CN101423623B - Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine - Google Patents
Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine Download PDFInfo
- Publication number
- CN101423623B CN101423623B CN2007101564923A CN200710156492A CN101423623B CN 101423623 B CN101423623 B CN 101423623B CN 2007101564923 A CN2007101564923 A CN 2007101564923A CN 200710156492 A CN200710156492 A CN 200710156492A CN 101423623 B CN101423623 B CN 101423623B
- Authority
- CN
- China
- Prior art keywords
- workshop section
- depolymerization
- terephthalic acid
- high temperature
- temperature resistant
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for depolymerizing and recovering high temperature resistant nylon poly(p-phenylene-hexamethylenediamine), which is characterized by comprising the following steps in turn: sodium hydroxide and water are added into a reaction kettle, dissolved, added with crushed nylon PA5T, and subjected to depolymerizaton to obtain a alkali-hydrolyzable liquid; the alkali-hydrolyzable liquid passes through a filter, enters a workshop section of separation and extraction, and is extracted and separated by an arene/alcohol mixed extractant to obtain coarse hexamethylenediamine extract and terephthalic acid sodium salt faffinate; the coarse hexamethylenediamine extract is subjected to distillation and rectification to respectively obtain arene/alcohol/-hexamethylenediamine and arene/alcohol, an organic solvent which is distilled off is replenished with a fresh solvent and can be reused as an extractant, and refined hexamethylenediamine can be obtained after removal of a extracting solvent with low boiling point by means of distillation, and decompression and rectification; and the terephthalic acid sodium salt solution is subjected to decolorization, neutralization, filtration and separation to obtain a terephthalic acid, and a refined terephthalic acid is obtained after water scrubbing and drying of the terephthalic acid. The method has reasonable and practical technology, can reutilize the solvent, reduces the recovery cost, simultaneously reduces environmental pollution, and improves the resource utilization rate.
Description
Technical field
The present invention relates to the method for a kind of high temperature resistant nylon poly hexamethylene terephthalamide (PA6T) depolymerization, relate in particular to a kind of method that is applicable to a kind of high temperature resistant nylon PA6T depolymerization that industrialized production is used.
Background technology
Nylon (PA) has excellent mechanical mechanics property, wear resistance, self lubricity, oil-proofness, anti-stability becomes domestic and international application one of plastics the most widely, first of the row five large-engineering plastics.High temperature resistant PA6T is the resin that is formed by terephthalic acid and hexanediamine polycondensation, has the not available characteristic of other nylon, and is particularly particularly remarkable aspect high temperature resistant.In recent years, along with its constantly being applied in a lot of fields, its goods are difficult to handle after being used, and not only cause waste, and environment is polluted, and therefore, recycling high temperature resistant PA6T has remarkable economic efficiency and social benefit.
Nylon reclaims and mainly contains certain methods at present: melt pelletization regeneration; Chemical recovery; Energy recovery; Landfill disposal etc.But because the nylon poor stability, melt pelletization regeneration back mechanical property descends significantly, and can not repeatedly repeat energy recovery is to adopt oil refining or incendiary method, and not only utility value is low, and atmosphere pollution.And landfill is cured the symptoms, not the disease.Therefore, most major companies adopt mostly is chemical recycling.For example sky, Liaoning becomes chemical industry company limited to declare a kind of Chinese patent of production method of useless nylon recycling, and patent publication No. is CN1569802; Shanxi applied chemistry institute has carried out the pilot scale research that hexanodioic acid, hexanediamine are produced in nylon-66 waste material hydrolysis; Minte Nylon Industry Co., Ltd., Ningbo has applied for a kind ofly producing the Chinese patent of the technology of hexanodioic acid, hexanediamine with nylon-66 disaggregation, and patent publication No. is CN1611477; Du pont company has carried out the experiment of nitric acid depolymerization nylon-66, with hydrogenation method nitric acid hydrogenation ammonification is made hexanediamine.The patent that adopts the poly-nylon-66 of alkaline hydrolysis was declared in China by Holland DSM N. V. in 1998, publication number is CN1205330A.U.S. Pat A-5302756, USA-5233021 have described a kind of at high temperature by amine and adopt the method depolymerization nylon of supercritical extraction respectively.
Yet, though it is many to produce the company of PA6T, such as E.I.Du Pont Company etc., the document or the patent of not seeing the recovery of relevant PA6T so far.
Summary of the invention
Technical problem to be solved by this invention provides a kind of depolymerization and recovery method of high temperature resistant nylon poly hexamethylene terephthalamide, and its reasonable and practical process can reuse solvent, reduces cost recovery, reduces environmental pollution simultaneously, improves resource utilization.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the depolymerization and recovery method of the poly-hexamethylene terephthalamide of a kind of high-temperature nylon, it is characterized in that steps in sequence is an alkali lye depolymerization workshop section, separating and extracting workshop section, the refining workshop section of distillation arranged side by side and in and crystallization workshop section, each workshop section is as described below:
(1), alkali lye depolymerization workshop section, sodium hydroxide and water are added in the reactor, the dissolving back adds the nylon PA6T that pulverizes, and reacts 5～8 hours under the condition that keeps 70-90 ℃ of temperature, pressure 0.1～0.6MPa, obtains alkali solution liquid;
(2), separating and extracting workshop section, alkali solution liquid is entered separating and extracting workshop section through strainer, carry out extracting and separating with aromatic hydrocarbons/alcohols mixed extractant and obtain thick hexanediamine extraction liquid and terephthalic acid sodium salt raffinate;
(3), the refining workshop section of distillation, the thick hexanediamine extraction liquid that obtains in the step (2) is distilled and rectifying, obtain aromatic hydrocarbons/alcohol/hexanediamine respectively, aromatic hydrocarbons/alcohol, the organic solvent that distills can be again as the extraction agent utilization after replenishing fresh solvent, and distillation is removed behind the lower boiling extraction solvent by obtaining the purified hexanediamine after the rectification under vacuum;
(4), in and crystallization workshop section, the terephthalic acid sodium salt solution that step (2) obtains is used activated carbon decolorizing in the decolouring still, add then be equipped with excess sulfuric acid in and in the still, stirring makes and reacts completely, the pH value that makes neutralization back solution is less than 3, filter to isolate terephthalic acid, obtain the purified terephthalic acid after washing, the oven dry.
Concentration sodium hydroxide described in described step (1) the alkali lye depolymerization workshop section is 1%～50%, and is preferred 20%, is mass percent.
Sodium hydroxide described in described step (1) the alkali lye depolymerization workshop section and the mol ratio of PA6T are 2: 1～4: 1, are preferably 2.5: 1.
Aromatic hydrocarbons is benzene, toluene or dimethylbenzene in aromatic hydrocarbons/alcohols mixed extractant described in described step (2) the separating and extracting workshop section, and alcohol is propyl carbinol or primary isoamyl alcohol, and its molar ratio is 1: 2～2: 1, is preferably 1: 1.Compared with prior art, the invention has the advantages that: (PA6T) carries out depolymerization and recovery to the high temperature resistant nylon poly hexamethylene terephthalamide, can obtain new high temperature resistant nylon PA6T, reduce environmental pollution, improve resource utilization, and the processing method advantages of simple, can reuse extraction solvent, reduce cost, increase the benefit, very practical.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method;
Fig. 2 is the depolymerization mechanism figure of the inventive method.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
In reactor, add 500Kg solid sodium hydroxide and water 1000Kg, add the useless nylon PA6T that pulverizes after the stirring and dissolving, the mol ratio of sodium hydroxide and PA6T is 2: 1, stir, under the condition that keeps 70-90 ℃ of temperature, pressure 0.1～0.6MPa, reacted 5～8 hours, make to react completely, obtain alkali solution liquid; Then alkali solution liquid is filtered by coarse filter, remove solid residue, the cooling back adds benzene/propyl carbinol mixed extractant, the mol ratio of extraction agent is 2: 1, extract thick hexanediamine, extraction liquid carries out fractionation operation in rectifying tower, continue to serve as extraction agent behind the composite fresh solvent of the organic solvent that distills in the next production cycle; Distillation is carried out rectification under vacuum after removing lower boiling extraction solvent, and control hexanediamine fraction collection temperature is lower than 170 ℃, obtains purity greater than 99.1% hexanediamine; Aforesaid raffinate is the terephthalic acid sodium salt solution, the gac that adds weight ratio 4% in the decolouring still stirs decolouring, adding sulfuric acid is neutralized to pH less than 3 after removing by filter gac, obtaining the crude terephthalic acid solid (slowly adds sulfuric acid while stirring and prevents to dash material, foreign matter content is too high in the terephthalic acid solid that prevents to cause too soon owing to crystallization), wash three times after the filtration with water removing the impurity in the solid and the acid solution of adhering to, obtain purity greater than 99.2% terephthalic acid in oven dry below 80 ℃.
Embodiment 2
In reactor, add 250Kg solid sodium hydroxide and water 1000Kg, add the useless nylon PA6T that pulverizes after the stirring and dissolving, the mol ratio of sodium hydroxide and PA6T is 2.5: 1, stir, under the condition that keeps 70-90 ℃ of temperature, pressure 0.1～0.6MPa, reacted 5～8 hours, make to react completely, obtain alkali solution liquid; Then alkali solution liquid is filtered by coarse filter, remove solid residue, the cooling back adds benzene/propyl carbinol mixed extractant, the mol ratio of extraction agent is 1: 1, extract thick hexanediamine, extraction liquid carries out fractionation operation in rectifying tower, continue to serve as extraction agent behind the composite fresh solvent of the organic solvent that distills in the next production cycle; Distillation is carried out rectification under vacuum after removing lower boiling extraction solvent, and control hexanediamine fraction collection temperature is lower than 170 ℃, obtains purity greater than 99.7% hexanediamine; Aforesaid raffinate is the terephthalic acid sodium salt solution, the gac that adds weight ratio 3% in the decolouring still stirs decolouring, adding sulfuric acid is neutralized to pH less than 3 after removing by filter gac, obtaining the crude terephthalic acid solid (slowly adds sulfuric acid while stirring and prevents to dash material, foreign matter content is too high in the terephthalic acid solid that prevents to cause too soon owing to crystallization), wash three times after the filtration with water removing the impurity in the solid and the acid solution of adhering to, obtain purity greater than 99.5% terephthalic acid in oven dry below 80 ℃.
Execute example 3
In reactor, add 1000Kg solid sodium hydroxide and water 1000Kg, add the useless nylon PA6T that pulverizes after the stirring and dissolving, the mol ratio of sodium hydroxide and PA6T is 4: 1, stir, under the condition that keeps 70-90 ℃ of temperature, pressure 0.1～0.6MPa, reacted 5～8 hours, make to react completely, obtain alkali solution liquid; Then alkali solution liquid is filtered by coarse filter, remove solid residue, the cooling back adds toluene/propyl carbinol mixed extractant, the mol ratio of extraction agent is 1: 2, extract thick hexanediamine, extraction liquid carries out fractionation operation in rectifying tower, continue to serve as extraction agent behind the composite fresh solvent of the organic solvent that distills in the next production cycle; Distillation is carried out rectification under vacuum after removing lower boiling extraction solvent, and control hexanediamine fraction collection temperature is lower than 170 ℃, obtains purity greater than 99.3% hexanediamine; Aforesaid raffinate is the terephthalic acid sodium salt solution, the gac that adds weight ratio 3% in the decolouring still stirs decolouring, adding sulfuric acid is neutralized to pH less than 3 after removing by filter gac, obtaining the crude terephthalic acid solid (slowly adds sulfuric acid while stirring and prevents to dash material, foreign matter content is too high in the terephthalic acid solid that prevents to cause too soon owing to crystallization), wash three times after the filtration with water removing the impurity in the solid and the acid solution of adhering to, obtain purity greater than 99.3% terephthalic acid in oven dry below 80 ℃.
Claims (5)
1. the depolymerization and recovery method of a high temperature resistant nylon poly hexamethylene terephthalamide is characterized in that steps in sequence is an alkali lye depolymerization workshop section, separating and extracting workshop section, the refining workshop section of distillation arranged side by side and in and crystallization workshop section, each workshop section is as described below:
(1), alkali lye depolymerization workshop section, sodium hydroxide and water are added in the reactor, the dissolving back adds the nylon PA6T that pulverizes, and reacts 5～8 hours under the condition that keeps 70-90 ℃ of temperature, pressure 0.1～0.6MPa, obtains alkali solution liquid;
Concentration sodium hydroxide described in described step (1) the alkali lye depolymerization workshop section is 1%～50%, is mass percent;
Sodium hydroxide described in described step (1) the alkali lye depolymerization workshop section and the mol ratio of PA6T are 2: 1～4: 1;
(2), separating and extracting workshop section, alkali solution liquid is entered separating and extracting workshop section through strainer, carry out extracting and separating with aromatic hydrocarbons/alcohols mixed extractant and obtain thick hexanediamine extraction liquid and terephthalic acid sodium salt raffinate;
(3), the refining workshop section of distillation, the thick hexanediamine extraction liquid that obtains in the step (2) is distilled and rectifying, obtain aromatic hydrocarbons/alcohol/hexanediamine respectively, aromatic hydrocarbons/alcohol, the organic solvent that distills can be again as the extraction agent utilization after replenishing fresh solvent, and distillation is removed behind the lower boiling extraction solvent by obtaining the purified hexanediamine after the rectification under vacuum;
(4), in and crystallization workshop section, the terephthalic acid sodium salt solution that step (2) obtains is used activated carbon decolorizing in the decolouring still, add then be equipped with excess sulfuric acid in and in the still, stirring makes and reacts completely, the pH value that makes neutralization back solution is less than 3, filter to isolate terephthalic acid, obtain the purified terephthalic acid after washing, the oven dry
2. the depolymerization and recovery method of a kind of high temperature resistant nylon poly hexamethylene terephthalamide according to claim 1 is characterized in that the concentration sodium hydroxide described in step (1) the alkali lye depolymerization workshop section is 20%, is mass percent.
3. the depolymerization and recovery method of a kind of high temperature resistant nylon poly hexamethylene terephthalamide according to claim 1 is characterized in that sodium hydroxide described in step (1) the alkali lye depolymerization workshop section and the mol ratio of PA6T are 2.5: 1.
4. the depolymerization and recovery method of a kind of high temperature resistant nylon poly hexamethylene terephthalamide according to claim 1, it is characterized in that aromatic hydrocarbons is benzene, toluene or dimethylbenzene in the aromatic hydrocarbons/alcohols mixed extractant described in step (2) the separating and extracting workshop section, alcohol is propyl carbinol or primary isoamyl alcohol, and its molar ratio is 1: 2～2: 1.
5. the depolymerization and recovery method of a kind of high temperature resistant nylon poly hexamethylene terephthalamide according to claim 4 is characterized in that aromatic hydrocarbons/pure molar ratio is 1: 1 in the aromatic hydrocarbons/alcohols mixed extractant described in step (2) the separating and extracting workshop section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101564923A CN101423623B (en) | 2007-11-02 | 2007-11-02 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101564923A CN101423623B (en) | 2007-11-02 | 2007-11-02 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101423623A CN101423623A (en) | 2009-05-06 |
| CN101423623B true CN101423623B (en) | 2011-05-11 |
Family
ID=40614520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101564923A Expired - Fee Related CN101423623B (en) | 2007-11-02 | 2007-11-02 | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101423623B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276789B (en) * | 2011-05-15 | 2013-01-23 | 山东莱芜润达化工有限公司 | Method for recovering and utilizing waste and old paper-based copper-coated board non-metallic material |
| CN104017205B (en) * | 2014-06-11 | 2017-01-18 | 李兆顺 | Method for regenerating nylon |
| EP3222649B1 (en) * | 2016-03-23 | 2018-04-18 | Ems-Patent Ag | High temperature resistant polyamide moulding masses and their application, in particular in the field of automobiles |
| CN107056624B (en) * | 2017-04-19 | 2019-04-16 | 青岛科技大学 | A kind of alcoholysis recovery method of nylon 66 material |
| CN110563570B (en) * | 2019-09-24 | 2020-10-30 | 中国科学院山西煤炭化学研究所 | Method for preparing terephthalic acid and p-phenylenediamine by degrading p-aramid |
| CN114163622B (en) * | 2021-12-15 | 2023-03-21 | 浙江新和成特种材料有限公司 | Method for preparing biodegradable material by recycling semi-aromatic polyamide waste and product thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233021A (en) * | 1992-05-13 | 1993-08-03 | Georgia Tech Research Corporation | Recycling of polymeric materials from carpets and other multi-component structures by means of supercritical fluid extraction |
| US5302756A (en) * | 1992-12-23 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Ammonolysis of nylon |
| WO1996018613A1 (en) * | 1994-12-12 | 1996-06-20 | Basf Aktiengesellschaft | Method of obtaining caprolactam by hydrolytic splitting of molten polycaprolactam |
| CN1205330A (en) * | 1997-05-01 | 1999-01-20 | Dsm有限公司 | Depolymerization of polymides |
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN1374296A (en) * | 2001-03-14 | 2002-10-16 | 李智范 | Production process of caprolactam with waste nylon 6 |
| CN1569802A (en) * | 2004-05-13 | 2005-01-26 | 辽阳天成化工有限公司 | Production method with reclaimed waste nylon as material |
| CN1611477A (en) * | 2003-10-29 | 2005-05-04 | 宁波敏特尼龙工业有限公司 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
-
2007
- 2007-11-02 CN CN2007101564923A patent/CN101423623B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233021A (en) * | 1992-05-13 | 1993-08-03 | Georgia Tech Research Corporation | Recycling of polymeric materials from carpets and other multi-component structures by means of supercritical fluid extraction |
| US5302756A (en) * | 1992-12-23 | 1994-04-12 | E. I. Du Pont De Nemours And Company | Ammonolysis of nylon |
| WO1996018613A1 (en) * | 1994-12-12 | 1996-06-20 | Basf Aktiengesellschaft | Method of obtaining caprolactam by hydrolytic splitting of molten polycaprolactam |
| CN1205330A (en) * | 1997-05-01 | 1999-01-20 | Dsm有限公司 | Depolymerization of polymides |
| CN1374296A (en) * | 2001-03-14 | 2002-10-16 | 李智范 | Production process of caprolactam with waste nylon 6 |
| CN1324789A (en) * | 2001-06-26 | 2001-12-05 | 中国科学院长春应用化学研究所 | Polyimide hydrolyzing recovery process |
| CN1611477A (en) * | 2003-10-29 | 2005-05-04 | 宁波敏特尼龙工业有限公司 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
| CN1569802A (en) * | 2004-05-13 | 2005-01-26 | 辽阳天成化工有限公司 | Production method with reclaimed waste nylon as material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101423623A (en) | 2009-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423623B (en) | Depolymerization and recovery method of high temperature resistant nylon poly-para-phenylene diformyl hexane diamine | |
| CN1213096C (en) | Chenical recovery method for thermosetting epoxy compound material | |
| CN111826177B (en) | Method for pyrolysis treatment of waste light-emitting diode packaging material and recovery of rare earth phosphor powder | |
| CN109705635A (en) | A kind of damaged tire cracking black carbon deliming and the method for ZnO recycling | |
| CN1141190C (en) | Process for recovering waste liner of aluminium electrolyzer | |
| CN102206196A (en) | Method for recovering morpholine from acidic waste water containing morpholine | |
| CN101270420A (en) | Process for recovering cobalt from cobalt based fischer-tropsch synthetic catalyst | |
| CN102675242A (en) | Refining method of vulkacit M | |
| CN111138347A (en) | Vinylpyridine compound water-separation industrialization method and device | |
| CN1752021A (en) | Method of producing ranadium pentoxide using vanadium containing waste catalyst | |
| CN101134824A (en) | Method for reclaiming solvent from aramid fiber polymeric compound | |
| CN101423478B (en) | Method for producing adipic acid and hexamethylene diamine by using nylon-66 depolymerization | |
| CN114437752B (en) | Method and system for preparing hydrocarbon products from waste plastics | |
| CN102628104A (en) | Production process for extracting high-purity rare earth and zirconium compound from solid waste | |
| CN102134500B (en) | Method for extracting naphthalene, 1-methylnaphthalene and 2-methylnaphthalene from ethylene tar | |
| CN102321053B (en) | Treatment method for recovering tetrahydrofuran from grignard reaction | |
| CN102079687B (en) | Recycling method of residual liquor in production of trichloroethylene | |
| CN111848359B (en) | Method for separating phenolic substances in medium and low temperature coal tar | |
| CN104560099B (en) | A kind of preparation technology that fuel oil is produced using waste rubber | |
| CN102642946B (en) | Treatment method of waste water produced in process for producing caprolactam by utilizing toluene method | |
| CN110923450B (en) | Method for recovering C272 from waste C272 extraction organic phase | |
| CN102807513B (en) | Process utilizing H acid mother liquor to recover and produce chromotropic acid sodium salt | |
| CN102381795A (en) | Separation and extraction method for caprolactam, cyclohexane carboxylic acid, cyclohexane carboxylic sulfonic acid and organic oil in waste liquid generated in caprolactam production by toluene method | |
| CN203222565U (en) | Nitrobenzene rectification residue recycling system | |
| CN104445770A (en) | Ink recovery treatment method |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110511 Termination date: 20131102 |