technical scope that any those of ordinary skill in the art disclose in the present invention, can make various amendments to the present embodiment easily, and application of principle described herein is executed and needn't be passed through creative work to other example.Therefore, the invention is not restricted to the embodiment here, do not depart from category of the present invention make improve and amendment all should be encompassed in protection scope of the present invention within.
Claims (2)
1. a method for Perfluorocaprylic Acid in electrochemical oxidation degree of depth mineralized water, is characterized in that, taking 1.0～2.0g/L sodium perchlorate as supporting electrolyte, receives brilliant Ti/SnO with porous
2-Sn/Ce-PbO
2electrode is anode, taking Ti or 304 stainless steels as negative electrode, Perfluorocaprylic Acid concentration is at room temperature carried out to the processing of electrochemical oxidation mineralising as the waste water of 5-1000mg/L, and actuating current is 5～40mA/cm
2, electrode pad spacing is 5～20mm,
Described porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode, comprises the following steps preparation:
Ti substrate pretreated: first with 200 order sand paper to the capable polishing of Ti matrix, remove oxide on surface, then immerse 1h in 8% the sodium hydroxide solution of 100 DEG C, to remove surperficial greasy dirt, taking-up is cleaned with distilled water, etching 2.5h in 100 DEG C of oxalic acid solutions of 10% afterwards, to obtain grey even curface;
The polymerization forerunner colloidal sol preparation of tin antimony: at 60 DEG C of temperature, a certain amount of citric acid is dissolved in ethylene glycol, after dissolving completely, steady temperature 30min, with fully esterified, is then heated to 90 DEG C, adds SnCl45H
2o and SbCl
3, fully stir until complete dissolving, be warming up to afterwards 100 DEG C and constant temperature 1～3h, after naturally cooling, obtain the polymeric precursor colloidal sol of tin-antimony, wherein ethylene glycol: citric acid: SnCl
45H
2o: SbCl
3mol ratio be 120: 30: 9: 1;
Ti/SnO
2-Sb electrode preparation: adopt and draw formulation that the polymeric precursor colloidal sol of the tin-antimony of preparation is overlayed on Ti matrix, in the baking oven of 140 DEG C, keep afterwards 15min to make colloidal sol transfer gel to, then proceed in 500 DEG C of retort furnaces roasting 15min in air atmosphere, after taking out naturally cooling cleaning, drying, repeat again front process, 20 times repeatedly, when last roasting, 2h annealing naturally, make Ti/SnO
2-Sb electrode;
Porous is received brilliant Ti/SnO
2-Sn/Ce-PbO
2electrode preparation: the electrodeposit liquid of preparation 0.5mol/L lead nitrate, 0.001mol/L cerous nitrate and 0.5g/L Sodium Fluoride composition, and with nitre acid for adjusting pH value to 1.4, with Ti/SnO
2-Sb electrode, as base electrode, taking Ti as negative electrode, is 200A/m at electric current
2under carry out galvanic deposit 20min.
2. the method for Perfluorocaprylic Acid in electrochemical oxidation degree of depth mineralized water according to claim 1, is characterized in that, in described waste water, Perfluorocaprylic Acid concentration is 100mg/L.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210172442.5A CN102701329B (en) | 2012-07-17 | 2012-07-17 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
| CN201410279964.4A CN104030403B (en) | 2012-07-17 | 2012-07-17 | Porous receives brilliant Ti/SnO 2-Sn/Ce-PbO 2the preparation method of electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210172442.5A CN102701329B (en) | 2012-07-17 | 2012-07-17 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410279964.4A Division CN104030403B (en) | 2012-07-17 | 2012-07-17 | Porous receives brilliant Ti/SnO 2-Sn/Ce-PbO 2the preparation method of electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102701329A CN102701329A (en) | 2012-10-03 |
| CN102701329B true CN102701329B (en) | 2014-08-06 |
Family
ID=46894469
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210172442.5A Expired - Fee Related CN102701329B (en) | 2012-07-17 | 2012-07-17 | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes |
| CN201410279964.4A Expired - Fee Related CN104030403B (en) | 2012-07-17 | 2012-07-17 | Porous receives brilliant Ti/SnO 2-Sn/Ce-PbO 2the preparation method of electrode |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410279964.4A Expired - Fee Related CN104030403B (en) | 2012-07-17 | 2012-07-17 | Porous receives brilliant Ti/SnO 2-Sn/Ce-PbO 2the preparation method of electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN102701329B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614712B (en) * | 2013-12-04 | 2016-05-18 | 淮南师范学院 | Sol-gel process is prepared Sb, Ce codope SnO2The method in intermediate layer |
| CN104591343B (en) * | 2014-12-18 | 2016-08-17 | 北京师范大学 | Porous PbO for organic industrial sewage advanced treating2the preparation method of electrode |
| CN104556312A (en) * | 2014-12-18 | 2015-04-29 | 北京师范大学 | Method for preparing porous PbO2 electrode for deep sewage treatment |
| CN105600879A (en) * | 2015-12-28 | 2016-05-25 | 北京帝力伟业科技开发有限公司 | Electrocatalytic oxidation reaction device for treating toxic organic wastewater |
| CN105954613A (en) * | 2016-04-29 | 2016-09-21 | 中国船舶重工集团公司第七二五研究所 | Titanium electrode acceleration life testing device |
| CN106167290A (en) * | 2016-08-23 | 2016-11-30 | 杨梅 | A kind of rare earth Ce doping Ti/Sb SnO2the preparation method of electrode |
| CN106757248B (en) * | 2016-11-28 | 2018-08-31 | 深圳市橘井舒泉技术有限公司 | The preparation facilities and method of lead dioxide electrode |
| CN108675406A (en) * | 2018-05-16 | 2018-10-19 | 中大立信（北京）技术发展有限公司 | A kind of novel SnO2Electrode and its preparation method and application |
| CN109772295B (en) * | 2019-03-11 | 2020-09-08 | 中南大学 | Bismuth tungstate modified antimony-doped tin dioxide composite photoelectric catalytic electrode, preparation method and application |
| CN110980890A (en) * | 2019-12-26 | 2020-04-10 | 西安泰金工业电化学技术有限公司 | Titanium-based lead dioxide electrode for degrading rhodamine B and preparation method and application thereof |
| CN112978869B (en) * | 2021-03-17 | 2022-03-11 | 东莞理工学院 | Efficient selective Ti/SnO2Preparation method and application of (E) -Sb-MI anode material |
| CN114933349A (en) * | 2022-05-16 | 2022-08-23 | 桂林电子科技大学 | Titanium-based metal oxide coating filtering membrane, preparation method and application thereof, coupling reactor and sewage treatment method |
| CN115010222B (en) * | 2022-08-09 | 2022-11-15 | 广东工业大学 | Filtering type electrodeposition device, electrodeposition system and preparation method of DSA membrane electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095764A (en) * | 2008-10-16 | 2010-04-30 | Japan Carlit Co Ltd:The | Electrode for electrolysis and method for producing the same |
-
2012
- 2012-07-17 CN CN201210172442.5A patent/CN102701329B/en not_active Expired - Fee Related
- 2012-07-17 CN CN201410279964.4A patent/CN104030403B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095764A (en) * | 2008-10-16 | 2010-04-30 | Japan Carlit Co Ltd:The | Electrode for electrolysis and method for producing the same |
Non-Patent Citations (4)
| Title |
|---|
| 卓琼芳等.掺硼金刚石电极对全氟辛酸钠的降解.《第六届全国环境化学大会暨环境科学仪器与分析仪器展览会摘要集》.2011,第508页. |
| 掺杂Ti基二氧化铅电极的制备及性能研究;李晓乐;《郑州大学硕士学位论文》;20060510;见第9页和第27页 * |
| 掺硼金刚石电极对全氟辛酸钠的降解;卓琼芳等;《第六届全国环境化学大会暨环境科学仪器与分析仪器展览会摘要集》;20111231;第508页 * |
| 李晓乐.掺杂Ti基二氧化铅电极的制备及性能研究.《郑州大学硕士学位论文》.2006,见第9页和第27页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102701329A (en) | 2012-10-03 |
| CN104030403B (en) | 2016-03-02 |
| CN104030403A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102701329B (en) | Preparation method of porous nanometer crystal electrodes and application of porous nanometer crystal electrodes | |
| CN103739043B (en) | A kind of granule electrode of photochemical catalysis three-dimensional electrode/electro-Fenton system and preparation method | |
| CN102659224A (en) | Preparation method and application of nano coated electrode | |
| Chen et al. | Construction of rGO@ Ti/SnO2–Sb composite electrode for electrochemical degradation of fluoroquinolone antibiotic | |
| CN104746096A (en) | Preparation method of nickel-base catalytic electrode for electrocatalytic oxidation of urea | |
| CN104016449B (en) | A kind of Sb-Ni-Nd codoped SnO 2the preparations and applicatio of high catalytic activity anode | |
| CN109867334A (en) | The method and application of catalysed particulate electrode activation persulfate under electric field driven | |
| CN105858818B (en) | A kind of method that the more metal nano electrodes of Zn/Cu/Ti efficiently remove nitrate in groundwater | |
| CN102701333B (en) | Preparation method of Ce (cerium) doped titanium base SnO2 (stannic oxide) electrodes and metronidazole wastewater treatment method | |
| CN102211830B (en) | Method for treating cutting liquid wastewater by electro-catalytic oxidation | |
| CN104528890B (en) | Ti/SnO2 electrode as well as preparation method and application | |
| US20230331595A1 (en) | System and Method for Electrochemical Oxidation of Polyfluoroalkyl Substances in Water | |
| CN104389011B (en) | Electrochemical decontamination electrolyte | |
| CN105776441A (en) | Three-dimensional porous titanium substrate lead dioxide electrode as well as preparation method and application thereof | |
| CN108017120A (en) | A kind of method using Novel anode electrocatalytic oxidation processing phenol organic wastewater | |
| CN105036259A (en) | Modification method of double-metal-modified activated carbon fiber electrode by electrolytic deposition and application | |
| CN103435134A (en) | Method for improving biodegradability of semi-coking wastewater based on CNTs/Fe3O4 three-dimensional electric-Fenton | |
| KR100699556B1 (en) | The equipment for producing hydrogen gas by using photocatalyst and biocatalyst | |
| CN105239095A (en) | Method for preparing Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode and degrading reactive blue 117 through Ti/Sb-SnO2/Nd-nano TiO2-PbO2 electrode | |
| CN104591343A (en) | Method for preparing porous PbO2 electrode for advanced treatment of industrial organic wastewater | |
| CN108793342A (en) | A kind of preparation method for the high dispersive cobalt titanium composite Nano electrode that nitrate nitrogen restores in water | |
| CN103121737B (en) | Method for electrochemically treating printing and dyeing wastewater | |
| CN109516527A (en) | A kind of continuous flow electrochemical filtration system and its application in degradation of ammonia nitrogen waste water | |
| CN109603844A (en) | FeMnC aeroge Fenton cathode and preparation method thereof and application in degrading perfluorinated compound | |
| CN109626513A (en) | The method that photocatalytic fuel cell couples degradation of contaminant with persulfate and improves electricity production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140806 Termination date: 20180717 |