CN102836739B - Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure - Google Patents
Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure Download PDFInfo
- Publication number
- CN102836739B CN102836739B CN201210304770.6A CN201210304770A CN102836739B CN 102836739 B CN102836739 B CN 102836739B CN 201210304770 A CN201210304770 A CN 201210304770A CN 102836739 B CN102836739 B CN 102836739B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- temperature
- mcm
- oil product
- room temperature
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure. The method comprises the following steps: adding acetylacetone nickel, triphenyl phosphine and MCM-41 interface confucius screen to tri-n-octylamine, and evenly stirring a mixture at room temperature; adding slurry obtained in the first step to a normal-pressure stirring reactor, heating the slurry to 330 DEG C with an increment of 2 DEG C per minute in nitrogen flow of 100mL/min; keeping the temperature constantly for 3 hours, and reducing the temperature to the room temperature, finally, passivating the slurry for 1 hour by O2/N2 mixing gas containing 10% of oxygen; filtering the passivated slurry under reduced pressure by a sand-core hopper; washing an obtained filter cake with mixed solution of ethanol and carbon tetrachloride based on volume ratio of 1: 1 at 50 DEG C; and drying the filter cake at 100 DEG C and tabletting the filter cake so as to obtain a catalyst finished product. According to the invention, the prepared supported oil product hydrodesulphurization catalyst disclosed by the invention has the advantages of soft condition, little dependence on equipment, little impurity and high desulphurization rate.
Description
Technical field
The invention belongs to hydrodesulfurizationcatalyst catalyst for oil product technical field, be specifically related to a kind of method that solvothermal method at normal pressure prepares support type hydrodesulfurizationcatalyst catalyst for oil product.
Background technology
Along with people are to the continuous concern of environmental problem, environmental regulation is more and more stricter to the sulfur content restriction in fuel oil.Fuel desulfuration technology progressively turns to the degree of depth and ultra-deep desulfurization field, and current commercial transient metal sulfide hydrodesulfurization (HDS) catalyst has been difficult to meet this requirement.Therefore, improve original sulfide catalyst and find the focus that new efficient substitute has become the research of nearest researcher.Ni
2p is a kind of material with high hydrodesulfurization activity found in recent years.In identical test condition, Ni
2p/SiO
2the specific activity NiMo/Al of catalyst
2o
3and CoMo/Al
2o
3all want high, the active order of similar phosphide is: Ni
2p>WP>MoP>CoPGr eatT.GreaT.GTFe
2p.Ni
2p has higher mechanical strength, heat endurance, electric conductivity, and HDS catalytic activity, the stability of special crystal structure and excellence, along with the low sulfuration of environmental regulation proposition, without sulfuration trend, will be most possibly the substitute of commercial sulfur compound catalyst.
The synthesis Ni reported at present
2p catalyst method mainly contains temperature-programmed reduction method, pyrolysis hypophosphites method and solvent-thermal method.Temperature programmed reduction synthesis Ni
2p catalyst is usually with nickel nitrate (Ni (NO
3)
26H
2and diammonium hydrogen phosphate ((NH O)
4)
2hPO
4) salt-mixture be presoma, process is simple but need higher reduction temperature (generally at 600 ~ 750 DEG C), not only waste a large amount of energy in building-up process, and high temperature can cause the reunion of active phase, and the selection of carrier is had higher requirement (as the TiO of anatase
2carrier just can not bear so high temperature).Pyrolysis hypophosphites method synthesis Ni
2p catalyst is usually with nickel chloride (NiCl
26H
2and sodium hypophosphite (NaH O)
2pO
2h
2o) salt-mixture is presoma, does not need higher temperature process to generate Ni under nitrogen atmosphere
2p, but the catalyst of synthesis contains a large amount of phosphate impurities, and the catalyst hydrodesulfurization active of the therefore preparation of the method is not high.Traditional solvent-thermal method synthesizes at the alkali condition high pressure of ammoniacal liquor, or adopt expensive trioctylphosphine phosphorus to be phosphorus source, and atmospheric synthesis under the liquid phase environment of oleyl amine, due to the restriction by cost and reaction condition, is difficult to the requirement realizing large-scale industrial production.
Summary of the invention
In order to solve Problems existing in background technology, the invention provides a kind of method that solvothermal method at normal pressure prepares support type hydrodesulfurizationcatalyst catalyst for oil product, instant invention overcomes the respective shortcoming of temperature-programmed reduction method, pyrolysis hypophosphites method and the hot method of conventional solvent, triphenyl phosphorus is adopted to be phosphorus source respectively, take tri-n-octyl amine as liquid-phase reaction system, required catalyst preparing temperature is about 330 DEG C, reaction is carried out at ambient pressure, at least lower than the reduction temperature needed for temperature-programmed reduction method 300 DEG C; Higher than the catalyst purity of pyrolysis hypophosphites method synthesis, more cheap than traditional solvent structure condition milder, raw material.In a word, the high and applicable commercial introduction of the catalyst desulfurizing performance prepared of this method.
The technical solution adopted in the present invention is: a kind of solvothermal method at normal pressure prepares the method for support type hydrodesulfurizationcatalyst catalyst for oil product:
The first step, is equipped with reaction raw materials slurries:
According to the nickel acetylacetonate of certain metering ratio, triphenyl phosphorus and the mesoporous son sieve of MCM-41 (or TiO
2in carrier) join in tri-n-octyl amine, be at room temperature stirred to and fully mix.Wherein, the mass ratio of nickel acetylacetonate, triphenyl phosphorus, the mesoporous son sieve of MCM-41, tri-n-octyl amine is 1:(2 ~ 10): (0.67 ~ 2.60): 32.
Second step, reaction Kaolinite Preparation of Catalyst:
The slip that the first step obtains is joined in atmospheric agitation reactor, 330 DEG C are heated under agitation with the heating rate of 2 DEG C per minute in the nitrogen stream of 100 mL/min, constant temperature was cooled to room temperature after 3 hours at such a temperature, finally with the O containing oxygen 10% (V/V)
2/ N
2gaseous mixture passivation 1 hour.
3rd step, filter, wash and drying:
Slip sand core funnel after passivation is carried out filtration under diminished pressure, with ethanol and the filter cake of carbon tetrachloride mixed solution at 50 DEG C after washing and filtering (repeating filtration washing 3 times) that volume ratio is 1:1, after dry at 100 DEG C, compression molding is to obtain finished catalyst.
This novel had beneficial effect is: required catalyst preparing temperature is about 330 DEG C, and reaction is carried out at ambient pressure, at least lower than the reduction temperature needed for temperature-programmed reduction method 300 DEG C; Compared to the method for pyrolysis hypophosphites, almost phosphate free impurity in the catalysis of synthesis, catalytic desulfurhydrogenation performance is high, and the catalyst of synthesis is more suitable for the theoretical research doing catalyst of phosphatizing nickel; Less than the dependence of traditional solvent-thermal method to equipment, raw material is more cheap, is more suitable for industrial production; Within 120 hours, active appraisal experiment shows, dibenzothiophenes desulfurization degree can remain on about 100 %, and catalyst shows high activity and stability.
accompanying drawing illustrates:
Fig. 1 is the XRD analysis result of embodiment 1 sample;
Fig. 2 is that embodiment 1 catalyst sample HDS is active;
Fig. 3 is the XRD analysis result of embodiment 2 sample;
Fig. 4 is that embodiment 2 catalyst sample HDS is active;
Fig. 5 is the XRD analysis result of embodiment 3 sample;
Fig. 6 is that embodiment 3 catalyst sample HDS is active;
detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is further described:
embodiment 1, to synthesize initial Ni/P mol ratio be the Ni of 1/2
2p/MCM-41 catalyst, and catalyst is characterized and desulphurizing activated mensuration.
The first step, is equipped with reaction raw materials slurries:
Join in tri-n-octyl amine according to the nickel acetylacetonate of certain metering ratio, triphenyl phosphorus and the mesoporous son sieve of MCM-41, be at room temperature stirred to and fully mix.Wherein, the mass ratio of nickel acetylacetonate, triphenyl phosphorus, the mesoporous son sieve of MCM-41, tri-n-octyl amine is 1:2:0.67:32.
Second step, reaction Kaolinite Preparation of Catalyst:
The slip that the first step obtains is joined in atmospheric agitation reactor, 330 DEG C are heated under agitation with the heating rate of 2 DEG C per minute in the nitrogen stream of 100 mL/min, constant temperature was cooled to room temperature after 3 hours at such a temperature, finally with the O containing oxygen 10% (V/V)
2/ N
2gaseous mixture passivation 1 hour.
3rd step, filter, wash and drying:
Slip sand core funnel after passivation is carried out filtration under diminished pressure, with ethanol and the filter cake of carbon tetrachloride mixed solution at 50 DEG C after washing and filtering (repeating filtration washing 3 times) that volume ratio is 1:1, after dry at 100 DEG C, compression molding is to obtain finished catalyst.
Activity rating: evaluating catalyst carries out in fixed bed high-pressure micro-device.Reaction procatalyst processes 2 h at 500 DEG C of logical hydrogen (80 ml/min), then is down to reaction temperature 340 DEG C.The model compound adopted is the mixed solution of dibenzothiophenes, dodecane and decahydronaphthalene, and its content is respectively 2 %, 1 % and 97 %.Wherein, decahydronaphthalene is solvent, and dodecane is internal standard compound.Reaction condition is, 340 DEG C, 3.0 MPa, hydrogen-oil ratio 500 (V/V), air speed 2.0 h
-1.The liquid product analyses obtained is carried out on the GC-14C type gas chromatograph of Japanese Shimadzu Corporation.
Experimental result: the XRD analysis result of catalyst as shown in Figure 1.XRD analysis result shows, and the degree of crystallization of active phase is very high, occurs obvious diffraction maximums, this and Ni at 2 θ about 40.7 °, 44.6 °, 47.3 °, 54.1 ° 54.8 °, 66.1 °, 72.5 ° and 74.5 ° of places
2the main diffraction peak (PDF:03-0953) of P phase is consistent, shows that the crystalline phase of the catalyst synthesized is Ni
2p.With the Ni that Scherrer formulae discovery goes out
2the size of P crystal grain is approximately 20 nm.Have no other peaks of metal phosphorus and nickel in XRD spectra, show that the nickel phosphide thing in catalyst sample is mutually equal to Ni
2p form exists.Therefore, the Ni of MCM-41 load that what the method synthesized is
2p catalyst.
The Ni of the MCM-41 load of the present embodiment synthesis
2the hydrodesulfurization activity result of P catalyst as shown in Figure 2, is less than 12 hours in the reaction time, and the activity of catalyst improves along with the increase in reaction time, and at 12 hours, desulfurization reached 100%, and the desulfurization degree of rear catalyst is stabilized in about 100%.Visible, the support type Ni synthesized by the method
2p catalyst has good hydrodesulfurization activity.
embodiment 2, to synthesize initial Ni/P mol ratio be the Ni of 1/6
2p/MCM-41 catalyst, and catalyst is characterized and desulphurizing activated mensuration.
The first step, is equipped with reaction raw materials slurries:
Join in tri-n-octyl amine according to the nickel acetylacetonate of certain metering ratio, triphenyl phosphorus and the mesoporous son sieve of MCM-41, be at room temperature stirred to and fully mix.Wherein, the mass ratio of nickel acetylacetonate, triphenyl phosphorus, the mesoporous son sieve of MCM-41, tri-n-octyl amine is 1:6:0.67:32.
Second step, reaction Kaolinite Preparation of Catalyst:
The slip that the first step obtains is joined in atmospheric agitation reactor, 330 DEG C are heated under agitation with the heating rate of 2 DEG C per minute in the nitrogen stream of 100 mL/min, constant temperature was cooled to room temperature after 3 hours at such a temperature, finally with the O containing oxygen 10% (V/V)
2/ N
2gaseous mixture passivation 1 hour.
3rd step, filter, wash and drying:
Slip sand core funnel after passivation is carried out filtration under diminished pressure, with ethanol and the filter cake of carbon tetrachloride mixed solution at 50 DEG C after washing and filtering (repeating filtration washing 3 times) that volume ratio is 1:1, after dry at 100 DEG C, compression molding is to obtain finished catalyst.
Activity rating: evaluating catalyst carries out in fixed bed high-pressure micro-device.Reaction procatalyst processes 2 h at 500 DEG C of logical hydrogen (80 ml/min), then is down to reaction temperature 340 DEG C.The model compound adopted is the mixed solution of dibenzothiophenes, dodecane and decahydronaphthalene, and its content is respectively 2 %, 1 % and 97 %.Wherein, decahydronaphthalene is solvent, and dodecane is internal standard compound.Reaction condition is, 340 DEG C, 3.0 MPa, hydrogen-oil ratio 500 (V/V), air speed 2.0 h
-1.The liquid product analyses obtained is carried out on the GC-14C type gas chromatograph of Japanese Shimadzu Corporation.
Experimental result: the XRD analysis result of catalyst as shown in Figure 3.XRD analysis result shows, and the degree of crystallization of active phase is very high, occurs obvious diffraction maximums, this and Ni at 2 θ about 40.7 °, 44.6 °, 47.3 °, 54.1 ° 54.8 °, 66.1 °, 72.5 ° and 74.5 ° of places
2the main diffraction peak (PDF:03-0953) of P phase is consistent, shows that the crystalline phase of the catalyst synthesized is Ni
2p.With the Ni that Scherrer formulae discovery goes out
2the size of P crystal grain is approximately 16 nm.Have no other peaks of metal phosphorus and nickel in XRD spectra, show that the nickel phosphide thing in catalyst sample is mutually equal to Ni
2p form exists.Therefore, the Ni of MCM-41 load that what the method synthesized is
2p catalyst.
The Ni of the MCM-41 load of the present embodiment synthesis
2the hydrodesulfurization activity result of P catalyst as shown in Figure 4, is less than 12 hours in the reaction time, and the activity of catalyst improves along with the increase in reaction time, and at 12 hours, desulfurization reached 100%, and the desulfurization degree of rear catalyst is stabilized in about 100%.Visible, the support type Ni synthesized by the method
2p catalyst has good hydrodesulfurization activity.
embodiment 3,synthesizing initial Ni/P mol ratio is the Ni of 1/10
2p/MCM-41 catalyst, and catalyst is characterized and desulphurizing activated mensuration.
The first step, is equipped with reaction raw materials slurries:
Join in tri-n-octyl amine according to the nickel acetylacetonate of certain metering ratio, triphenyl phosphorus and the mesoporous son sieve of MCM-41, be at room temperature stirred to and fully mix.Wherein, the mass ratio of nickel acetylacetonate, triphenyl phosphorus, the mesoporous son sieve of MCM-41, tri-n-octyl amine is 1:10:0.67:32.
Second step, reaction Kaolinite Preparation of Catalyst:
The slip that the first step obtains is joined in atmospheric agitation reactor, 330 DEG C are heated under agitation with the heating rate of 2 DEG C per minute in the nitrogen stream of 100 mL/min, constant temperature was cooled to room temperature after 3 hours at such a temperature, finally with the O2/N2 gaseous mixture passivation 1 hour containing oxygen 10% (V/V).
3rd step, filter, wash and drying:
Slip sand core funnel after passivation is carried out filtration under diminished pressure, with ethanol and the filter cake of carbon tetrachloride mixed solution at 50 DEG C after washing and filtering (repeating filtration washing 3 times) that volume ratio is 1:1, after dry at 100 DEG C, compression molding is to obtain finished catalyst.
Activity rating: evaluating catalyst carries out in fixed bed high-pressure micro-device.Reaction procatalyst processes 2 h at 500 DEG C of logical hydrogen (80 ml/min), then is down to reaction temperature 340 DEG C.The model compound adopted is the mixed solution of dibenzothiophenes, dodecane and decahydronaphthalene, and its content is respectively 2 %, 1 % and 97 %.Wherein, decahydronaphthalene is solvent, and dodecane is internal standard compound.Reaction condition is, 340 DEG C, 3.0 MPa, hydrogen-oil ratio 500 (V/V), air speed 2.0 h
-1.The liquid product analyses obtained is carried out on the GC-14C type gas chromatograph of Japanese Shimadzu Corporation.
Experimental result: the XRD analysis result of catalyst as shown in Figure 5.XRD analysis result shows, and the degree of crystallization of active phase is very high, occurs obvious diffraction maximums, this and Ni at 2 θ about 40.7 °, 44.6 °, 47.3 °, 54.1 ° 54.8 °, 66.1 °, 72.5 ° and 74.5 ° of places
2the main diffraction peak (PDF:03-0953) of P phase is consistent, shows that the crystalline phase of the catalyst synthesized is Ni
2p.With the Ni that Scherrer formulae discovery goes out
2the size of P crystal grain is approximately 14 nm.Have no other peaks of metal phosphorus and nickel in XRD spectra, show that the nickel phosphide thing in catalyst sample is mutually equal to Ni
2p form exists.Therefore, the Ni of MCM-41 load that what the method synthesized is
2p catalyst.
The Ni of the MCM-41 load of the present embodiment synthesis
2the hydrodesulfurization activity result of P catalyst as shown in Figure 6, is less than 12 hours in the reaction time, and the activity of catalyst improves along with the increase in reaction time, and at 12 hours, desulfurization reached 100%, and the desulfurization degree of rear catalyst is stabilized in about 100%.Visible, the support type Ni synthesized by the method
2p catalyst has good hydrodesulfurization activity.
Claims (1)
1. the support type hydrodesulfurizationcatalyst catalyst for oil product prepared of solvothermal method at normal pressure, this catalyst is obtained by following method:
The first step, is equipped with reaction raw materials slurries:
According to the nickel acetylacetonate of certain metering ratio, triphenyl phosphorus and MCM-41 mesopore molecular sieve or TiO
2carrier joins in tri-n-octyl amine, is at room temperature stirred to and fully mixes, wherein, and nickel acetylacetonate by mass: triphenyl phosphorus: MCM-41 mesopore molecular sieve or TiO
2: tri-n-octyl amine=1:(2 ~ 10): (0.67 ~ 2.60): 32,
Second step, reaction Kaolinite Preparation of Catalyst
The slip that the first step obtains is joined in atmospheric agitation reactor, 330 DEG C are heated under agitation with the heating rate of 2 DEG C per minute in the nitrogen stream of 100 mL/min, constant temperature was cooled to room temperature after 3 hours at such a temperature, finally with the O containing oxygen 10% (V/V)
2/ N
2gaseous mixture passivation 1 hour;
3rd step, filters, washs and drying
Slip sand core funnel after passivation is carried out filtration under diminished pressure, is ethanol and the filter cake of carbon tetrachloride mixed solution at 50 DEG C after washing and filtering of 1:1 by volume ratio, repeats filtration washing 3 times, and after dry at 100 DEG C, compression molding is to obtain finished catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210304770.6A CN102836739B (en) | 2012-08-25 | 2012-08-25 | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210304770.6A CN102836739B (en) | 2012-08-25 | 2012-08-25 | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102836739A CN102836739A (en) | 2012-12-26 |
| CN102836739B true CN102836739B (en) | 2014-12-17 |
Family
ID=47364618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210304770.6A Expired - Fee Related CN102836739B (en) | 2012-08-25 | 2012-08-25 | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102836739B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117382B (en) * | 2013-04-26 | 2016-08-10 | 中国石油天然气股份有限公司 | Hydrothermal preparation method of supported nickel phosphide catalyst |
| CN103861625A (en) * | 2014-02-28 | 2014-06-18 | 天津大学 | Preparation method of supported Ni2P catalyst |
| CN107088432B (en) * | 2017-04-12 | 2019-09-06 | 南京师范大学 | A kind of two dimension Ru doping Ni2P plate-like nano flake and its preparation method and application |
| CN113426463A (en) * | 2021-07-01 | 2021-09-24 | 中国石油大学(华东) | In-situ preparation and application of high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734633B (en) * | 2008-11-14 | 2012-01-11 | 南京大学 | Preparation method of nickel phosphide |
-
2012
- 2012-08-25 CN CN201210304770.6A patent/CN102836739B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102836739A (en) | 2012-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101327439B (en) | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst | |
| CN102451765B (en) | Preparation method for composite oxide carrier | |
| CN110327933B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation, preparation method and application thereof | |
| CN102836739B (en) | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure | |
| CN102580758B (en) | NiO-MoO3/ TiO2 catalyst and preparation method thereof | |
| CN103240114A (en) | Hydrocracking catalyst, preparation and application thereof | |
| CN108745385A (en) | A kind of autovulcanization oil-soluble molybdenum bimetallic catalyst and its preparation method and application | |
| CN101905175B (en) | Method for preparing heavy distillate hydrotreating catalyst | |
| CN107486248B (en) | The circulation utilization method of oil-soluble molybdenum base slurry bed system hydrocracking catalyst | |
| CN102847548B (en) | Method for preparing hydrodesulfurization catalyst for oil product under mild condition | |
| KR101828965B1 (en) | Catalyst suitable for production of aviation kerosene from biomass fischer-tropsch synthesis oil and preparation method therefor | |
| CN110215927A (en) | A kind of preparation method of the support type catalyst of phosphatizing nickel of high dispersive | |
| CN110479283B (en) | Catalyst with nickel loaded on surface of copper ferrite spinel, preparation method and application thereof | |
| CN110305330B (en) | To CO2Iron-based metal organic framework material with high catalytic activity in cycloaddition reaction and preparation method and application thereof | |
| CN114011415B (en) | Preparation method of high-loading layered cobalt catalyst for preparing green diesel oil through grease hydrodeoxygenation | |
| CN108568309B (en) | Oil product deep hydrodesulfurization catalyst and preparation method thereof | |
| CN107376963A (en) | Catalyst of phosphatizing nickel and preparation method and application | |
| CN106268856A (en) | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application | |
| CN111167459A (en) | Catalyst for preparing methanol from mixed gas and preparation method and application thereof | |
| CN108435233B (en) | Method for improving deep hydrodesulfurization of oil product | |
| CN103801346A (en) | Preparation method for hydrotreatment catalyst | |
| CN109759104B (en) | Preparation method of catalyst for low-temperature methanol synthesis | |
| CN101733114A (en) | Superfine powder composite metallic oxide catalyst and application thereof | |
| CN102476827A (en) | Preparation of TiO with large pore volume2Method for producing powder | |
| CN110975910B (en) | Bulk catalyst without waste liquid generation, preparation method thereof and hydrogenation catalyst containing bulk catalyst |
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: 20141217 Termination date: 20150825 |
|
| EXPY | Termination of patent right or utility model |