CN100586316C - Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke - Google Patents
Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke Download PDFInfo
- Publication number
- CN100586316C CN100586316C CN200510040544A CN200510040544A CN100586316C CN 100586316 C CN100586316 C CN 100586316C CN 200510040544 A CN200510040544 A CN 200510040544A CN 200510040544 A CN200510040544 A CN 200510040544A CN 100586316 C CN100586316 C CN 100586316C
- Authority
- CN
- China
- Prior art keywords
- hours
- molecular sieve
- halide
- tobacco
- cigarette smoke
- 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
Images
Landscapes
- Manufacture Of Tobacco Products (AREA)
Abstract
The invention discloses a spout stick addictive for reducing nitrite amine peculiar in smoke gas, and the method for preparing the same. The addictive comprises granular molecular screen with granularsize being 150-500 micrometer, and noble metal or its oxide compound evenly distributed on said molecular screen with granular size being 1-50 nm, and rare-earth metal or its oxide compound. The method comprises following steps: (1) preparing granular molecular screen with size being 150-500 micrometer; (2) putting molecular screen into rare earth metal solution for 8-24 hours, washing and dryingunder 50-80 Deg. C for 3-6 hours, treating under 120-200 Deg. C for 2-5 hours; (3) putting molecular screen into noble metal solution for 8-24 hours, drying at 50-80 Deg. C for 3-6 hours, treating at120-200 Deg. C for 2-5 hours, treating at 230-300 Deg. C for 3-6 hours, and getting said spout stick addictive.
Description
Technical field
The present invention relates to a kind of cigarette filter tip and add material and method for making, the mouth rod that especially reduces tobacco-specific nitrosamine in the cigarette smoke (TSNAs) adds material and preparation method thereof.
Background technology
As everyone knows, cigarette is in the quilt process that smokes, and the harmful substance in the flue gas will produce harm to the health of human body.At present, people have done various effort in order to reduce this harm, as a kind of " the dispeling of the material that is harmful to health in the cigarette " that discloses among the disclosed Chinese invention patent ublic specification of application CN 1172617A on February 11st, 1998.It is intended to provide a kind of material that can dispel the material that is harmful to health in the cigarette effectively, this material is for obtaining NaY type zeolite molecular sieve through Copper Ion Exchange, it is added on the filter tip of cigarette during use, makes the flue gas of sucking-off after it fully adsorbs, just suck human body or tell in air.But this material exists weak point, at first, can not reduce the distinctive nitrosamine of tobacco in the cigarette smoke, and nitrosamine is a kind of material that human body is had strong carcinogenesis; Secondly, to the material that other is harmful to health in the cigarette smoke, can not dispel or reduce as nicotine, TPM.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of mouth rod that can reduce tobacco-specific nitrosamine in the cigarette smoke effectively to add material and preparation method thereof for overcoming weak point of the prior art.
The mouth rod that reduces tobacco-specific nitrosamine in the cigarette smoke adds material and comprises molecular sieve, particularly this interpolation material is to be 150～500 microns particulate molecular sieve and to be evenly distributed on noble metal on this particulate molecular sieve or its oxide and rare earth metal or its oxide constitute by particle diameter, wherein, the particle diameter of noble metal or its oxide and rare earth metal or its oxide is 1～50nm.
As the further improvement of the mouth rod interpolation material that reduces tobacco-specific nitrosamine in the cigarette smoke, described molecular sieve is NaY molecular sieve or NaX molecular sieve or NaA molecular sieve; Described noble metal or its oxide are palladium (Pd) or its oxide or platinum (Pt) or its oxide or rhodium (Rh) or its oxide or aforesaid two or more; Described rare earth metal or its oxide are cerium (Ce) or its oxide or neodymium (Nd) or its oxide or lanthanum (La) or its oxide or praseodymium (Pr) or its oxide or aforesaid two or more.
The mouth rod that reduces tobacco-specific nitrosamine in the cigarette smoke adds preparation methods and comprises ion-exchange to molecular sieve, and particularly it is finished according to the following steps: (1), molecular sieve is made particle diameter is 150～500 microns graininess; Granular molecular sieve was placed rare earth compound solution exchange reaction 8～24 hours (2), earlier, again with its washing back in 50～80 ℃ of dryings 3～6 hours, afterwards, handled 2～5 hours down in 120～200 ℃; (3), earlier the granular molecular sieve that will handle placed the noble metal compound solution load 8～24 hours, again with it in 50～80 ℃ of dryings 3～6 hours, then, it is handled 2～5 hours, 230～300 ℃ in 120～200 ℃ successively handled 3～6 hours; Perhaps, after step (1), carry out step (3) earlier, carry out step (2) again, make the mouth rod that reduces tobacco-specific nitrosamine in the cigarette smoke and add material.
Add the further improvement of preparation methods as the mouth rod that reduces tobacco-specific nitrosamine in the cigarette smoke, described molecular sieve is NaY molecular sieve or NaX molecular sieve or NaA molecular sieve; The concentration of described rare earth compound solution is 0.5～5.0wt%; Described rare earth compound is the halide of the halide of the halide of the halide of cerium (Ce) or neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more; The concentration of described noble metal compound solution is 0.01～5.0wt%; Described precious metal chemical complex is the halide of the halide of the halide of palladium (Pd) or platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more.
Beneficial effect with respect to prior art is, one adds material to the molecular sieve that makes and mouth rod respectively and uses field emission scanning electron microscope to characterize, and from the stereoscan photograph that obtains as can be known, molecular sieve is a graininess, and its particle diameter is 150～500 microns.Mouth rod adds material to be 150～500 microns particulate molecular sieve by particle diameter and to be evenly distributed on noble metal on this particulate molecular sieve or its oxide and rare earth metal or its oxide constitute, wherein, the particle diameter of noble metal or its oxide and rare earth metal or its oxide is 1～50nm; They are two years old, respectively the halide of the halide of the halide of the palladium (Pd) of the halide of the halide of the halide of the halide of the cerium (Ce) that uses rare earth compound or neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more and precious metal chemical complex or platinum (Pt) or chloroplatinic acid or rhodium (Rh) or the aforesaid two or more mouth rod of preparing on as NaY molecular sieve or NaX molecular sieve or NaA molecular sieve in molecular sieve being added material characterizes with x-ray photoelectron spectroscopy, from the collection of illustrative plates that obtains as can be known, load has the palladium (Pd) of noble metal with catalytic performance or its oxide or its oxide or platinum (Pt) or its oxide or rhodium (Rh) or its oxide or aforesaid two or more and have the rare earth metal of coordination catalysis effect or the cerium of its oxide (Ce) or its oxide or neodymium (Nd) or its oxide or lanthanum (La) or its oxide or praseodymium (Pr) or its oxide or aforesaid two or more on NaY molecular sieve or NaX molecular sieve or the NaA molecular sieve; They are three years old, respectively the cigarette that does not add mouth rod interpolation material is placed on the excellent cigarette that adds material of adding mouth and collects flue gas on the smoking machine, after using gas chromatograph and thermal energy analyzer (GC-TEA) to test, analyze, draw the content such as the following table of the peculiar N-nitrosamine of tobacco (TSNAs) in the cigarette smoke to flue gas:
As seen from the above table, four kinds of unique nitrosamines of tobacco have all had reduction by a relatively large margin in the flue gas of the cigarette of adding mouth rod interpolation material, NNK are reduced reached 48%, and average reduction has reached 32.2%, has obtained the effect that reduces TSNAs preferably; Its four, mouth rod adds material not only has reduction effect preferably to TSNAs, the material to other the harmful health in the tobacco also has reduction effect preferably simultaneously, its effect is as shown in the table,
| Title | Component | Weight g/ props up | Resistance to suction Pa | The mouth number | CO mg/ props up | TPM mg/ props up | Nicotine mg/ props up | Moisture mg/ props up | Tar mg/ props up |
| Blank | - | 0.84 | 1130 | 6.1 | 14.2 | 15.69 | 1.25 | 2.93 | 11.5 |
| Add material | 0.93 | 1240 | 6.3 | 13.3 | 13.18 | 1.10 | 2.10 | 10.0 | |
| The range of decrease | - | -- | -- | -- | 6.3％ | 16.0％ | 12.0％ | 28.3％ | 13.0％ |
As can be seen from the above table, add material and reduced by 12% nicotine and 16% TPM, also reduced by 6.3% CO and 13% tar, thereby can protect smoker and people healthy on every side thereof effectively; Its five, preparation process is simple, is easy to suitability for industrialized production, mouth rod adds the suitable business-like application of material.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 carries out blank molecular sieve observing the photo of taking after 100 times the amplification with JEOL JSM-6300F type field emission scanning electron microscope, the size of the form of molecular sieve and particle diameter as can be seen from photo;
Fig. 2 observes the photo of taking with JEOL JSM-6300F type field emission scanning electron microscope to blank molecular sieve after carrying out 20000 times amplification on the basis of Fig. 1, the configuration of surface of single blank molecular sieve as can be seen from photo;
Fig. 3 observes the photo of taking after adding the amplification that material carries out 20000 times with JEOL JSM-6300F type field emission scanning electron microscope lip-syncing rod, the mouth rod configuration of surface and the formation of adding material as can be seen from photo, and the particle diameter of noble metal or its oxide and rare earth metal or its oxide.
The specific embodiment
At first make or buy business-like NaY molecular sieve and NaX molecular sieve and NaA molecular sieve from market with conventional method.
1), the NaY molecular sieve is made particle diameter is 150 microns graininess, obtains to be similar to molecular sieve illustrated in figures 1 and 2 embodiment 1: completing steps is as follows:.2), earlier granular NaY molecular sieve being placed concentration is the rare earth compound solution exchange reaction 24 hours of 0.5wt%, again with its washing back in 50 ℃ of dryings 6 hours, afterwards, handled 5 hours down in 120 ℃; Wherein, rare earth compound is the halide (or halide of the halide of the halide of neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more) of cerium (Ce).3), to place concentration be the noble metal compound solution load 24 hours of 0.01wt% for the granular NaY molecular sieve that will handle earlier, again with it in 50 ℃ of dryings 6 hours, then, it is handled 5 hours, 230 ℃ in 120 ℃ successively handled 6 hours; Wherein, precious metal chemical complex is the halide (or halide of the halide of platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more) of palladium (Pd).Perhaps, after step 1), carry out step 3) earlier, carry out step 2 again), the mouth rod that makes tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 adds material.
1), the NaY molecular sieve is made particle diameter is 250 microns graininess, obtains to be similar to molecular sieve illustrated in figures 1 and 2 embodiment 2: completing steps is as follows:.2), earlier granular NaY molecular sieve being placed concentration is the rare earth compound solution exchange reaction 20 hours of 1.5wt%, again with its washing back in 58 ℃ of dryings 5.5 hours, afterwards, handled 4.5 hours down in 140 ℃; Wherein, rare earth compound is the halide (or halide of the halide of the halide of neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more) of cerium (Ce).3), to place concentration be the noble metal compound solution load 20 hours of 1wt% for the granular NaY molecular sieve that will handle earlier, again with it in 58 ℃ of dryings 5.5 hours, then, it is handled 4.5 hours, 250 ℃ in 140 ℃ successively handled 5.5 hours; Wherein, precious metal chemical complex is the halide (or halide of the halide of platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more) of palladium (Pd).Perhaps, after step 1), carry out step 3) earlier, carry out step 2 again), the mouth rod that makes tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 adds material.
1), the NaY molecular sieve is made particle diameter is 330 microns graininess, obtains molecular sieve as depicted in figs. 1 and 2 embodiment 3: completing steps is as follows:.2), earlier granular NaY molecular sieve being placed concentration is the rare earth compound solution exchange reaction 16 hours of 3wt%, again with its washing back in 65 ℃ of dryings 4.5 hours, afterwards, handled 3.5 hours down in 160 ℃; Wherein, rare earth compound is the halide (or halide of the halide of the halide of neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more) of cerium (Ce).3), to place concentration be the noble metal compound solution load 16 hours of 3wt% for the granular NaY molecular sieve that will handle earlier, again with it in 65 ℃ of dryings 4.5 hours, then, it is handled 3.5 hours, 265 ℃ in 160 ℃ successively handled 4.5 hours; Wherein, precious metal chemical complex is the halide (or halide of the halide of platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more) of palladium (Pd).Perhaps, after step 1), carry out step 3) earlier, carry out step 2 again), the mouth rod that makes tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 adds material.
1), the NaY molecular sieve is made particle diameter is 410 microns graininess, obtains to be similar to molecular sieve illustrated in figures 1 and 2 embodiment 4: completing steps is as follows:.2), earlier granular NaY molecular sieve being placed concentration is the rare earth compound solution exchange reaction 12 hours of 4wt%, again with its washing back in 73 ℃ of dryings 4 hours, afterwards, handled 2.8 hours down in 180 ℃; Wherein, rare earth compound is the halide (or halide of the halide of the halide of neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more) of cerium (Ce).3), to place concentration be the noble metal compound solution load 12 hours of 4wt% for the granular NaY molecular sieve that will handle earlier, again with it in 73 ℃ of dryings 4 hours, then, it is handled 2.8 hours, 280 ℃ in 180 ℃ successively handled 4 hours; Wherein, precious metal chemical complex is the halide (or halide of the halide of platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more) of palladium (Pd).Perhaps, after step 1), carry out step 3) earlier, carry out step 2 again), the mouth rod that makes tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 adds material.
1), the NaY molecular sieve is made particle diameter is 500 microns graininess, obtains to be similar to molecular sieve illustrated in figures 1 and 2 embodiment 5: completing steps is as follows:.2), earlier granular NaY molecular sieve being placed concentration is the rare earth compound solution exchange reaction 8 hours of 5.wt%, again with its washing back in 80 ℃ of dryings 3 hours, afterwards, handled 2 hours down in 200 ℃; Wherein, rare earth compound is the halide (or halide of the halide of the halide of neodymium (Nd) or lanthanum (La) or praseodymium (Pr) or aforesaid two or more) of cerium (Ce).3), to place concentration be the noble metal compound solution load 8 hours of 5.wt% for the granular NaY molecular sieve that will handle earlier, again with it in 80 ℃ of dryings 3 hours, then, it is handled 2 hours, 300 ℃ in 200 ℃ successively handled 3 hours; Wherein, precious metal chemical complex is the halide (or halide of the halide of platinum (Pt) or chloroplatinic acid or rhodium (Rh) or aforesaid two or more) of palladium (Pd).Perhaps, after step 1), carry out step 3) earlier, carry out step 2 again), the mouth rod that makes tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 adds material.
Select NaX molecular sieve or NaA molecular sieve more respectively for use, repeat the foregoing description 1～5, the mouth rod that has made tobacco-specific nitrosamine in the reduction cigarette smoke as shown in Figure 3 equally adds material.
Obviously, those skilled in the art can add material and preparation method thereof to the mouth of tobacco-specific nitrosamine in the reduction cigarette smoke of the present invention rod and carries out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (5)
1, a kind of mouth rod that reduces tobacco-specific nitrosamine in the cigarette smoke adds preparation methods, comprises the ion-exchange to molecular sieve, it is characterized in that finishing according to the following steps:
Step 1, it is 150～500 microns graininess that molecular sieve is made particle diameter;
Step 2 earlier placed rare earth compound solution exchange reaction 8～24 hours with granular molecular sieve, again with its washing back in 50～80 ℃ of dryings 3～6 hours, afterwards, handled 2～5 hours down in 120～200 ℃;
Step 3, the granular molecular sieve that to handle earlier placed the noble metal compound solution load 8～24 hours, again with it in 50～80 ℃ of dryings 3～6 hours, then, it is handled 2～5 hours, 230～300 ℃ in 120～200 ℃ successively handled 3～6 hours, wherein, precious metal chemical complex is the halide of the halide of the halide of palladium or platinum or chloroplatinic acid or rhodium or aforesaid two or more;
Perhaps, after step 1, carry out step 3 earlier, carry out step 2 again, making noble metal that particle diameter is 1～50nm or its oxide and rare earth metal or its oxide, to be evenly distributed on particle diameter be that the mouth rod of tobacco-specific nitrosamine adds material in the reduction cigarette smoke on 150～500 microns the particulate molecular sieve.
2, the mouth of tobacco-specific nitrosamine rod adds preparation methods in the reduction cigarette smoke according to claim 1, it is characterized in that molecular sieve is NaY molecular sieve or NaX molecular sieve or NaA molecular sieve.
3, the mouth of tobacco-specific nitrosamine rod adds preparation methods in the reduction cigarette smoke according to claim 1, and the concentration that it is characterized in that rare earth compound solution is 0.5～5.0wt%.
4, add preparation methods according to the mouth of tobacco-specific nitrosamine in claim 1 or 3 described reduction cigarette smokes rod, it is characterized in that rare earth compound is the halide of the halide of the halide of the halide of cerium or neodymium or lanthanum or praseodymium or aforesaid two or more.
5, the mouth of tobacco-specific nitrosamine rod adds preparation methods in the reduction cigarette smoke according to claim 1, and the concentration that it is characterized in that noble metal compound solution is 0.01～5.0wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510040544A CN100586316C (en) | 2005-06-13 | 2005-06-13 | Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510040544A CN100586316C (en) | 2005-06-13 | 2005-06-13 | Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1879511A CN1879511A (en) | 2006-12-20 |
| CN100586316C true CN100586316C (en) | 2010-02-03 |
Family
ID=37518048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510040544A Expired - Fee Related CN100586316C (en) | 2005-06-13 | 2005-06-13 | Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100586316C (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209970A (en) * | 1998-09-02 | 1999-03-10 | 南京大学 | Cigarette with low or moderate nitrosamines content in smoke and preparation thereof |
| CN1259059A (en) * | 1997-06-04 | 2000-07-05 | 崔文艳 | A compound for removing harmful components from cigarette smoking and a method for preparing the compound |
| CN1460641A (en) * | 2003-06-06 | 2003-12-10 | 南京大学 | Mesopore solid alkali, mesopore functional material, its preparation method and application |
| CN1620945A (en) * | 2003-11-29 | 2005-06-01 | 南昌大学 | Use of catalyst in tobacco leaf and tobacco filament |
-
2005
- 2005-06-13 CN CN200510040544A patent/CN100586316C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259059A (en) * | 1997-06-04 | 2000-07-05 | 崔文艳 | A compound for removing harmful components from cigarette smoking and a method for preparing the compound |
| CN1209970A (en) * | 1998-09-02 | 1999-03-10 | 南京大学 | Cigarette with low or moderate nitrosamines content in smoke and preparation thereof |
| CN1460641A (en) * | 2003-06-06 | 2003-12-10 | 南京大学 | Mesopore solid alkali, mesopore functional material, its preparation method and application |
| CN1620945A (en) * | 2003-11-29 | 2005-06-01 | 南昌大学 | Use of catalyst in tobacco leaf and tobacco filament |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1879511A (en) | 2006-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6959712B2 (en) | Method of making a smoking composition | |
| CN101317695B (en) | Adsorption material for cigarette filter-tip and preparation method thereof | |
| CN103347408A (en) | Smoking articles | |
| CN104244745A (en) | Smoking articles | |
| CN105597675A (en) | Graphene adsorbing material, preparation method and application thereof and cigarette filter tip | |
| CN108030142A (en) | Suitable for making an addition to the tobacco composition of dry process reproduction tobacco leaf coating fluid and its application in terms of cigarette is not burnt in preparation heating | |
| CN101611927B (en) | Catalyst capable of reducing carbon monoxide content in cigarette smoke, preparation method and application of same | |
| CN103141940B (en) | Entrapment agent for selectively lowering crotonaldehyde content in cigarette smoke and filter stick | |
| WO2003041519A1 (en) | Extraction method for polyaromatic hydrocarbon analysis | |
| CN100586316C (en) | Method for preparing tip addictive material for decreasing tobacco specified nitrosamine in cigarette smoke | |
| JP4824568B2 (en) | Cigarette smoke filter | |
| CN104432507B (en) | Cigarette filter-tip additive agent of aldehyde material and its preparation method and application in a kind of removable cigarette mainstream flue gas | |
| CN1757337A (en) | Use of four kinds of porphyrin compounds to remove carcinogenic substances from smoke of cigarette | |
| Cvetkovic et al. | Catalytic reduction of NO and NOx content in tobacco smoke | |
| CN101992058A (en) | Mesoporous copper oxide-aluminum oxide adsorbing agent for reducing hydrogen cyanide content in main stream smoke of cigarette, and preparation and application | |
| CN1214743C (en) | Filter tip for cigarette | |
| CN102228311A (en) | Adsorbent for reducing phenol in mainstream smoke of cigarettes selectively | |
| EP2098129A1 (en) | Method for production of tobacco leaf | |
| CN103159224A (en) | Preparation method of all-silicon type amorphous porous material and application of all-silicon type amorphous porous material in cigarette filters | |
| CN107080287A (en) | A kind of activated carbon dipping method of modifying and application | |
| CN101982406B (en) | Hollow carbon sphere material and cigarette containing same | |
| CN101618350A (en) | Mesoporous alumina carrier capable of reducing content of carbon monoxide in cigarette smoke, preparation method and application thereof | |
| CN113598412B (en) | Composite filter tip for adsorbing 2-acetylpyridine in cigarette smoke and cigarette | |
| CN103330285B (en) | Cigarette filter stick added with water-containing material and cigarette | |
| CN100551283C (en) | A kind of cigarette with binary composite tip stick and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20140613 |
|
| EXPY | Termination of patent right or utility model |