CN102942434A - Method extracting high purity n-hexane by integrating rectification and extraction - Google Patents
Method extracting high purity n-hexane by integrating rectification and extraction Download PDFInfo
- Publication number
- CN102942434A CN102942434A CN2012104979534A CN201210497953A CN102942434A CN 102942434 A CN102942434 A CN 102942434A CN 2012104979534 A CN2012104979534 A CN 2012104979534A CN 201210497953 A CN201210497953 A CN 201210497953A CN 102942434 A CN102942434 A CN 102942434A
- Authority
- CN
- China
- Prior art keywords
- tower
- extraction
- normal hexane
- section
- filler
- 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.)
- Granted
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method extracting high purity n-hexane by integrating rectification and extraction. The method utilizes aromatic hydrocarbon raffinate oil as a raw material and adopts a three-tower technological process which combines continuous rectification and extractive distillation. Firstly, distillate lighter than n-hexane is removed in a rectifying tower, and n-hexane distillate which is around 80% in content is obtained at the bottom of the tower. The distillate at the bottom of the tower is adopted as the raw material of an extractive distillation tower, N-methyl pyrrolidone is adopted as an extracting solvent to be delivered into the extractive distillation tower, and the proportion of the N-methyl pyrrolidone and raw oil is 8:1, after extractive distillation, high purity n-hexane is extracted at the top of the tower by integrating rectification and extraction, and heavy components which are rich in methylcyclopentane and the extracting solvent are at the bottom of the tower. Materials at the bottom of the tower are delivered into a solvent recovery tower, distillate oil which is rich in methylcyclopentane is separated at the top of the tower, and N-methyl pyrrolidone solvent is at the bottom of the tower and sent back to the extractive distillation tower to be recycled. By means of the method, n-hexane content can achieve 99%, no extracting solvent is contained in products, solvent consumption is smaller than 0.1%, one-off yield of n-hexane is larger than 95%, and compared with traditional rectification, energy consumption can be saved over 50%.
Description
Technical field
The present invention relates to a kind of chemical solvents and produce, more particularly mainly as extraction solvent, the pharmaceutical extraction solvent of solvent, rubber and coating and the thinner of pigment etc. of olefin polymerization catalysis with solvent, edible vegetable oil.
Background technology
It is different to the content requirement of normal hexane that hexane solvent is applied to different industries, and such as the food plant oil extraction solvent, hexane content reaches more than 60% and can meet the demands.And the hexane solvent that the chemical process polymerization is used requires hexane content to reach (such as CSPC ethylene unit chemical industry polymerization hexane solvent) more than 99%.At present domestic used purity be 99% normal hexane solvent all from external import, price is high.Approximately 10000 tons of present domestic import volumes, principal market are developed this products substitution imported product in the areas to the south, the Changjiang river, satisfy domestic market demand, have preferably economic benefit and social benefit.
The raw material that this project adopts is that the aromatic hydrocarbons of oil refining apparatus production is raffinated oil, and the raw material main ingredient is C
5～C
8, wherein normal hexane content is 25%, methylcyclopentane content is 2.5%.Because normal hexane and methylcyclopentane boiling point approach, if employing conventional rectification method, not only energy consumption is large, and separation accuracy does not reach requirement, is difficult to obtain the normal hexane more than 99%.
Summary of the invention
The purpose of this invention is to provide a kind of rectifying and the method that extracts integrated extraction high purity normal hexane, the three tower process flow processs that it adopts continuous rectification to combine with extractive distillation, the key of continuous rectification process is component lighter than normal hexane in the raw material is excised, and the extractive distillation charging is about 80% normal hexane fraction (control isohexane content is less than 0.1%); Obtain 99% normal hexane through extractive distillation, product easily separates with extraction solvent, do not carry phenomenon secretly, do not contain extraction solvent in the product, do not affect quality product, the extraction solvent consumption is less than 0.1%, and normal hexane content is more than 99% in the product, yield of product is greater than 95%, and comparing with traditional rectifying can energy efficient more than 50%.
Technical solution of the present invention is to adopt continuous rectifying tower, extraction distillation column and extraction solvent recovery tower three tower process flow and methods, raffinate oil with the aromatic hydrocarbons of oil refining apparatus production and to be raw material, first with component excision lighter than normal hexane in the raw material, cat head is lighting end, and discharging is about 80% normal hexane fraction (isohexane content is less than 0.1%) at the bottom of the tower; Fraction is as extraction distillation column stock oil at the bottom of the tower, and stock oil is from the charging of extraction distillation column middle and lower part; Take the high boiling point N-Methyl pyrrolidone as extraction solvent and stock oil in the 8:1 ratio simultaneously continuously from the charging of extraction distillation column middle and upper part, after extractive distillation column separates, cat head obtains the normal hexane more than 99%, is that the higher restructuring of methylcyclopentane content divides and extraction solvent at the bottom of the extraction distillation column; Last material at the bottom of extraction distillation column is as extraction solvent recovery tower raw material, and the extraction solvent recovery tower ejects material and is the higher distillate of methylcyclopentane content, is extraction solvent at the bottom of the extraction solvent recovery tower tower, and extraction solvent is circulated to extraction distillation column, recycles.
The above raw material adopts the aromatic hydrocarbons of oil refining apparatus production to raffinate oil, foreign matter content extremely low (sulphur content is less than 1.0PPM, and olefin(e) centent is less than 10PPM, and aromaticity content is less than 50PPM) in the raw material, and the raw material main ingredient is C
5～C
8, wherein normal hexane content is 25%, methylcyclopentane content is 2.5%.
Above three tower indices of the present invention are as follows:
1, continuous rectifying tower of the present invention (T-1 tower) adopts the band press operation, working pressure is 160kPa(a), the design tower diameter is φ 1400mm, adopt efficient DZ-II type filler, the packing section height is 35200mm, be divided into into eight sections, each section highly is respectively 4000mm, 4000mm, 4800mm, 4800mm, 4800mm, 4800mm, 4000mm, 4000mm, adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, opening for feed is arranged between second segment and the 3rd section filler, and side is adopted mouth and is arranged between the 6th section and the 7th section filler.
2, extractive distillation column of the present invention (T-2 tower) adopts decompression operation, working pressure is 70kPa(a), the design tower diameter is φ 1200mm, adopt efficient DZ-III type filler, the total filler height is 30100mm, be divided into into seven sections, each section highly is respectively 3000mm, 4600mm, 4600mm, 4700mm, 4400mm, 4400mm, 4400mm, adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, the extractant feed mouth is arranged between first paragraph filler and the second segment filler, and material inlet is arranged between the 4th section filler and the 5th section filler.
3, extraction solvent recovery tower of the present invention (T-3 tower) adopts decompression operation, and working pressure is 40kPa(a), the design tower diameter is φ 1000mm, rectifying section adopts efficient DZ-III type filler, highly be 5000mm, stripping section adopts DZ-II type filler, packed height 5500mm.Adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, opening for feed is arranged between two sections fillers.
Hexane is different from the content of methylcyclopentane in the selected raw material of the present invention, and is all influential to consumption, product yield and the energy consumption of the working ability of rectifying and extractive distillation, extraction solvent, so preferred feedstock of the present invention has very large meaning.
Advantage of the present invention is raw material and the extraction solvent wide material sources of selecting.Both easily separate, and do not carry phenomenon secretly, do not contain extraction solvent in the product, normal hexane content is more than 99%, and yield of product is greater than 95%, the extraction solvent Heat stability is good, the extraction solvent consumption is less than 0.1%, and comparing with traditional precision fractional distillation can save energy more than 50%.
Description of drawings:
Fig. 1 process flow diagram of the present invention.
Embodiment:
1, technical process explanation
According to shown in Figure 1, the raw material 1 of feed sump is entered from the middle part of continuous rectifying tower T1 continuously, the cut 2 that is obtained by continuous rectifying tower T1 cat head is the light constituent (light constituent that normal hexane is following, such as the 3-methylpentane), by T1 continuous rectifying tower tower reactor extraction feed liquid 3(control isohexane content less than 0.1%) send into the T2 extraction distillation column, take N-Methyl pyrrolidone as extraction solvent, from the charging of extractive distillation top, obtaining cut 4(mass content from the T2 column overhead is normal hexane more than 99%) be qualified product, material 5 by extraction at the bottom of the T2 extraction distillation column tower is sent to T3 extraction solvent recovery tower, the discharging 6 of T3 column overhead is main heavy distillate for methylcyclopentane, and the extraction solvent 7(extraction solvent content that is reclaimed by T3 tower tower reactor is more than 99.9%) circulating after cooling enters the T2 extraction distillation column.
2, processing condition
Major technique sees Table 1.
The main design of table 1 and operating parameters
3, three tower designs
3.1 T1 continuous rectifying tower
The T1 continuous rectifying tower adopts the band press operation, working pressure is 160kPa(a), the design tower diameter is φ 1400mm, adopt efficient DZ-II type filler, the packing section height is 35200mm, be divided into into eight sections, each section highly is respectively 4000mm, 4000mm, 4800mm, 4800mm, 4800mm, 4800mm, 4000mm, 4000mm.Adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower.Opening for feed is arranged between second segment and the 3rd section filler, and side is adopted mouth and is arranged between the 6th section and the 7th section filler.
3.2 T2 extraction distillation column
The T2 extraction distillation column adopts decompression operation, working pressure is 70kPa(a), the design tower diameter is φ 1200mm, adopt efficient DZ-III type filler, the total filler height is 30100mm, be divided into into seven sections, each section highly is respectively 3000mm, 4600mm, 4600mm, 4700mm, 4400mm, 4400mm, 4400mm.Adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower.The extractant feed mouth is arranged between first paragraph filler and the second segment filler, and material inlet is arranged between the 4th section filler and the 5th section filler.
3.3 T3 extraction solvent recovery tower
T3 extraction solvent recovery tower adopts decompression operation, and working pressure is 40kPa(a), the design tower diameter is φ 1000mm, and rectifying section adopts efficient DZ-III type filler, highly is 5000mm, and stripping section adopts DZ-II type filler, packed height 5500mm.Adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower.Opening for feed is arranged between two sections fillers.
4, raw material scheme
The aromatic hydrocarbons of oil refining apparatus production raffinates oil 1 as raw material.
5, intermediates scheme
Obtaining containing 80% hexane fraction 3 (the following light constituent content of normal hexane is controlled at below 0.1%) at the bottom of the continuous rectifying tower tower enters extraction distillation column and again purifies, the material 5 that obtains at the bottom of the extraction distillation column tower enters the extraction solvent recovery tower, extraction solvent 7 enters continuous rectifying tower again at the bottom of the extraction solvent recovery tower tower, recycles.
6, the finished product scheme
99% above normal hexane cut 4 is qualified normal hexane solvent, as the solvent of extraction agent, rubber and the coating of the solvent of for olefines polymerization, edible vegetable oil and the thinner of pigment.
Claims (7)
1. rectifying and the method that extracts integrated extraction high purity normal hexane, it is characterized in that raffinating oil as raw material take the aromatic hydrocarbons of oil refining apparatus production, the three tower process flow processs that adopt continuous rectification to combine with extractive distillation, first with component excision lighter than normal hexane in the raw material, cat head is lighting end, and discharging is that isohexane content is less than the normal hexane fraction of about 80% below 0.1% at the bottom of the tower; Fraction is as extraction distillation column stock oil at the bottom of the tower, and stock oil is from the charging of extraction distillation column middle and lower part; Take the high boiling point N-Methyl pyrrolidone as extraction solvent and stock oil in the 8:1 ratio continuously from the charging of extraction distillation column middle and upper part, after extractive distillation column separates, cat head obtains the normal hexane more than 99%, is that the higher restructuring of methylcyclopentane content divides and extraction solvent at the bottom of the extraction distillation column; Last material at the bottom of extraction distillation column is as extraction solvent recovery tower raw material, and the extraction solvent recovery tower ejects material and is the higher distillate of methylcyclopentane content, is extraction solvent at the bottom of the extraction solvent recovery tower tower, and extraction solvent is circulated to extraction distillation column, recycles.
2. the method for described rectifying and the integrated extraction high purity normal hexane of extraction according to claim 1, it is raw material that the aromatic hydrocarbons of aromatic extraction unit production of it is characterized in that refining oil is raffinated oil, raw material sources are extensive; The raw material main ingredient is C
5～C
8, wherein normal hexane content is 25%, methylcyclopentane content is 2.5%.
3. according to claim 1 described rectifying and the method that extracts integrated extraction high purity normal hexane is characterized in that adopting three tower process flow processs, its operational condition such as table 1:
Table 1 three tower process flow operations conditions
。
4. according to claim 3 described rectifying and the method that extracts integrated extraction high purity normal hexane, it is characterized in that rectifying tower T-1 adopts the band press operation, working pressure is 160kPa/a, the design tower diameter is φ 1400mm, adopt efficient DZ-II type filler, the packing section height is 35200mm, be divided into into eight sections, each section highly is respectively 4000mm, 4000mm, 4800mm, 4800mm, 4800mm, 4800mm, 4000mm, 4000mm, adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, opening for feed are arranged between second segment and the 3rd section filler, and side is adopted mouth and is arranged between the 6th section and the 7th section filler.
5. according to claim 3 described rectifying and the method that extracts integrated extraction high purity normal hexane, it is characterized in that extractive distillation column T-2 adopts decompression operation, working pressure is φ 1200mm for 70kPa/a designs tower diameter, adopt efficient DZ-III type filler, the total filler height is 30100mm, be divided into into seven sections, each section highly is respectively 3000mm, 4600mm, 4600mm, 4700mm, 4400mm, 4400mm, 4400mm, adopt high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, the extractant feed mouth is arranged between first paragraph filler and the second segment filler, and material inlet is arranged between the 4th section filler and the 5th section filler.
6. according to claim 3 described rectifying and the method that extracts integrated extraction high purity normal hexane, it is characterized in that extraction solvent recovery tower T-3 adopts decompression operation, working pressure is 40kPa/a, and the design tower diameter is φ 1000mm, and rectifying section adopts efficient DZ-III type filler, highly be 5000mm, stripping section adopts DZ-II type filler, and packed height 5500mm adopts high-efficiency liquid distributor between cat head and the packing section, configuration snappiness liquid header in the tower, opening for feed is arranged between two sections fillers.
7. according to claim 1 described rectifying and the method that extracts integrated extraction high purity normal hexane, it is characterized in that adopting the normal hexane content of continuous rectification and the production of extractive distillation process integration more than 99%, do not contain extraction solvent in the product, solvent consumption is less than 0.1%, yield of normal hexane is greater than 95%, and comparing with traditional rectifying can energy efficient more than 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210497953.4A CN102942434B (en) | 2012-11-29 | 2012-11-29 | Method extracting high purity n-hexane by integrating rectification and extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210497953.4A CN102942434B (en) | 2012-11-29 | 2012-11-29 | Method extracting high purity n-hexane by integrating rectification and extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102942434A true CN102942434A (en) | 2013-02-27 |
| CN102942434B CN102942434B (en) | 2014-12-03 |
Family
ID=47725455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210497953.4A Expired - Fee Related CN102942434B (en) | 2012-11-29 | 2012-11-29 | Method extracting high purity n-hexane by integrating rectification and extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942434B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242120A (en) * | 2013-04-27 | 2013-08-14 | 天津大学 | Circulating device and refining method of extractant in normal hexane, isohexane and benzene separation process |
| CN103664446A (en) * | 2013-12-17 | 2014-03-26 | 赛鼎工程有限公司 | Technology for separating n-hexane-methylcyclopentane through extractive distillation |
| CN104045500A (en) * | 2013-03-15 | 2014-09-17 | 中石化广州工程有限公司 | Highly pure polymer-grade n-hexane production method |
| CN105085142A (en) * | 2014-05-20 | 2015-11-25 | 中石化广州工程有限公司 | Production method for high-purity n-hexane |
| CN105085140A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of n-hexane for liquid chromatography-mass spectrometer |
| CN105194899A (en) * | 2015-10-16 | 2015-12-30 | 青岛科技大学 | Variable-diameter rectifying device and method for separating methylbenzene-isobutylbenzene mixture |
| CN107698481A (en) * | 2017-11-06 | 2018-02-16 | 黄河三角洲京博化工研究院有限公司 | A kind of renovation process of n-hexane, isohexane separator extractant |
| CN110256190A (en) * | 2019-06-20 | 2019-09-20 | 山东京博石油化工有限公司 | A kind of production method of food-grade n-hexane |
| WO2021017620A1 (en) * | 2019-07-26 | 2021-02-04 | 厦门金达威维生素有限公司 | Device and method for continuously extracting and drying butenone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765857A (en) * | 2005-11-16 | 2006-05-03 | 南京工业大学 | Extractive distillation separation method of normal hexane and methylcyclopentane |
| CN101696359A (en) * | 2009-10-30 | 2010-04-21 | 河北科技大学 | Method for preparing normal hexan solvent oil by using absorption-method deep debenzolization |
| CN101974347A (en) * | 2010-09-17 | 2011-02-16 | 天津精华石化有限公司 | Process for producing solvent oil by removing aromatic hydrocarbon from raffinate oil |
-
2012
- 2012-11-29 CN CN201210497953.4A patent/CN102942434B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765857A (en) * | 2005-11-16 | 2006-05-03 | 南京工业大学 | Extractive distillation separation method of normal hexane and methylcyclopentane |
| CN101696359A (en) * | 2009-10-30 | 2010-04-21 | 河北科技大学 | Method for preparing normal hexan solvent oil by using absorption-method deep debenzolization |
| CN101974347A (en) * | 2010-09-17 | 2011-02-16 | 天津精华石化有限公司 | Process for producing solvent oil by removing aromatic hydrocarbon from raffinate oil |
Non-Patent Citations (3)
| Title |
|---|
| 李春利 等: "正己烷-甲基环戊烷-N-甲基吡咯烷酮三组分系汽液平衡的测定及萃取精馏的模拟", 《石油化工》 * |
| 李章平 等: "芳烃抽余油的综合利用", 《精细石油化工》 * |
| 赵利霞 等: "正己烷生产纯化工艺的理论及设备研究进展", 《现代化工》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045500A (en) * | 2013-03-15 | 2014-09-17 | 中石化广州工程有限公司 | Highly pure polymer-grade n-hexane production method |
| CN104045500B (en) * | 2013-03-15 | 2016-04-13 | 中石化广州工程有限公司 | A kind of production method of high purity polymerization-grade normal hexane |
| CN103242120A (en) * | 2013-04-27 | 2013-08-14 | 天津大学 | Circulating device and refining method of extractant in normal hexane, isohexane and benzene separation process |
| CN103242120B (en) * | 2013-04-27 | 2015-11-04 | 天津大学 | Extraction agent circulation device and process for purification in a kind of normal hexane, isohexane and benzene sepn process |
| CN103664446A (en) * | 2013-12-17 | 2014-03-26 | 赛鼎工程有限公司 | Technology for separating n-hexane-methylcyclopentane through extractive distillation |
| CN105085140A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of n-hexane for liquid chromatography-mass spectrometer |
| CN105085142A (en) * | 2014-05-20 | 2015-11-25 | 中石化广州工程有限公司 | Production method for high-purity n-hexane |
| CN105085142B (en) * | 2014-05-20 | 2018-03-20 | 中石化广州工程有限公司 | A kind of production method of high-purity n-hexane |
| CN105194899A (en) * | 2015-10-16 | 2015-12-30 | 青岛科技大学 | Variable-diameter rectifying device and method for separating methylbenzene-isobutylbenzene mixture |
| CN107698481A (en) * | 2017-11-06 | 2018-02-16 | 黄河三角洲京博化工研究院有限公司 | A kind of renovation process of n-hexane, isohexane separator extractant |
| CN110256190A (en) * | 2019-06-20 | 2019-09-20 | 山东京博石油化工有限公司 | A kind of production method of food-grade n-hexane |
| WO2021017620A1 (en) * | 2019-07-26 | 2021-02-04 | 厦门金达威维生素有限公司 | Device and method for continuously extracting and drying butenone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102942434B (en) | 2014-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102942434B (en) | Method extracting high purity n-hexane by integrating rectification and extraction | |
| CN103086823B (en) | Method and device for separating n-hexane, isohexane and benzene | |
| CN103520945B (en) | The refining plant of crude benzole hydrogenation product and method | |
| CN103073383B (en) | Method and device for separating isohexane, n-hexane and benzene | |
| CN101050159B (en) | Method for separating butane and butylenes, and dedicated installation | |
| CN103242121B (en) | The working method of normal hexane and benzene extracting rectifying | |
| CN105367368B (en) | The method that high-purity isobutylene is prepared from C_4 hydrocarbon | |
| KR101970761B1 (en) | 1,2,4-Trimethylbenzene separation equipment using extractive distillation and separation method with the equipment | |
| EP2432755B1 (en) | Fractional extraction of butadiene | |
| CN102190555A (en) | Method for recovering styrene | |
| EP3942000B1 (en) | Method of producing hexane from a c5-c6 isomerization unit stream using a dividing wall column | |
| CN101234947B (en) | Method for removing micro-benzene in solvent oil or hexane refining process | |
| CN102951986A (en) | Method for separation of C5 fraction and preparation of chemical grade isoprene | |
| CN111647427A (en) | Method for increasing carbon chain length of Fischer-Tropsch alpha-olefin | |
| US10047022B2 (en) | Process and apparatus for separating C5 di-olefins from pyrolysis gasoline | |
| CN105503499B (en) | C9Between aromatic hydrocarbons mixture extracting rectifying, the separation method of p-methyl-ethylbenzene | |
| CN101830830A (en) | Method for separating acetonitrile-toluene by extractive distillation through dividing wall rectifying tower | |
| CN202246472U (en) | Device for extracting normal hexane and isohexane from crude hexane | |
| CN103242120B (en) | Extraction agent circulation device and process for purification in a kind of normal hexane, isohexane and benzene sepn process | |
| CN107879881A (en) | A kind of separation method of polymerization grade isoprene | |
| CN102527072A (en) | Batch extraction distillation separation method for propyl alcohol-propyl formate azeotropic mixture | |
| CN104557409B (en) | The method of the amylene of high-purity 1 | |
| CN104557410B (en) | A kind of method of the amylene of high-purity 1 | |
| CN105218313B (en) | Methanol purification process containing acetaldehyde impurities | |
| CN103864551A (en) | Method for increasing acetonitrile method 1,3-butadiene extraction equipment raffinate product specification |
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: 20141203 Termination date: 20201129 |