CN103285901B - Preparation method of porous carbon-loaded metal oxide catalyst - Google Patents
Preparation method of porous carbon-loaded metal oxide catalyst Download PDFInfo
- Publication number
- CN103285901B CN103285901B CN201310168762.8A CN201310168762A CN103285901B CN 103285901 B CN103285901 B CN 103285901B CN 201310168762 A CN201310168762 A CN 201310168762A CN 103285901 B CN103285901 B CN 103285901B
- Authority
- CN
- China
- Prior art keywords
- preparation
- metal oxide
- porous carbon
- catalyst
- oxidation
- 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
Abstract
The invention relates to a preparation method of a porous carbon-loaded metal oxide catalyst, and particularly relates to a composite catalyst preparation method for enhancing the desulfurization capacity of catalysts by using the synergistic effect of the strong adsorption of porous carbon and the good catalytic oxidation desulfurization capacity of metal oxides. The method is a porous carbon-loaded metal oxide catalyst preparation process implemented through combining porous carbon, H2O2 and metal oxides mainly in a sol-gel method-carbonization mode, wherein the porous carbon adsorbs H2O2 in a water phase, the H2O2 has a catalytic action and can catalyze the adsorption of the porous carbon, and the metal oxides can slowly and permanently release HO.
Description
Technical field
The present invention relates to a kind of preparation method of porous charcoal metal oxide supporting catalyst, particularly a kind of synergy utilizing the strong adsorptivity of porous charcoal and the good catalytic oxidation desulfurization ability of metal oxide, promotes the method for the desulphurizing ability of catalyst.
Background technology
In recent decades, the development of auto industry is very swift and violent, for very large contribution has been made in human civilization and social progress.But the consumption of vehicle fuel oil also increases greatly, the air pollution that motor vehicle exhaust emission causes also is on the rise.The burning of sulfide in petrol causes very large harm to environment and human health, cause the common concern of the public, in recent years, countries in the world all propose new requirement to quality of gasoline, therefore, the sulfur method seeking a kind of high-efficiency and economic has become the focus that scholars falls over each other research.
At present, in the face of the huge challenge of Clean Fuel Production, China develops the new technology of various production clean fuel, especially produces low-sulfur, super low-sulfur oil and biodiesel technology.The sulfur method of current fuel oil development mainly contains hydro desulfurization, absorption method, acid-alkali refining method, extraction, complexometry, oxidizing process and biological desulfurization method etc.Compared with hydrodesulfurization technology, oxidation sweetening and adsorption desulfurize technology are without the need to HTHP and use expensive hydrogen, not reducing octane number, reaction condition is gentle, simple to operate, cost of investment is low, is the gasoline desulfur technology very with prospects for commercial application.But the application of these technology also exists many difficulties at present, the catalytic activity wherein just comprising gasoline oxidation desulphurization catalyst is lower, poor to the removal effect of thiophenes sulfides organic in gasoline.Although a lot of to the report of the thiophene derivants such as catalytic oxidative desulfurization BT, DBT, DMDBT in the world, then less to the report of thiophene, and effect is not ideal enough.
Summary of the invention
Technical problem to be solved by this invention is the metal oxide-loaded preparation method of a kind of novel catalyst-porous carbon, and the method, mainly by the mode of sol-gal process-charing, will have and adsorb H in aqueous phase
2o
2porous carbon, and there is catalytic action, can the H of catalytic porous carbon adsorption
2o
2, slowly lasting release HO
.metal oxide combine and preparation a kind of porous charcoal metal oxide supporting catalyst.The method technique is simple, and cost is low, can produce in enormous quantities.
One of the object of the invention is to provide a kind of method preparing porous charcoal metal oxide supporting catalyst newly.
Two of the object of the invention is to provide a kind of porous charcoal metal oxide supporting catalyst.
Three of the object of the invention is the application providing this porous charcoal metal oxide supporting catalyst.
Invention is achieved by the following technical programs:
First, invention provides a kind of preparation method of porous charcoal metal oxide supporting catalyst, comprises the following steps:
S1. the preparation of collosol and gel: prepare poly-vinyl alcohol solution, source metal in poly-vinyl alcohol solution, obtains gel sample;
S2. pre-oxidation is carried out to gel sample cooled in S1;
S3. process is carbonized: further the sample after pre-oxidation is carried out high-temperature process under inert gas shielding, obtain product.
Preferably, the metal of described source metal is manganese, vanadium, nickel, cobalt or tungsten.
More preferably, described source metal is manganese nitrate, ammonium metavanadate, nickel nitrate, cobalt chloride or sodium tungstate.
Preferably, in S1, the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1.Described source metal and ZnCl
2mol ratio be 1:1 ~ 1:3.
Preferably, when preparing poly-vinyl alcohol solution, be solvent with water, being prepared into mass fraction 10 ~ 20%(please supplement) poly-vinyl alcohol solution.
The oxidizing condition of described S2 preoxidation process is oxidizing temperature 100 DEG C ~ 200 DEG C, oxidization time 1 ~ 9 hour.
High-temperature process described in S3 is with the heating rate of 2 ~ 5 DEG C/min, is warming up to 550 DEG C ~ 750 DEG C from room temperature, keeps 15 min ~ 120 min.
Preferably, after the product cooling after S3 high-temperature process, also through washing and drying further, obtain finished product.Preferably, 150 DEG C or following are cooled to.
The present invention discloses simultaneously and protects the porous charcoal metal oxide supporting catalyst prepared by said method.
Except this, the present invention also discloses and protects the application of above-mentioned porous charcoal metal oxide supporting catalyst in catalytic oxidation desulfurization.
Specifically, the substrate of institute's catalysis can be thiophene.
Catalysis process is: dropped into by described catalyst in thiophene, add H
2o
2and CH
3cOOH is carry out catalytic oxidation desulfurization under the condition of 40 ~ 70 DEG C in reaction temperature.
Described thiophene can thiophene (200-500 ppm)-normal heptane simulation oil product form exist.
Described thiophene (200-500 ppm)-normal heptane simulation oil product and the H added
2o
2and CH
3cOOH, calculates according to volume parts, is respectively 50 parts, 2 ~ 3 parts, 2 ~ 5 parts.
Pass between the amount of the catalyst added and the amount of thiophene is: in every 50mL thiophene, the consumption of catalyst is 0.05 ~ 0.2g.The concentration of preferred thiophene is 100 ppm.
In particular, for probing into the catalytic effect of catalyst, being put into by a certain amount of catalyst in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, Gu use water--oily three-phase system, is 40 ~ 70 DEG C, H in reaction temperature
2o
2consumption is 2 ~ 3 mL, CH
3cOOH consumption is the catalytic oxidation desulfurization under 2 ~ 5 mL conditions.Oxidation sweetening rate can reach 80 ~ 97.5%.
As a kind of specific embodiment, described catalyst can be prepared by the following method:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, adding mass fraction is 10 ~ 20% polyvinyl alcohol (PVA), constantly stirs, adds 10g ZnCl after making it dissolve completely
2and the source metal of different quality, make a series of sample;
Source metal in the preparation process of described collosol and gel is manganese nitrate or ammonium metavanadate;
In the preparation process of described collosol and gel, the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into baking oven and carry out pre-oxidation;
Pre-oxidizing conditions in described preoxidation process is respectively, and (100 DEG C, 2 h), and (120 DEG C, 2 h), and (140 DEG C, 1 h), and (160 DEG C, 1 h), and (180 DEG C, 1 h), (200 DEG C, constant temperature spends the night).
3) carbonize
Pre-oxidation products obtained therefrom is placed in high temperature carbonization furnace respectively under nitrogen protection (flow velocity 400 mL/min), with the heating rate of 5 DEG C/min from room temperature directly be raised to uniform temperature after keep certain hour, when retort in-furnace temperature is down to below 150 DEG C take out sample;
In described carbonization process, the upper limit of raised temperature is 550 DEG C ~ 750 DEG C, and the retention time is 15 min ~ 120 min.
4) sample post processing
By sample pure water supersound washing 4h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product.
Using thiophene as catalytic substrate, then being put into by a certain amount of catalyst in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, is 50 in reaction temperature
oc, H
2o
2consumption is 2 ~ 3 mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 2 ~ 5 mL conditions can reach 80 ~ 97.5%.
As wherein a kind of preferred scheme, the source metal that the present invention adopts is manganese nitrate or ammonium metavanadate.With manganese nitrate or ammonium metavanadate and polyvinyl alcohol for presoma, a kind of composite catalyst prepared by sol-gel process.
Compared with prior art, the present invention has following originality feature and beneficial effect:
Polyvinyl alcohol (PVA) in the preparation process of collosol and gel of the present invention is carbon source, ZnCl
2for pore-foaming agent, NaCl is presoma prepared by dispersion stabilizer;
Solid-phase catalyst prepared by the present invention, under the catalytic action of metal oxide, can must discharge HO slowly lastingly
., by CH
3cOOH is oxidized to CH
3cOOOH, CH
3cOOOH enters oxidation of thiophene in the simulation oil product of thiophene-normal heptane composition;
The catalyst that porous charcoal prepared by the present invention is metal oxide-loaded, is the synergy utilizing the strong adsorptivity of porous charcoal and the good catalytic oxidation desulfurization ability of metal oxide, promotes the desulphurizing ability of catalyst.
Detailed description of the invention
In order to explain technical solution of the present invention further, invention provides following specific embodiment further, but following examples can not as the restriction of invention protection domain.
Embodiment 1:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 5g polyvinyl alcohol (PVA), constantly stir, after making it dissolve completely, add 10g ZnCl
2and 18.3g manganese nitrate (source metal and ZnCl
2mol ratio be 1:1);
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation 2 h under baking oven 100 DEG C of conditions;
3) carbonize
By 2) in pre-oxidation products obtained therefrom under nitrogen protection (flow velocity 400 mL/min), be placed in high temperature carbonization furnace, with the heating rate of 5 DEG C/min from room temperature directly be raised to 550 DEG C after keep 120min, wait carbonize in-furnace temperature be down to less than 150 DEG C time taking-up sample;
4) sample post processing
By sample pure water supersound washing 4h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product;
Using thiophene as catalytic substrate, then being put into by 0.1g catalyst in 50 mL thiophene (200ppm)-normal heptane simulation oil product, is 70 in reaction temperature
oc, H
2o
2consumption is 3 mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 2mL condition can reach 88.2%.
Embodiment 2:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 8 g polyvinyl alcohol (PVA), constantly stir, after making it dissolve completely, add 10g ZnCl
2and 2.86g ammonium metavanadate (source metal and ZnCl
2mol ratio be 1:3);
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, under putting into baking oven 200 DEG C of conditions, pre-oxidation constant temperature spends the night;
3) carbonize
By 2) in pre-oxidation products obtained therefrom under nitrogen protection (flow velocity 400 mL/min), be placed in high temperature carbonization furnace, with the heating rate of 2 DEG C/min from room temperature directly be raised to 750 DEG C after keep 90min, when retort in-furnace temperature is down to below 150 DEG C take out sample;
4) sample post processing
By sample pure water supersound washing 4 h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product.
Being put into by the catalyst 1g prepared under this condition in 50 mL thiophene (500 ppm)-normal heptane simulation oil product, Gu use water--oily three-phase system, is 40 in reaction temperature
oc, H
2o
2consumption is 2mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 5 mL conditions can reach 95.7%.
Embodiment 3:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 10g polyvinyl alcohol (PVA), constantly stir, after making it dissolve completely, add 10g ZnCl
2and 21.33g nickel nitrate (source metal and ZnCl
2mol ratio be 1:1), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 1h under baking oven 160 DEG C of conditions;
3) carbonize
By 2) in pre-oxidation products obtained therefrom under nitrogen protection (flow velocity 400 mL/min), be placed in high temperature carbonization furnace, with the heating rate of 4 DEG C/min from room temperature directly be raised to 600 DEG C after keep 15min, when retort in-furnace temperature is down to below 150 DEG C take out sample;
4) sample post processing
By sample pure water supersound washing 4 h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product.
Being put into by the catalyst 0.3g prepared under this condition in 50 mL thiophene (300 ppm)-normal heptane simulation oil product, Gu use water--oily three-phase system, is 60 in reaction temperature
oc, H
2o
2consumption is 3 mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 4mL condition can reach 90.7%.
Embodiment 4:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 10g polyvinyl alcohol (PVA), constantly stir, after making it dissolve completely, add 10g ZnCl
2and 8.73g cobalt chloride (source metal and ZnCl
2mol ratio be 1:2), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 1h under baking oven 180 DEG C of conditions;
3) carbonize
By 2) in pre-oxidation products obtained therefrom under nitrogen protection (flow velocity 400 mL/min), be placed in high temperature carbonization furnace, with the heating rate of 4 DEG C/min from room temperature directly be raised to 650 DEG C after keep 20min, when retort in-furnace temperature is down to below 150 DEG C take out sample;
4) sample post processing
By sample pure water supersound washing 4 h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product.
Being put into by the catalyst prepared under this condition in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, Gu use water--oily three-phase system, is 50 in reaction temperature
oc, H
2o
2consumption is 3 mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 4mL condition can reach 93.3%.
Embodiment 5:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 6g polyvinyl alcohol (PVA), constantly stir, after making it dissolve completely, add 10g ZnCl
2and 8.07g sodium tungstate (source metal and ZnCl
2mol ratio be 1:3), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 9h under baking oven 100 DEG C of conditions;
3) carbonize
By 2) in pre-oxidation products obtained therefrom under nitrogen protection (flow velocity 400 mL/min), be placed in high temperature carbonization furnace, with the heating rate of 3 DEG C/min from room temperature directly be raised to 700 DEG C after keep 30min, when retort in-furnace temperature is down to below 150 DEG C take out sample;
4) sample post processing
By sample pure water supersound washing 4 h, suction filtration, is placed in 120 DEG C of baking oven inner dryings and obtains testing required product.
Being put into by the catalyst 0.4g prepared under this condition in 50 mL thiophene (400 ppm)-normal heptane simulation oil product, Gu use water--oily three-phase system, is 50 in reaction temperature
oc, H
2o
2consumption is 3 mL, CH
3cOOH consumption is that the catalytic oxidation desulfurization rate under 4mL condition can reach 82.8%.
Claims (8)
1. a preparation method for porous charcoal metal oxide supporting catalyst, is characterized in that, comprises the following steps:
S1: the preparation of collosol and gel: prepare poly-vinyl alcohol solution, adds ZnCl in poly-vinyl alcohol solution
2and source metal, obtain gel sample,
S2: pre-oxidation is carried out to gel sample cooled in S1;
S3: charing process: further the sample after oxidation is carried out high-temperature process under inert gas shielding, obtain product;
Wherein, the poly-vinyl alcohol solution in described step S1 adopts NaCl as dispersion stabilizer; The oxidizing condition of the preoxidation process in described step S2 is oxidizing temperature 100 DEG C ~ 200 DEG C, oxidization time 1 ~ 9 hour; High-temperature process in described step S3 is with the heating rate of 2 ~ 5 DEG C/min, is warming up to 550 DEG C ~ 750 DEG C from room temperature, keeps 15min ~ 120min.
2. preparation method as claimed in claim 1, is characterized in that the metal of described source metal is manganese, vanadium, nickel, cobalt or tungsten.
3. preparation method as claimed in claim 2, is characterized in that described source metal is manganese nitrate, ammonium metavanadate, nickel nitrate, cobalt chloride or sodium tungstate.
4. preparation method as claimed in claim 1, it is characterized in that in S1, the mass fraction of poly-vinyl alcohol solution is 10 ~ 20%, and the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1; Described source metal and ZnCl
2mol ratio be 1:1 ~ 1:3.
5. preparation method as claimed in claim 1, after it is characterized in that the cooling of the product after S3 high-temperature process, also through washing further and dry, obtain finished product, described cooling is cooled to 150 DEG C or following.
6. the porous charcoal metal oxide supporting catalyst for preparing of the method for claim 1.
7. the application of porous charcoal metal oxide supporting catalyst in catalytic oxidation desulfurization as claimed in claim 6.
8. apply as claimed in claim 7, it is characterized in that catalytic substrate is thiophene, catalysis process is: dropped into by described catalyst in thiophene, add H
2o
2and CH
3cOOH is carry out catalytic oxidation desulfurization under the condition of 40 ~ 70 DEG C in reaction temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310168762.8A CN103285901B (en) | 2013-05-09 | 2013-05-09 | Preparation method of porous carbon-loaded metal oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310168762.8A CN103285901B (en) | 2013-05-09 | 2013-05-09 | Preparation method of porous carbon-loaded metal oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103285901A CN103285901A (en) | 2013-09-11 |
| CN103285901B true CN103285901B (en) | 2015-05-20 |
Family
ID=49087741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310168762.8A Expired - Fee Related CN103285901B (en) | 2013-05-09 | 2013-05-09 | Preparation method of porous carbon-loaded metal oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103285901B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN113648987A (en) * | 2021-09-08 | 2021-11-16 | 东北大学 | Preparation method of porous carbon and carbon supported catalyst |
| CN115382538A (en) * | 2022-09-17 | 2022-11-25 | 湖州师范学院 | Novel metal-based carbon catalyst for hydrogen production by catalytic degradation of organic wastewater and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376114A (en) * | 2008-10-09 | 2009-03-04 | 大连理工大学 | Method for preparing metal or metallic oxide/carbon composite material |
| US7572427B2 (en) * | 2001-07-03 | 2009-08-11 | Facultes Universitaires Notre-Dame De La Paix | Catalyst supports and carbon nanotubes produced thereon |
-
2013
- 2013-05-09 CN CN201310168762.8A patent/CN103285901B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7572427B2 (en) * | 2001-07-03 | 2009-08-11 | Facultes Universitaires Notre-Dame De La Paix | Catalyst supports and carbon nanotubes produced thereon |
| CN101376114A (en) * | 2008-10-09 | 2009-03-04 | 大连理工大学 | Method for preparing metal or metallic oxide/carbon composite material |
Non-Patent Citations (1)
| Title |
|---|
| 活性炭及甲酸催化过氧化氢氧化噻吩脱硫研究;余国贤等;《燃料化学学报》;20050228;第33卷(第1期);第74-78页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103285901A (en) | 2013-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102580675B (en) | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon | |
| CN103752276A (en) | Cuprous modified metal organic skeleton adsorbent, preparation method and application | |
| Koriakin et al. | Denitrogenation of raw diesel fuel by lithium-modified mesoporous silica | |
| CN103691476B (en) | A kind of low-temperature synchronous denitration desulphurization catalyst and preparation method | |
| CN104190478B (en) | A kind of denitration desulphurized aetivated carbon catalyst recovery process | |
| CN104190432B (en) | Low-temperature denitration and synergetic desulfurization active carbon catalyst and preparation method thereof | |
| CN105921139B (en) | A kind of mercury absorbent and its preparation method and application | |
| CN103285901B (en) | Preparation method of porous carbon-loaded metal oxide catalyst | |
| CN105289732B (en) | The immobilized metal peroxides catalyst of MOF | |
| CN102962064A (en) | Gamma-form alumina loaded metallic oxide catalyst as well as preparation method and application thereof | |
| CN103331161B (en) | Catalyst for diesel desulfurization, preparation method and application | |
| CN101259417B (en) | Regeneration method of sulphur absorption V2O5/AC catalytic adsorption agent | |
| CN103143322A (en) | Preparation method of modified active carbon-based gasoline desulfurization adsorbent | |
| CN104475165A (en) | Preparation method of oxidative desulfurization catalyst | |
| CN104437653A (en) | Bio-based rubble paper-like catalyst for low-temperature synchronous denitration and desulfurization and preparation method thereof | |
| CN107434980A (en) | A kind of preparation of activated carbon and the method for the absorption desulfurization of refinery's distillate | |
| CN104307469B (en) | It is a kind of for desulfuration adsorbent of refined diesel oil deep desulfuration and preparation method thereof | |
| CN105727888A (en) | Reproducible SO2 adsorbent and preparation method therefor | |
| CN104383959B (en) | A kind of preparation method and applications of the titanium-containing meso-porous Y type molecular sieve with catalytic oxidation activity | |
| CN110157466A (en) | A method of utilizing dibenzothiophenes in zeolite molecular sieve support type composite catalyst catalysis oxidation removal oil product | |
| CN113145103B (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
| CN104069734B (en) | A kind of dephosphorization catalytic reaction technique of yellow phosphoric tail gas and catalyst | |
| CN102773010B (en) | Method for purifying thiophene in industrial tail gas | |
| CN112608772A (en) | Method for removing organic sulfur in blast furnace gas | |
| CN101805640B (en) | High-temperature coal gas desulfurizing agent of composite oxides of mesoporous rare soil 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: 20150520 Termination date: 20190509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |