CN106977449B - A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine - Google Patents
A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine Download PDFInfo
- Publication number
- CN106977449B CN106977449B CN201710169308.2A CN201710169308A CN106977449B CN 106977449 B CN106977449 B CN 106977449B CN 201710169308 A CN201710169308 A CN 201710169308A CN 106977449 B CN106977449 B CN 106977449B
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- ethylpyridine
- molecular sieve
- ammonia
- reaction
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
Abstract
The invention discloses the process for catalytic synthesis of one kind 3,5- dimethyl -2- ethylpyridine, this method are as follows: in fixed bed reactors, use AEL topological type molecular sieve as catalyst, using propionic aldehyde and ammonia as raw material, 3,5- dimethyl -2- ethylpyridine is catalyzed and synthesized under the conditions of gas-solid phase.AEL type molecular sieve includes AlPO4- 11 and ZnAPO-11, MgAPO-11, CoAPO-11 molecular sieve of metal heteroatom is introduced, reaction temperature is 250~400 DEG C, and pressure is 0.1~1MPa, and the raw materials components mole ratio of propionic aldehyde and ammonia is 1:0.5~4, and volume space velocity is 400~1400h‑1.This synthesis technology reaction raw materials are cheap and easy to get, and reaction condition is mild, easy to operate, and the yield and selectivity of 3,5- dimethyl -2- ethylpyridines are high.
Description
Technical field
The present invention relates to the process for catalytic synthesis of one kind 3,5- dimethyl -2- ethylpyridine, belong to pyridine compounds and their
Synthetic technology.
Background technique
3,5- dimethyl -2- ethylpyridines (EDMP), yellow transparent liquid are the alkyl such as 2,3,5- trimethylpyridine of synthesis
The important intermediate of pyridine, 2,3,5- trimethylpyridines are important solvent, and the intermediate of synthesis Omeprazole, and the country is simultaneously
Wei You producer produces 3,5- dimethyl -2- ethylpyridine.
Foreign countries have the preparation method of some synthesis 3,5- dimethyl -2- ethylpyridines, such as:
(1) using allylamine as raw material, the processes such as itself deamination, cyclisation, dehydrogenation occur for allylamine, generate 3,5- dimethyl-
2- ethylpyridine, the disadvantages of the method are as follows generating 4- ethyl -3,5- lutidines and another by-product, the production of reaction simultaneously
Lower rate is 36%, and reaction raw materials allylamine is severe poisonous chemicals, is control class commodity, expensive and be difficult to obtain.
(2) ethylene is 4~13MPa in pressure with hydrogen, carbon monoxide and ammonia, when temperature is 150~300 DEG C, reaction
3,5- dimethyl -2- ethylpyridine is generated, catalyst is the γ-Al for loading 1% rhodium (Rh)2O3Catalyst, the time of reaction are 4
~5h, gas conversions are 70~80%, and the content of major product can reach 80%, the disadvantages of the method are as follows reaction pressure is higher,
And catalyst is more expensive.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of new 3,5- dimethyl -2- ethylpyridine synthetic methods, with solution
The problems such as product yield present in certainly existing production method is low, expensive starting materials, severe reaction conditions, to realize raising reaction
Selectivity and product yield reduce waste discharge, it is easier to the purpose of industrialized production.The purpose of the present invention is be achieved
: using propionic aldehyde and ammonia as raw material, mixed after propionic aldehyde is vaporized with warmed-up ammonia, it is anti-in the fixed bed for having been charged into catalyst
It answers and gas-solid catalysis occurs in device, condensation reaction condensation preparation 3,5- dimethyl -2- ethylpyridine occurs for propionic aldehyde and ammonia.
Technical solution: the present invention is the process for catalytic synthesis of one kind 3,5- dimethyl -2- ethylpyridine, the side of catalyzing and synthesizing
Method synthesizes 3,5- dimethyl -2- ethylpyridine, propionic aldehyde and ammonia in fixed bed reactors, using propionic aldehyde and ammonia as catalytic material
Raw materials components mole ratio be 1:0.5~4, reaction condition are as follows: 250~400 DEG C of reaction temperature, 0.1~1MPa of reaction pressure, volume is empty
400~1400h of speed-1, successive reaction Aldehyde-ammonia Condensation preparation 3,5- dimethyl -2- ethylpyridine.
The specific preparation step of the process for catalytic synthesis are as follows:
1) propionic aldehyde is mixed into reactor after vaporizing with ammonia, and the raw materials components mole ratio of propionic aldehyde and ammonia is 1:0.5~4;
2) it is packed into catalyst, in N2In atmosphere, 250~300 DEG C of temperature activated, in 250~400 DEG C, 0.1~1MPa
Under reacted;
3) product obtained after fully reacting obtains 3,5- dimethyl -2- ethylpyridine product by separation, vacuum distillation.
The molecular sieve of the catalyst choice AEL type molecular sieve and introducing metal heteroatom is as catalyst.
The molecular sieve, the metallic element of introducing are Zn, Mg or Co, be denoted as respectively ZnAPO-11, MgAPO-11,
The molar ratio of Al content is between 0.01~0.2 in the additive amount and molecular sieve of CoAPO-11 molecular sieve, Zn, Mg or Co.
The CoAPO-11 molecular sieve is the molar ratio of the content of Al in Co additive amount and molecular sieve 0.03~0.1
Between CoAPO-11 molecular sieve.
Preferably 350~400 DEG C of the reaction temperature, reaction pressure preferably 0.1~0.3MPa.
The utility model has the advantages that
(1) reaction raw materials be propionic aldehyde and ammonia, it is less expensive;Reaction temperature and pressure is not high, mild condition.
(2) metallic atom is introduced into molecular sieve, enhances acidic zeolite, improved molecular sieve activity, then improve 3,5- bis-
The yield of methyl -2- ethylpyridine.
(3) synthesis technology very simple provided by the present invention is suitable for large-scale production convenient for operation.
Specific embodiment
Selected catalyst is voluntarily prepared in 3,5- dimethyl -2- ethylpyridine production method involved in inventing
AEL topological type aluminium phosphate molecular sieve (AlPO4- 11) and the molecular sieve of introducing metallic atom, the metal for introducing molecular sieve selection are first
Element is Zn, Mg or Co (ZnAPO-11, MgAPO-11, CoAPO-11), mole of Al content in their additive amount and molecular sieve
Than between 0.01~0.2.Catalyst selects 40~120 mesh of partial size, and surface area is in 190~210m2Between/g, have good
Hydrothermal stability and thermal stability, the condition being relatively suitble in this method fixed bed reaction.
The step of 3,5- dimethyl -2- ethylpyridine synthesis technology of the present invention, is specific as follows:
(1) propionic aldehyde is mixed into reactor after vaporizing with ammonia, and the raw materials components mole ratio of propionic aldehyde and ammonia is 1:0.5~4;
(2) it is packed into catalyst, in N2In atmosphere, 250~300 DEG C of temperature activated, 250~400 DEG C, 0.1~
1MPa, 400~1400h of volume space velocity-1Under reacted;
(3) product obtained after fully reacting obtains the production of 3,5- dimethyl -2- ethylpyridine by separation, vacuum distillation
Product.
The present invention is done below with reference to embodiment and is further explained.Inventor passes through test of many times, there is more success
Embodiment, it is believed that embodiment can be as follows: reaction tube is internal diameter 12mm, the stainless steel tube of length 50cm makes, wherein being catalyzed
The loadings of agent are 4~7g.Propionic aldehyde is squeezed into efficient liquid-phase chromatographic pump, carries out temperature control, temperature control using precise temperature control equipment
Precision is ± 0.2 DEG C, and mass flowmenter uses solenoid valve control, can preferably control gas flow.Following embodiments not with
Any mode limits the present invention, and all technical solutions obtained by the way of equivalent substitution or equivalent transformation are in this hair
Among bright protection scope.
Embodiment 1
(1) 5g AlPO is added in fixed bed reaction pipe4- 11 molecular sieves, Size of Zeolite are 40~120 mesh, increase temperature
Degree, activated catalyst;
(2) it is passed through propionic aldehyde and ammonia is reacted, the molar ratio of propionic aldehyde and ammonia charging is 1:4, volume space velocity 800h-1, instead
Answering temperature is 250 DEG C, reaction pressure 0.1MPa;
(3) collection product is fractionated and obtains thick 3,5- dimethyl -2- ethylpyridine product after fully reacting, is subtracted three times
Pressure rectifying obtains yellow oily liquid, identifies that products obtained therefrom is 3,5- dimethyl -2- through chromatography, mass spectrum, infrared and nuclear magnetic resonance
Ethylpyridine;
(4) according to gas chromatographic analysis as a result, calculating 3,5- dimethyl -2- ethylpyridine yield and selectivity.
3, the 5- dimethyl -2- ethylpyridine average yield that the present embodiment obtains is 28.8%, and selectivity is 50.6%.
Embodiment 2
The synthetic method and embodiment 1 of 3,5- dimethyl -2- ethylpyridine are almost the same in embodiment 2, and catalyst is still
It is AlPO4- 11 molecular sieves, volume space velocity 800h-1, difference is that reaction temperature is promoted to 350 DEG C, mole of propionic aldehyde and ammonia charging
Than for 1:2.When the present embodiment obtains stable reaction, 3,5- dimethyl -2- ethylpyridine average yields are 53.7%, average to select
Property is 70.8%.
Embodiment 3
The synthetic method and embodiment 1 of 3,5- dimethyl -2- ethylpyridine are almost the same in embodiment 3, and catalyst is
AlPO4- 11 molecular sieves, reaction temperature are 350 DEG C, reaction pressure 0.2MPa, volume space velocity 1000h-1, successively investigate different
The yield and selectivity of 3,5- dimethyl -2- ethylpyridine under the conditions of aldehyde ammonia raw materials components mole ratio (2:1,1:1,1:2,1:3,1:4),
It the results are shown in Table 1.
Table 1
By table it can be seen that the additional amount of ammonia is smaller, the receipts of 3,5- dimethyl -2- ethylpyridines when aldehyde ammonia ratio is 2:1
Rate and selectivity;Gradually increase charging in ammonia amount when, in order to keep air speed constant, need to reduce charging in propionic aldehyde amount, third
Aldehyde can sufficiently react at this time with ammonia, improve the yield and selectivity of 3,5- dimethyl -2- ethylpyridine;When charging aldehyde ammonia mole
Than basically reaching maximum, average yield 53.5%, selectivity for 1:2, the yield of 3,5- dimethyl -2- ethylpyridines and selection
71.8%;3,5- dimethyl -2- ethylpyridine yield and selectivity slightly decrease when aldehyde ammonia ratio is 1:4.
Embodiment 4
The synthetic method and embodiment 1 of 3,5- dimethyl -2- ethylpyridine are almost the same in embodiment 4, and reaction pressure is
0.1MPa, volume space velocity 1000h-1, difference is that catalyst is ZnAPO-11 molecular sieve, Al content in Zn introduction volume and molecular sieve
Molar ratio is 0.03, and propionic aldehyde and ammonia feed molar ratio are 1:2, and reaction temperature is 350 DEG C, the results are shown in Table 2.
Embodiment 5
The synthetic method and embodiment 1 of 3,5- dimethyl -2- ethylpyridine are almost the same in embodiment 5, and reaction pressure is
0.1MPa, volume space velocity 1000h-1, difference is that catalyst is MgAPO-11 molecular sieve, Al content in Mg introduction volume and molecular sieve
Molar ratio be 0.06, propionic aldehyde and ammonia feed molar ratio are 1:2, and reaction temperature is 350 DEG C, the results are shown in Table 2.
Embodiment 6
The synthetic method and embodiment 1 of 3,5- dimethyl -2- ethylpyridine are almost the same in embodiment 6, and reaction pressure is
0.1MPa, volume space velocity 1000h-1, difference is that catalyst is CoAPO-11 molecular sieve, Al content in Co introduction volume and molecular sieve
Molar ratio be 0.04, propionic aldehyde and ammonia feed molar ratio are 1:2, and reaction temperature is 350 DEG C, the results are shown in Table 2.
Table 2
The yield of 3,5- dimethyl -2- ethylpyridine when embodiment 2,4,5,6 compared different molecular sieve as catalyst
And selectivity, by table 2 relative to AlPO4- 11, after introducing hetero-atoms, the catalytic activity of molecular sieve increases, and shows as
The selective yield of 3,5- dimethyl -2- ethylpyridines all increased, 3 when wherein CoAPO-11 is catalyst, 5- dimethyl -
The yield highest of 2- ethylpyridine, average yield reach 80.03%, are secondly ZnAPO-11, MgAPO-11 respectively.
By embodiment interpretation of result, using suitable reaction condition and the metal-modified molecular sieve of selection in reaction process
Catalyst activity can be improved as catalyst, increase by the yield and selectivity of 3,5- dimethyl -2- ethylpyridine.
A kind of 3,5- dimethyl -2- ethylpyridine production method of the invention is retouched by specific example
It states, those skilled in the art can use for reference the content of present invention, and the links such as appropriate feed change, process conditions are corresponding other to realize
Purpose, correlation change all without departing from the contents of the present invention, and all similar substitutions and modifications are for those skilled in the art
For be it will be apparent that being considered as being included within the scope of the present invention.
Claims (3)
1. one kind 3, the process for catalytic synthesis of 5- dimethyl -2- ethylpyridine, it is characterised in that the process for catalytic synthesis is in fixation
In bed reactor, 3,5- dimethyl -2- ethylpyridine is synthesized using propionic aldehyde and ammonia as catalytic material, the charging of propionic aldehyde and ammonia rubs
You are than being 1:1~4, reaction condition are as follows: 250~400 DEG C of reaction temperature, 0.1~1MPa of reaction pressure, volume space velocity 400~
1400h-1, successive reaction Aldehyde-ammonia Condensation preparation 3,5- dimethyl -2- ethylpyridine;
The specific preparation step of the process for catalytic synthesis are as follows:
1) propionic aldehyde is mixed into reactor after vaporizing with ammonia, and the raw materials components mole ratio of propionic aldehyde and ammonia is 1:1~4;
2) it is packed into catalyst, in N2In atmosphere, 250~300 DEG C of temperature activated, at 250~400 DEG C, 0.1~1MPa into
Row reaction;
3) product obtained after fully reacting obtains 3,5- dimethyl -2- ethylpyridine product by separation, vacuum distillation;
The catalyst is selected from the AEL type molecular sieve for introducing metal heteroatom as catalyst;
The metallic element of the molecular sieve, introducing is Zn, Mg or Co, is denoted as ZnAPO-11, MgAPO-11, CoAPO-11 respectively
The molar ratio of Al content is between 0.01~0.2 in the additive amount and molecular sieve of molecular sieve, Zn, Mg or Co.
2. the process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine according to claim 1, it is characterised in that described
CoAPO-11 molecular sieve is CoAPO-11 of the molar ratio of the content of Al in Co additive amount and molecular sieve between 0.03~0.1
Molecular sieve.
3. the process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine according to claim 1, it is characterised in that described
Preferably 350~400 DEG C of reaction temperature, reaction pressure preferably 0.1~0.3MPa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710169308.2A CN106977449B (en) | 2017-03-21 | 2017-03-21 | A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710169308.2A CN106977449B (en) | 2017-03-21 | 2017-03-21 | A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106977449A CN106977449A (en) | 2017-07-25 |
CN106977449B true CN106977449B (en) | 2019-11-12 |
Family
ID=59339111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710169308.2A Active CN106977449B (en) | 2017-03-21 | 2017-03-21 | A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106977449B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2452187A (en) * | 1946-02-21 | 1948-10-26 | Du Pont | Synthesis of nitriles |
US3931191A (en) * | 1972-09-27 | 1976-01-06 | Petrolite Corporation | Conversion of tetrahydropyrimidines to pyridines |
CN101012194A (en) * | 2006-12-27 | 2007-08-08 | 浙江大学 | Method for preparing 2,3,5-trimethylpyridine |
-
2017
- 2017-03-21 CN CN201710169308.2A patent/CN106977449B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2452187A (en) * | 1946-02-21 | 1948-10-26 | Du Pont | Synthesis of nitriles |
US3931191A (en) * | 1972-09-27 | 1976-01-06 | Petrolite Corporation | Conversion of tetrahydropyrimidines to pyridines |
CN101012194A (en) * | 2006-12-27 | 2007-08-08 | 浙江大学 | Method for preparing 2,3,5-trimethylpyridine |
Non-Patent Citations (3)
Title |
---|
丙醛与氨气固相环合催化反应机理的研究;肖国民,等;《东南大学学报(自然科学版)》;20010930;第31卷(第5期);第80-84页 * |
气相法合成2-乙基-3,5-二甲基吡啶的研究;肖国民,等;《科技进展》;19991231(第10期);第17-19页 * |
气相转移法合成AEL型磷铝分子筛;韶辉,等;《化学反应工程与工艺》;20111231;第27卷(第6期);第509-520页 * |
Also Published As
Publication number | Publication date |
---|---|
CN106977449A (en) | 2017-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jiang et al. | Kinetic mechanism for the reaction between methanol and water over a Cu-ZnO-Al2O3 catalyst | |
CN103896768A (en) | Method used for preparing methyl acetate | |
CN108620127B (en) | Catalyst for preparing 1, 5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol, preparation method and application thereof | |
Arai et al. | Hydroformylation and hydrogenation of olefins over rhodium zeolite catalyst | |
CN100503534C (en) | Method for synthesis of isopropanol | |
Feimer et al. | Steady-state study of the Fischer-Tropsch reaction | |
CA1060467A (en) | Process for producing acetic acid, ethanol, and acetaldehyde from synthesis gas | |
CN103896767B (en) | A kind of method preparing methyl acetate | |
EP2850045B1 (en) | Process for the preparation of methanol and methanol-derived products from carbon oxides | |
CN109734601A (en) | A method of preparing 1,3- propane diamine | |
CN100553771C (en) | The catalyst that is used for direct preparation of dimethyl ether by using synthesis gas | |
CN106977449B (en) | A kind of process for catalytic synthesis of 3,5- dimethyl -2- ethylpyridine | |
CN102557854B (en) | Method for producing light olefin by promoting transformation of propane | |
CN114522740B (en) | Method for preparing 3-acetoxypropanol from vinyl acetate | |
CN103370295A (en) | Process for the selective preparation of iso-propanol, iso-butanol and other C3+ alcohols from synthesis gas and methanol | |
CN102531825A (en) | Method for promoting transformation of propane for preparing aromatic hydrocarbon | |
CN115770608A (en) | Amination catalyst for synthesizing amine compound from olefin, and preparation method and application thereof | |
Calafat et al. | Factors affecting the carbonylation of methanol over sulfided CoMo/C catalysts at atmospheric pressure | |
US4454321A (en) | Preparation of amines from olefins using certain transition metal catalysts | |
Breman et al. | A kinetic model for the methanol-higher alcohol synthesis from CO/CO2/H2 over Cu/ZnO-based catalysts including simultaneous formation of methyl esters and hydrocarbons | |
CN112430472A (en) | CO (carbon monoxide)2Method for directly preparing low-carbon alcohol and co-producing gasoline by hydrogenation | |
NO803817L (en) | PREPARATION OF METHYL AND ETHYLAMINES WITH RODIUM IRON CATALYST | |
RU2616623C1 (en) | Two-stage process of obtaining propionic acid | |
CN209923225U (en) | System for preparing aldehyde through olefin hydroformylation | |
NO801919L (en) | PROCEDURE FOR THE PREPARATION OF OXYGENIC COMPOUNDS CONTAINING TWO CARBON ATOMS FROM SYNTHESIC GAS |
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 |