CN102649662B - There is the method for lower phenylacetylene height selec-tive hydrogenation in vinylbenzene - Google Patents
There is the method for lower phenylacetylene height selec-tive hydrogenation in vinylbenzene Download PDFInfo
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Abstract
The present invention relates to a kind of method that vinylbenzene exists lower phenylacetylene height selec-tive hydrogenation.Mainly solve in conventional art and there is the high technical problem of vinylbenzene rate of loss.The present invention is by adopting with the hydrocarbon fraction containing phenylacetylene for raw material, and temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, wherein, metal oxide catalyst comprises following component by weight percentage: the metallic nickel of (a) 2 ~ 50.0% or its oxide compound; (b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound; C the technical scheme of the carrier of () 40 ~ 88%, solves this problem preferably, can be used for vinylbenzene and exist in the industrial production of lower hydrogenation removing phenylacetylene.
Description
Technical field
The present invention relates to a kind of method that vinylbenzene exists lower phenylacetylene height selec-tive hydrogenation, particularly about with the C8 hydrocarbon fraction containing phenylacetylene for raw material, the method for removing phenylacetylene.
Background technology
Vinylbenzene (ST) is the important monomer producing polystyrene (PS), ABS resin and styrene-butadiene rubber(SBR) etc.Its production method, based on ethylbenzene dehydrogenation method, in recent years, along with the development of ethylene industry and the maximization of scale, makes extracting and reclaiming vinylbenzene technology from pyrolysis gasoline become one of volume increase vinylbenzene technology received much concern.
Pyrolysis gasoline is the by-product of ethylene industry, output is about 60% ~ 70% of ethene production capacity, rich in styrene and xylol in C8 fraction wherein, a set of 1000kt/a ethylene unit, the vinylbenzene of 24 ~ 42kt/a can be obtained, recyclable xylol simultaneously, make cracking C8 fraction be upgraded to chemical values from fuel value, from pyrolysis gasoline, the cinnamic production cost of extracting and reclaiming is about 1/2 of dehydrogenation of ethylbenzene to styrene.
Cinnamic method is reclaimed from pyrolysis gasoline, generally believe it is possible that extractive distillation method at present, but, phenylacetylene (PA) is similar to cinnamic chemical structure, both are also similar to the interaction between extractive distillation solvent, therefore can not realize effectively being separated of vinylbenzene and PA by extracting rectifying.And the existence of PA, not only can increase catalyst consumption amount during anionic polymerization of styrene, affect chain length and polymerization velocity, and polystyrene performance depreciation can be caused, as variable color, degraded, spoiled and discharge smell etc.Therefore, exploitation highly selective Selective Hydrogenation Catalyst Phenylacetylene and technique become core and the key of pyrolysis gasoline extracting and reclaiming vinylbenzene technology.In addition, what need special concern is, carry out in phenylacetylene hydrogenation process under vinylbenzene exists, how reducing cinnamic loss is to greatest extent that in pyrolysis gasoline, whether extracting and reclaiming vinylbenzene possesses skills one of the key technical index of competitive power, cinnamic loss is lower, its Technical Economy is better, and technological competitiveness is stronger.
Patent CN1852877A, discloses a kind of method of phenylacetylene contaminant of reducing under styrene monomer exists.To the styrene monomer stream supply hydrogenation reactor of a small amount of phenylacetylene be comprised, also supply hydrogeneous hydrogenated gas.Styrene monomer stream is contacted with the beds comprising catalyzer with hydrogen, and described catalyzer is included in the copper compound of the reduction on θ alumina supporter.Hydrogenation reactor operates under 30psig pressure at least 60 DEG C of temperature with at least, and hydrogenation of phenylacetylene generates vinylbenzene.Hydrogenated gas comprises the mixture of nitrogen and hydrogen, and this technology temperature of reaction is higher, and phenylacetylene hydrogenation rate low (about 70%), exists catalyst life shorter simultaneously, and vinylbenzene exists rate of loss high (about about 3%).
Patent CN10878902A, disclose a kind of method and apparatus adopting hydride process to carry out the styrene monomer in purified styrene stream, it dilutes hydrogen by adopting hydrogen to add thinner such as nitrogen, discharge gas with ethylbenzene dehydrogenation and hydrogen is provided, reactor by multistage catalytic bed makes phenylacetylene contaminant hydrogenation be vinylbenzene, but only speak of lower concentration in this proprietary catalysts on the one hand if the selectivity of 300ppm phenylacetylene content is except alkynes method, simultaneously to phenylacetylene hydrogenation rate low (about 95%), it is high to there is loss in vinylbenzene.
In sum, mainly there is the high technical problem of vinylbenzene rate of loss in prior art, this brings larger difficulty to industrial practical application.
Summary of the invention
Technical problem to be solved by this invention is the technical problem that the vinylbenzene existed in previous literature exists that in lower phenylacetylene selec-tive hydrogenation process, vinylbenzene rate of loss is high, provides a kind of new vinylbenzene to there is the method for lower phenylacetylene height selec-tive hydrogenation.The method has the low advantage of vinylbenzene rate of loss.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of vinylbenzene exists the method for lower phenylacetylene height selec-tive hydrogenation, and with the hydrocarbon fraction containing phenylacetylene for raw material, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, and reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and wherein, metal oxide catalyst comprises following component by weight percentage:
The metallic nickel of (a) 2 ~ 50.0% or its oxide compound;
(b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound;
The carrier of (c) 40 ~ 88%.
In technique scheme, reaction conditions is preferably: temperature of reaction is 25 ~ 80 DEG C, and weight space velocity is 1 ~ 60 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 20: 1, and reaction pressure is 0 ~ 2.0MPa; By weight percentage, the consumption preferable range of metallic nickel or its oxide compound is 8.0 ~ 40.0% to metal oxide catalyst; The consumption preferable range being selected from least one element in rare earth or its oxide compound is 0.1 ~ 6.0%.Element in rare earth is preferably selected from least one in lanthanum, cerium or praseodymium; Carrier is preferably selected from least one in aluminum oxide, silicon oxide or molecular sieve, is more preferably selected from aluminum oxide.
In technique scheme phenylacetylene hydrocarbon fraction in, by weight percentage, styrene content is 20 ~ 60%, and the content of phenylacetylene is 0.03 ~ 2%.
In this technology, vinylbenzene rate of loss calculation formula is: vinylbenzene quality × 100% in (in the vinylbenzene quality-product in raw material cinnamic quality)/raw material.
The preparation method of catalyzer of the present invention is: the solution impregnation cocatalyst component used in the nickel compound of carrier aequum and catalyzer be made into, and namely the carrier drying after dipping, in atmosphere 320 ~ 450 DEG C of roastings obtain oxidative catalyst finished product.Above-mentioned steps can be repeated and obtain required nickel content.Finished catalyst needs to use hydrogen reducing before use.
As everyone knows, the hydrogenation reaction of phenylacetylene is a typical cascade reaction, and intermediate product is vinylbenzene, if excessive hydrogenation can generate ethylbenzene, and in recycling vinyl benzene with pyrolysis gasoline technology, the added value of ethylbenzene is far below cinnamic added value, and meanwhile, the existence of micro-benzene acetylene is unfavorable to later separation, for this reason, how to maximize conversion phenylacetylene, avoid to greatest extent cinnamicly adding hydrogen loss, be the key reclaiming vinylbenzene technology simultaneously.We find in large quantity research, homemade nickel-base catalyst is adopted to carry out in phenylacetylene hydrogenation reaction process, there is good phenylacetylene hydrogenation selectivity, and dynamics research finds, nickel-base catalyst is adopted to carry out in phenylacetylene selective hydrogenation reaction process, phenylacetylene hydrogenation generates the activation energy of reaction activity far below styrene hydrogenation generation ethylbenzene reactions steps of vinylbenzene step, this transforms phenylacetylene for realizing maximizing, avoid to greatest extent cinnamicly adding hydrogen loss simultaneously, provide most important theories basis and theories integration from reaction kinetics angle.In addition, be also surprised to find in research process, nickel-base catalyst, by adding auxiliary agent, modulation carried out to activity, can further improve phenylacetylene hydrogenation selectivity, reducing cinnamic loss.
Adopt technical scheme of the present invention, with the hydrocarbon fraction containing phenylacetylene for raw material, adopt metallic nickel metal oxides to be catalyzer, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material and catalyst exposure, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and in reactor final effluent, the content of phenylacetylene preferably can reach 0, and vinylbenzene can reach free of losses, even part phenylacetylene hydrogenation is that vinylbenzene occurs that vinylbenzene increases (or vinylbenzene rate of loss is negative value), achieves good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take θ alumina supporter 20 grams, its specific surface area 200 meters
2/ gram, joining nickelous nitrate content is 12%, and the content of lanthanum nitrate is in the solution of 3%, carries out equivalent impregnation, and 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst A, make nickel content be 8% of catalyst weight, lanthanum content was 0.2%.By above-mentioned obtained catalyzer hydrogen 300 DEG C of reduction 6 hours, then by weight percentage, containing 40% vinylbenzene, 10% ethylbenzene, carbon eight cut of 0.1% phenylacetylene is raw material, temperature of reaction 45 DEG C, weight space velocity 2 hours
-1, hydrogen/alkynes mol ratio is 2: 1, and reaction pressure is under the condition of 0.2MPa, and adopt fixed-bed reactor to make raw material and catalyst exposure, react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 5ppm.
[embodiment 2]
According to condition and the method for embodiment 1, just change the amount of steeping fluid, adopt equivalent impregnation method dipping equally, 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst B, make nickel content be 15% of catalyst weight, lanthanum content was 0.8%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0.5%, and in reaction effluent, the content of phenylacetylene is 3ppm.
[embodiment 3]
Be carrier with gamma-alumina, its specific surface area 280 meters
2/ gram, according to condition and the method for embodiment 1, the amount changing steeping fluid adopts equivalent impregnation method dipping, and 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst C, make nickel content be 20% of catalyst weight, lanthanum content was 1.2%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0.2%, and in reaction effluent, the content of phenylacetylene is 1ppm.
[embodiment 4]
With ZSM-5 molecular sieve (silica alumina ratio SiO
2/ Al
2o
3be 150) be carrier, its specific surface area 300 meters
2/ gram, according to condition and the method for embodiment 1, nickelous nitrate content is adopted to be the solution of 20% respectively, equivalent impregnation method dipping is carried out with the solution that the content of praseodymium nitrate is 6%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst D, make nickel content be 30% of catalyst weight, praseodymium content is 3%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0.8%, and in reaction effluent, the content of phenylacetylene is 10ppm.
[embodiment 5]
Be carrier with gamma-alumina, its specific surface area 100 meters
2/ gram, according to condition and the method for embodiment 1, nickelous nitrate content is adopted to be the solution of 25% respectively, equivalent impregnation method dipping is carried out with the solution that the content of cerous nitrate is 1%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst E, make nickel content be 40% of catalyst weight, cerium content is 3%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 0.
[embodiment 6]
With gamma-alumina is carrier, its specific surface area 80 meters
2/ gram, according to condition and the method for embodiment 1, nickelous carbonate content is adopted to be the solution of 15% respectively, equivalent impregnation method dipping is carried out with the solution that the content of cerous carbonate is 8%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst F, make nickel content be 50% of catalyst weight, cerium content is 4%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is-0.2%, and in reaction effluent, the content of phenylacetylene is 0.
[embodiment 7]
With silicon oxide is carrier, its specific surface area 180 meters
2/ gram, according to condition and the method for embodiment 1, nickel acetate content is adopted to be the solution of 12% respectively, equivalent impregnation method dipping is carried out with the solution that the content of lanthanum acetate is 2%, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst G, make nickel content be 20% of catalyst weight, lanthanum content is 2%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0.5%, and in reaction effluent, the content of phenylacetylene is 8ppm.
[embodiment 8]
With gamma-alumina is carrier, its specific surface area 200 meters
2/ gram, according to condition and the method for embodiment 1, adopt that nickel acetate content is 12% respectively, the content of lanthanum acetate be 1% and the content of cerous nitrate be 2% solution carry out equivalent impregnation method dipping, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst H, makes nickel content be 25% of catalyst weight, cerium content is 0.2%, and lanthanum content is 0.5%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 5ppm.
[embodiment 9]
With gamma-alumina is carrier, its specific surface area 180 meters
2/ gram, according to condition and the method for embodiment 1, adopt that nickel acetate content is 6% respectively, the content of lanthanum acetate be 0.5% and the content of cerous nitrate be 2% solution carry out equivalent impregnation method dipping, then 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours, obtained nickel-base catalyst I, makes nickel content be 13% of catalyst weight, cerium content is 0.1%, and lanthanum content is 0.3%.Adopt embodiment 1 identical raw material composition and reaction conditions to react, reaction result is: cinnamic rate of loss is 0, and in reaction effluent, the content of phenylacetylene is 1ppm.
[comparative example 1]
According to each step and the condition of embodiment 1, just do not have lanthanum nitrate in steeping fluid, other condition and raw material are all identical, and obtained nickel-base catalyst J, makes nickel content be 8% of catalyst weight.Reaction result is: cinnamic rate of loss is 1.8%, and in reaction effluent, the content of phenylacetylene is 15ppm.
[comparative example 2]
According to each step and the condition of embodiment 5, just do not have cerous nitrate in steeping fluid, other condition and raw material are all identical, and obtained nickel-base catalyst K, makes nickel content be 40% of catalyst weight.Reaction result is: cinnamic rate of loss is 1.1%, and in reaction effluent, the content of phenylacetylene is 10ppm.
Claims (5)
1. there is a method for lower phenylacetylene height selec-tive hydrogenation in vinylbenzene, and with the hydrocarbon fraction containing phenylacetylene for raw material, temperature of reaction 15 ~ 100 DEG C, weight space velocity is 0.01 ~ 100 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 30: 1, and reaction pressure is under the condition of-0.08 ~ 5.0MPa, raw material contacts with metal oxide catalyst, in reaction effluent, phenylacetylene is hydrogenated as vinylbenzene, and wherein, metal oxide catalyst is composed of the following components by weight percentage:
The metallic nickel of (a) 2 ~ 50.0% or its oxide compound;
(b) 0.05 ~ 10% be selected from least one element in rare earth or its oxide compound;
The carrier of (c) 40 ~ 88%.
2. there is the method for lower phenylacetylene height selec-tive hydrogenation in vinylbenzene according to claim 1, and it is characterized in that temperature of reaction 25 ~ 80 DEG C, weight space velocity is 1 ~ 60 hour
-1, hydrogen/phenylacetylene mol ratio is 1 ~ 20: 1, and reaction pressure is 0 ~ 2.0MPa; By weight percentage, the consumption of metallic nickel or its oxide compound is 8.0 ~ 40.0% to metal oxide catalyst; The consumption being selected from least one element in rare earth or its oxide compound is 0.1 ~ 6.0%.
3. there is the method for lower phenylacetylene height selec-tive hydrogenation in vinylbenzene according to claim 2, it is characterized in that the element be selected from rare earth is selected from least one in lanthanum, cerium or praseodymium; At least one in support selected from alumina, silicon oxide or molecular sieve.
4. there is the method for lower phenylacetylene height selec-tive hydrogenation according to vinylbenzene described in claim 3, it is characterized in that support selected from alumina.
5. there is the method for lower phenylacetylene height selec-tive hydrogenation according to vinylbenzene described in claim 1, it is characterized in that in the hydrocarbon fraction containing phenylacetylene, by weight percentage, styrene content is 20 ~ 60%, and the content of phenylacetylene is 0.03 ~ 2%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1798716A (en) * | 2003-06-04 | 2006-07-05 | 约翰森·马瑟公开有限公司 | Selective hydrogenation process and catalyst therefor |
| CN101475439A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Phenylacetylene selective hydrogenation method using compound bed in the presence of phenylethylene |
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