CN102659231B - Preparation and application of water-soluble macromolecule heavy-metal collector - Google Patents
Preparation and application of water-soluble macromolecule heavy-metal collector Download PDFInfo
- Publication number
- CN102659231B CN102659231B CN2012101662734A CN201210166273A CN102659231B CN 102659231 B CN102659231 B CN 102659231B CN 2012101662734 A CN2012101662734 A CN 2012101662734A CN 201210166273 A CN201210166273 A CN 201210166273A CN 102659231 B CN102659231 B CN 102659231B
- Authority
- CN
- China
- Prior art keywords
- water
- heavy
- heavy metal
- chelating agent
- solution
- 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
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
Preparation and application of water-soluble macromolecule heavy-metal collector belong to the technical field of preparation of functional macromolecule materials and treatment of heavy-metal-containing waste water. The invention discloses a preparation method of the water-soluble macromolecule heavy-metal collector. The preparation method includes generating a macromolecule framework by crosslinking micromolecule amine ethylenediamine with triethylenetetramine, and grafting dithio carbamic acid group on the macromolecule framework to generate the water-soluble macromolecule heavy-metal collector. The like heavy-metal collector has effects of chelating heavy-metal ions and netting flocculation, can react with the free or complexing heavy-metal ions quickly in waste water at the normal temperature to generate insoluble precipitations, and is applicable to wide range of heavy-metal ions, the flocculation precipitation is large in particles, compact in structure and fast in settlement, the pH value ranges from 1 to 9, and removal rate of the heavy-metal ions in water is high and can reach above 95%.
Description
Technical field
A kind of preparation of water-soluble macromolecule heavy metal chelating agent and application, the present invention relates to the preparation of water-soluble macromolecule heavy metal chelating agent, can be used for capture, flocculation, the removal of heavy metals in industrial wastewater ion, reach the purpose of macromolecular material in the field of Environment Protection application.The present invention relates to prepare functionalized macromolecular material, environmental technology field, belong to especially the waste water treatment field of containing heavy metal ion.
Background technology
Production along with more and more type materials, increasing of organic additive, the heavy metal wastewater thereby composition is more and more complicated, difficulty of governance also constantly increases, the methods such as traditional neutralization precipitation, sulfuration method, ion-exchange, reverse osmosis and absorption, the problems such as treatment process is long, treatment condition are harsh owing to existing, waste residue is difficult to process, cost is higher, introduce secondary pollution, treatment capacity is limited, can not meet present needs.Particularly in waste water, have sequestrant, as halogen, cyanogen root, soil ulmin, citric acid, EDTA etc., heavy metal ion and its coordination form complex compound, and above method can't be to its effective removal.
In environmental pollution increasingly serious today, dithiocar-bamate (DTC) compounds relies on the extremely strong complex ability of itself and metal ion, becomes the focus of Pollution abatement area research.(U. S. Pat:4731187,1988) such as Moriya M. by low-molecular-weight DTC with after sodium sulphite, sodium polysulphide mix by a certain percentage jointly for wastewater treatment, improved flocculating effect.But the low-molecular-weight agent of recapturing, sulfide etc. remain in water, can cause secondary pollution, can cause that simultaneously the total content of organic carbon of discharge water uprises.(Mining Engineering, 1978,30 (1): 72-76) synthesized the Diethyldithiocarbamate heavy metal chelating agent, but the shortcomings such as its alumen ustum is little, poisonous, poorly water-soluble have limited its use such as Werneke M. F..
According to the structure of dithiocar-bamate and the relation of performance, synthetic heavy metal chelating agent that can widespread use is efforts at environmental protection person's research direction from now on.In addition, improve the stability, water-soluble etc. of heavy metal chelating agent, the improvement synthesis technique, make synthesis technique to gentle, future development efficiently, will promote the further commercialization of DTC class heavy metal chelating agent.
Summary of the invention
The object of the invention is to: overcome the defect of prior art, a kind of preparation method of water-soluble macromolecule heavy metal chelating agent is provided.The present invention is by being cross-linked into macromolecular skeleton by quadrol and triethylene tetramine, and then grafting dithiocarbonic anhydride on macromolecular skeleton, form dithiocarbamate-based group, can with most of heavy metal ion in trade effluent, as Cu
2+, Ni
2+, Cd
2+, Hg
2+, Pb
2+, Cr
3+Etc. quick complex reaction, and, because contain macromolecular skeleton, so have simultaneously net, catch effect, form flco closely knit, that volume is larger and settle down rapidly.By solid-liquid separation, can reach the purpose of heavy metal ion in efficient removal water.
?Purpose of the present invention is achieved through the following technical solutions, and namely the preparation method of water-soluble macromolecule heavy metal chelating agent comprises the following steps:
(1) the heavy metal chelating agent macromolecular skeleton is synthetic: the quadrol of total amount 1mol and triethylene tetramine are dissolved in 100mL water, wherein quadrol: the mol ratio of triethylene tetramine is 9～5:1～5, is mixed with small molecule amine-aqueous solution; In small molecule amine-aqueous solution, slowly drip the epoxy chloropropane of 1.071mol, in 3 hours, add, then reaction 3 hours under 40 ℃～50 ℃, hold over night, during do not stir and do not heat.Solution after above-mentioned spending the night is poured in four-hole boiling flask, under stir on limit, limit continue to drip epoxy chloropropane, drip simultaneously alkaline solution (50%, 0.895mol), epoxy chloropropane added in 6 hours, alkaline solution added in 2 hours, add the total amount of epoxy chloropropane: the total amount mol ratio of small molecule amine was 1.3～1.1:1,70～90 ℃ of lower stirring reactions 0.5 hour, then under the condition that stirs, do not heat, spend the night, obtain product.In above-mentioned reaction product, add 50% alkaline solution, under normal temperature, mix and blend is mixed with 30% the aqueous solution, obtains macromolecular skeleton solution, is the transparent yellow liquid of thickness.Wherein add the alkaline solution total amount: epoxy chloropropane total amount mol ratio is 1:1.
(2) the dithiocarbamate-based group of grafting on macromolecular skeleton: the macromolecular skeleton solution of weighing certain mass is in there-necked flask, add 50% alkaline solution, macromolecular skeleton solution: the alkaline solution mass ratio is 1:1, under condition of ice bath, add again the dithiocarbonic anhydride with the alkaline solution equimolar amount, in 15 minutes, drip, then reaction 1 hour under ice bath, prevent dithiocarbonic anhydride volatilization, then be warmed up to room temperature reaction and got final product in 30 minutes.
In above-mentioned preparation method, it is characterized in that a kind of as in potassium hydroxide and sodium hydroxide of the alkali that uses in reaction process.
Heavy metal chelating agent prepared by the present invention has following characteristics:
(1) the heavy metal chelating agent good water solubility for preparing of the present invention, reach 20g/100g water 25 ℃ of lower solubleness, can in water, with heavy metal ion, fully react;
(2) the heavy metal chelating agent applicable pH range for preparing of the present invention is wider, in pH value 1～9 scope, can use;
(3) cost of material that uses of the present invention is cheap, and technique is simple, and easy handling is applicable to electroplate, the processing of the industry heavy metal wastewater therebies such as battery, printing;
(4) heavy metal chelating agent for preparing of the present invention can with most of complexes reactions, flocculation sediment, for Cu
2+, Ni
2+, Cd
2+, Hg
2+, Pb
2+, Cr
3+Clearance etc. heavy metal ion can reach more than 95%, obvious processing effect.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment 1
Synthesizing of heavy metal chelating agent macromolecular skeleton: the quadrol of total amount 1mol (0.9mol) and triethylene tetramine (0.1mol) are dissolved in 100mL water, are mixed with small molecule amine-aqueous solution.In small molecule amine-aqueous solution, slowly drip the 1.071mol epoxy chloropropane, in 3 hours, add, then reaction 3 hours under 40 ℃, hold over night, during do not stir and do not heat.Solution after above-mentioned spending the night is poured in four-hole boiling flask, in situation about stirring, continue to drip the 0.129mol epoxy chloropropane, (50%, 0.895mol), epoxy chloropropane added in 6 hours to drip simultaneously the 72mL sodium hydroxide solution, sodium hydroxide added in 2 hours, continuation, 70 ℃ of lower stirring reactions 0.5 hour, is spent the night under the condition that stir, does not heat, and obtains product.(50%, 0.305mol), under normal temperature, mix and blend is mixed with 30% the aqueous solution, obtains macromolecular skeleton solution, is the transparent yellow liquid of thickness in above-mentioned reaction product, to add sodium hydroxide solution.
The dithiocarbamate-based group of grafting: weighing 62.88g macromolecular skeleton solution is in there-necked flask, add 10g sodium hydroxide solution (50%, 0.125mol), under condition of ice bath, add again the dithiocarbonic anhydride of 0.125mol, in 15 minutes, drip, then under ice bath, reacted 1 hour, prevent the dithiocarbonic anhydride volatilization, be warmed up to again room temperature reaction 30 minutes, and obtained the product of transparent orange.
Embodiment 2
The synthetic parameter of heavy metal chelating agent macromolecular skeleton refers to table 1, and the building-up process of the dithiocarbamate-based group of grafting is with embodiment 1.
Embodiment 3
The synthetic parameter of heavy metal chelating agent macromolecular skeleton refers to table 1, and the building-up process of the dithiocarbamate-based group of grafting is with embodiment 1.
Embodiment 4
The synthetic parameter of heavy metal chelating agent macromolecular skeleton refers to table 1, and the building-up process of the dithiocarbamate-based group of grafting is with embodiment 1.
Embodiment 5
The synthetic parameter of heavy metal chelating agent macromolecular skeleton refers to table 1, and the building-up process of the dithiocarbamate-based group of grafting is with embodiment 1.
Embodiment 6
The synthetic parameter of heavy metal chelating agent macromolecular skeleton refers to table 1, and the building-up process of the dithiocarbamate-based group of grafting is with embodiment 1.
Table 1
| Parameter | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| The n(quadrol): the n(triethylene tetramine) | 8:2 | 7:3 | 6:4 | 5:5 | 9:1 |
| For the first time the crosslinking reaction temperature/℃ | 40 | 45 | 50 | 40 | 50 |
| For the second time the crosslinking reaction temperature/℃ | 70 | 75 | 80 | 85 | 90 |
| The total epoxy chloropropane of n(): the total amine of n() | 1.1 | 1.15 | 1.2 | 1.25 | 1.3 |
| The amount that adds for the first time epoxy chloropropane | 1.071mol | 1.071mol | 1.071mol | 1.071mol | 1.071mol |
| The amount that adds for the second time epoxy chloropropane | 0.029mol | 0.079mol | 0.129mol | 0.179mol | 0.229mol |
| The amount that adds for the first time sodium hydroxide | 0.895mol | 0.895mol | 0.895mol | 0.895mol | 0.895mol |
| The amount that adds for the second time sodium hydroxide | 0.205mol | 0.255mol | 0.305mol | 0.355mol | 0.405mol |
Embodiment 7
Selecting the copper of Wuxi plastic electroplating factory is electroplating wastewater, and recording copper ion concentration is 123.14mg/L, and pH is 4.8.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 50mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its cupric ion of Atomic Absorption Spectrometry.Obtaining corresponding clearance is 99.52%, 99.36%, 99.64%, 99.86%, 99.86%, 99.77%.
Embodiment 8
Selecting the copper of Wuxi plastic electroplating factory is electroplating wastewater, and recording copper ion concentration is 123.14mg/L, and pH is 4.8.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 60mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its cupric ion of Atomic Absorption Spectrometry.Obtaining corresponding clearance is 99.73%, 99.86%, 99.94%, 99.96%, 99.89%, 99.97%.
Embodiment 9
Selecting the chromium of Wuxi plastic electroplating factory is electroplating wastewater, contains Cr
3+Ionic concn is 10.335 mg/L, and pH is 2.5.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 70mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its chromium ion of Atomic Absorption Spectrometry.Obtaining corresponding clearance is 96.81%, 95.85%, 95.56%, 95.82%, 96.99%, 95.69%.
Embodiment 10
Selecting the chromium of Wuxi plastic electroplating factory is electroplating wastewater, contains Cr
3+Ionic concn is 10.335 mg/L, and pH is 2.5.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 80mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its chromium ion of Atomic Absorption Spectrometry.Obtaining corresponding clearance is 97.82%, 96.65%, 97.64%, 96.28%, 97.99%, 96.62%.
Embodiment 11
Selecting the nickel of Wuxi plastic electroplating factory is electroplating wastewater, records Ni
2+Ionic concn is 7.88mg/L.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 50mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its nickel ion of Atomic Absorption Spectrometry, obtaining corresponding clearance is 95.23%, 95.67%, 97.22%, 97.89%, 98.76%, 97.26%.
Embodiment 12
Selecting the nickel of Wuxi plastic electroplating factory is electroplating wastewater, records Ni
2+Ionic concn is 7.88mg/L.The heavy metal chelating agent that adds embodiment 1～embodiment 6 of 70mg/L, under 30r/min, standing filtration after stirring reaction 1min, get the concentration of supernatant liquor with its nickel ion of Atomic Absorption Spectrometry, obtaining corresponding clearance is 97.82%, 97.33%, 98.12%, 98.80%, 99.26%, 99.63%.
Patent of the present invention has the same performance that similarly captures to other heavy metal ion.
Claims (3)
1. the preparation method of a water-soluble macromolecule heavy metal chelating agent, it is characterized in that adopting the crosslinked generation macromolecular skeleton of two kinds of small molecules amine quadrols and triethylene tetramine, then the dithiocarbamate-based group of grafting on macromolecular skeleton, generate the water miscible heavy metal chelating agent of a kind of macromole; Comprise the following steps:
(1) the heavy metal chelating agent macromolecular skeleton is synthetic: the quadrol of total amount 1mol and triethylene tetramine are dissolved in 100mL water, wherein quadrol: the mol ratio of triethylene tetramine is 9～5:1～5, is mixed with small molecule amine-aqueous solution; In small molecule amine-aqueous solution, slowly drip the epoxy chloropropane of 1.071mol, in 3 hours, add, then reaction 3 hours under 40 ℃～50 ℃, hold over night, during do not stir and do not heat; Solution after above-mentioned spending the night is poured in four-hole boiling flask, under stir on limit, epoxy chloropropane is continued to drip in limit, drip simultaneously the alkaline solution of concentration 50%, 0.895mol, epoxy chloropropane added in 6 hours, and alkaline solution added in 2 hours, add the total amount of epoxy chloropropane: the total amount mol ratio of small molecule amine is 1.3～1.1:1,70～90 ℃ of lower stirring reactions 0.5 hour, then under the condition that stirs, do not heat, spend the night, obtain product; In above-mentioned reaction product, add 50% alkaline solution, under normal temperature, mix and blend is mixed with 30% the aqueous solution, obtains macromolecular skeleton solution, is the transparent yellow liquid of thickness; Wherein add the alkaline solution total amount: epoxy chloropropane total amount mol ratio is 1:1;
(2) the dithiocarbamate-based group of grafting on macromolecular skeleton: the macromolecular skeleton solution of weighing certain mass is in there-necked flask, add 50% alkaline solution, macromolecular skeleton solution: the alkaline solution mass ratio is 1:1, under condition of ice bath, add again the dithiocarbonic anhydride with the alkaline solution equimolar amount, in 15 minutes, drip, then reaction 1 hour under ice bath, prevent dithiocarbonic anhydride volatilization, then be warmed up to room temperature reaction and got final product in 30 minutes.
2. preparation method according to claim 1, is characterized in that, a kind of as in potassium hydroxide and sodium hydroxide of the alkali that uses in reaction process.
3. the application of the water-soluble macromolecule heavy metal chelating agent for preparing with claim 1 method, is characterized in that removing for the chelating of plastic electroplating heavy metal ions in wastewater, and the addition of this macromole heavy metal chelating agent is 50～80mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101662734A CN102659231B (en) | 2012-05-26 | 2012-05-26 | Preparation and application of water-soluble macromolecule heavy-metal collector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101662734A CN102659231B (en) | 2012-05-26 | 2012-05-26 | Preparation and application of water-soluble macromolecule heavy-metal collector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659231A CN102659231A (en) | 2012-09-12 |
| CN102659231B true CN102659231B (en) | 2013-11-20 |
Family
ID=46768849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101662734A Expired - Fee Related CN102659231B (en) | 2012-05-26 | 2012-05-26 | Preparation and application of water-soluble macromolecule heavy-metal collector |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659231B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792714A (en) * | 2020-07-09 | 2020-10-20 | 深圳市点石源水处理技术有限公司 | Complex nickel remover and preparation method and application thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936980B (en) * | 2014-03-12 | 2016-05-18 | 中国海洋石油总公司 | A kind of synthetic method of dithiocar-bamate type water purification agent |
| CN104118921B (en) * | 2014-08-20 | 2015-06-03 | 江西省恩皓环保有限公司 | Heavy metal sewage treatment agent |
| CN104192968B (en) * | 2014-08-28 | 2016-08-17 | 中山市宏科化工有限公司 | A kind of hyperbranched type heavy metal chelating agent and preparation method thereof |
| CN104211957B (en) * | 2014-08-28 | 2016-08-17 | 中山市宏科化工有限公司 | A kind of nano-silicon dioxide modified flying dust metal ion chelation agent and preparation method thereof |
| TWI545080B (en) * | 2015-02-16 | 2016-08-11 | 達興材料股份有限公司 | A heavy metal scavenger and a method of removing heavy metals from an aqueous solution |
| CN105413662B (en) * | 2015-12-31 | 2018-06-29 | 重庆工商大学 | One heavy metal species polymer chelating agent and its preparation method and application |
| CN107082512A (en) * | 2017-05-25 | 2017-08-22 | 苏州利比奥环保科技有限公司 | A kind of effluent containing heavy metal ions processing system and its method of wastewater treatment |
| CN106995221B (en) * | 2017-06-14 | 2021-02-09 | 北京市理化分析测试中心 | Heavy metal ion remover with self-flocculation function and synthesis method thereof |
| CN109970165B (en) * | 2017-12-28 | 2021-11-30 | 南京源泉环保科技股份有限公司 | Heavy metal trapping agent and preparation method thereof |
| CN110937676A (en) * | 2019-12-20 | 2020-03-31 | 中海油天津化工研究设计院有限公司 | Preparation method of hyperbranched dithiocarbamate heavy metal remover |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1708613A (en) * | 2002-10-30 | 2005-12-14 | 荷兰联合利华有限公司 | Fabric care composition |
| CN101314492A (en) * | 2007-05-29 | 2008-12-03 | 陈德琪 | Method for preparing novel remover for heavy metal ion and application thereof |
| CN101857296A (en) * | 2010-06-29 | 2010-10-13 | 湖南科技大学 | Ethylenediamine-based heavy metal chelating agent and preparation method thereof |
-
2012
- 2012-05-26 CN CN2012101662734A patent/CN102659231B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1708613A (en) * | 2002-10-30 | 2005-12-14 | 荷兰联合利华有限公司 | Fabric care composition |
| CN101314492A (en) * | 2007-05-29 | 2008-12-03 | 陈德琪 | Method for preparing novel remover for heavy metal ion and application thereof |
| CN101857296A (en) * | 2010-06-29 | 2010-10-13 | 湖南科技大学 | Ethylenediamine-based heavy metal chelating agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111792714A (en) * | 2020-07-09 | 2020-10-20 | 深圳市点石源水处理技术有限公司 | Complex nickel remover and preparation method and application thereof |
| CN111792714B (en) * | 2020-07-09 | 2022-05-10 | 深圳市点石源水处理技术有限公司 | Complex nickel remover and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659231A (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102659231B (en) | Preparation and application of water-soluble macromolecule heavy-metal collector | |
| CN101857296B (en) | Ethylenediamine-based heavy metal chelating agent and preparation method thereof | |
| US11807542B2 (en) | Method for preparing urea ammonium nitrate solution from waste nitric acid after stripping tin from circuit board | |
| US20180215636A1 (en) | Dendritic polymer heavy metal precipitant with double functions of chelation and self-flocculation and its application | |
| CN103553195B (en) | Dendritic polyamidoamine and hyperbranched polyamidoamine composite heavy metal water treatment agent and preparation method thereof | |
| CN105858852B (en) | A kind of synthesis and its application of high molecular heavy metals trapping agent | |
| CN105664872A (en) | Modified sodium lignin sulfonate heavy metal capture agent and preparation method thereof | |
| WO2004013219A1 (en) | A heavy maetal chelate composition containing chitosan derivatives and uses thereof | |
| CN106315808A (en) | Heavy metal trapping agent and preparation method thereof | |
| CN104558324A (en) | Resource recycling application of heavy metals in wastewater | |
| US11236206B2 (en) | Ethoxylated pentaerythritol core hyperbranched polymer with dithiocarboxylate as side group and terminal group and applications of chelating heavy metals | |
| CN102702367B (en) | Method for preparing cationic cross-linked starch xanthate | |
| CN103663663A (en) | Efficient composite heavy metal chelating agent | |
| CN104117344B (en) | The preparation method of novel chitosan metal ion adsorbent | |
| CN109704974B (en) | Heavy metal chelating agent and preparation method and application thereof | |
| CN103495589B (en) | A kind of plating waste residue recoverying and utilizing method | |
| CN109293053A (en) | A kind of chelating precipitation method removing heavy metals in industrial wastewater | |
| US11242268B2 (en) | Compound heavy metal chelating agent containing dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer | |
| CN101173019A (en) | Method for synthesizing polymer chelating agent with polyvinyl alcohol as base chain | |
| CN104436512A (en) | Polyamide tree-like heavy metal chelating agent and preparation method thereof | |
| CN101898824B (en) | Sulfide heavy metal chelating trapping agent and preparation method thereof | |
| CN109502726A (en) | A kind of preparation method of efficient heavy chelating agent | |
| CN1197906C (en) | Heavy metal chelator compound containing chitosan derivative | |
| CN110217872B (en) | Heavy metal trapping agent and preparation method and application thereof | |
| CN106865679B (en) | Nickel ion chelating agent for electroplating nickel-containing wastewater treatment and preparation method and application thereof |
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 |
Granted publication date: 20131120 Termination date: 20150526 |
|
| EXPY | Termination of patent right or utility model |