CN106513028B - A kind of catalyst and preparation method thereof and the application in reduction nitro compound - Google Patents
A kind of catalyst and preparation method thereof and the application in reduction nitro compound Download PDFInfo
- Publication number
- CN106513028B CN106513028B CN201610969457.2A CN201610969457A CN106513028B CN 106513028 B CN106513028 B CN 106513028B CN 201610969457 A CN201610969457 A CN 201610969457A CN 106513028 B CN106513028 B CN 106513028B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nitrogen
- preparation
- nitro compound
- cobalt
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
The invention belongs to catalyst technical field, specially a kind of catalyst and preparation method thereof and catalysis reduction nitro compound prepare the application in aminated compounds, the catalyst is using cobalt peptide cyanines as precursor, SiO2It for hard template, is obtained by high temperature pyrolysis under nitrogen protection, which cannot be only used for catalytic hydrogenating reduction nitro compound under temperate condition, apply also for being catalyzed other hydrogen sources such as CO/H2O, the reaction of the nitro compound reducing of n-butanol, isopropanol, benzyl alcohol, formic acid etc..Method for preparing catalyst in the present invention is simple, and the stability of catalyst is preferable, is recycled 16 times or more, has good prospects for commercial application.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of catalyst and preparation method thereof, and its in reduction nitre
Application in base class compound.
Background technique
Aminated compounds (mainly aniline) is a kind of important industrial chemicals and fine-chemical intermediate, is widely used in
Dyestuff, medicine, explosive, fragrance, the industries such as thiofide and special type function material.Industrially mainly pass through nitro at present
The preparation of class compound (mainly nitrobenzene) hydrogenation method, reaction usually require higher temperature and elevated pressures, easily cause reactor
The security risk of hot-spot, the high requirements on the equipment, and production process is big.So exploitation aminated compounds (mainly aniline) is new
Synthesis technology and technology industrially have having significant practical applications.
Nitro compound (mainly nitrobenzene) plus hydrogen are mainly catalyzed by noble metal catalyst at present, or are needed in height
It is carried out under warm high pressure.Such as: Matthias Beller etc. prepares amine by hydrogen source of hydrogen using base metal Co catalyst
It closes object (mainly aniline), under the pressure of 50bar, 4 hours conversion ratios and selectivity reach 100% [Nature
Chemistry [J], 2013,5,537-543.].Yongquan Qu etc. uses precious metals pd catalyst reduction nitro compound
(mainly nitrobenzene), this method can be in 5bar H2Lower progress, 2h conversion ratio and selectivity reach 100% [Joumal of
The American Chemical Society [J], 2016,138,2629-37.].
It is all used however, preparing major part in nitro compound (mainly nitrobenzene) method disclosed in the prior art
Noble metal catalyst, and still require that higher Hydrogen Vapor Pressure, it is unfavorable for being mass produced.
Summary of the invention
According to the shortcomings of the prior art, the object of the present invention is to provide a kind of base metal Co catalyst (CoN@CN)
And preparation method thereof and catalysis reduction nitro compound prepare the application in aminated compounds.Wherein catalyst is load Co
Nitrogen-doped carbon material, abbreviation CoN@CN.
To achieve the above object the present invention adopts the following technical scheme:
The present invention provides a kind of catalyst, which is nitrogen-doped carbon material load cobalt catalyst, with nitrogen-doped carbon
Material is skeleton, binding activity component on skeleton, and active constituent is CoN in catalystx, Co element quality point in the catalyst
Number is 0.18%-1%, and X-ray diffraction (XRD) CoN occurs in 2 θ=43.7 °xCharacteristic peak (JCPDS No.41-0943).
The preparation method of above-mentioned nitrogen-doped carbon material load cobalt catalyst, comprising the following steps:
(1) mass ratio is added to N, N- diformazan for 1: 1-1: 20 tetranitro cobalt peptide cyanines (referred to as CoPc) and silica solution
Base formamide (DMF) and H2The in the mixed solvent stirring of O is abundant, the in the mixed solvent DMF and H2O volume ratio is 1: 1-1:
5；
(2) vacuum distillation removal solvent, obtains tetranitro cobalt peptide cyanines and SiO2Composite material: CoPc/SiO2；
(3) by CoPc/SiO obtained in step (2)2High temperature pyrolysis under nitrogen protection, pyrolysis temperature are 600 DEG C -900
DEG C, calcination time is 2 hours；
(4) using the template SiO of aqueous hydrogen fluoride solution removal step (3) obtained solid of 1wt%-20wt%2And metal
State Co nanoparticle is washed to centrifugal vacuum drying to obtain CoN@CN catalyst after neutrality.
Application of the above-mentioned nitrogen-doped carbon material load cobalt catalyst in reduction nitro compound, the steps include: to urge
Agent, solvent, nitro compound proportionally 40mg: 5-16mL: 0.49-1mmol are added in reaction vessel, are filled with
1bar-20bar reproducibility or protective gas react 1-12h at 40-160 DEG C, obtain reduzate.
The reducibility gas is hydrogen or carbon monoxide, and the protective gas is the nitrogen for preventing oxidation.
The solvent is water, acetonitrile, ethyl alcohol, isopropanol, n-butanol, benzyl alcohol, toluene, dioxane, ethyl acetate
Or one of limonene.
The nitro compound is
Compared with prior art, catalyst of the present invention and its application the advantages of and beneficial effect be:
Relative to other noble metal catalysts such as Pd, Ru, Au etc., the active component of this catalyst is relative low price
Cobalt.
Catalyst activity of the present invention is high, can be in low pressure (1bar H2) under realize nitro compound restore to obtain amine
Close the reaction of object.
Catalyst of the present invention can be catalyzed the nitrobenzene reduction under different hydrogen sources simultaneously, such as: carbon monoxide and water combination, first
Acid, alcohols, olefines.
This catalyst can reach higher conversion ratio suitable for organic solvent or water.
The stability of this catalyst is preferable, is recycled 16 times or more, has good prospects for commercial application.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of CoN@CN.
Specific embodiment
Some specific embodiments are listed below, and invention is further explained, but is not limited to model of the invention
It encloses.
The source of silica solution and tetranitro cobalt peptide cyanines is as follows:
Silica solution: it is bought from Sigma-Aldrich company；
Tetranitro cobalt peptide cyanines: by 4- nitro phthalic nitrile, cobalt acetate, 1,8- diazabicylo [5.4.0], 11 carbon -7- alkene4: 1.2: 0.01 ratio is added in n-butanol and stirs 2 days for 130 DEG C in molar ratio, and acquired solution filters
The solid again with methanol washing drying arrived.
Embodiment 1:
A kind of preparation method of nitrogen-doped carbon material load Co (CoN@CN) catalyst, its step are as follows:
Mass ratio is added to DMF and H for 1: 10 tetranitro cobalt peptide cyanines and silica solution2The in the mixed solvent stirring of O is filled
Point, the DMF and H2O volume ratio is 1: 3, and then vacuum distillation removes solvent and obtains tetranitro cobalt peptide cyanines and SiO2Composite wood
Material: CoPc/SiO2；Nitrogen protection is calcined 2 hours at 900 DEG C；Template SiO is washed away with 1wt%HF solution2It is received with metallic state Co
Rice corpuscles is washed to neutral vacuum drying and obtains CoN CN catalyst, and wherein active component is cobalt nitride, the quality of Co element
Content is 0.18%, and the XRD spectrum of gained CoN@CN catalyst is as shown in Figure 1, there is CoN in 2 θ=43.7 °xCharacteristic peak
(JCPDS No.41-0943)。
Embodiment 2:
A kind of preparation method of nitrogen-doped carbon material load Co (CoN@CN) catalyst, its step are as follows:
Mass ratio is added to DMF and H for 1: 1 tetranitro cobalt peptide cyanines and silica solution2The in the mixed solvent stirring of O is filled
Point, the DMF and H2O volume ratio is 1: 1, and then vacuum distillation removes solvent and obtains tetranitro cobalt peptide cyanines and SiO2Composite wood
Material: CoPc/SiO2；Nitrogen protection is calcined 2 hours at 800 DEG C；Template SiO is washed away with 15wt%HF solution2It is unstable with surface
Metallic state Co, be washed to neutral vacuum drying and obtain CoN CN catalyst, wherein active component is cobalt nitride, Co element
Mass content is 0.25%, and gained CoN@CN catalyst carries out XRD detection, CoN occurs in 2 θ=43.7 °xCharacteristic peak (JCPDS
No.41-0943)。
Embodiment 3:
A kind of preparation method of nitrogen-doped carbon material load Co (CoN@CN) catalyst, its step are as follows:
Mass ratio is added to DMF and H for 1: 20 tetranitro cobalt peptide cyanines and silica solution2The in the mixed solvent stirring of O is filled
Point, the DMF and H2O volume ratio is 1: 5, and then vacuum distillation removes solvent and obtains tetranitro cobalt peptide cyanines and SiO2Composite wood
Material: CoPc/SiO2；Nitrogen protection is calcined 2 hours at 600 DEG C；Template SiO is washed away with 20wt%HF solution2It is unstable with surface
Metallic state Co, be washed to neutral vacuum drying and obtain CoN CN catalyst, wherein active component is cobalt nitride, Co element
Mass content is 1%, and gained CoN@CN catalyst carries out XRD detection, CoN occurs in 2 θ=43.7 °xCharacteristic peak (JCPDS
No.41-0943)。
Embodiment 4:
Application of the CoN@CN catalyst prepared using embodiment 1 in reduction nitrobenzene, its step are as follows:
By nitrobenzene (0.6mmol), the catalyst (40mg) of the different calcination temperatures of water (5mL) and the preparation of embodiment 1 adds
Enter into 25mL stainless steel cauldron, is filled with 3.5bar hydrogen, reacts 1.5h at 90 DEG C.Through gas chromatographic detection, it is in following table
Calcination temperature is on active influence:
Embodiment 5: the activity of CoN@CN catalyst under different hydrogen source pressure
Application of the CoN@CN catalyst prepared using embodiment 1 in reduction nitrobenzene, its step are as follows:
By nitrobenzene (0.98mmol), the catalyst (40mg) of water (10mL) and the preparation of embodiment 1 is added to reaction kettle
In, it is filled with the hydrogen of 10bar to 1bar different pressures, 110 DEG C is heated to and reacts 1.5 hours.Through gas chromatographic detection, nitrobenzene
Conversion ratio is as follows:
H in upper table2Pressure is 1aIndicate that it is 6h, other conditions that nitrobenzene 0.49mmol, 1bar, 110 DEG C reaction time, which is added,
It is identical；
H in upper table2Pressure is 1bIt indicates that nitrobenzene 0.49mmol, 1bar, 40 DEG C of reaction 12h are added, other conditions are identical.
Embodiment 6: the activity of CoN@CN catalyst under different solvents
Application of the CoN@CN catalyst prepared using embodiment 1 in reduction nitrobenzene, its step are as follows:
By nitrobenzene (0.98mmol), the catalyst (40mg) of solvent (16mL) and the preparation of embodiment 1 is added to 25mL not
Become rusty steel reaction kettle in, with hydrogen displaced air three times after, all mixtures are placed in 10bar hydrogen, 110 DEG C of reactions are added to
1.5h.Through gas chromatographic detection, nitrobenzene conversion rate is as follows:
Embodiment 7: the activity of CoN@CN catalyst under different hydrogen sources and solvent
Application of the CoN@CN catalyst prepared using embodiment 1 in reduction nitrobenzene, its step are as follows:
By nitrobenzene (0.98mmol), the catalyst (40mg) of solvent (10mL) and the preparation of embodiment 2 is added to 25mL not
It becomes rusty in steel reaction kettle, after nitrogen displaced air 3 times, mixture is placed in 20bar nitrogen, reacts 12h at different temperatures.
Through gas chromatographic detection, aniline yield is as follows:
H in upper table2OaExpression adds 3mmol HCOOH as hydrogen source, and other conditions are identical；
H in upper table2ObWith 5bIndicate that 5bar CO, which is added, replaces N2, other conditions are identical；
100cThe yield for indicating n-butanal aniline condensation product is 100%；
100dIndicate that N- benzylidene aniline yield is 100%.
Activity of the embodiment 8:CoN@CN catalyst to different substrates
Application of the CoN@CN catalyst prepared using embodiment 1 in reduction nitro compound, its step are as follows:
By different nitro compound 1mmol, the catalyst (40mg) of solvent (10mL) and the preparation of embodiment 3 is added
Into 25mL stainless steel cauldron, after nitrogen displaced air 3 times, mixture is placed in 3.5bar hydrogen, 90 DEG C of reactions
1.5h.Through gas chromatographic detection, nitrobenzene derivative conversion ratio is as follows:
Experiment is recycled in embodiment 9:CoN@CN
According to 4 conditioned response of embodiment, centrifugation obtains catalyst after having reacted, and is washed 3 times with water and ethyl alcohol respectively, after dry
It reuses, the conversion ratio of each access times is as follows:
Claims (5)
1. a kind of preparation method of nitrogen-doped carbon material load cobalt catalyst, it is characterised in that: the nitrogen-doped carbon material load
Co catalysts are using nitrogen-doped carbon material as skeleton, binding activity component cobalt nitride on skeleton, the matter of Co element in the catalyst
Amount content is 0.18%-1%, and X-ray diffraction CoN occurs in 2 θ=43.7 °xCharacteristic peak；
The preparation method of the nitrogen-doped carbon material load cobalt catalyst the following steps are included:
(1) tetranitro cobalt peptide cyanines and silica solution that mass ratio is 1:1-1:20 are added to N,N-dimethylformamide DMF and H2O
In the mixed solvent stirring sufficiently, the in the mixed solvent DMF and H2O volume ratio is 1:1-1:5；
(2) vacuum distillation removal solvent, obtains tetranitro cobalt peptide cyanines and SiO2Composite material: CoPc/SiO2；
(3) by CoPc/SiO obtained in step (2)2High temperature pyrolysis under nitrogen protection, pyrolysis temperature are 600 DEG C -900 DEG C, heat
Solving the time is 2 hours；
(4) using the template SiO of hydrogen fluoride solution removal step (3) obtained solid of 1wt%-20wt%2With Co nanometers of metallic state
Particle to get arrive CoN@CN catalyst.
2. the nitrogen-doped carbon material load cobalt catalyst of the preparation of preparation method described in claim 1 is in reduction nitro compound
Application, the steps include: catalyst, solvent described in claim 1, nitro compound proportionally 40mg:5-16mL:
0.49-1mmol is added in reaction vessel, is filled with 1bar-20bar reproducibility or protective gas, is reacted at 40-160 DEG C
1-12h obtains reduzate.
3. application according to claim 2, it is characterised in that: the reducibility gas be hydrogen or carbon monoxide,
The protective gas is the nitrogen for preventing oxidation.
4. application according to claim 2, it is characterised in that: the solvent is water, acetonitrile, ethyl alcohol, isopropanol, positive fourth
One of alcohol, benzyl alcohol, toluene, dioxane, ethyl acetate or limonene.
5. application according to claim 2, it is characterised in that: the nitro compound is
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610969457.2A CN106513028B (en) | 2016-10-28 | 2016-10-28 | A kind of catalyst and preparation method thereof and the application in reduction nitro compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610969457.2A CN106513028B (en) | 2016-10-28 | 2016-10-28 | A kind of catalyst and preparation method thereof and the application in reduction nitro compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106513028A CN106513028A (en) | 2017-03-22 |
| CN106513028B true CN106513028B (en) | 2019-01-25 |
Family
ID=58326070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610969457.2A Expired - Fee Related CN106513028B (en) | 2016-10-28 | 2016-10-28 | A kind of catalyst and preparation method thereof and the application in reduction nitro compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106513028B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138309B (en) * | 2020-01-21 | 2023-05-16 | 浙江工业大学 | Catalytic hydrogenation reduction method for aromatic nitro compound |
| CN113429301B (en) * | 2021-06-28 | 2023-11-17 | 河北工业大学 | Method for preparing toluenediamine by hydrogenation of dinitrotoluene with isopropanol as hydrogen source |
| CN113457708B (en) * | 2021-06-30 | 2023-10-20 | 常州大学 | CoN@C porous material, preparation method thereof and application thereof in synthesis of aromatic nitrile compound |
| CN114345387A (en) * | 2022-01-10 | 2022-04-15 | 兰州市三青化学有限公司 | Preparation method of nitrogen-doped carbon-supported cobalt catalyst |
| CN114210332A (en) * | 2022-01-10 | 2022-03-22 | 兰州市三青化学有限公司 | Preparation method of cobalt metal-nitrogen co-doped carbon material catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302939A (en) * | 2011-07-05 | 2012-01-04 | 上海大学 | Method for preparing metal-free nitrogen-doped graphitic porous carbon-based oxygen reduction catalyst |
| CN105749948A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Supported non-noble metal catalyst and preparation and application thereof |
| US20160279619A1 (en) * | 2015-03-25 | 2016-09-29 | Brown University | Graphene-Supported NiPd Alloy Nanoparticles for Effective Catalysis of Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds |
-
2016
- 2016-10-28 CN CN201610969457.2A patent/CN106513028B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102302939A (en) * | 2011-07-05 | 2012-01-04 | 上海大学 | Method for preparing metal-free nitrogen-doped graphitic porous carbon-based oxygen reduction catalyst |
| CN105749948A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Supported non-noble metal catalyst and preparation and application thereof |
| US20160279619A1 (en) * | 2015-03-25 | 2016-09-29 | Brown University | Graphene-Supported NiPd Alloy Nanoparticles for Effective Catalysis of Tandem Dehydrogenation of Ammonia Borane and Hydrogenation of Nitro/Nitrile Compounds |
Non-Patent Citations (3)
| Title |
|---|
| "Electrochemical performance of annealed cobalt–benzotriazole/CNTs catalysts towards the oxygen reduction reaction";Adina Morozan et al.;《Physical Chemistry Chemical Physics》;20111109;第48卷(第12期);第21601页左栏第3段 |
| "High performance of a cobalt–nitrogen complex for the reduction and reductive coupling of nitro compounds into amines and their derivatives";Peng Zhou et al.;《Science Advances》;20170217;第3卷;e1601945 |
| Hai-Wei Liang et al.."Mesoporous Metal−Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction".《Journal of the American Chemical Society》.2013,第135卷 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106513028A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106513028B (en) | A kind of catalyst and preparation method thereof and the application in reduction nitro compound | |
| CN110433823B (en) | Catalyst for synthesizing diaminomethylcyclohexane, and preparation method and application thereof | |
| CN106552661A (en) | A kind of nitrogen-doped carbon material load cobalt catalyst and the method for preparing aminated compoundss using its catalytic hydrogenating reduction amination | |
| CN100467432C (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN109675602B (en) | Supported cobalt-nitrogen doped carbon catalyst and preparation method and application thereof | |
| CN107597160B (en) | Preparation method of silicon dioxide loaded carbon nitrogen coated cobalt ruthenium catalyst and method for catalytic transfer hydrogenation of unsaturated compound by using same | |
| CN112138698B (en) | Preparation method of nitrogen-doped carbon nano material and application of nitrogen-doped carbon nano material in nitrobenzene hydrogenation reaction | |
| CN108325551B (en) | Nitrogen-doped carbon-based transition metal catalyst and preparation method thereof | |
| CN105399705B (en) | A kind of method that furfuryl alcohol is prepared using hydrogen transfer reaction | |
| CN106008228B (en) | A kind of method synthesizing amino benzenes compounds and its catalyst used | |
| CN109734601B (en) | Method for preparing 1, 3-propane diamine | |
| CN106824244B (en) | A kind of nitrogen-doped carbon material package Co catalysts prepare the application in secondary-amine compound in reductive coupling reaction | |
| CN108273507B (en) | Method for reducing nitrile compound by catalytic hydrogenation | |
| CN104402736B (en) | Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline | |
| Shanmugapriya et al. | A suitable modified palladium immobilized on imidazolium supported ionic liquid catalysed transfer hydrogenation of nitroarenes | |
| CN101914036B (en) | Method for preparing azobenzene derivatives | |
| CN108160098B (en) | C-N material catalyst and method for preparing amine compound by using same to catalyze reduction of nitro compound | |
| CN104387233B (en) | A kind of method of synthesizing tricyclic decane dimethanol | |
| CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
| CN109678655B (en) | Application of nickel-iron hydrotalcite catalyst in preparation of benzyl alcohol | |
| CN107652154B (en) | Method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by sodium niobate supported ruthenium catalyst | |
| CN106631731B (en) | Method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol with binuclear morpholine phosphotungstate | |
| CN113786837A (en) | Method for preparing cyclopentanone and cyclopentanol through furfural hydrogenation rearrangement | |
| CN110152661A (en) | A kind of nitrobenzene compounds hydrogenation synthesis amino benzenes compounds nanometer Au-CeO2(cube) catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190125 Termination date: 20211028 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |