CN101289362A - Process for preparing 1-amylene by separating C5 distillate of petroleum - Google Patents
Process for preparing 1-amylene by separating C5 distillate of petroleum Download PDFInfo
- Publication number
- CN101289362A CN101289362A CNA2007100396742A CN200710039674A CN101289362A CN 101289362 A CN101289362 A CN 101289362A CN A2007100396742 A CNA2007100396742 A CN A2007100396742A CN 200710039674 A CN200710039674 A CN 200710039674A CN 101289362 A CN101289362 A CN 101289362A
- Authority
- CN
- China
- Prior art keywords
- amylene
- tower still
- temperature
- tower
- extraction agent
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method which is used for preparing 1-pentene by separating petroleum C5 fraction and takes raffinate C5 obtained after separating diolefin and isoamylene by extracting as raw materials. The process comprises that the raw materials are extracted and distilled, and the extractant is N and N-dimethylformamide, the feeding weight ratio of the raw materials and the extractant is 1:5 to 1:12, C5 saturated hydrocarbon materials are discharged from a column top, and the materials richly containing 1-pentene and the extractant are obtained in a column bottom; the materials in the column bottom obtained in the process 1 are distilled so as to recycle the extractant, the materials richly containing 1-pentene are obtained in the column top, the extractant is obtained in the column bottom, and the extractant can be recycled; the materials in the column top obtained in the process 2 are distilled and separated so as to remove heavy components, the crude product of 1-pentene are obtained from the column top, and the materials with heavy components are discharged from the column bottom; and the crude product of 1-pentene obtained in the process 3 is distilled and refined so as to remove light components, the materials in the column bottom are taken and a refined product of 1-pentene is obtained. By processing at a much deeper degree, the method of the invention solves a technical problem that 1-pentene in C5 fraction can not be utilized by the prior art.
Description
Technical field
The present invention relates to the separation method of Petrocarbon 5 distillate, particularly separate the method for producing the 1-amylene by the Petrocarbon 5 distillate by technological processs such as rectifying, extracting rectifyings.
Background technology
The a considerable amount of C5 fractions of process by-product of petroleum cracking system ethene, its amount is about 10% of ethylene yield, is the effective way that improves the ethylene production economic benefit to the comprehensive utilization of C5 fraction.The comprehensive utilization of C5 fraction at present mainly is extracting to be carried out in C5 fraction separate, and obtains being worth diolefin and isopentene such as higher m-pentadiene, isoprene and dicyclopentadiene.The raffinate carbon-5 material that has separated diolefin and isopentene through extracting accounts for 10～15% of C5 fraction raw material.The component boiling point of raffinate carbon-5 is very approaching, its separation difficulty, and the oil that generally only acts as a fuel uses.For this raffinate carbon-5 material, existing deep processing and utilization is the mixture that obtains pentane and iso-pentane by full hydrogenation, introduces as Chinese patent ZL02145057.9, ZL02145056.0.The mixture of pentane, pentane and iso-pentane can be used as whipping agent, extraction agent, green refrigerant and organic solvent etc., and this method has further improved the utility value of raffinate carbon-5.But, in fact contain 30～40% the amylene of having an appointment in the raffinate carbon-5 material and (comprise 1-amylene and 2-amylene, both ratios are about 1: 2), and the amylene higher industrial chemicals that is using value, as the 1-amylene is synthetic, the medicine synthetic important monomer of polymer modification and complicated organometallics, and its price is also far above pentane and iso-pentane.The defective of full hydrogenation technique is to make that amylene can't obtain utilizing.
Summary of the invention
The invention provides and a kind ofly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, it is by carrying out the more processing of the degree of depth to the oil C5 fraction, can't utilize this technical problem of 1-amylene in the C5 fraction to solve prior art.
Below be the detailed technical scheme of the present invention:
A kind ofly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, this method is a raw material with the raffinate carbon-5 that extracting has separated behind diolefin and the isopentene, and its process comprises:
1) raw material carries out extracting rectifying, extraction agent is N, dinethylformamide, raw material is 1: 5～1: 12 with the feed weight ratio of extraction agent, the extractant feed temperature is 20～45 ℃, tower top temperature is 25～36 ℃, tower still temperature is 60～120 ℃, and working pressure is a normal pressure, and reflux ratio is 1～6, cat head is discharged carbon five stable hydrocarbon materials, and the tower still gets the material of enrichment amylene-1 and extraction agent;
2) the tower still material of process 1 carries out rectifying to reclaim extraction agent, and tower top temperature is 26～32 ℃, and tower still temperature is 110～150 ℃, and working pressure is a normal pressure, and reflux ratio is 1～6, and cat head gets the material of enrichment 1-amylene, and the tower still gets extraction agent, the extraction agent recycled;
3) the cat head material of process 2 carries out rectifying separation to remove heavy constituent, and tower top temperature is 26～32 ℃, and tower still temperature is 35～45 ℃, and working pressure is a normal pressure, and reflux ratio is 20～50, gets the thick product of 1-amylene by cat head, and the tower still is discharged the heavy constituent material;
4) the thick product of 1-amylene that obtains of process 3 carries out that rectified purified tower top temperature is 25～29 ℃ to remove light constituent, and tower still temperature is 35～45 ℃, working pressure is a normal pressure, reflux ratio is 20～50, and cat head is discharged the light constituent material, gets tower still material and gets 1-amylene purified product.
Said process 1 described raw material is preferably 1: 6 with the feed weight ratio of extraction agent～and 1: 10, the extractant feed temperature is preferably 30～40 ℃, and tower still temperature is preferably 65～100 ℃, and reflux ratio is preferably 1～4;
Process 2 described tower top temperatures are preferably 27～30 ℃, and tower still temperature is preferably 120～140 ℃, and reflux ratio is preferably 1～4;
Process 3 described tower top temperatures are preferably 27～30 ℃, and tower still temperature is preferably 38～42 ℃, and reflux ratio is preferably 30～40;
Process 4 described tower still temperature are preferably 38～42 ℃, and reflux ratio is preferably 30～40.
Key of the present invention is to have selected a kind of suitable technology, to isolate 1-amylene product effectively from raffinate carbon-5.Whole technological process mainly comprises four parts, wherein:
The purpose of process 1 is the saturated alkane of removing in the raw material material, is mainly iso-pentane.Because iso-pentane is difficult to be separated with the 1-amylene with the method for rectifying, adopt extracting rectifying.The key of process 1 is selection of Extractant and Selection of technological conditions.Extractive distillation column can adopt packing tower, and theoretical plate number is advisable with 30～60.The same with most of extraction rectification techniques, extraction agent is preferably by the top charging of tower, and material preferably by in the stripping section near the position charging of tower still.
Process 2 is simple rectifying, its objective is to realize separating of extraction agent and carbon five materials, because both atmospheric boiling point differences are bigger, can realize both separation fully by the simple rectifying once the step.The extraction agent that reclaims can return the abstraction distillation system recycled.Rectifying tower can adopt packing tower, and theoretical plate number is advisable with 15～30, material preferably by in the stripping section near the position charging of tower still.
The purpose of process 3 is the heavy constituent in the removal process 2 cat head materials, mainly comprises Skellysolve A, 2-amylene and a spot of isopentene.The atmospheric boiling point of these heavy constituent materials and 1-amylene are also comparatively approaching, so adopt precise distillation.Rectifying tower can adopt packing tower, and theoretical plate number is at least 40, generally can be no more than 100, is advisable with 40～80, and it is comparatively suitable near the position of tower still that the material feeding mouth is arranged in stripping section.
Process 4 is a precise distillation also, its objective is that the thick product of 1-amylene that process 3 is obtained makes with extra care, and isolates light constituent impurity.Rectifying tower can adopt packing tower, and theoretical plate number is at least 40, generally can be no more than 100, is advisable with 40～80, and it is comparatively suitable near the position of tower still that the material feeding mouth is arranged in stripping section.
Positive effect of the present invention is the working depth by further raising raffinate carbon-5 material, has obtained higher carbon five products of economic worth, and the more perfect comprehensive utilization means of C 5 fraction are exhausted the waste that has reduced petroleum resources possibly.
Below further describe details of the present invention by specific embodiment.1-amylene product yield is defined as among the embodiment:
The raffinate carbon-5 fraction raw material composition that each embodiment uses sees Table 1,
Table 1.
| Component | Content (weight %) |
| The 1-amylene | 17.5 |
| The 2-amylene | 28.6 |
| Skellysolve A | 42.1 |
| Iso-pentane | 5.5 |
| Isopentene | 4.3 |
| 1, the 4-pentadiene | 1.3 |
| Materials such as other hydro carbons | Surplus |
Embodiment
[embodiment 1～10]
Separate by following process as the listed raffinate carbon-5 raw material of table 1 forming:
1) raw material carries out extracting rectifying, and extraction agent is N, dinethylformamide.Extractive distillation column is a packing tower, and theoretical plate number is 40, and material is by the position charging of the 32nd column plate, and extraction agent is by the position charging of the 4th column plate, and material feeding speed is 1.0kg/h.Working pressure is a normal pressure, and it is 2 listed that other rectification process condition sees Table.Cat head is discharged carbon five stable hydrocarbon materials, and the tower still gets the material of enrichment 1-amylene and extraction agent;
2) the tower still material of process 1 carries out rectifying to reclaim extraction agent, and rectifying tower is a packing tower, and theoretical plate number is 20, and raw material is by the position charging of the 16th column plate.Working pressure is a normal pressure, and it is 3 listed that other extraction rectification technique condition sees Table.Cat head gets the material of enrichment 1-amylene, and the tower still gets extraction agent, and extraction agent returns the abstraction distillation system recycled;
3) the cat head material of process 2 carries out rectifying separation to remove heavy constituent, and rectifying tower is a packing tower, and theoretical plate number is 50, and raw material is by the position charging of the 40th column plate, and working pressure is a normal pressure, and it is 4 listed that other rectification process condition sees Table.Get the thick product of 1-amylene by cat head, the tower still is discharged the heavy constituent material;
4) the thick product of 1-amylene that obtains of process 3 carries out that rectified purified rectifying tower is a packing tower to remove light constituent, and theoretical plate number is 50, and raw material is by the position charging of the 40th column plate.Working pressure is a normal pressure, and it is 5 listed that other rectification process condition sees Table.Cat head is discharged the light constituent material, gets tower still material and gets 1-amylene purified product.
It is 6 listed that product yield, the product purity of each embodiment 1-amylene sees Table.
Table 2.
| Material/extraction agent (feed weight ratio) | The extractant feed temperature (℃) | Tower top temperature (℃) | Tower still temperature (℃) | Reflux ratio | |
| Embodiment 1 | 1∶5 | 20 | 25 | 60 | 6 |
| Embodiment 2 | 1∶6 | 30 | 33 | 65 | 3 |
| Embodiment 3 | 1∶7 | 35 | 35 | 69 | 1 |
| Embodiment 4 | 1∶7.5 | 40 | 34 | 73 | 4 |
| Embodiment 5 | 1∶8 | 38 | 35 | 78 | 3 |
| Embodiment 6 | 1∶8.5 | 36 | 34 | 84 | 2 |
| Embodiment 7 | 1∶9 | 37 | 35 | 91 | 1 |
| Embodiment 8 | 1∶9.5 | 39 | 36 | 95 | 2 |
| Embodiment 9 | 1∶10 | 42 | 34 | 100 | 3 |
| Embodiment 10 | 1∶12 | 45 | 35 | 120 | 2 |
Table 3.
| Tower top temperature (℃) | Tower still temperature (℃) | Reflux ratio | |
| Embodiment 1 | 26 | 110 | 6 |
| Embodiment 2 | 29 | 128 | 1 |
| Embodiment 3 | 30 | 125 | 4 |
| Embodiment 4 | 30 | 140 | 3 |
| Embodiment 5 | 30 | 135 | 2 |
| Embodiment 6 | 30 | 138 | 3 |
| Embodiment 7 | 29 | 150 | 2 |
| Embodiment 8 | 27 | 120 | 3 |
| Embodiment 9 | 30 | 132 | 2 |
| Embodiment 10 | 32 | 145 | 1 |
Table 4.
| Tower top temperature (℃) | Tower still temperature (℃) | Reflux ratio | |
| Embodiment 1 | 26 | 37 | 50 |
| Embodiment 2 | 28 | 39 | 36 |
| Embodiment 3 | 29 | 40 | 38 |
| Embodiment 4 | 29 | 38 | 30 |
| Embodiment 5 | 30 | 36 | 25 |
| Embodiment 6 | 29 | 35 | 32 |
| Embodiment 7 | 29 | 41 | 34 |
| Embodiment 8 | 27 | 45 | 20 |
| Embodiment 9 | 29 | 38 | 45 |
| Embodiment 10 | 32 | 42 | 40 |
Table 5.
| Tower top temperature (℃) | Tower still temperature (℃) | Reflux ratio | |
| Embodiment 1 | 25 | 36 | 40 |
| Embodiment 2 | 25 | 38 | 38 |
| Embodiment 3 | 26 | 35 | 36 |
| Embodiment 4 | 26 | 37 | 32 |
| Embodiment 5 | 29 | 40 | 25 |
| Embodiment 6 | 27 | 39 | 30 |
| Embodiment 7 | 27 | 42 | 45 |
| Embodiment 8 | 25 | 45 | 20 |
| Embodiment 9 | 28 | 41 | 34 |
| Embodiment 10 | 29 | 40 | 50 |
Table 6.
| 1-amylene product yield (%) | 1-amylene product purity (%) | |
| Embodiment 1 | 79.2 | 97.0 |
| Embodiment 2 | 81.0 | 96.8 |
| Embodiment 3 | 80.8 | 97.2 |
| Embodiment 4 | 80.5 | 97.5 |
| Embodiment 5 | 82.2 | 97.3 |
| Embodiment 6 | 81.3 | 97.1 |
| Embodiment 7 | 81.5 | 97.4 |
| Embodiment 8 | 80.9 | 97.0 |
| Embodiment 9 | 79.9 | 97.3 |
| Embodiment 10 | 80.1 | 97.4 |
Claims (5)
1, a kind ofly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, this method is a raw material with the raffinate carbon-5 that extracting has separated behind diolefin and the isopentene, and its process comprises:
1) raw material carries out extracting rectifying, extraction agent is N, dinethylformamide, raw material is 1: 5～1: 12 with the feed weight ratio of extraction agent, the extractant feed temperature is 20～45 ℃, tower top temperature is 25～36 ℃, tower still temperature is 60～120 ℃, and working pressure is a normal pressure, and reflux ratio is 1～6, cat head is discharged carbon five stable hydrocarbon materials, and the tower still gets the material of enrichment 1-amylene and extraction agent;
2) the tower still material of process 1 carries out rectifying to reclaim extraction agent, and tower top temperature is 26～32 ℃, and tower still temperature is 110～150 ℃, and working pressure is a normal pressure, and reflux ratio is 1～6, and cat head gets the material of enrichment 1-amylene, and the tower still gets extraction agent, the extraction agent recycled;
3) the cat head material of process 2 carries out rectifying separation to remove heavy constituent, and tower top temperature is 26～32 ℃, and tower still temperature is 35～45 ℃, and working pressure is a normal pressure, and reflux ratio is 20～50, gets the thick product of 1-amylene by cat head, and the tower still is discharged the heavy constituent material;
4) the thick product of 1-amylene that obtains of process 3 carries out that rectified purified tower top temperature is 25～29 ℃ to remove light constituent, and tower still temperature is 35～45 ℃, working pressure is a normal pressure, reflux ratio is 20～50, and cat head is discharged the light constituent material, gets tower still material and gets 1-amylene purified product.
2, the method for producing the 1-amylene of separating by the Petrocarbon 5 distillate according to claim 1, it is characterized in that the process 1 described raw material and the feed weight ratio of extraction agent are 1: 6～1: 10, the extractant feed temperature is 30～40 ℃, and tower still temperature is 65～100 ℃, and reflux ratio is 1～4.
3, according to claim 1ly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, it is characterized in that process 2 described tower top temperatures are 27～30 ℃, tower still temperature is 120～140 ℃, and reflux ratio is 1～4.
4, according to claim 1ly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, it is characterized in that process 3 described tower top temperatures are 27～30 ℃, tower still temperature is 38～42 ℃, and reflux ratio is 30～40.
5, according to claim 1ly separate the method produce the 1-amylene by the Petrocarbon 5 distillate, it is characterized in that process 4 described tower still temperature are 38～42 ℃, reflux ratio is 30～40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710039674A CN101289362B (en) | 2007-04-19 | 2007-04-19 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710039674A CN101289362B (en) | 2007-04-19 | 2007-04-19 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101289362A true CN101289362A (en) | 2008-10-22 |
| CN101289362B CN101289362B (en) | 2012-10-24 |
Family
ID=40033841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710039674A Active CN101289362B (en) | 2007-04-19 | 2007-04-19 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101289362B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333042A (en) * | 2013-07-24 | 2013-10-02 | 上海派尔科化工材料有限公司 | Method for preparing pentene |
| CN103333041A (en) * | 2013-07-24 | 2013-10-02 | 上海派尔科化工材料有限公司 | Method for preparing n-pentene |
| CN103724194A (en) * | 2012-10-16 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing acetic acid sec-pentyl ester |
| CN104557407A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of isomerizing 2-pentene into 1-pentene |
| CN104557409A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of preparing high-purity 1-pentene |
| CN104557410A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of preparing high-purity 1-pentene |
| CN105061128A (en) * | 2015-07-31 | 2015-11-18 | 濮阳市新豫石油化工有限责任公司 | Extraction dechlorination method for petroleum unpolymerized C5 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5681526A (en) * | 1979-12-06 | 1981-07-03 | Nippon Zeon Co Ltd | Polymerization prevention of conjugated dienes |
| CN1055281C (en) * | 1996-03-20 | 2000-08-09 | 中国石油化工总公司 | Method for separation of petroleum cracking C5 fraction by liquid phase feeding extraction rectification |
| CN1331830C (en) * | 2004-12-24 | 2007-08-15 | 中国石化上海石油化工股份有限公司 | Refining separation method for coarse piperyene |
-
2007
- 2007-04-19 CN CN200710039674A patent/CN101289362B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724194A (en) * | 2012-10-16 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing acetic acid sec-pentyl ester |
| CN103333041B (en) * | 2013-07-24 | 2015-09-23 | 上海派尔科化工材料有限公司 | A kind of preparation method of positive amylene |
| CN103333041A (en) * | 2013-07-24 | 2013-10-02 | 上海派尔科化工材料有限公司 | Method for preparing n-pentene |
| CN103333042A (en) * | 2013-07-24 | 2013-10-02 | 上海派尔科化工材料有限公司 | Method for preparing pentene |
| CN103333042B (en) * | 2013-07-24 | 2015-09-23 | 上海派尔科化工材料有限公司 | A kind of preparation method of amylene |
| CN104557407A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of isomerizing 2-pentene into 1-pentene |
| CN104557410A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of preparing high-purity 1-pentene |
| CN104557409A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A method of preparing high-purity 1-pentene |
| CN104557410B (en) * | 2013-10-11 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of the amylene of high-purity 1 |
| CN104557407B (en) * | 2013-10-11 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of 2 pentene isomerization is the method for 1 amylene |
| CN104557409B (en) * | 2013-10-11 | 2018-03-20 | 中国石油化工股份有限公司 | The method of the amylene of high-purity 1 |
| CN105061128A (en) * | 2015-07-31 | 2015-11-18 | 濮阳市新豫石油化工有限责任公司 | Extraction dechlorination method for petroleum unpolymerized C5 |
| CN105061128B (en) * | 2015-07-31 | 2016-08-10 | 濮阳市新豫石油化工有限责任公司 | A kind of the most poly-C5 of oil extracts dechlorination method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101289362B (en) | 2012-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101289363B (en) | Process for preparing 1-amylene by separating C5 distillate of petroleum | |
| CN101289362B (en) | Process for preparing 1-amylene by separating C5 distillate of petroleum | |
| CN102010285B (en) | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions | |
| CN100447118C (en) | Extractive distillation separation method of normal hexane and methylcyclopentane | |
| CN103086823B (en) | Method and device for separating n-hexane, isohexane and benzene | |
| CN111377800B (en) | Separation device and separation method for coal-to-ethanol liquid phase product | |
| CN101289360B (en) | Process for preparing 2-amylene by separating C5 distillate of petroleum | |
| CN103242121B (en) | The working method of normal hexane and benzene extracting rectifying | |
| CN101774879B (en) | Method for simultaneously extracting high-purity beta-methylnaphthalene and indole from coal tar | |
| CN101289361B (en) | Process for preparing 2-amylene by separating C5 distillate of petroleum | |
| CN102633597A (en) | Process of recovering ethanol, propyl alcohol and isobutyl alcohol from polyalcohol-water mixture | |
| CN109704907B (en) | Method for preparing hexane from raffinate oil | |
| CN101234947B (en) | Method for removing micro-benzene in solvent oil or hexane refining process | |
| CN102336622A (en) | Reclaiming device and separation method for heavy component residue of coked crude benzene hydrogenation process | |
| CN106478339A (en) | A kind of isolating cyclopentane and the method for 2,2- dimethylbutane | |
| CN104276912A (en) | Method for separating byproducts C9-C10 fractions in ethylene preparation through petroleum cracking and increasing yield | |
| CN105585412A (en) | Method for preparing polymer-grade piperylene | |
| CN101643379A (en) | Preparation method of high-purity 1,3-pentadiene | |
| CN109704908B (en) | Method for preparing hexane from aromatic raffinate oil | |
| CN100503529C (en) | Separation method for refining coarse piperyene | |
| CN102399122A (en) | Method for preparing cyclopentadiene and methyl cyclopentadiene | |
| CN100503526C (en) | Method for refining crude piperyene | |
| CN104557410B (en) | A kind of method of the amylene of high-purity 1 | |
| CN103570486A (en) | Method for obtaining isoprene from C5 fraction | |
| CN104557409B (en) | The method of the amylene of high-purity 1 |
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 |