CN107011193A - A kind of method for preparing N methyl P-nethoxyaniline - Google Patents
A kind of method for preparing N methyl P-nethoxyaniline Download PDFInfo
- Publication number
- CN107011193A CN107011193A CN201710320824.0A CN201710320824A CN107011193A CN 107011193 A CN107011193 A CN 107011193A CN 201710320824 A CN201710320824 A CN 201710320824A CN 107011193 A CN107011193 A CN 107011193A
- Authority
- CN
- China
- Prior art keywords
- nethoxyaniline
- catalyst
- methyl
- molecular sieve
- active component
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7607—A-type
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method for preparing N methyl P-nethoxyaniline, using P-nethoxyaniline and methanol as reaction raw materials, using molecular sieve carried active component as catalyst, in 150 350 DEG C of reaction temperature, the h of liquid volume air speed 0.1 2.0‑1、N2As being reacted under conditions of carrier gas in continuous flow reactor of fixed bed, N methyl P-nethoxyaniline is produced；Active component is at least one of Cu and Ni, and its content is 0.01 30 wt% of catalyst quality；Molecular sieve is one kind in 3A, 4A, 5A molecular sieve.The present invention have the advantages that in high yield, simple to operate, mild condition, catalyst performance stabilised, low cost, low stain.
Description
Technical field
The present invention relates to a kind of method for preparing N- methyl P-nethoxyaniline.Be specifically with P-nethoxyaniline and
Methanol is raw material, using molecular sieve carried cupro-nickel as catalyst, and N- monomethylations are realized and high selection by amine alcohol alkylated reaction
The method that property prepares N- methyl P-nethoxyaniline.
Background technology
Octane number is the most important quality index of motor petrol, the national petroleum refining industry's level of its concentrated expression one and vehicle
Design level, is the important means for improving motor petrol octane number using anti-knock agent.Anti-knock agent mainly has alkyl lead, methyl ring penta
Diene manganese tricarbonyl, methyl tertiary butyl ether(MTBE), tert amyl methyl ether(TAME), the tert-butyl alcohol, methanol, ethanol etc..Nuisanceless antiknock dope is
The direction of Future Development.
Lead tetraethide has the advantage that technique is simple, with low cost, effect is protruded, since being found from nineteen twenty-one always by
It is widely applied.However, the need for automobile emission control and environmental protection, having limited added into gasoline in the world
Alkyl lead, and the low leaded of gasoline is done step-by-step and unleaded.Nineteen fifty-nine the U.S. be proposed methyl cyclopentyl-dialkyl-tricarbon manganium resist
Detonator, but the anti-knock agent shortens spark plug life, and cause in engine combustion chamber internal surface formation porous deposit
Manganese content rises in environment, therefore is prohibitted the use of by the U.S. in 1978.First is further used after 1970s both at home and abroad
Alcohol, ethanol, methyl tertiary butyl ether(MTBE) and tert-butyl alcohol etc. are as organic non-metal anti-knock agent, so as to seek new gasoline compounding scheme
There is provided selection.But, these organic anti-knock agents have volatility, corrosivity, toxicity and waste gas discharge and economy etc.
Problem.Typical anti-knock agent methyl tertiary butyl ether(MTBE) therein is in the U.S. because being prohibited from using the reason for polluted water.
The performance study of aromatic amine and other nitrogen-containing compounds shows that it has the effect for preferably improving octane number, simultaneously
The low advantage of its volatility effectively promote its development.Wherein, methylphenylamine as RONA have been obtained for compared with
To be widely applied.However, methylphenylamine there is also toxicity it is higher, pollution environment the problems such as.How to develop efficient and clear
Clean anti-knock agent turns into the important topic in clean gasoline production.Compared with methylphenylamine, N- methyl P-nethoxyaniline is made
For the characteristics of anti-knock agent has small toxicity, performance is more excellent, as the ideal chose for substituting methylphenylamine.
There are some researches show using methanol as alkylating reagent with P-nethoxyaniline reaction production N- methyl to methoxyl group
Aniline is the most economic, environment-friendly route, patent CN 103124717 A, the CN for having same or like structural compounds
103570553 B, RU 2270187, US 8901354, US 5068434, US 5055617, the report displays of US 4029707, instead
The N- monomethyl compounds produced in process are answered easily further to react N, N- di-methylation products with alcohol；Patent CN
105924363 A use P-nethoxyaniline and paraformaldehyde for raw material, and N- methyl is prepared to methoxybenzene by reduction amination
The method of amine there is also it is a large amount of using non-green solvents, need the problems such as high pressure hydrogen, process are unable to continuous production, based on
Upper reason, also no enterprise realizes N- methyl P-nethoxyaniline industrialized productions both at home and abroad so far.It is pointed out that
Many external manufacturing enterprises are just researched and developed with regard to N- methyl P-nethoxyaniline industrialized production catalyst at present, correlation technique
Competition is very fierce, accelerates related research and development and Industrialization is imperative.
The content of the invention
It is an object of the invention to provide a kind of method for preparing N- methyl P-nethoxyaniline.
The present invention is under relatively simple equipment and relatively mild reaction condition, using P-nethoxyaniline and methanol as original
Material, N- methyl P-nethoxyaniline compounds are efficiently synthesized by catalyst of molecular sieve carried cupro-nickel.The present invention have in high yield,
Simple to operate, mild condition, catalyst performance stabilised, low cost, the advantage of low stain.
It is brilliant that active metallic ion is embedded in molecular sieve by molecular sieve carried copper-nickel catalyst of the present invention by ion exchange
In lattice, the effect of reaction molecular and catalyst activity metal ion is controlled using the pore size of molecular sieve, and pass through dynamics
The regulation and control of factor, control reaction molecular and catalyst time of contact so that reduce N- monomethylations product further with methanol
Reaction generation N, N- dimethyl P-nethoxyaniline accessory substances realize prepared by the high selectivity of product；And active metallic ion by
In the protective effect of molecular sieve lattice, it is to avoid the cluster of nano-particle, the catalytic activity time is extended, improve catalyst
Overall performance.
A kind of method for preparing N- methyl P-nethoxyaniline, it is characterised in that using P-nethoxyaniline and methanol as reaction
Raw material, using molecular sieve carried active component as catalyst, in 150-350 DEG C of reaction temperature, liquid volume air speed 0.1-2.0 h-1、
N2As being reacted under conditions of carrier gas in continuous flow reactor of fixed bed, N- methyl P-nethoxyaniline is produced；The work
Property component be at least one of Cu and Ni, its content be catalyst quality 0.01-30 wt%；The molecular sieve be 3A, 4A,
One kind in 5A molecular sieves.
The mol ratio of the methanol and P-nethoxyaniline is 0.8：1~20：1.
The carrier gas N2Volume space velocity in 100-600 h-1。
The catalyst, which is prepared by the following method, to be obtained：Molecular sieve is added to the water of the soluble-salt containing active component
In solution, be stirred at room temperature 5-24 hours carry out ion exchange, then 50-180 DEG C drys 1-5 hours, 200-800 DEG C roast
Burn 5-15 hours, with hydrogen reducing produce the catalyst within 1-5 hours at 200-800 DEG C.
The soluble-salt is the nitrate or chloride of the active component.
Compared to prior art, the method that the present invention prepares N- methyl P-nethoxyaniline uses P-nethoxyaniline and first
Alcohol is Ji Yuan, economical and easily available and atom utilization is high；Catalyst Design used in the present invention is simply ingenious, cheap, high
Effect is stable, and accessory substance is few, and the selectivity to N- methyl P-nethoxyaniline is high.
Embodiment
The present invention is described in detail with embodiment and embodiment below, but the present invention implements to be not limited to these embodiments：
The preparation of catalyst
Embodiment 1
The commercially available g of six water nickel nitrate 2.91 (10 mmol) is weighed, is added in 150 mL deionized waters, in 500 mL round bottoms
Flask stirring and dissolving, weighs 40 g 3A molecular sieves and is added in above-mentioned solution and be sufficiently stirred for 12 h, treats that solution is changed into from blueness
Colourless i.e. ion exchange is completed.Filtering, by 80 DEG C of 3 h of drying of solid sample, 400 DEG C of Muffle furnace is calcined 6 hours, uses program liter
Under warm reduction furnace, hydrogen atmosphere, 10 DEG C/min are warming up to 450 DEG C, the reductase 12 h at 450 DEG C, obtain catalyst 3A0-10.
Embodiment 2
Weigh the commercially available mg of nitrate trihydrate copper 482 (2 mmol), the g of six water nickel nitrate 2.33（8 mmol）It is added to 150 mL
In deionized water, in 500 mL round-bottomed flask stirring and dissolvings, weigh 40 g 3A molecular sieves and be added in above-mentioned solution and fully stir
Mix 12 h, treat solution become colorless i.e. ion exchange completion.Filtering, by 80 DEG C of 3 h of drying of solid sample, 400 DEG C of roastings of Muffle furnace
Burn 6 hours, using temperature programmed reduction stove, under hydrogen atmosphere, 10 DEG C/min are warming up to 450 DEG C, the reductase 12 h at 450 DEG C,
Obtain catalyst 3A2-8.
Embodiment 3
Be the same as Example 2 is operated, simply copper nitrate and nickel nitrate are respectively 4mmol and 6mmol, obtain catalyst 3A4-6.
Embodiment 4
Be the same as Example 2 is operated, simply copper nitrate and nickel nitrate are respectively 6mmol and 4mmol, obtain catalyst 3A6-4.
Embodiment 5
Be the same as Example 2 is operated, simply copper nitrate and nickel nitrate are respectively 8mmol and 2mmol, obtain catalyst 3A8-2.
Embodiment 6
Be the same as Example 1 is operated, nickel nitrate is simply replaced with 10 mmol copper nitrate, catalyst 3A10-0 is obtained.
Embodiment 7
Reference implementation example 1-6 is operated, 3A molecular sieves are simply changed to 4A or 5A molecular sieves, 4A6-4 is respectively obtained and 5A6-4 is urged
Agent.
The preparation of N- methyl P-nethoxyaniline
Embodiment 8-28
The g of catalyst 7 (about 10 mL) prepared in embodiment 1-7 is weighed, is loaded into φ 8mm fixed bed reactors, is passed through nitrogen
Air-blowing is swept and heated up in 2 h, is reached and is started charging after temperature.Start and Agilent 5977A/7890B are used after sample
GC-MS gaseous mass analyzers and Agilent 7890A (30m × 0.25mm × 0.33 μm capillary column, hydrogen flame ionization detector)
Qualitative and quantitative analysis is carried out, table 1 is the instant conversion ratio and selectivity that each embodiment reacts 24 h under different condition.Pass through table 1
Data can be seen that 7g 3A6-4 catalyst in 300 DEG C of reaction temperature, N2The h of volume space velocity 480-1, hydramine compare 10:1st, raw material
The h of volume space velocity 1.0-1Under conditions of, the conversion ratio 84% during 24 h of operating, to the selectivity 76% of N- methyl P-nethoxyaniline.
Table 1
The present invention uses P-nethoxyaniline and methanol for raw material, and molecular sieve carried copper-nickel catalyst continuously flows in fixed bed
Realize the efficient preparation of N- methyl P-nethoxyaniline on reactor, it is whole process economy, cheap and environment-friendly；Used
Catalyst can simply and inexpensively be made, and with high catalytic activity；Reaction condition is more gentle, catalyst choice it is good and
Performance is stable, the bright prospects with industrialized production.
Claims (5)
1. a kind of method for preparing N- methyl P-nethoxyaniline, it is characterised in that former using P-nethoxyaniline and methanol as reaction
Material, using molecular sieve carried active component as catalyst, in 150-350 DEG C of reaction temperature, liquid volume air speed 0.1-2.0 h-1、N2
As being reacted under conditions of carrier gas in continuous flow reactor of fixed bed, N- methyl P-nethoxyaniline is produced；The activity
Component is at least one of Cu and Ni, and its content is the 0.01-30 wt% of catalyst quality；The molecular sieve is 3A, 4A, 5A
One kind in molecular sieve.
2. the method as described in claim 1, it is characterised in that the mol ratio of the methanol and P-nethoxyaniline is 0.8：1~
20：1.
3. the method as described in claim 1, it is characterised in that the carrier gas N2Volume space velocity in 100-600 h-1。
4. the method as described in claim 1, it is characterised in that the catalyst, which is prepared by the following method, to be obtained：By molecular sieve
In the aqueous solution for adding the soluble-salt containing active component, it is stirred at room temperature 5-24 hours and carries out ion exchange, then in 50-
180 DEG C it is dry 1-5 hours, be calcined 5-15 hour at 200-800 DEG C, produced within 1-5 hours with hydrogen reducing at 200-800 DEG C described in
Catalyst.
5. method as claimed in claim 4, it is characterised in that the soluble-salt is the nitrate or chlorine of the active component
Compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710320824.0A CN107011193B (en) | 2017-05-09 | 2017-05-09 | Method for preparing N-methyl p-anisidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710320824.0A CN107011193B (en) | 2017-05-09 | 2017-05-09 | Method for preparing N-methyl p-anisidine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107011193A true CN107011193A (en) | 2017-08-04 |
| CN107011193B CN107011193B (en) | 2020-05-26 |
Family
ID=59449799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710320824.0A Active CN107011193B (en) | 2017-05-09 | 2017-05-09 | Method for preparing N-methyl p-anisidine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107011193B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2663790C1 (en) * | 2017-11-23 | 2018-08-09 | Общество с ограниченной ответственностью "ИФОТОП" | Use of n,n-dimethyl-para-anisidine as a corrosion inhibitor in hydrocarbon fuel |
| RU2667265C1 (en) * | 2018-02-05 | 2018-09-18 | Общество с ограниченной ответственностью "ИФОТОП" | Application of n,n-dimethyl-para-anisidine as inhibitor of hydrogen sulfide corrosion and hydrogen enhancing |
| CN113735722A (en) * | 2021-09-26 | 2021-12-03 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-p-anisidine |
| CN115845914A (en) * | 2022-11-21 | 2023-03-28 | 金宏气体股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2270187C2 (en) * | 2004-04-14 | 2006-02-20 | Валерий Александрович Головачев | Method for preparing n-methylaniline |
| CN1864855A (en) * | 2005-05-20 | 2006-11-22 | 中国科学院大连化学物理研究所 | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol |
| CN102728367A (en) * | 2012-06-09 | 2012-10-17 | 浙江大学 | Method and catalyst for synthesizing N,N-dimethylaniline |
| CN103570553A (en) * | 2012-08-01 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Method for preparing N-substituted amine compound by virtue of catalytic alkylation |
-
2017
- 2017-05-09 CN CN201710320824.0A patent/CN107011193B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2270187C2 (en) * | 2004-04-14 | 2006-02-20 | Валерий Александрович Головачев | Method for preparing n-methylaniline |
| CN1864855A (en) * | 2005-05-20 | 2006-11-22 | 中国科学院大连化学物理研究所 | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol |
| CN102728367A (en) * | 2012-06-09 | 2012-10-17 | 浙江大学 | Method and catalyst for synthesizing N,N-dimethylaniline |
| CN103570553A (en) * | 2012-08-01 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Method for preparing N-substituted amine compound by virtue of catalytic alkylation |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2663790C1 (en) * | 2017-11-23 | 2018-08-09 | Общество с ограниченной ответственностью "ИФОТОП" | Use of n,n-dimethyl-para-anisidine as a corrosion inhibitor in hydrocarbon fuel |
| WO2019103638A1 (en) * | 2017-11-23 | 2019-05-31 | Общество с ограниченной ответственностью "ИФОТОП" | Use of n,n-dimethyl-para-anisidine as corrosion inhibitor in hydrocarbon fuel |
| RU2667265C1 (en) * | 2018-02-05 | 2018-09-18 | Общество с ограниченной ответственностью "ИФОТОП" | Application of n,n-dimethyl-para-anisidine as inhibitor of hydrogen sulfide corrosion and hydrogen enhancing |
| WO2019151884A1 (en) * | 2018-02-05 | 2019-08-08 | Общество С Ограниченной Ответственностью "Ифотоп " | Use of n,n-dimethyl-para-anisidine as an inhibitor of hydrogen sulfide corrosion and hydrogen embrittlement |
| CN113735722A (en) * | 2021-09-26 | 2021-12-03 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-p-anisidine |
| CN113735722B (en) * | 2021-09-26 | 2023-05-16 | 武汉炼化工程设计有限责任公司 | Preparation process of N-methyl-para-aminoanisole |
| CN115845914A (en) * | 2022-11-21 | 2023-03-28 | 金宏气体股份有限公司 | Catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107011193B (en) | 2020-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107011193A (en) | A kind of method for preparing N methyl P-nethoxyaniline | |
| CN107418619B (en) | A kind of preparation method of aromatic naphtha | |
| CN109225337B (en) | MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof | |
| Gu et al. | Creation of Active Sites in MOF‐808 (Zr) by a Facile Route for Oxidative Desulfurization of Model Diesel Oil | |
| CN102698806B (en) | A kind of catalyst without mercury synthesizing vinyl chloride for acetylene hydrochlorination | |
| CN104148117B (en) | Alumina carrier as well as catalyst and application | |
| Wang et al. | Methanol Promoted Palladium‐Catalyzed Amine Formylation with CO2 and H2 by the Formation of HCOOCH3 | |
| WO2023193343A1 (en) | Catalyst for synthesizing dimethyl carbonate by means of methanol oxidative carbonylation and preparation method for and application of catalyst | |
| CN1736596A (en) | Catalyst for synthesizing dimethyl carbonate and its preparing process | |
| CN106744677B (en) | Use RhNiCo/CeO2@C3N4The method of nanocatalyst Compounds with Hydrazine Hydrate Catalyzed dehydrogenation | |
| Al‐Huniti et al. | Metal‐Catalyzed Dehydration of Primary Amides to Nitriles | |
| CN106672899A (en) | Method for catalyzing hydrazine hydrate dehydrogenation with RhNiFe/CeO2@C3N4 nanometer catalyst | |
| Valverde-Gonzalez et al. | Amino-functionalized zirconium and cerium MOFs: Catalysts for visible light induced aerobic oxidation of benzylic alcohols and microwaves assisted N-Alkylation of amines | |
| Srivastava et al. | Multitasking FeOCN Composite as an Economic, Heterogeneous Catalyst for 1‐Octene Hydroformylation and Hydration Reactions | |
| Hu et al. | Ambient‐temperature reductive amination of 5‐hydroxymethylfurfural over Al2O3‐supported carbon‐doped nickel catalyst | |
| Ma et al. | One‐Pot Transfer Hydrogenation of methyl levulinate into valerolactone and 1, 4‐pentanediol over in situ Reduced Cu/ZrOCO3 in 2‐PrOH | |
| CN114887625A (en) | Fe-based metal organic framework material derived catalyst and preparation method and application thereof | |
| CN114160143A (en) | CO (carbon monoxide)2Catalyst for preparing methanol by hydrogenation, preparation method and application thereof | |
| JP2021016832A (en) | Dehydrogenation catalyst | |
| CN103566933B (en) | A kind of acetate preparation of ethanol by hydrogenating catalyst and preparation method thereof | |
| CN107199051B (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof | |
| CN104072376B (en) | A kind of by CO 2with the method for methanol-fueled CLC methylcarbonate | |
| CN108178732B (en) | Preparation method of N-methyl p-methoxyaniline | |
| CN110484315B (en) | Gasoline detergent and preparation method thereof | |
| CN108570013B (en) | A kind of synthesis technology of tridemorph |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |