CN102516419A - Three-kettle condensation method used in solution polymerization production of synthetic rubber - Google Patents
Three-kettle condensation method used in solution polymerization production of synthetic rubber Download PDFInfo
- Publication number
- CN102516419A CN102516419A CN2011104074640A CN201110407464A CN102516419A CN 102516419 A CN102516419 A CN 102516419A CN 2011104074640 A CN2011104074640 A CN 2011104074640A CN 201110407464 A CN201110407464 A CN 201110407464A CN 102516419 A CN102516419 A CN 102516419A
- Authority
- CN
- China
- Prior art keywords
- still
- cohesion
- solvent
- hot water
- condensation
- 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
- Adhesives Or Adhesive Processes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a three-kettle condensation method used in solution polymerization production of synthetic rubber. The method comprises the following steps: a, fully mixing a rubber solution obtained after polymerization with cyclically used hot water and a dispersant so as to form a heterogeneous mixture; b, injecting the mixture into a primary condensation kettle, injecting steam from the bottom of the primary condensation kettle, allowing a vapor phase with a solvent to enter into a condenser from the top of the primary condensation kettle and to enter into an oil-water layering tank after condensation in the condenser, and after separation, allowing the solvent to enter into a refining system, condensed water to enter into a condensation system and the rubber solution to be condensed into rubber particles; c, sending the rubber particles and hot water in the primary condensation kettle to a secondary condensation kettle, injecting steam from the bottom of the secondary condensation kettle and allowing a vapor phase with a solvent to enter into the primary condensation kettle after pressurization; and d, sending the rubber particles and water in the secondary condensation kettle to a ternary condensation kettle, allowing a vapor phase with a solvent to enter into the primary condensation kettle after pressurization, sending the rubber particles to subsequent procedures and conveying hot water into the primary condensation kettle for cyclic utilization. The method greatly improves heat and mass transfer effects in the condensation process of the rubber solution, has the advantages of low consumption of steam, small residual of the solvent, uniform rubber particle size, etc., and has obvious economic benefits and substantial environmental benefits.
Description
Technical field
The invention belongs to the viton production technical field, relate to three still condensing methods in a kind of solution polymerization process viton production process with good energy conservation and consumption reduction effects.
Background technology
During the solution polymerization process viton is produced; The polymerization process of reaction monomers is in a large amount of solvents, to accomplish; Generally reaction monomers is dense is controlled between 5%～20%; The polymers soln of accomplishing reaction generally adopts elutriation coacervation water steam stripped in hot water to remove solvent and unreacted monomer at present, and the rubber cohesion is particulate state, and then changes subsequent processing over to and dehydrate.
Traditional elutriation cohesion process is to adopt two still condensation techniques; This method adopts two cohesion stills; Spray into glue in the first still, hot water gets into from top, and steam gets into from the bottom; Glue is condensed into and gets into second still with the hot water pumping behind the micelle and further remove solvent wherein, is sent to postprocessing working procedures then and carries out further drying.Solvent and unreacted monomer reclaim after condensation and use with the top extraction of gas phase form self coagulation still.
Because a large amount of solvents need reclaim through agglomeration process, so cohesion process becomes energy consumption and the maximum operation of solvent consumption in the viton production process.In agglomeration process, what at first will guarantee is solvent recovering yield, reduce the residual quantity of solvent in the micelle of cohesion back as far as possible, can be through improving condensation temperature, and measures such as the increase cohesion residence time are to reach this purpose; The variation of condensation temperature and pressure simultaneously directly has influence on the consumption of steam, and in viton was produced, the steam consumption of cohesion process accounted for more than 60% of the total steam consumption of device; In addition, guarantee that the size of cohesion back micelle also is the main task of cohesion process, excessive or too small micelle all can cause the obstruction of operation delivery system thereafter, influences ordinary production.
According to agglomeration process mechanism, be the deceleration agglomeration phase in the later stage of agglomeration process, a large amount of solvents has been accomplished vaporescence, and remaining solvent is limited by in micelle velocity of diffusion from inside to outside in a small amount of micelle.Therefore to reach and reduce residual solvent requirement in the polymkeric substance, need to prolong pool time.The two still condensation techniques that generally adopt in producing at present can make the remaining solvent of cohesion post polymerization thing reduce to about 1%, and lower residual quantity need consume more substantial steam or reduce productivity levels.The solvent that residues in the polymerization is diffused in the air as fugitive constituent when postprocessing working procedures is carried out the extrusion dehydration drying, and atmospheric environment is all caused detrimentally affect.Along with the implementation of HSE management system, improving constantly of environmental protection consciousness requires improving constantly to material consumption in the synthetic rubber production and energy consumption, and key is updating of elutriation cohesion process and perfect.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned pair of still cohesion process, three still condensing methods in a kind of solution polymerization process viton production are provided, to solve steam consumption height in the agglomeration process, the problem that dissolvent residual content is higher.
Three still condensing methods during a kind of solution polymerization process viton provided by the invention is produced, this method is undertaken by following step:
Glue after a, the polyreaction carries out thorough mixing with hot water and the dispersion agent that recycles, and forms non-homogeneous mixture;
B, this mixture sprayed inject the first still of cohesion; Steam injects from condensing first still bottom; The vapour phase of entrapment solvent is gone into condensing surface from the still jacking, after condenser condenses, gets into the profit stratified, and the solvent after separating gets into refining system; Water of condensation gets into condensed system and recycles, and glue is condensed into micelle;
C, the micelle that will condense in the first still are sent into still in the cohesion with hot water, and steam still bottom from cohesion is injected, and the pressurized back of the vapour phase of entrapment solvent gets into the first still of cohesion;
D, will condense in micelle water in the still be sent to the last still of cohesion, the vapour phase pressurization back of entrapment solvent gets into the first still of cohesion, micelle is sent into postprocessing working procedures, hot water is sent to the first still of cohesion and reuses;
Wherein, the temperature of condensing first still is 70～90 ℃, and pressure is 0.01～0.1Mpa, and the temperature of still is 80～98 ℃ in the cohesion, and pressure is 0.01～0.06Mpa, and the temperature of condensing last still is 80～95 ℃, and pressure is 0.01～0.04Mpa.
In step a, the concentration of glue is 5～20%, 85～98 ℃ of the temperature of hot water, and the volume ratio of hot water and glue flow is 2～10, the content of dispersion agent in condensed system is 5～100ppm.
For improving the glue flocculating result; The present invention has adopted multiple measure with the heat and mass effect in the strengthening process; Like ternary premix technology, the uniform mixing through hot water and dispersion agent and glue not only improves the glue dispersion effect; The glue of preheating has simultaneously guaranteed the heat and mass effect in the agglomeration process; Adopted the vapo(u)r blasting technology; Still is drawn with last still High Temperature Gas mutually in will condensing; The thermal source of the first still of conduct cohesion after the vapor jet pump pressurization; On the one hand reduce the open steam flow in the agglomeration process, can effectively control the service temperature pressure of still and last still in the cohesion on the other hand, reduced the thermosteresis of agglomeration process; Adopted new and effective dispersion agent, the micelle granularity after reducing to condense, because particle size analysis reduces, solvent diffusion speed improves, thereby improves solvent recuperation efficient; Adopt the water of condensation recovery and utilization technology, reduce the consumption of water, reduce influence environment.
Technology of the present invention can be widely used in various solution polymerization process viton such as cis-1,4-polybutadiene rubber (BR), solution styrene butadiene rubber (SSBR), solution polymerization process ethylene-propylene rubber(EPR), polyisoprene rubber (IR) and styrenic block copolymer SBC (SBS, SIS, the SEBS) production, and employed solvent is carbon six oil, normal hexane or hexanaphthene etc.Compared with prior art,
The present invention strengthens the heat transfer and the mass transfer process of agglomeration process when prolonging the cohesion residence time, make full use of the cohesion process characteristics, reaches energy saving purposes.The present invention has obviously improved flocculating result, through the enhancements to agglomeration process, solvent remaining in the polymer billet is obviously reduced, and the steam consumption in the agglomeration process also declines to a great extent, and remarkable economic efficiency and social benefit are arranged.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment further specifies the present invention below in conjunction with the polyisoprene rubber cohesion, but and unrestricted range of application of the present invention.
Embodiment 1:
As shown in Figure 1; The glue of the glue content 10% after the polyreaction is delivered to cohesion process, carry out thorough mixing, form non-homogeneous mixture through ternary premixed device 1 and the hot water and the dispersion agent that recycle; Wherein, 85 ℃ of the temperature of hot water, hot water and glue throughput ratio are 2, dispersion agent content in mixture is 20ppm.
Inject the first still 8 of cohesion through the glue nozzle ejection then, steam injects from condensing first still 8 bottoms, and the circulating hot water still middle part of confessing one's crime gets into and mends to keep level stability; Glue and steam, hot water under stirring action, the abundant heat and mass effect of glue and hot water and vapor generation, glue disperses rapidly; The vapour phase of entrapment solvent is gone into condensing surface 2 from the still jacking; After condensing surface 2 condensations, get into profit stratified 4, the solvent after separating gets into refining system, and water of condensation gets into condensed system and recycles.
And glue is condensed into micelle and sends into cohesion still 6 by particle pump 7 from still middle part or top with the mixture of hot water; Steam still 6 bottoms from cohesion are injected and are kept temperature in the still to keep; Under stirring action, the vapour phase of entrapment solvent is got into the first still 8 of cohesion by vapor jet pump 3 pressurization backs.
Micelle water is sent to the last still 5 of cohesion through particle pump 9; In the last still 5 of cohesion; Residual solvent in the micelle progressively spreads and volatilizees, and the vapour phase of entrapment solvent is got into the first still 8 of cohesion by vapor jet pump 3 pressurization backs, and the micelle water of accomplishing agglomeration process is sent to postprocessing working procedures through particle pump 10 to be separated; Micelle gets into postprocessing working procedures, and hot water is sent to the first still 8 of cohesion through hot water pump and reuses.
Wherein, the temperature of condensing first still 8 is 70 ℃, and pressure is 0.1Mpa, and the temperature of still 6 is 98 ℃ in the cohesion, and pressure is 0.01Mpa, and the temperature of condensing last still 5 is 80 ℃, and pressure is 0.04Mpa.
This viton cohesion process makes the micelle residence time increase by 1 times, and solvent is lower than 0.10% in the micelle, and steam consumption only is about 80% of two still cohesions.
Embodiment 2:
As shown in Figure 1; The glue of the glue content 20% after the polyreaction is delivered to cohesion process, carry out thorough mixing, form non-homogeneous mixture through ternary premixed device 1 and the hot water and the dispersion agent that recycle; Wherein, 98 ℃ of the temperature of hot water, hot water and glue throughput ratio are 4, dispersion agent content in mixture is 20ppm.
Inject the first still 8 of cohesion through the glue nozzle ejection then, steam injects from condensing first still 8 bottoms, and the circulating hot water still middle part of confessing one's crime gets into and mends to keep level stability; Glue and steam, hot water under stirring action, the abundant heat and mass effect of glue and hot water and vapor generation, glue disperses rapidly; The vapour phase of entrapment solvent is gone into condensing surface 2 from the still jacking; After condensing surface 2 condensations, get into profit stratified 4, the solvent after separating gets into refining system, and water of condensation gets into condensed system and recycles.
And glue is condensed into micelle and sends into cohesion still 6 by particle pump 7 from still middle part or top with the mixture of hot water; Steam still 6 bottoms from cohesion are injected and are kept temperature in the still to keep; Under stirring action, the vapour phase of entrapment solvent is got into the first still 8 of cohesion by vapor jet pump 3 pressurization backs.
Micelle water is sent to the last still 5 of cohesion through particle pump 9; In the last still 5 of cohesion; Residual solvent in the micelle progressively spreads and volatilizees, and the vapour phase of entrapment solvent is got into the first still 8 of cohesion by vapor jet pump 3 pressurization backs, and the micelle water of accomplishing agglomeration process is sent to postprocessing working procedures through particle pump 10 to be separated; Micelle gets into postprocessing working procedures, and hot water is sent to the first still 8 of cohesion through hot water pump and reuses.
Wherein, the temperature of condensing first still 8 is 90 ℃, and pressure is 0.01Mpa, and the temperature of still 6 is 80 ℃ in the cohesion, and pressure is 0.06Mpa, and the temperature of condensing last still 5 is 95 ℃, and pressure is 0.01Mpa.
This viton cohesion process makes the micelle residence time increase by 1 times, and solvent is lower than 0.08% in the micelle, and steam consumption only is about 90% of two still cohesions.
Claims (2)
1. three still condensing methods during a solution polymerization process viton is produced is characterized in that this method is undertaken by following step:
Glue after a, the polyreaction carries out thorough mixing with hot water and the dispersion agent that recycles, and forms non-homogeneous mixture;
B, this mixture sprayed inject the first still of cohesion; Steam injects from condensing first still bottom; The vapour phase of entrapment solvent is gone into condensing surface from the still jacking, after condenser condenses, gets into the profit stratified, and the solvent after separating gets into refining system; Water of condensation gets into condensed system and recycles, and glue is condensed into micelle;
C, the micelle that will condense in the first still are sent into still in the cohesion with hot water, and steam still bottom from cohesion is injected, and the pressurized back of the vapour phase of entrapment solvent gets into the first still of cohesion;
D, will condense in micelle water in the still be sent to the last still of cohesion, the vapour phase pressurization back of entrapment solvent gets into the first still of cohesion, micelle is sent into postprocessing working procedures, hot water is sent to the first still of cohesion and reuses;
Wherein, the temperature of condensing first still is 70～90 ℃, and pressure is 0.01～0.1Mpa, and the temperature of still is 80～98 ℃ in the cohesion, and pressure is 0.01～0.06Mpa, and the temperature of condensing last still is 80～95 ℃, and pressure is 0.01～0.04Mpa.
2. three still condensing methods during a kind of solution polymerization process viton according to claim 1 is produced; It is characterized in that; In step a, the concentration of glue is 5～20%, 85～98 ℃ of the temperature of hot water; The volume ratio of hot water and glue flow is 2～10, and the content of dispersion agent in condensed system is 5～100ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110407464 CN102516419B (en) | 2011-12-08 | 2011-12-08 | Three-kettle condensation method used in solution polymerization production of synthetic rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110407464 CN102516419B (en) | 2011-12-08 | 2011-12-08 | Three-kettle condensation method used in solution polymerization production of synthetic rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516419A true CN102516419A (en) | 2012-06-27 |
| CN102516419B CN102516419B (en) | 2013-07-31 |
Family
ID=46287527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110407464 Expired - Fee Related CN102516419B (en) | 2011-12-08 | 2011-12-08 | Three-kettle condensation method used in solution polymerization production of synthetic rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516419B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961846A (en) * | 2015-07-03 | 2015-10-07 | 新疆蓝德精细石油化工股份有限公司 | Apparatus for improving separation effect of rubber oil in coagulation step and application method thereof |
| CN105330764A (en) * | 2014-06-25 | 2016-02-17 | 中国石油化工股份有限公司 | Glue solution coacervation method of ethylene propylene rubber |
| CN109806609A (en) * | 2018-08-30 | 2019-05-28 | 新疆寰球工程公司 | A kind of solution polymerized rubber stripping kettle device and its compress control method |
| CN111234059A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN112111026A (en) * | 2019-06-20 | 2020-12-22 | 中国石油化工股份有限公司 | Method for coagulating isoprene rubber solution |
| CN112111027A (en) * | 2019-06-20 | 2020-12-22 | 中国石油化工股份有限公司 | Double-kettle coagulation method for isoprene rubber solution |
| CN112125987A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Method for coagulating styrene thermoplastic elastomer solution |
| CN112125988A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Coagulation method for styrene thermoplastic elastomer solution |
| CN112142876A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Method for coagulating butadiene rubber solution |
| CN112142877A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Coagulation method for butadiene rubber solution |
| CN112175112A (en) * | 2019-07-02 | 2021-01-05 | 中国石油化工股份有限公司 | Three-kettle coagulation method for solution polymerized butadiene styrene rubber |
| CN115636891A (en) * | 2021-07-19 | 2023-01-24 | 中国石油天然气股份有限公司 | Ethylene propylene rubber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314086A (en) * | 2008-07-12 | 2008-12-03 | 青岛伊科思新材料股份有限公司 | Polymer solution steam stripping flocculation separation method and apparatus |
| CN102040676A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for depriving solvent for cis-polybutadiene |
-
2011
- 2011-12-08 CN CN 201110407464 patent/CN102516419B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314086A (en) * | 2008-07-12 | 2008-12-03 | 青岛伊科思新材料股份有限公司 | Polymer solution steam stripping flocculation separation method and apparatus |
| CN102040676A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Method for depriving solvent for cis-polybutadiene |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330764A (en) * | 2014-06-25 | 2016-02-17 | 中国石油化工股份有限公司 | Glue solution coacervation method of ethylene propylene rubber |
| CN105330764B (en) * | 2014-06-25 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of method of EP rubbers glue cohesion |
| CN104961846B (en) * | 2015-07-03 | 2017-03-08 | 新疆蓝德精细石油化工股份有限公司 | Improve device and its using method of cohesion process rubber oil separating effect |
| CN104961846A (en) * | 2015-07-03 | 2015-10-07 | 新疆蓝德精细石油化工股份有限公司 | Apparatus for improving separation effect of rubber oil in coagulation step and application method thereof |
| CN109806609A (en) * | 2018-08-30 | 2019-05-28 | 新疆寰球工程公司 | A kind of solution polymerized rubber stripping kettle device and its compress control method |
| CN112111027B (en) * | 2019-06-20 | 2022-08-19 | 中国石油化工股份有限公司 | Double-kettle coagulation method for isoprene rubber solution |
| CN112111026A (en) * | 2019-06-20 | 2020-12-22 | 中国石油化工股份有限公司 | Method for coagulating isoprene rubber solution |
| CN112111027A (en) * | 2019-06-20 | 2020-12-22 | 中国石油化工股份有限公司 | Double-kettle coagulation method for isoprene rubber solution |
| CN112111026B (en) * | 2019-06-20 | 2022-08-19 | 中国石油化工股份有限公司 | Method for coagulating isoprene rubber solution |
| CN112125988B (en) * | 2019-06-24 | 2023-04-11 | 中国石油化工股份有限公司 | Coagulation method for styrene thermoplastic elastomer solution |
| CN112125987A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Method for coagulating styrene thermoplastic elastomer solution |
| CN112125988A (en) * | 2019-06-24 | 2020-12-25 | 中国石油化工股份有限公司 | Coagulation method for styrene thermoplastic elastomer solution |
| CN112142876A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Method for coagulating butadiene rubber solution |
| CN112142877A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Coagulation method for butadiene rubber solution |
| CN112142876B (en) * | 2019-06-27 | 2022-08-19 | 中国石油化工股份有限公司 | Method for coagulating butadiene rubber solution |
| CN112142877B (en) * | 2019-06-27 | 2022-09-20 | 中国石油化工股份有限公司 | Coagulation method for butadiene rubber solution |
| CN112175112A (en) * | 2019-07-02 | 2021-01-05 | 中国石油化工股份有限公司 | Three-kettle coagulation method for solution polymerized butadiene styrene rubber |
| CN112175112B (en) * | 2019-07-02 | 2022-08-19 | 中国石油化工股份有限公司 | Three-kettle coagulation method for solution polymerized butadiene styrene rubber |
| CN111234059A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN115636891A (en) * | 2021-07-19 | 2023-01-24 | 中国石油天然气股份有限公司 | Ethylene propylene rubber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516419B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102516419B (en) | Three-kettle condensation method used in solution polymerization production of synthetic rubber | |
| CN103159893B (en) | Preparation method of high-solid-content butadiene-styrene latex | |
| CN102399565B (en) | Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof | |
| CN104558319A (en) | Method for improving forming of low-viscosity polyvinyl alcohol | |
| CN102040676B (en) | Method for depriving solvent for cis-polybutadiene | |
| CN103351321B (en) | The continuous production method of a kind of NMP | |
| CN105175730A (en) | Method for preparing silicone rubber from organosilicon hydrolysate | |
| CN102079797B (en) | Demonomerization and defoamation method of acrylonitrile polymerization solution | |
| CN102649920B (en) | Device and method for continuously preparing biodiesel under intermediate-temperature and medium-pressure condition | |
| CN108239473A (en) | A kind of preparation method of lower shrinkage ultraviolet-curing paint | |
| CN204121793U (en) | A kind of C5 Petropols remove the device of light component | |
| CN202359051U (en) | Three-kettle condensing device of synthetic rubber | |
| CN106188400B (en) | A kind of preparation process of polystyrene multi-component copolymer high molecular material | |
| CN101831081A (en) | Method and device for recovering nylon powder from tire cord by solvent method | |
| CN203947052U (en) | The device of a kind of refining trioxymethylene and recovery benzene | |
| CA3097086A1 (en) | Method and system for drying mine tailings | |
| CN102489036A (en) | Method for extracting lycopene by using continuous countercurrent ultrasonic extractor | |
| CN111494976B (en) | Diluent removing device in slurry method polyethylene process | |
| CN104353403B (en) | A kind of realize the system that energy recovery couples with continuous coke cleaning | |
| CN113527548A (en) | Method for preparing high chlorinated polypropylene by aqueous phase suspension method | |
| CN103772608B (en) | Steam exhaust recovering device in a kind of polymer production and method | |
| CN106674404A (en) | Method for continuously producing carbon-hydrogen resin by aid of molecular distillation technologies | |
| CN105858621A (en) | Method for concentrating titanium white waste acids through gas-liquid contact technology | |
| CN201722318U (en) | Material recycling device | |
| CN201990621U (en) | Device for synthetizing isoprene rubber through wet coagulation process |
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: 20130731 Termination date: 20151208 |
|
| EXPY | Termination of patent right or utility model |