CN106423239A - High-stability styrene catalyst - Google Patents
High-stability styrene catalyst Download PDFInfo
- Publication number
- CN106423239A CN106423239A CN201510493326.7A CN201510493326A CN106423239A CN 106423239 A CN106423239 A CN 106423239A CN 201510493326 A CN201510493326 A CN 201510493326A CN 106423239 A CN106423239 A CN 106423239A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- grams
- parts
- preparation
- iron oxide
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a high-stability styrene catalyst and a preparation method thereof. A purpose of the present invention is to mainly solve the problem of not enough high activity of the catalyst in the prior art. The high-stability styrene catalyst comprises the following active components by weight: a) 55-94 parts of Fe2O3, b) 5-30 parts of K2O, c) 3-15 parts of Ce2O3, d) 0.1-5 parts of MoO3 and/or WO3, e) 0.1-5 parts of W2C, and f) 0.1-10 parts of at least one oxide of an alkaline earth metal selected from Mg, Ca, Sr and Ba. With the technical program of the present invention, the problem in the prior art is well solved. The high-stability styrene catalyst can be used in the industrial production of styrene.
Description
Technical field
The present invention relates to high stable phenylethylene catalyst and preparation method thereof.
Background technology
Industrial at present cinnamic be mostly realized by ethylbenzene direct catalytic thermal dehydrogenation.Used catalyst basic
Composition includes major catalyst, promoter and porogen, reinforcing agent etc..Report about catalyst generally can be divided into two big class,
One class is the Fe-K series catalysts containing Cr of early stage, United States Patent (USP) US4467046, US4684619 and Europe such as disclosed in oneself
Patent EP0195252A2 etc..Although the activity of such catalyst and stability are preferably, more or less exist due in composition
The oxide of Cr, thus certain environmental pollution in the preparation of catalyst, operation and dead catalyst processing procedure, can be caused, oneself
Gradually eliminated.Another kind of is the Fe-K-Ce-Mo series that early eighties are succeeded in developing, United States Patent (USP) such as disclosed in oneself
US5190906, US4804799, world patent W009839278A1 etc..Such catalyst is replaced with Ce, Mo binary auxiliary agent
, so that catalyst is on the basis of maintaining original stability, activity, selectivity are compared with the former for the role that generation was taken on by Cr originally
Improve, adopted by countries in the world production of styrene producer, the subject matter that it exists is due to Mo component
Volatility, lead to the stability of catalyst low, and some patent reports substitute less stable with the very high W of heat stability
Mo is although solve MoO3Sublimation problem, but catalysis activity is not high enough.For this reason, it is cinnamic low to find a kind of production
Warm high activity, high stability catalyst are always people's problem very interested.
Content of the invention
One of the technical problem to be solved is to overcome to have in previous literature that catalyst activity is not high enough, stability is inclined
Low shortcoming, provides a kind of new phenylethylene catalyst.This catalyst has and can improve conversion of ethylbenzene, and catalyst is steady simultaneously
Qualitative good feature.
The two of the technical problem to be solved are the preparation methoies of above-mentioned catalyst.
The three of the technical problem to be solved are applications in ethylbenzene dehydrogenation ethylbenzene for the above-mentioned catalyst.
For solving one of above-mentioned technical problem, technical scheme is as follows：Phenylethylene catalyst, in parts by weight, bag
Include following active constituent：
A) 55～94 parts of Fe2O3；
B) 5～30 parts of K2O；
C) 3～15 parts of Ce2O3；
D) 0.1～5 part of MoO3And/or WO3；
E) 0.1～5 part of W2C；
F) 0.1～10 part of oxide being selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
In technique scheme, MoO3And/or WO3It is preferably 0.1～3 part.
In technique scheme, W2C is preferably 0.1～3 part.
In technique scheme, the oxide consumption selected from least one of Mg, Ca, Sr, Ba is preferably 0.5～7 part.
In technique scheme, in described catalyst, preferably also the cement containing less than 10 parts is binding agent.
In above-mentioned technical side, further preferably contain Mo2C, still more preferably with weight ratio meter Mo2C：W2C=(0～100):
1.
For solving the two of above-mentioned technical problem, technical scheme is as follows：In the technical scheme of one of above-mentioned technical problem
The preparation method of catalyst described in any one, comprises the following steps：The raw material of component, porogen is needed to mix all with water by described
Even, mediate, extrusion, be dried, pelletizing, roasting.
In technique scheme, the preferred autoxidisable substance of raw material of the oxide of described alkaline-earth metal, hydroxide or its salt, more
Salt preferably nitrate described further, nitrite, carbonate or carboxylate.
In technique scheme, Fe2O3Raw material be preferably iron oxide red and/or iron oxide yellow, more preferably with weight ratio meter, iron oxide yellow:Iron oxide red
For (0～0.5): 1, the most further preferred iron oxide yellow:Iron oxide red is (0～0.3): 1.
In technique scheme, K2The optional K of raw material of O2O, KOH are fired to generate K2The potassium salt of O, these potassium salt examples
As being potassium nitrate, potassium nitrite, potassium carbonate, potassium bicarbonate or carboxylic acid potassium.
In technique scheme, Mo2C or W2The raw material of C can be with the form of its own.In the present invention, tungsten carbide is
W2C, in the present invention, molybdenum carbide refers both to Mo2C.
In technique scheme, Ce2O3Raw material can be that the oxide of cerium, hydroxide or metallic salt form add, and
Metallic salts such as, but not limited to, nitrate.
In technique scheme, described porogen can be chosen from graphite, polystyrene microsphere, carboxymethyl cellulose etc.；Its
Consumption is preferably the 1～4% of catalyst weight.
The method for preparing catalyst of the such as present invention can be specially：
The described raw material needing component, binding agent, porogen are added appropriate deionized water, makes toughness, fit through mediating
Close the paste of extrusion, become a diameter of 3 millimeters, long 5～10 millimeters of granule through extrusion, pelletizing, in 40～150 DEG C of dryings 1～
10 hours, then roasting 1～8 hour at 400～1000 DEG C, you can obtain finished catalyst.
Catalyst of the present invention can carry out performance evaluation and use in isotherm formula fixed bed.Carry out ethylbenzene in isotherm formula fixed bed
For dehydrogenation preparation of styrene activity rating, summary process is as follows：
By ethylbenzene and deionized water respectively through preheating in dosing pump input mixer, enter reactor, reactor in a gaseous form
Using electric-heating-wire-heating, make up to predetermined temperature.Reactor inside diameter be 1 " stainless steel tube, interior load 100 milliliters,
Particle diameter is 3.0 millimeters of catalyst.The dehydrogenation product that flowed out by reactor water cooled solidifying after with chromatographic, it forms.
In isotherm formula fixed bed reactors, evaluating catalyst condition is as follows：By 100 milliliters, particle diameter be that 3 millimeters of catalyst is put into
The isothermal reactor of internal diameter 1 ", reaction pressure is normal pressure, ethylbenzene air speed 1.0 hours-1, 620 DEG C of reaction temperature, water ratio (water/
Ethylbenzene) (weight) 2.0.
Conversion of ethylbenzene and selectivity of styrene calculate as follows：
(%)=conversion of ethylbenzene (%) × selectivity of styrene (%) received by styrene list.
The main side reaction of ethylbenzene dehydrogenation is to generate toluene and benzene.Have shown that through research：The rate-determining step of reaction is that the ethylbenzene of absorption exists
The dehydrogenation step of catalyst surface, and W2C ensures that catalyst has good low temperature active, increases the stability of catalyst, takes
Obtained preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
By 195 iron oxide reds, 80.5 grams of iron oxide yellows, 60.6 grams of potassium carbonate, 90.5 grams of nitric acid Fructus Kakis, 13.3 grams of ammonium molybdates, 1.1
Gram molybdenum carbide, 10.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 15 grams of cement and 10 grams of carboxymethyl celluloses stir 1 in kneader
Hour, add 83 grams of deionized waters, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, 5～10 millimeters of length
Granule, puts into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.
【Embodiment 2】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates,
6.2 grams of molybdenum carbides, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 in kneader
Hour, add 76 grams of deionized waters, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, 5～10 millimeters of length
Granule, puts into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 3】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates,
6.2 grams of tungsten carbides, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 in kneader
Hour, add 76 grams of deionized waters, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, 5～10 millimeters of length
Granule, puts into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 4】
By 123.7 iron oxide reds, 167.5 grams of iron oxide yellows, 65.6 grams of potassium carbonate, 70.7 grams of nitric acid Fructus Kakis, 1.3 grams of ammonium molybdates, 9.2
Gram tungsten carbide, 10.1 grams of magnesium oxide, 8.5 grams of calcium oxide, 19 grams of cement and 12 grams of carboxymethyl celluloses stir 1 in kneader
Hour, add 73 grams of deionized waters, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, 5～10 millimeters of length
Granule, puts into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Embodiment 5】
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates,
3.1 grams of molybdenum carbides, 3.1 grams of tungsten carbides, 8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses exist
Stir 1 hour in kneader, add 76 grams of deionized waters, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, length
The granule of 5～10 millimeters of degree, puts into baking oven, and 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours systems of 780 DEG C of roastings
Obtain catalyst.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
【Comparative example 1】
In addition to being added without molybdenum carbide, remaining is all same as Example 2, specially for the preparation method of catalyst：
By 130.3 iron oxide reds, 152.6 grams of iron oxide yellows, 60.3 grams of potassium carbonate, 80.3 grams of nitric acid Fructus Kakis, 10.6 grams of ammonium molybdates,
8.4 grams of magnesium oxide, 19.5 grams of calcium oxide and 25 grams of cement and 8 grams of carboxymethyl celluloses stir 1 hour in kneader, add 76
Gram deionized water, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, put into baking
Case, 80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From comparative example 1 and embodiment 2 on year-on-year basis knowable to, include Mo due in catalyst2C is hence it is evident that improve the second of catalyst
Benzene conversion ratio, and make catalyst of the present invention have more preferable stability.
【Comparative example 2】
In addition to being added without tungsten carbide, remaining is all same as Example 4, specially for the preparation method of catalyst：
By 123.7 iron oxide reds, 167.5 grams of iron oxide yellows, 65.6 grams of potassium carbonate, 70.7 grams of nitric acid Fructus Kakis, 1.3 grams of ammonium molybdates, 10.1
Gram magnesium oxide, 8.5 grams of calcium oxide, 19 grams of cement and 12 carboxymethyl celluloses stir 1 hour in kneader, add？Gram de-
Ionized water, then mix and stir half an hour, take out extrusion, be extruded into 3 millimeters of diameter, the granule of 5～10 millimeters of length, put into baking oven,
80 DEG C are dried 4 hours, are subsequently placed in muffle furnace, in 6 hours prepared catalyst of 780 DEG C of roastings.
For ease of comparing, the inventory in catalyst preparation is listed in Table 1 below, the evaluating catalyst result of 200 hours is listed in
Table 2.The evaluation result of 200 hours and other evaluation times is listed in table 3.
From comparative example 2 and embodiment 4 on year-on-year basis knowable to, include W due in catalyst2C, the ethylbenzene that improve catalyst turns
Rate, and make the stability that catalyst of the present invention had.
Table 1
Table 2
*：Catalyst performance is the evaluation meansigma methodss of 200 hours.
Table 3
| 200 hours single receipts* | 1000 hours single receipts* | Single receipts reduction rate, % | |
| Comparative example 1 | 69.0 | 68.0 | 1.45 |
| Comparative example 2 | 69.1 | 68.1 | 1.45 |
| Embodiment 2 | 71.4 | 71.0 | 0.56 |
| Embodiment 4 | 71.0 | 70.7 | 0.42 |
| Embodiment 6 | 71.5 | 71.3 | 0.28 |
*：Catalyst performance is the meansigma methodss in corresponding evaluation time.
Claims (10)
1. high stable phenylethylene catalyst, in parts by weight, including following active constituent：
A) 55～94 parts of Fe2O3；
B) 5～30 parts of K2O；
C) 3～15 parts of Ce2O3；
D) 0.1～5 part of MoO3And/or WO3；
E) 0.1～5 part of W2C；
F) 0.1～10 part of oxide being selected from least one of Mg, Ca, Sr and Ba alkaline-earth metal.
2. high stable phenylethylene catalyst according to claim 1 is it is characterised in that MoO3And/or WO3For 0.1～
3 parts.
3. high stable phenylethylene catalyst according to claim 1 is it is characterised in that W2C is 0.1～3 part.
4. high stable phenylethylene catalyst according to claim 1 is it is characterised in that be selected from Mg, Ca, Sr, Ba
At least one of oxide consumption be 0.5～7 part.
5. high stable phenylethylene catalyst according to claim 1 it is characterised in that also contain in catalyst 10 parts with
Under cement be binding agent.
6. the preparation method of the high stable catalyst described in any one of Claims 1 to 5, comprises the following steps：By institute
State and need the raw material of active component, porogen to mix homogeneously with water, mediate, extrusion, be dried, pelletizing, roasting.
7. preparation method according to claim 6 is it is characterised in that the raw material of the oxide of alkaline-earth metal is selected from oxidation
Thing, hydroxide or its salt.
8. preparation method according to claim 6 is it is characterised in that Fe2O3Raw material be iron oxide red and/or iron oxide yellow.
9. preparation method according to claim 8 is it is characterised in that with weight ratio meter, iron oxide yellow:Iron oxide red is (0～0.5):
1.
10. application in ethyl benzene dehydrogenation preparation of styrene for the catalyst any one of Claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493326.7A CN106423239B (en) | 2015-08-12 | 2015-08-12 | High stable phenylethylene catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493326.7A CN106423239B (en) | 2015-08-12 | 2015-08-12 | High stable phenylethylene catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423239A true CN106423239A (en) | 2017-02-22 |
| CN106423239B CN106423239B (en) | 2019-01-25 |
Family
ID=58092622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510493326.7A Active CN106423239B (en) | 2015-08-12 | 2015-08-12 | High stable phenylethylene catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423239B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018593A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst having a bimodal pore size distribution |
| CN1207330A (en) * | 1997-08-01 | 1999-02-10 | 舒德化学公司 | Catalysts for dehydrogenating ethylbenzene to styrene |
| US6166280A (en) * | 1996-03-08 | 2000-12-26 | Montecatini Technologies S.R.L. | Catalyst for the dehydrogenation of ethylbenzene to styrene |
| CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof |
| CN102069002A (en) * | 2010-12-31 | 2011-05-25 | 浙江工业大学 | Preparation method of wolfram carbide-carbon (WC-C) composite material with large specific surface area |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
-
2015
- 2015-08-12 CN CN201510493326.7A patent/CN106423239B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996018593A1 (en) * | 1994-12-14 | 1996-06-20 | Shell Internationale Research Maatschappij B.V. | Dehydrogenation catalyst having a bimodal pore size distribution |
| US6166280A (en) * | 1996-03-08 | 2000-12-26 | Montecatini Technologies S.R.L. | Catalyst for the dehydrogenation of ethylbenzene to styrene |
| CN1207330A (en) * | 1997-08-01 | 1999-02-10 | 舒德化学公司 | Catalysts for dehydrogenating ethylbenzene to styrene |
| CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
| CN101992095A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through dehydrogenation by using rough ethylbenzene and preparation method thereof |
| CN102069002A (en) * | 2010-12-31 | 2011-05-25 | 浙江工业大学 | Preparation method of wolfram carbide-carbon (WC-C) composite material with large specific surface area |
| CN103030523A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing styrene by ethylbenzene dehydrogenation |
| CN103357408A (en) * | 2012-03-31 | 2013-10-23 | 浙江工业大学 | WC/CNT (wolfram carbide/carbon nano-tube), WC/CNT/Pt (wolfram carbide/carbon nano-tube/platinum) composite materials and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HENRY H. HWU ET AL.: ""Surface Chemistry of transition Metal Carbides"", 《CHEMICAL REVIEWS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423239B (en) | 2019-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100531905C (en) | Catalysts for ethyl benzene dehydrogenation for preparation of styrene | |
| CN106582687B (en) | Catalyst of low-water ratio ethylbenzene dehydrogenation and preparation method thereof | |
| CN102039204B (en) | Method for preparing styrene catalyst by ethyl benzene dehydrogenation | |
| CN103537291B (en) | Catalyst of ethyl benzene dehydrogenation preparation of styrene and preparation method thereof | |
| CN101993336B (en) | Method for preparing vinyl benzene from ethylbenzene dehydrogenation under low water ratio condition | |
| CN106582693B (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN100391604C (en) | Dehydrogenating catalyst for preparing styrene | |
| CN101279263B (en) | Catalyst for preparation of styrene by ethylbenzene dehydrogenation | |
| CN101623642B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio | |
| CN103028421B (en) | Low-water ratio ethylbenzene dehydrogenation catalyst | |
| CN109569638A (en) | Low-temperature alkyl arene dehydrogenating catalyst and preparation method thereof | |
| CN106582681B (en) | catalyst for low-water-ratio ethylbenzene dehydrogenation | |
| CN109569639A (en) | It is used to prepare the dehydrogenation and preparation method thereof of styrene | |
| CN106582692B (en) | The ethylbenzene dehydrogenation catalyst with low water ratio of high activity | |
| CN106582691B (en) | Ethylbenzene dehydrogenation catalyst with low water ratio and preparation method thereof | |
| CN110681391A (en) | Low-water ratio ethylbenzene dehydrogenation catalyst and preparation method thereof | |
| CN106423239A (en) | High-stability styrene catalyst | |
| CN106582688B (en) | It is used to prepare the dehydrogenation and preparation method thereof of styrene | |
| CN106582685B (en) | Low-temperature ethyl benzene dehydrogenation catalyst and preparation method thereof | |
| CN105478132B (en) | Catalyst for phenylethylene dehydrogenation of low-carbon type and its preparation method and application | |
| CN106423187A (en) | Styrene catalyst | |
| CN106423238A (en) | Styrene catalyst and preparation method thereof | |
| CN106423240A (en) | Styrene catalyst and preparation method thereof | |
| CN103537296A (en) | Ethylbenzene dehydrogenation catalyst in low water ratio | |
| CN103537295B (en) | The low temperature catalyst of ethyl benzene dehydrogenation preparation of styrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |